Phosphonic acid based ion exchange resins

DOEpatents

Horwitz, E.P.; Alexandratos, S.D.; Gatrone, R.C.; Chiarizia, R.

1994-01-25

An ion exchange resin is described for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene. 9 figures.

Using amino acids for the chromatofocusing of metal ions on silica with bonded tetraethylenepentamine groups

NASA Astrophysics Data System (ADS)

Ivanov, A. V.

2014-09-01

Amino acid-based eluents are used for the chromatofocusing of metal ions on Tetren-SiO2 chelating sorbent (silica with bonded tetraethylenepentamine groups) for the first time. The smoothest quasilinear pH gradients form for eluents based on glutamic and aspartic acids. The separation of Mn2+, Cr3+, Co2+, Ni2+, and Cu2+ is achieved.

Potential of ethylenediaminedi(o-hydroxyphenylacetic acid) and N,N'-bis(hydroxybenzyl)ethylenediamine-N,N'-diacetic acid for the determination of metal ions by capillary electrophoresis.

PubMed

Krokhin, O V; Kuzina, O V; Hoshino, H; Shpigun, O A; Yotsuyanagi, T

2000-08-25

Two aromatic polyaminocarboxylate ligands, ethylenediaminedi(o-hydroxyphenylacetic acid) (EDDHA) and N,N'-bis(hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED), were applied for the separation of transition and heavy metal ions by the ion-exchange variant of electrokinetic chromatography. EDDHA structure contains two chiral carbon centers. It makes it impossible to use the commercially available ligand. All the studied metal ions showed two peaks, which correspond to meso and rac forms of the ligand. The separation of metal-HBED chelates was performed using poly(diallyldimethylammonium) polycations in mixed acetate-hydroxide form. Simultaneous separation of nine single- and nine double-charged HBED chelates, including In(III), Ga(III), Co(II)-(III) and Mn(II)-(III) pairs demonstrated the efficiency of 40,000-400,000 theoretical plates. The separation of Co(III), Fe(III) complexes with different arrangements of donor groups and oxidation of Co(II), Mn(H), Fe(II) ions in reaction with HBED have been discussed.

Boric-Acid-Functional Lanthanide Metal-Organic Frameworks for Selective Ratiometric Fluorescence Detection of Fluoride Ions.

PubMed

Yang, Zhong-Rui; Wang, Man-Man; Wang, Xue-Sheng; Yin, Xue-Bo

2017-02-07

Here, we report that boric acid is used to tune the optical properties of lanthanide metal-organic frameworks (LMOFs) for dual-fluorescence emission and improves the selectivity of LMOFs for the determination of F - ions. The LMOFs are prepared with 5-boronoisophthalic acid (5-bop) and Eu 3+ ions as the precursors. Emission mechanism study indicates that 5-bop is excited with UV photons to produce its triplet state, which then excites Eu 3+ ions for their red emission. This is the general story of the antenna effect, but electron-deficient boric acid decreases the energy transfer efficiency from the triplet state of 5-bop to Eu 3+ ions, so dual emission from both 5-bop and Eu 3+ ions is efficiently excited at the single excitation of 275 nm. Moreover, boric acid is used to identify fluoride specifically as a free accessible site. The ratiometric fluorescent detection of F - ions is validated with the dual emission at single excitation. The LMOFs are very monodisperse, so the determination of aqueous F - ions is easily achieved with high selectivity and a low detection limit (2 μM). For the first time, we reveal that rational selection of functional ligands can improve the sensing efficiency of LMOFs through tuning their optical property and enhancing the selectivity toward targets.

Potentiometric Determination of Phytic Acid and Investigations of Phytate Interactions with Some Metal Ions.

PubMed

Marolt, Gregor; Pihlar, Boris

2015-01-01

Determination of correct amount (concentration) of phytic acid is of vital importance when dealing with protonation and/or metal complexation equilibria. A novel approach for precise and reliable assay of phytic acid, based on the difference between end points by potentiometric titration, has been presented. Twelve phytic acid protons are classified into three groups of acidity, which enables detection of 2 to 3 distinct equivalent points (EPs) depending on experimental conditions, e.g. counter-ion concentration. Using the differences between individual EPs enables correct phytate determination as well as identification of potential contamination and/or determination of initial protonation degree. Impact of uncertainty of phytate amount on the calculation of protonation constants has been evaluated using computer simulation program (Hyperquad2013). With the analysis of titration curves different binding sites on phytate ligand have been proposed for complexation of Ca2+ and Fe3+ ions.

THE ROLES OF METAL IONS IN REGULATION BY RIBOSWITCHES

PubMed Central

2012-01-01

Metal ions are required by all organisms in order to execute an array of essential molecular functions. They play a critical role in many catalytic mechanisms and structural properties. Proper homeostasis of ions is critical; levels that are aberrantly low or high are deleterious to cellular physiology. To maintain stable intracellular pools, metal ion-sensing regulatory (metalloregulatory) proteins couple metal ion concentration fluctuations with expression of genes encoding for cation transport or sequestration. However, these transcriptional-based regulatory strategies are not the only mechanisms by which organisms coordinate metal ions with gene expression. Intriguingly, a few classes of signal-responsive RNA elements have also been discovered to function as metalloregulatory agents. This suggests that RNA-based regulatory strategies can be precisely tuned to intracellular metal ion pools, functionally akin to metalloregulatory proteins. In addition to these metal-sensing regulatory RNAs, there is a yet broader role for metal ions in directly assisting the structural integrity of other signal-responsive regulatory RNA elements. In this chapter, we discuss how the intimate physicochemical relationship between metal ions and nucleic acids is important for the structure and function of metal ion- and metabolite-sensing regulatory RNAs. PMID:22010271

Uncoupling metallonuclease metal ion binding sites via nudge mutagenesis.

PubMed

Papadakos, Grigorios A; Nastri, Horacio; Riggs, Paul; Dupureur, Cynthia M

2007-05-01

The hydrolysis of phosphodiester bonds by nucleases is critical to nucleic acid processing. Many nucleases utilize metal ion cofactors, and for a number of these enzymes two active-site metal ions have been detected. Testing proposed mechanistic roles for individual bound metal ions has been hampered by the similarity between the sites and cooperative behavior. In the homodimeric PvuII restriction endonuclease, the metal ion dependence of DNA binding is sigmoidal and consistent with two classes of coupled metal ion binding sites. We reasoned that a conservative active-site mutation would perturb the ligand field sufficiently to observe the titration of individual metal ion binding sites without significantly disturbing enzyme function. Indeed, mutation of a Tyr residue 5.5 A from both metal ions in the enzyme-substrate crystal structure (Y94F) renders the metal ion dependence of DNA binding biphasic: two classes of metal ion binding sites become distinct in the presence of DNA. The perturbation in metal ion coordination is supported by 1H-15N heteronuclear single quantum coherence spectra of enzyme-Ca(II) and enzyme-Ca(II)-DNA complexes. Metal ion binding by free Y94F is basically unperturbed: through multiple experiments with different metal ions, the data are consistent with two alkaline earth metal ion binding sites per subunit of low millimolar affinity, behavior which is very similar to that of the wild type. The results presented here indicate a role for the hydroxyl group of Tyr94 in the coupling of metal ion binding sites in the presence of DNA. Its removal causes the affinities for the two metal ion binding sites to be resolved in the presence of substrate. Such tuning of metal ion affinities will be invaluable to efforts to ascertain the contributions of individual bound metal ions to metallonuclease function.

The enhancement of the hydrolysis of bamboo biomass in ionic liquid with chitosan-based solid acid catalysts immobilized with metal ions.

PubMed

Cheng, Jie; Wang, Nan; Zhao, Dezhou; Qin, Dandan; Si, Wenqing; Tan, Yunfei; Wei, Shun'an; Wang, Dan

2016-11-01

Three kinds of sulfonated cross-linked chitosan (SCCR) immobilized with metal ions of Cu(2+), Fe(3+) and Zn(2+) individually were synthesized and firstly used as solid acid catalysts in the hydrolysis of bamboo biomass. FTIR spectra showed that metal ions had been introduced into SCCR and the N-metal ions coordinate bound was formed. The particle sizes of these catalysts were about 500-1000μm with a pore size of 50-160μm. All of the three kinds of catalysts performed well for bamboo hydrolysis with 1-butyl-3-methyl-imidazolium chloride used as solvent. The most effective one was sulfonated cross-linked chitosan immobilized with Fe(3+) (Fe(3+)-SCCR). TRS yields were up to 73.42% for hydrolysis of bamboo powder in [C4mim]Cl with Fe(3+)-SCCR at 120°C and 20RPM after 24h. These novel chitosan-based metal ions immobilized solid acid catalysts with ionic liquids as the solvent might be promising to facilitate cost-efficient conversion of biomass into biofuels and bioproducts. Copyright © 2016 Elsevier Ltd. All rights reserved.

Multistage leaching of metals from spent lithium ion battery waste using electrochemically generated acidic lixiviant.

PubMed

Boxall, N J; Adamek, N; Cheng, K Y; Haque, N; Bruckard, W; Kaksonen, A H

2018-04-01

Lithium ion battery (LIB) waste contains significant valuable resources that could be recovered and reused to manufacture new products. This study aimed to develop an alternative process for extracting metals from LIB waste using acidic solutions generated by electrolysis for leaching. Results showed that solutions generated by electrolysis of 0.5 M NaCl at 8 V with graphite or mixed metal oxide (MMO) electrodes were weakly acidic and leach yields obtained under single stage (batch) leaching were poor (<10%). This was due to the highly acid-consuming nature of the battery waste. Multistage leaching with the graphite electrolyte solution improved leach yields overall, but the electrodes corroded over time. Though yields obtained with both electrolyte leach solutions were low when compared to the 4 M HCl control, there still remains potential to optimise the conditions for the generation of the acidic anolyte solution and the solubilisation of valuable metals from the LIB waste. A preliminary value proposition indicated that the process has the potential to be economically feasible if leach yields can be improved, especially based on the value of recoverable cobalt and lithium. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries.

PubMed

Chen, Xiangping; Chen, Yongbin; Zhou, Tao; Liu, Depei; Hu, Hang; Fan, Shaoyun

2015-04-01

Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt and lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe-Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC2O4 ⋅ 2H2O and Li2CO3 using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Xiangping; Chen, Yongbin; Zhou, Tao, E-mail: zhoutao@csu.edu.cn

2015-04-15

Highlights: • Selective precipitation and solvent extraction were adopted. • Nickel, cobalt and lithium were selectively precipitated. • Co-D2EHPA was employed as high-efficiency extraction reagent for manganese. • High recovery percentages could be achieved for all metal values. - Abstract: Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt andmore » lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe–Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC{sub 2}O{sub 4}⋅2H{sub 2}O and Li{sub 2}CO{sub 3} using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor.« less

Coordination ability determined transition metal ions substitution of Tb in Tb-Asp fluorescent nanocrystals and a facile ions-detection approach.

PubMed

Duan, Jiazhi; Ma, Baojin; Liu, Feng; Zhang, Shan; Wang, Shicai; Kong, Ying; Du, Min; Han, Lin; Wang, Jianjun; Sang, Yuanhua; Liu, Hong

2018-04-26

Although the synthesis and fluorescent properties of lanthanide-amino acid complex nanostructures have been investigated extensively, limited studies have been reported on metal ions' substitution ability for the lanthanide ions in the complex and their effect on the fluorescent property. In this study, taking biocompatible Tb-aspartic acid (Tb-Asp) complex nanocrystals as a model, the substitution mechanism of metal ions, particularly transition metals, for Tb ions in Tb-Asp nanocrystals and the change in the fluorescent property of the Tb-Asp nanocrystals after substitution were systematically investigated. The experimental results illustrated that metal ions with higher electronegativity, higher valence, and smaller radius possess stronger ability for Tb ions' substitution in Tb-Asp nanocrystals. Based on the effect of substituting ions' concentration on the fluorescent property of Tb-Asp, a facile method for copper ions detection with high sensitivity was proposed by measuring the fluorescent intensity of Tb-Asp nanocrystals' suspensions containing different concentrations of copper ions. The good biocompatibility, great convenience of synthesis and sensitive detection ability make Tb-Asp nanocrystals a very low cost and effective material for metal ions detection, which also opens a new door for practical applications of metal-Asp coordinated nanocrystals.

A versatile MOF-based trap for heavy metal ion capture and dispersion.

PubMed

Peng, Yaguang; Huang, Hongliang; Zhang, Yuxi; Kang, Chufan; Chen, Shuangming; Song, Li; Liu, Dahuan; Zhong, Chongli

2018-01-15

Current technologies for removing heavy metal ions are typically metal ion specific. Herein we report the development of a broad-spectrum heavy metal ion trap by incorporation of ethylenediaminetetraacetic acid into a robust metal-organic framework. The capture experiments for a total of 22 heavy metal ions, covering hard, soft, and borderline Lewis metal ions, show that the trap is very effective, with removal efficiencies of >99% for single-component adsorption, multi-component adsorption, or in breakthrough processes. The material can also serve as a host for metal ion loading with arbitrary selections of metal ion amounts/types with a controllable uptake ratio to prepare well-dispersed single or multiple metal catalysts. This is supported by the excellent performance of the prepared Pd 2+ -loaded composite toward the Suzuki coupling reaction. This work proposes a versatile heavy metal ion trap that may find applications in the fields of separation and catalysis.

Nucleic acids encoding metal uptake transporters and their uses

DOEpatents

Schroeder, Julian I.; Antosiewicz, Danuta M.; Schachtman, Daniel P.; Clemens, Stephan

1999-01-01

The invention provides LCT1 nucleic acids which encode metal ion uptake transporters. The invention also provides methods of modulating heavy metal and alkali metal uptake in plants. The methods involve producing transgenic plants comprising a recombinant expression cassette containing an LCT1 nucleic acid linked to a plant promoter.

Biostable L-DNAzyme for Sensing of Metal Ions in Biological Systems

PubMed Central

2015-01-01

DNAzymes, an important type of metal ion-dependent functional nucleic acid, are widely applied in bioanalysis and biomedicine. However, the use of DNAzymes in practical applications has been impeded by the intrinsic drawbacks of natural nucleic acids, such as interferences from nuclease digestion and protein binding, as well as undesired intermolecular interactions with other nucleic acids. On the basis of reciprocal chiral substrate specificity, the enantiomer of D-DNAzyme, L-DNAzyme, could initiate catalytic cleavage activity with the same achiral metal ion as a cofactor. Meanwhile, by using the advantage of nonbiological L-DNAzyme, which is not subject to the interferences of biological matrixes, as recognition units, a facile and stable L-DNAzyme sensor was proposed for sensing metal ions in complex biological samples and live cells. PMID:26691677

Tunicate-Inspired Gallic Acid/Metal Ion Complex for Instant and Efficient Treatment of Dentin Hypersensitivity.

PubMed

Prajatelistia, Ekavianty; Ju, Sung-Won; Sanandiya, Naresh D; Jun, Sang Ho; Ahn, Jin-Soo; Hwang, Dong Soo

2016-04-20

Dentin hypersensitivity is sharp and unpleasant pains caused by exposed dentinal tubules when enamel outside of the tooth wears away. The occlusion of dentinal tubules via in situ remineralization of hydroxyapatite is the best method to alleviate the symptoms caused by dentin hypersensitivity. Commercially available dental desensitizers are generally effective only on a specific area and are relatively toxic, and their performance usually depends on the skill of the clinician. Here, a facile and efficient dentin hypersensitivity treatment with remarkable aesthetic improvement inspired by the tunicate-self-healing process is reported. As pyrogallol groups in tunicate proteins conjugate with metal ions to heal the torn body armor of a tunicate, the ingenious mechanism by introducing gallic acid (GA) as a cheap, abundant, and edible alternative to the pyrogallol groups of the tunicate combined with a varied daily intake of metal ion sources is mimicked. In particular, the GA/Fe(3+) complex exhibits the most promising results, to the instant ≈52% blockage in tubules within 4 min and ≈87% after 7 d of immersion in artificial saliva. Overall, the GA/metal ion complex-mediated coating is facile, instant, and effective, and is suggested as an aesthetic solution for treating dentin hypersensitivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Retention of metal and sulphate ions from acidic mining water by anionic nanofibrillated cellulose.

PubMed

Venäläinen, Salla H; Hartikainen, Helinä

2017-12-01

We carried out an adsorption experiment to investigate the ability of anionic nanofibrillated cellulose (NFC) to retain metal and SO 4 2- ions from authentic highly acidic (pH3.2) mining water. Anionic NFC gels of different consistencies (1.1-%, 1.4-% and 1.8-% w/w) were allowed to react for 10min with mining water, after which NFC-induced changes in the metal and SO 4 2- concentrations of the mining water were determined. The sorption capacities of the NFC gels were calculated as the difference between the element concentrations in the untreated and NFC-treated mining water samples. All the NFCs efficiently co-adsorbed both metals and SO 4 2- . The retention of metals was concluded to take place through formation of metal-ligand complexes. The reaction between the NFC ligand and the polyvalent cations renders the cellulose nanofibrils positively charged and, thus, able to retain SO 4 2- electrostatically. Adsorption capacity of the NFC gels substantially increased upon decreasing DM content as a result of the dilution-induced weakening of the mutual interactions between individual cellulose nanofibrils. This outcome reveals that the dilution of the NFC gel not only increases its purification capacity but also reduces the demand for cellulosic raw material. These results suggest that anionic NFC made of renewable materials serves as an environmentally sound and multifunctional purification agent for acidic multimetal mining waters or AMDs of high ionic strength. Unlike industrial minerals traditionally used to precipitate valuable metals from acidic mining effluents before their permanent disposal from the material cycle, NFC neither requires mining of unrenewable raw materials nor produces inorganic sludges. Copyright © 2017 Elsevier B.V. All rights reserved.

Metal-ion interactions and the structural organization of Sepia eumelanin.

PubMed

Liu, Yan; Simon, John D

2005-02-01

The structural organization of melanin granules isolated from ink sacs of Sepia officinalis was examined as a function of metal ion content by scanning electron microscopy and atomic force microscopy. Exposing Sepia melanin granules to ethelenediaminetetraacetic acid (EDTA) solution or to metal salt solutions changed the metal content in the melanin, but did not alter granular morphology. Thus ionic forces between the organic components and metal ions in melanin are not required to sustain the natural morphology once the granule is assembled. However, when aqueous suspensions of Sepia melanin granules of varying metal content are ultra-sonicated, EDTA-washed and Fe-saturated melanin samples lose material to the solution more readily than the corresponding Ca(II) and Mg(II)-loaded samples. The solubilized components are found to be 5,6-dihydroxyindole-2-carboxylic acid (DHICA)-rich constituents. Associated with different metal ions, Na(I), Ca(II) and Mg(II) or Fe(III), these DHICA-rich entities form distinct two-dimensional aggregation structures when dried on the flat surface of mica. The data suggest multiply-charged ions play an important role in assisting or templating the assembly of the metal-free organic components to form the three-dimensional substructure distributed along the protein scaffold within the granule.

Process for the displacement of cyanide ions from metal-cyanide complexes

DOEpatents

Smith, Barbara F.; Robinson, Thomas W.

1997-01-01

The present invention relates to water-soluble polymers and the use of such water-soluble polymers in a process for the displacement of the cyanide ions from the metal ions within metal-cyanide complexes. The process waste streams can include metal-cyanide containing electroplating waste streams, mining leach waste streams, mineral processing waste streams, and related metal-cyanide containing waste streams. The metal ions of interest are metals that give very strong complexes with cyanide, mostly iron, nickel, and copper. The physical separation of the water-soluble polymer-metal complex from the cyanide ions can be accomplished through the use of ultrafiltration. Once the metal-cyanide complex is disrupted, the freed cyanide ions can be recovered for reuse or destroyed using available oxidative processes rendering the cyanide nonhazardous. The metal ions are released from the polymer, using dilute acid, metal ion oxidation state adjustment, or competing chelating agents, and collected and recovered or disposed of by appropriate waste management techniques. The water-soluble polymer can then be recycled. Preferred water-soluble polymers include polyethyleneimine and polyethyleneimine having a catechol or hydroxamate group.

Selective extraction of metal ions with polymeric extractants by ion exchange/redox

DOEpatents

Alexandratos, Spiro D.

1987-01-01

The specification discloses a method for the extraction of metal ions having a reduction potential of above about +0.3 from an aqueous solution. The method includes contacting the aqueous solution with a polymeric extractant having primary phosphinic acid groups, secondary phosphine oxide groups, or both phosphinic acid and phosphine oxide groups.

Responsiveness to acidity via metal ion regulators mediates virulence in the gastric pathogen Helicobacter pylori.

PubMed

Bury-Moné, Stéphanie; Thiberge, Jean-Michel; Contreras, Monica; Maitournam, Aboubakar; Labigne, Agnès; De Reuse, Hilde

2004-07-01

The virulence of pathogenic bacteria is dependent on their adaptation to and survival in the stressful conditions encountered in their hosts. Helicobacter pylori exclusively colonizes the acid stomach of primates, making it an ideal study model. Little is known about how H. pylori responds to the moderately acidic conditions encountered at its colonization site, the gastric mucus layer. Thus, we compared gene expression profiles of H. pylori 26695 grown at neutral and acidic pH, and validated the data for a selection of genes by real-time polymerase chain reaction, dot-blots or enzymatic assays. During growth in acidic conditions, 56 genes were upregulated and 45 genes downregulated. We found that acidity is a signal modulating the expression of several virulence factors. Regulation of genes related to metal ion homeostasis suggests protective mechanisms involving diminished transport and enhanced storage. Genes encoding subunits of the F0F1 ATPase and of a newly identified Na+/H+ antiporter (NhaC-HP0946) were downregulated, revealing that this bacterium uses original mechanisms to control proton entry. Five of the upregulated genes encoded proteins controlling intracellular ammonia synthesis, including urease, amidase and formamidase, underlining the major role of this buffering compound in the protection against acidity in H. pylori. Regulatory networks and transcriptome analysis as well as enzymatic assays implicated two metal-responsive transcriptional regulators (NikR and Fur) and an essential two-component response regulator (HP0166, OmpR-like) as effectors of the H. pylori acid response. Finally, a nikR-fur mutant is attenuated in the mouse model, emphasizing the link between response to acidity, metal metabolism and virulence in this gastric pathogen.

A multi-method analysis of the interaction between humic acids and heavy metal ions.

PubMed

Ke, Tao; Li, Lu; Rajavel, Krishnamoorthy; Wang, Zhenyu; Lin, Daohui

2018-03-08

Understanding of the interaction between humic acids (HAs) and heavy metal ions (HMIs) is essential for the assessment of environmental and health risks of HMIs. Multiple analyses, including fluorescence quenching of HAs; solution pH, zeta potential, and hydrodynamic size changes; and coprecipitation of HAs and HMIs, were carried out to investigate the interaction between two HAs and four HMIs (Ag + , Pb 2+ , Cd 2+ , and Cr 3+ ). The HA-HMI interaction mainly included chemical complexation, H + -HMI exchange, electrostatic attraction, and flocculation. The chemical complexation between HAs and HMIs revealed by the Stern-Volmer quenching constant was ordered as Ag < Cd < Pb < Cr. HMIs replaced protons in the acidic functional groups of HAs and thus lowered the pH of the solution. The electrostatic interaction between the negatively charged HAs and HMIs reduced the electronegativity of HAs. Interaction with HMIs, especially the high-valent ions, induced aggregation of HAs, causing precipitation of both HAs and HMIs in the sorptive solution. Cr 3+ flocculated and precipitated HAs, but at high concentrations, it reversed the surface charge of HAs and resuspended them. The HA-HMI interaction increased as the HA acidity and solution pH increased.

Quantitative description and local structures of trivalent metal ions Eu(III) and Cm(III) complexed with polyacrylic acid.

PubMed

Montavon, G; Bouby, M; Huclier-Markai, S; Grambow, B; Geckeis, H; Rabung, T; Pashalidis, I; Amekraz, B; Moulin, C

2008-11-15

The trivalent metal ion (M(III)=Cm, Eu)/polyacrylic acid (PAA) system was studied in the pH range between 3 and 5.5 for a molar PAA-to-metal ratio above 1. The interaction was studied for a wide range of PAA (0.05 mg L(-1)-50 g L(-1)) and metal ion concentrations (2x10(-9)-10(-3) M). This work aimed at 3 goals (i) to determine the stoichiometry of M(III)-PAA complexes, (ii) to determine the number of complexed species and the local environment of the metal ion, and (iii) to quantify the reaction processes. Asymmetric flow-field-flow fractionation (AsFlFFF) coupled to ICP-MS evidenced that size distributions of Eu-PAA complexes and PAA were identical, suggesting that Eu bound to only one PAA chain. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements performed with Eu and Cm showed a continuous shift of the spectra with increasing pH. The environment of complexed metal ions obviously changes with pH. Most probably, spectral variations arose from conformational changes within the M(III)-PAA complex due to pH variation. Complexation data describing the distribution of complexed and free metal ion were measured with Cm by TRLFS. They could be quantitatively described in the whole pH-range studied by considering the existence of only a single complexed species. This indicates that the slight changes in M(III) speciation with pH observed at the molecular level do not significantly affect the intrinsic binding constant. The interaction constant obtained from the modelling must be considered as a mean interaction constant.

Highly biocompatible yogurt-derived carbon dots as multipurpose sensors for detection of formic acid vapor and metal ions

NASA Astrophysics Data System (ADS)

Moonrinta, Sasaluck; Kwon, Binhee; In, Insik; Kladsomboon, Sumana; Sajomsang, Warayuth; Paoprasert, Peerasak

2018-07-01

Carbon dots are fascinating nanomaterials given their straightforward synthesis, unique optical properties, sensing capabilities, and biocompatibility. In this work, biocompatible carbon dots were prepared from yogurt using a two-step pyrolysis/hydrothermal method. The dots were spherical in shape with an average size of 4.7 nm. They showed blue emission under UV illumination with a quantum yield of 1.5%. Their photoluminescence was stable over three months and in both strong buffer solutions and highly concentrated salt solutions. The optical absorption and photoluminescence properties of the dots were employed for vapor and metal ion sensing, respectively. For the first time, the carbon dots were integrated into an optical electronic nose, and used for the detection of formic acid vapor at room temperature. Sensing was based on monitoring the optical transmission through a carbon dot film upon exposure to vapor, and the results were confirmed by UV-visible spectroscopy. The carbon dot-integrated electronic nose was able to distinguish vapor from formic acid/water solutions at different concentrations, with a detection limit of 7.3% v/v. The sensitivity of the dots to metal ions was tested by measuring the photoluminescence emission intensity at different excitation wavelengths. Principal component analysis was used to differentiate between the ions. The results suggested that interactions between carbon dots and metals ions occurred at a range of binding sites. The biocompability of the dots was demonstrated to be excellent. The study identified carbon dots produced from yogurt as multipurpose fluorescent nanomaterials with potential sensing and biomedical applications.

Reusable chelating resins concentrate metal ions from highly dilute solutions

NASA Technical Reports Server (NTRS)

Bauman, A. J.; Weetal, H. H.; Weliky, N.

1966-01-01

Column chromatographic method uses new metal chelating resins for recovering heavy-metal ions from highly dilute solutions. The absorbed heavy-metal cations may be removed from the chelating resins by acid or base washes. The resins are reusable after the washes are completed.

Adsorption of Heavy Metal Ions from Aqueous Solutions by Bentonite Nanocomposites.

PubMed

Ma, Jing; Su, Guojun; Zhang, Xueping; Huang, Wen

2016-08-01

A series of bentonite nanocomposites have been synthesized by modifying bentonite with hexadecyltrimethylammonium bromide (CTMAB) and the common complexing agents, complexone (ethylene diamine tetraacetic acid, EDTA) or mercaptocomplexant (2-Mercaptobenzothiazole, MBT). These adsorbents are used to remove heavy metal ions (Cu(2+), Zn(2+), Mn(2+),Co(2+)). The Bent-CTMAB-MBT adsorbed metal ions are higher than Bent-CTMAB-EDTA under the same ion concentration in AAS. Compared with the single ion system, the adsorption of the mixed ion system of Cu(2+), Zn(2+), Mn(2+), Co(2+) had decreased differently. In the mixed system, the adsorption of Mn(2+) is significantly lower, but the adsorption of Cu(2+) was highest. The adsorption sequence of these four metal ions was Cu(2+) > Zn(2+) > Co(2+) > Mn(2+), and the selective adsorption was closely related to the hydration energy of heavy metal ions. We could remove more metal ions in different stages with the adsorption sequence.

Studies on the biofilm produced by Pseudomonas aeruginosa grown in different metal fatty acid salt media and its application in biodegradation of fatty acids and bioremediation of heavy metal ions.

PubMed

Abinaya Sindu, P; Gautam, Pennathur

2017-01-01

Metal fatty acid salts (MFAS) in untreated industrial effluents cause environmental pollution. The use of biocompatible agents for remediation may help in reducing the harm caused to the ambient aquatic organism. Pseudomonas aeruginosa is a ubiquitous organism that thrives under harsh conditions and is resistant to toxic metal ions. The present study shows a proof-of-concept of using this organism in the biodegradation of MFAS. MFAS were prepared and we studied their effect on the growth of the planktonic form and the formation of biofilm by P. aeruginosa. We observed biofilm formation in the presence of all the MFAS when used as the sole carbon source, albeit the quantity of biofilm formed in the presence of cadmium and copper was less. There was no effect on the planktonic form of the organism but the formation of biofilm increased in the presence of magnesium palmitate. This study shows that metal ions play a pivotal role in the formation of biofilm. HPLC (high-performance liquid chromatography) analysis of the biofilm polysaccharide showed that hexose sugar was a major component when compared with pentose sugar. The structure of biofilm polysaccharide and the coordination of the metal ion with the biofilm polysaccharide were confirmed by FTIR (Fourier transform infrared spectroscopy) and Raman spectroscopy.

Inhibition studies of soybean (Glycine max) urease with heavy metals, sodium salts of mineral acids, boric acid, and boronic acids.

PubMed

Kumar, Sandeep; Kayastha, Arvind M

2010-10-01

Various inhibitors were tested for their inhibitory effects on soybean urease. The K(i) values for boric acid, 4-bromophenylboronic acid, butylboronic acid, and phenylboronic acid were 0.20 +/- 0.05 mM, 0.22 +/- 0.04 mM, 1.50 +/- 0.10 mM, and 2.00 +/- 0.11 mM, respectively. The inhibition was competitive type with boric acid and boronic acids. Heavy metal ions including Ag(+), Hg(2+), and Cu(2+) showed strong inhibition on soybean urease, with the silver ion being a potent inhibitor (IC(50) = 2.3 x 10(-8) mM). Time-dependent inhibition studies exhibited biphasic kinetics with all heavy metal ions. Furthermore, inhibition studies with sodium salts of mineral acids (NaF, NaCl, NaNO(3), and Na(2)SO(4)) showed that only F(-) inhibited soybean urease significantly (IC(50) = 2.9 mM). Competitive type of inhibition was observed for this anion with a K(i) value of 1.30 mM.

Generic NICA-Donnan model parameters for metal-ion binding by humic substances.

PubMed

Milne, Christopher J; Kinniburgh, David G; van Riemsdijk, Willem H; Tipping, Edward

2003-03-01

A total of 171 datasets of literature and experimental data for metal-ion binding by fulvic and humic acids have been digitized and re-analyzed using the NICA-Donnan model. Generic parameter values have been derived that can be used for modeling in the absence of specific metalion binding measurements. These values complement the previously derived generic descriptions of proton binding. For ions where the ranges of pH, concentration, and ionic strength conditions are well covered by the available data,the generic parameters successfully describe the metalion binding behavior across a very wide range of conditions and for different humic and fulvic acids. Where published data for other metal ions are too sparse to constrain the model well, generic parameters have been estimated by interpolating trends observable in the parameter values of the well-defined data. Recommended generic NICA-Donnan model parameters are provided for 23 metal ions (Al, Am, Ba, Ca, Cd, Cm, Co, CrIII, Cu, Dy, Eu, FeII, FeIII, Hg, Mg, Mn, Ni, Pb, Sr, Thv, UVIO2, VIIIO, and Zn) for both fulvic and humic acids. These parameters probably represent the best NICA-Donnan description of metal-ion binding that can be achieved using existing data.

A microporous lanthanum metal-organic framework as a bi-functional chemosensor for the detection of picric acid and Fe(3+) ions.

PubMed

Zhang, Chuanqi; Yan, Yan; Pan, Qinhe; Sun, Libo; He, Hongming; Liu, Yunling; Liang, Zhiqiang; Li, Jiyang

2015-08-07

A microporous lanthanum metal-organic framework [La(TPT)(DMSO)2]·H2O (La-MOF ()), has been synthesized using a rigid unsymmetrical tricarboxylate ligand of p-terphenyl-3,4'',5-tricarboxylic acid (H3TPT). The structure of is constructed by bi-nuclear lanthanum clusters and fully deprotonated TPT(3-) ligands, which can be simplified into a 3,6-connected flu-3,6-C2/c topology with a point symbol of (4(4)·6)2(4·6(2)·8(7)·10(2)). The π-electron rich ligand H3TPT enables to have blue luminescence when excited at 342 nm at ambient temperature. Meanwhile, exhibits the selective detection of picric acid (PA) and Fe(3+) ions in ethanol solution over other nitroaromatic compounds and metal ions. The high quenching efficiency and selectivity of makes it a potential bi-functional chemosensor for both PA and Fe(3+) ions.

Comprehensive evaluation on effective leaching of critical metals from spent lithium-ion batteries.

PubMed

Gao, Wenfang; Liu, Chenming; Cao, Hongbin; Zheng, Xiaohong; Lin, Xiao; Wang, Haijuan; Zhang, Yi; Sun, Zhi

2018-05-01

Recovery of metals from spent lithium-ion batteries (LIBs) has attracted worldwide attention because of issues from both environmental impacts and resource supply. Leaching, for instance using an acidic solution, is a critical step for effective recovery of metals from spent LIBs. To achieve both high leaching efficiency and selectivity of the targeted metals, improved understanding on the interactive features of the materials and leaching solutions is highly required. However, such understanding is still limited at least caused by the variation on physiochemical properties of different leaching solutions. In this research, a comprehensive investigation and evaluation on the leaching process using acidic solutions to recycle spent LIBs is carried out. Through analyzing two important parameters, i.e. leaching speed and recovery rate of the corresponding metals, the effects of hydrogen ion concentration, acid species and concentration on these two parameters were evaluated. It was found that a leachant with organic acids may leach Co and Li from the cathode scrap and leave Al foil as metallic form with high leaching selectivity, while that with inorganic acids typically leach all metals into the solution. Inconsistency between the leaching selectivity and efficiency during spent LIBs recycling is frequently noticed. In order to achieve an optimal status with both high leaching selectivity and efficiency (especially at high solid-to-liquid ratios), it is important to manipulate the average leaching speed and recovery rate of metals to optimize the leaching conditions. Subsequently, it is found that the leaching speed is significantly dependent on the hydrogen ion concentration and the capability of releasing hydrogen ions of the acidic leachant during leaching. With this research, it is expected to improve understanding on controlling the physiochemical properties of a leaching solution and to potentially design processes for spent LIBs recycling with high industrial

Metal ion removal from aqueous solution using physic seed hull.

PubMed

Mohammad, Masita; Maitra, Saikat; Ahmad, Naveed; Bustam, Azmi; Sen, T K; Dutta, Binay K

2010-07-15

The potential of physic seed hull (PSH), Jantropha curcas L. as an adsorbent for the removal of Cd(2+) and Zn(2+) metal ions from aqueous solution has been investigated. It has been found that the amount of adsorption for both Cd(2+) and Zn(2+) increased with the increase in initial metal ions concentration, contact time, temperature, adsorbent dosage and the solution pH (in acidic range), but decreased with the increase in the particle size of the adsorbent. The adsorption process for both metal ions on PSH consists of three stages-a rapid initial adsorption followed by a period of slower uptake of metal ions and virtually no uptake at the final stage. The kinetics of metal ions adsorption on PSH followed a pseudo-second-order model. The adsorption equilibrium data were fitted in the three adsorption isotherms-Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The data best fit in the Langmuir isotherm indication monolayer chemisorption of the metal ions. The adsorption capacity of PSH for both Zn(2+) and Cd(2+) was found to be comparable with other available adsorbents. About 36-47% of the adsorbed metal could be leached out of the loaded PSH using 0.1M HCl as the eluting medium. 2010 Elsevier B.V. All rights reserved.

Coordination chemistry of vitamin C. Part I. Interaction of L-ascorbic acid with alkaline earth metal ions in the crystalline solid and aqueous solution.

PubMed

Tajmir-Riahi, H A

1990-10-01

The interaction of L-ascorbic acid with alkaline earth metal ions has been investigated in aqueous solution at pH 6-7. The solid salts of the type Mg(L-ascorbate)2.4H2O, Ca(L-ascorbate)2.2H2O, Sr(L-ascorbate)2.2H2O and Ba(L-ascorbate)2.2H2O were isolated and characterized by means of 13C NMR and FT-IR spectroscopy. Spectroscopic and other evidence suggested that in aqueous solution, the binding of the alkaline earth metal ions is through the O-3 atom of the ascorbate anion, while in the solid state the binding of the Mg(II) is different from those of the other alkaline earth metal ion salts. The Mg(II) ion binds to the O-3, O-1 atom of the two ascorbate anions and to two H2O molecules, while the eight-coordination around the Ca(II), Sr(II), and Ba(II) ions would be completed by the coordination of three acid anions, through O-5, O-6 of the first, O-3, O-5, O-6 of the second and O-1 of the third anion as well as to two H2O molecules. The structural properties of the alkaline earth metal-ascorbate salts are different in the solid and aqueous solution.

Models of metal binding structures in fulvic acid from the Suwannee River, Georgia

USGS Publications Warehouse

Leenheer, J.A.; Brown, G.K.; MacCarthy, P.; Cabaniss, S.E.

1998-01-01

Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The 'metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-1R spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short- chain aliphatic dibasic acid structures. The Ca2+ binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca2+ ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The `metal binding' fraction was characterized by quantitative 13C NMR, 1H NMR, and FT-IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that

Material Removes Heavy Metal Ions From Water

NASA Technical Reports Server (NTRS)

Philipp, Warren H., Jr.; Street, Kenneth W.; Hill, Carol; Savino, Joseph M.

1995-01-01

New high capacity ion-exchange polymer material removes toxic metal cations from contaminated water. Offers several advantages. High sensitivities for such heavy metals as lead, cadmium, and copper and capable of reducing concentrations in aqueous solutions to parts-per-billion range. Removes cations even when calcium present. Material made into variety of forms, such as thin films, coatings, pellets, and fibers. As result, adapted to many applications to purify contaminated water, usually hard wherever found, whether in wastewater-treatment systems, lakes, ponds, industrial plants, or homes. Another important feature that adsorbed metals easily reclaimed by either destructive or nondestructive process. Other tests show ion-exchange polymer made inexpensively; easy to use; strong, flexible, not easily torn; and chemically stable in storage, in aqueous solutions, and in acidic or basic solution.

Label-free histamine detection with nanofluidic diodes through metal ion displacement mechanism.

PubMed

Ali, Mubarak; Ramirez, Patricio; Duznovic, Ivana; Nasir, Saima; Mafe, Salvador; Ensinger, Wolfgang

2017-02-01

We design and characterize a nanofluidic device for the label-free specific detection of histamine neurotransmitter based on a metal ion displacement mechanism. The sensor consists of an asymmetric polymer nanopore fabricated via ion track-etching technique. The nanopore sensor surface having metal-nitrilotriacetic (NTA-Ni 2+ ) chelates is obtained by covalent coupling of native carboxylic acid groups with N α ,N α -bis(carboxymethyl)-l-lysine (BCML), followed by exposure to Ni 2+ ion solution. The BCML immobilization and subsequent Ni 2+ ion complexation with NTA moieties change the surface charge concentration, which has a significant impact on the current-voltage (I-V) curve after chemical modification of the nanopore. The sensing mechanism is based on the displacement of the metal ion from the NTA-Ni 2+ chelates. When the modified pore is exposed to histamine solution, the Ni 2+ ion in NTA-Ni 2+ chelate recognizes histamine through a metal ion coordination displacement process and formation of stable Ni-histamine complexes, leading to the regeneration of metal-free NTA groups on the pore surface, as shown in the current-voltage characteristics. Nanomolar concentrations of the histamine in the working electrolyte can be detected. On the contrary, other neurotransmitters such as glycine, serotonin, gamma-aminobutyric acid, and dopamine do not provoke significant changes in the nanopore electronic signal due to their inability to displace the metal ion and form a stable complex with Ni 2+ ion. The nanofluidic sensor exhibits high sensitivity, specificity and reusability towards histamine detection and can then be used to monitor the concentration of biological important neurotransmitters. Copyright © 2016 Elsevier B.V. All rights reserved.

Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids.

PubMed

Carraher, Jack M; Pestovsky, Oleg; Bakac, Andreja

2012-05-21

Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe(3+) in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe(2+). The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe(2+). The photochemistry in the presence of halide ions (X(-) = Cl(-), Br(-)) generates ethyl halides via halogen atom abstraction from FeX(n)(3-n) by ethyl radicals. Near-quantitative yields of C(2)H(5)X are obtained at ≥0.05 M X(-). Competition experiments with Co(NH(3))(5)Br(2+) provided kinetic data for the reaction of ethyl radicals with FeCl(2+) (k = (4.0 ± 0.5) × 10(6) M(-1) s(-1)) and with FeBr(2+) (k = (3.0 ± 0.5) × 10(7) M(-1) s(-1)). Photochemical decarboxylation of propionic acid in the presence of Cu(2+) generates ethylene and Cu(+). Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu(+) to Cu(2+), and removes gaseous olefins to prevent accumulation of Cu(+)(olefin) complexes and depletion of Cu(2+). The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

Formation of [b3 - 1 + cat]+ ions from metal-cationized tetrapeptides containing beta-alanine, gamma-aminobutyric acid or epsilon-aminocaproic acid residues.

PubMed

Osburn, Sandra M; Ochola, Sila O; Talaty, Erach R; Van Stipdonk, Michael J

2008-11-01

The presence and position of a single beta-alanine (betaA), gamma-aminobutyric acid (gammaABu) or epsilon-aminocaproic acid (Cap) residue has been shown to have a significant influence on the formation of b(n)+ and y(n)+ product ions from a series of model, protonated peptides. In this study, we examined the effect of the same residues on the formation of analogous [b3 - 1 + cat]+ products from metal (Li+, Na+ and Ag+)-cationized peptides. The larger amino acids suppress formation of b3+ from protonated peptides with general sequence AAXG (where X = beta-alanine, gamma-aminobutyric acid or epsilon-aminocaproic acid), presumably because of the prohibitive effect of larger cyclic intermediates in the 'oxazolone' pathway. However, abundant [b3 - 1 + cat]+ products are generated from metal-cationized versions of AAXG. Using a group of deuterium-labeled and exchanged peptides, we found that formation of [b3 - 1 + cat]+ involves transfer of either amide or alpha-carbon position H atoms, and the tendency to transfer the atom from the alpha-carbon position increases with the size of the amino acid in position X. To account for the transfer of the H atom, a mechanism involving formation of a ketene product as [b3 - 1 + cat]+ is proposed.

Low coefficient of thermal expansion polyimides containing metal ion additives

NASA Technical Reports Server (NTRS)

Stoakley, D. M.; St. Clair, A. K.

1992-01-01

Polyimides have become widely used as high performance polymers as a result of their excellent thermal stability and toughness. However, lowering their coefficient of thermal expansion (CTE) would increase their usefulness for aerospace and electronic applications where dimensional stability is a requirement. The incorporation of metal ion-containing additives into polyimides, resulting in significantly lowered CTE's, has been studied. Various metal ion additives have been added to both polyamic acid resins and soluble polyimide solutions in the concentration range of 4-23 weight percent. The incorporation of these metal ions has resulted in reductions in the CTE's of the control polyimides of 12 percent to over 100 percent depending on the choice of additive and its concentration.

Magnetic chitosan nanocomposites: a useful recyclable tool for heavy metal ion removal.

PubMed

Liu, Xiaowang; Hu, Qiyan; Fang, Zhen; Zhang, Xiaojun; Zhang, Beibei

2009-01-06

Magnetic chitosan nanocomposites have been synthesized on the basis of amine-functionalized magnetite nanoparticles. These nanocomposites can be removed conveniently from water with the help of an external magnet because of their exceptional properties. The nanocomposites were applied to remove heavy metal ions from water because chitosan that is inactive on the surface of the magnetic nanoparticles is coordinated with them. The interaction between chitosan and heavy metal ions is reversible, which means that those ions can be removed from chitosan in weak acidic deionized water with the assistance of ultrasound radiation. On the basis of the reasons referred to above, synthesized magnetic chitosan nanocomposites were used as a useful recyclable tool for heavy metal ion removal. This work provides a potential platform for developing a unique route for heavy metal ion removal from wastewater.

NOVEL POLY-GLUTAMIC ACID FUNCTIONALIZED MICROFILTRATION MEMBRANES FOR SORPTION OF HEAVY METALS AT HIGH CAPACITY

EPA Science Inventory

Various sorbent/ion exchange materials have been reported in the literature for metal ion entrapment. We have developed a highly innovative and new approach to obtain high metal pick-up utilizing poly-amino acids (poly-L-glutamic acid, 14,000 MW) covalently attached to membrane p...

Metal Ions, Not Metal-Catalyzed Oxidative Stress, Cause Clay Leachate Antibacterial Activity

PubMed Central

Otto, Caitlin C.; Koehl, Jennifer L.; Solanky, Dipesh; Haydel, Shelley E.

2014-01-01

Aqueous leachates prepared from natural antibacterial clays, arbitrarily designated CB-L, release metal ions into suspension, have a low pH (3.4–5), generate reactive oxygen species (ROS) and H2O2, and have a high oxidation-reduction potential. To isolate the role of pH in the antibacterial activity of CB clay mixtures, we exposed three different strains of Escherichia coli O157:H7 to 10% clay suspensions. The clay suspension completely killed acid-sensitive and acid-tolerant E. coli O157:H7 strains, whereas incubation in a low-pH buffer resulted in a minimal decrease in viability, demonstrating that low pH alone does not mediate antibacterial activity. The prevailing hypothesis is that metal ions participate in redox cycling and produce ROS, leading to oxidative damage to macromolecules and resulting in cellular death. However, E. coli cells showed no increase in DNA or protein oxidative lesions and a slight increase in lipid peroxidation following exposure to the antibacterial leachate. Further, supplementation with numerous ROS scavengers eliminated lipid peroxidation, but did not rescue the cells from CB-L-mediated killing. In contrast, supplementing CB-L with EDTA, a broad-spectrum metal chelator, reduced killing. Finally, CB-L was equally lethal to cells in an anoxic environment as compared to the aerobic environment. Thus, ROS were not required for lethal activity and did not contribute to toxicity of CB-L. We conclude that clay-mediated killing was not due to oxidative damage, but rather, was due to toxicity associated directly with released metal ions. PMID:25502790

Ab Initio Molecular Dynamics Study on the Interactions between Carboxylate Ions and Metal Ions in Water.

PubMed

Mehandzhiyski, Aleksandar Y; Riccardi, Enrico; van Erp, Titus S; Trinh, Thuat T; Grimes, Brian A

2015-08-20

The interaction between a carboxylate anion (deprotonated propanoic acid) and the divalent Mg(2+), Ca(2+), Sr(2+), Ba(2+) metal ions is studied via ab initio molecular dynamics. The main focus of the study is the selectivity of the carboxylate-metal ion interaction in aqueous solution. The interaction is modeled by explicitly accounting for the solvent molecules on a DFT level. The hydration energies of the metal ions along with their diffusion and mobility coefficients are determined and a trend correlated with their ionic radius is found. Subsequently, a series of 16 constrained molecular dynamics simulations for every ion is performed, and the interaction free energy is obtained from thermodynamic integration of the forces between the metal ion and the carboxylate ion. The results indicate that the magnesium ion interacts most strongly with the carboxylate, followed by calcium, strontium, and barium. Because the interaction free energy is not enough to explain the selectivity of the reaction observed experimentally, more detailed analysis is performed on the simulation trajectories to understand the steric changes in the reaction complex during dissociation. The solvent dynamics appear to play an important role during the dissociation of the complex and also in the observed selectivity behavior of the divalent ions.

Removal of metal ions and humic acids through polyetherimide membrane with grafted bentonite clay.

PubMed

Hebbar, Raghavendra S; Isloor, Arun M; Prabhu, Balakrishna; Inamuddin; Asiri, Abdullah M; Ismail, A F

2018-03-16

Functional surfaces and polymers with branched structures have a major impact on physicochemical properties and performance of membrane materials. With the aim of greener approach for enhancement of permeation, fouling resistance and detrimental heavy metal ion rejection capacity of polyetherimide membrane, novel grafting of poly (4-styrenesulfonate) brushes on low cost, natural bentonite was carried out via distillation-precipitation polymerisation method and employed as a performance modifier. It has been demonstrated that, modified bentonite clay exhibited significant improvement in the hydrophilicity, porosity, and water uptake capacity with 3 wt. % of additive dosage. SEM and AFM analysis showed the increase in macrovoides and surface roughness with increased additive concentration. Moreover, the inclusion of modified bentonite displayed an increase in permeation rate and high anti-irreversible fouling properties with reversible fouling ratio of 75.6%. The humic acid rejection study revealed that, PEM-3 membrane having rejection efficiency up to 87.6% and foulants can be easily removed by simple hydraulic cleaning. Further, nanocomposite membranes can be significantly employed for the removal of hazardous heavy metal ions with a rejection rate of 80% and its tentative mechanism was discussed. Conspicuously, bentonite clay-bearing poly (4-styrenesulfonate) brushes are having a synergistic effect on physicochemical properties of nanocomposite membrane to enhance the performance in real field applications.

Incorporation of metal ions into polyimides

NASA Technical Reports Server (NTRS)

Taylor, L. T.; Carver, V. C.; Furtsch, T. A.; Saint Clair, A. K.

1980-01-01

The effects of the incorporation of metal ions into various polyimides on polyimide properties are investigated. Polyimide films derived from 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride (BDTA) 3,3'-diaminobenzophenone (m,m'-DABP), 4,4'-diaminobenzophenone (p,p'-DABP) or 4,4'-oxydianiline were prepared with the concurrent addition of approximately 20 metals in a variety of forms. In general, it is found that the films derived from BDTA + p,p'-DABP were brittle and of poor quality, with brittle films also produced in most of the BDTA + m, m'-DABP polyimides regardless of whether the added metal was hydrate or anhydrous. Thermomechanical analysis, torsional braid analysis, thermal gravimetric analysis, infrared spectral analysis and isothermal studies on many of the polyimide films produced indicate that the softening temperature is generally increased upon the addition of metal ions, at the expense of thermal stability, while no changes in chemical functionality are observed. The best system studied in regard to polymer property enhancement appears to be tri(acetylacetonato)aluminum(III) added to the m, m'-DABP polyamide, which has been found to exhibit four times the lap shear strength of the polyimide alone.

Iminodiacetic acid functionalised organopolymer monoliths: application to the separation of metal cations by capillary high-performance chelation ion chromatography.

PubMed

Moyna, Áine; Connolly, Damian; Nesterenko, Ekaterina; Nesterenko, Pavel N; Paull, Brett

2013-03-01

Lauryl methacrylate-co-ethylene dimethacrylate monoliths were polymerised within fused silica capillaries and subsequently photo-grafted with varying amounts of glycidyl methacrylate (GMA). The grafted monoliths were then further modified with iminodiacetic acid (IDA), resulting in a range of chelating ion-exchange monoliths of increasing capacity. The IDA functional groups were attached via ring opening of the epoxy group on the poly(GMA) structure. Increasing the amount of attached poly(GMA), via photo-grafting with increasing concentrations of GMA, from 15 to 35%, resulted in a proportional and controlled increase in the complexation capacity of the chelating monoliths. Scanning capacitively coupled contactless conductivity detection (sC(4)D) was used to characterise and verify homogenous distribution of the chelating ligand along the length of the capillaries non-invasively. Chelation ion chromatographic separations of selected transition and heavy metals were carried out, with retention factor data proportional to the concentration of grafted poly(GMA). Average peak efficiencies of close to 5,000 N/m were achieved, with the isocratic separation of Na, Mg(II), Mn(II), Co(II), Cd(II) and Zn(II) possible on a 250-mm-long monolith. Multiple monolithic columns produced to the same recipes gave RSD data for retention factors of <15% (averaged for several metal ions). The monolithic chelating ion-exchanger was applied to the separation of alkaline earth and transition metal ions spiked in natural and potable waters.

Elucidation of metal-ion accumulation induced by hydrogen bonds on protein surfaces by using porous lysozyme crystals containing Rh(III) ions as the model surfaces.

PubMed

Ueno, Takafumi; Abe, Satoshi; Koshiyama, Tomomi; Ohki, Takahiro; Hikage, Tatsuo; Watanabe, Yoshihito

2010-03-01

Metal-ion accumulation on protein surfaces is a crucial step in the initiation of small-metal clusters and the formation of inorganic materials in nature. This event is expected to control the nucleation, growth, and position of the materials. There remain many unknowns, as to how proteins affect the initial process at the atomic level, although multistep assembly processes of the materials formation by both native and model systems have been clarified at the macroscopic level. Herein the cooperative effects of amino acids and hydrogen bonds promoting metal accumulation reactions are clarified by using porous hen egg white lysozyme (HEWL) crystals containing Rh(III) ions, as model protein surfaces for the reactions. The experimental results reveal noteworthy implications for initiation of metal accumulation, which involve highly cooperative dynamics of amino acids and hydrogen bonds: i) Disruption of hydrogen bonds can induce conformational changes of amino-acid residues to capture Rh(III) ions. ii) Water molecules pre-organized by hydrogen bonds can stabilize Rh(III) coordination as aqua ligands. iii) Water molecules participating in hydrogen bonds with amino-acid residues can be replaced by Rh(III) ions to form polynuclear structures with the residues. iv) Rh(III) aqua complexes are retained on amino-acid residues through stabilizing hydrogen bonds even at low pH (approximately 2). These metal-protein interactions including hydrogen bonds may promote native metal accumulation reactions and also may be useful in the preparation of new inorganic materials that incorporate proteins.

Cation-Size-Dependent Conformational Locking of Glutamic Acid by Alkali Ions: Infrared Photodissociation Spectroscopy of Cryogenic Ions.

PubMed

Klyne, Johanna; Bouchet, Aude; Ishiuchi, Shun-Ichi; Fujii, Masaaki; Dopfer, Otto

2018-03-01

Consolidated knowledge of conformation and stability of amino acids and their clusters is required to understand their biochemical recognition. Often, alkali ions interact with amino acids and proteins. Herein, infrared photodissociation (IRPD) spectra of cryogenic metalated glutamic acid ions (GluM + , M = Li-Cs) are systematically analyzed in the isomer-specific fingerprint and XH stretch ranges (1100-1900, 2600-3600 cm -1 ) to provide a direct measure for cation-size-dependent conformational locking. GluM + ions are generated by electrospray ionization and cooled down to 15 K in a cryogenic quadrupole ion trap. The assignment of the IRPD spectra is supported by density functional theory calculations at the dispersion-corrected B3LYP-D3/aug-cc-pVTZ level. In the global minimum of GluM + , the flexibility of Glu is strongly reduced by the formation of rigid ionic CO···M + ···OC metal bridges, corresponding to charge solvation. The M + binding energy decreases monotonically with increasing cation size from D 0 = 314 to 119 kJ/mol for Li-Cs. Whereas for Li and Na only the global minimum of GluM + is observed, for K-Cs at least three isomers exist at cryogenic temperature. The IRPD spectra of cold GluM + ions are compared to IR multiple-photon dissociation spectra measured at room temperature. Furthermore, we elucidate the differences of the impact of protonation and metalation on the structure and conformational locking of Glu.

Application of Freeze-Dried Powders of Genetically Engineered Microbial Strains as Adsorbents for Rare Earth Metal Ions.

PubMed

Moriwaki, Hiroshi; Masuda, Reiko; Yamazaki, Yuki; Horiuchi, Kaoru; Miyashita, Mari; Kasahara, Jun; Tanaka, Tatsuhito; Yamamoto, Hiroki

2016-10-12

The adsorption behaviors of the rare earth metal ions onto freeze-dried powders of genetically engineered microbial strains were compared. Cell powders obtained from four kinds of strains, Bacillus subtilis 168 wild type (WT), lipoteichoic acid-defective (ΔLTA), wall teichoic acid-defective (ΔWTA), and cell wall hydrolases-defective (EFKYOJLp) strains, were used as an adsorbent of the rare earth metal ions at pH 3. The adsorption ability of the rare earth metal ions was in the order of EFKYOJLp > WT > ΔLTA > ΔWTA. The order was the same as the order of the phosphorus quantity of the strains. This result indicates that the main adsorption sites for the ions are the phosphate groups and the teichoic acids, LTA and WTA, that contribute to the adsorption of the rare earth metal ions onto the cell walls. The contribution of WTA was clearly greater than that of LTA. Each microbial powder was added to a solution containing 16 kinds of rare earth metal ions, and the removals (%) of each rare earth metal ion were obtained. The scandium ion showed the highest removal (%), while that of the lanthanum ion was the lowest for all the microbial powders. Differences in the distribution coefficients between the kinds of lanthanide ions by the EFKYOJLp and ΔWTA powders were greater than those of the other strains. Therefore, the EFKYOJLp and ΔWTA powders could be applicable for the selective extraction of the lanthanide ions. The ΔLTA powder coagulated by mixing with a rare earth metal ion, although no sedimentation of the WT or ΔWTA powder with a rare earth metal ion was observed under the same conditions. The EFKYOJLp powder was also coagulated, but its flocculating activity was lower than that of ΔLTA. The ΔLTA and EFKYOJLp powders have a long shape compared to those of the WT or ΔWTA strain. The shapes of the cells will play an important role in the sedimentation of the microbial powders with rare earth metal ions. As the results, three kinds of the genetically

Nucleic acid-functionalized transition metal nanosheets for biosensing applications

PubMed Central

Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

2017-01-01

In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. PMID:27020066

A novel surface-enhanced Raman scattering nanosensor for detecting multiple heavy metal ions based on 2-mercaptoisonicotinic acid functionalized gold nanoparticles.

PubMed

Tan, Enzhong; Yin, Penggang; Lang, Xiufeng; Zhang, Hongyan; Guo, Lin

2012-11-01

A novel, effective and simple surface-enhanced Raman scattering (SERS) nanosensor for selectively and sensitively detecting heavy metal ions in aqueous solution has been developed in the form of 2-mercaptoisonicotinic acid (2 MNA)-modified gold nanoparticles (AuNPs). Multiple heavy metal ions can be identified and quantified by using relative peak intensity ratios of selected vibrational bands in the SERS spectra of 2 MNA. Especially, concentration of Hg(2+) and Pb(2+) ions are determined by comparing the intensity ratios of the bands 1160/1230 cm(-1) for Hg(2+) and 861/815 cm(-1) (or 815/1392 cm(-1)) for Pb(2+), with detection limits of 3.4×10(-8) and 1.0×10(-7)M, respectively. 2 MNA-AuNPs sensors show a high selectivity for Hg(2+) without masking reagent, and they can also be highly selective for Pb(2+) when using sodium thiosulphate and l-cysteine as masking reagents. These results demonstrate that these 2 MNA-AuNPs nanosensors are promising candidates for in situ heavy metal ions detection and quantification, maybe even inside living cells. Copyright © 2012 Elsevier B.V. All rights reserved.

Reexamination of the ORAC assay: effect of metal ions.

PubMed

Nkhili, E; Brat, P

2011-05-01

The oxygen radical absorbance capacity (ORAC) assay method has been employed extensively in the field of antioxidant and oxidative stress. It uses fluorescein as probe for oxidation by peroxyl radical. Hundreds of reports have been published on the use of this method to determine antioxidant capacity in food and biological samples. The question is whether the results of all these reports are influenced by antioxidant autoxidation, which occurs during the ORAC test. Indeed, the presence of metal ions in the studied matrix will influence antioxidant stability, thereby leading to the underestimation of their antioxidant properties. Ethylenediaminetetraacetic acid hydrate (EDTA) can be used as a metal complexation agent. This paper examines the effect of the addition of EDTA on the ORAC values of pure compounds (quercetin, ascorbic, and dehydroascorbic acid) and five food juices (kiwi, orange, tomato, red grape, and apple). Metal complexation by EDTA (80 μM) clearly increased the ORAC values, given that the antioxidant was protected against rapid autoxidation incited by trace metal ions within samples and then by free radicals. Our finding also undoubtedly demonstrated that the number of literature values is potentially underestimated.

MCTBI: a web server for predicting metal ion effects in RNA structures.

PubMed

Sun, Li-Zhen; Zhang, Jing-Xiang; Chen, Shi-Jie

2017-08-01

Metal ions play critical roles in RNA structure and function. However, web servers and software packages for predicting ion effects in RNA structures are notably scarce. Furthermore, the existing web servers and software packages mainly neglect ion correlation and fluctuation effects, which are potentially important for RNAs. We here report a new web server, the MCTBI server (http://rna.physics.missouri.edu/MCTBI), for the prediction of ion effects for RNA structures. This server is based on the recently developed MCTBI, a model that can account for ion correlation and fluctuation effects for nucleic acid structures and can provide improved predictions for the effects of metal ions, especially for multivalent ions such as Mg 2+ effects, as shown by extensive theory-experiment test results. The MCTBI web server predicts metal ion binding fractions, the most probable bound ion distribution, the electrostatic free energy of the system, and the free energy components. The results provide mechanistic insights into the role of metal ions in RNA structure formation and folding stability, which is important for understanding RNA functions and the rational design of RNA structures. © 2017 Sun et al.; Published by Cold Spring Harbor Laboratory Press for the RNA Society.

Metallic ions in the equatorial ionosphere

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Goldberg, R. A.

1972-01-01

Four positive ion composition measurements of the equatorial E region made at Thumba, India, are presented. During the day, the major ions between 90 and 125 km are NO(+) and O2(+). A metallic ion layer centered at 92 km is observed, and found to contain Mg(+), Fe(+), Ca(+), K(+), Al(+), and Na(+) ions. The layer is explained in terms of a similarly shaped latitude distribution of neutral atoms which are photoionized and charge-exchanged with NO(+) and O2(+). Three body reactions form molecular metallic ions which are rapidly lost by dissociative ion-electron recombination. Nighttime observations show downward drifting of the metallic ion layer caused by equatorial dynamo effects. These ions react and form neutral metals which exchange charges with NO(+) and O2(+) to produce an observed depletion of those ions within the metallic ion region.

Solution-phase electronegativity scale: insight into the chemical behaviors of metal ions in solution.

PubMed

Li, Keyan; Li, Min; Xue, Dongfeng

2012-04-26

By incorporating the solvent effect into the Born effective radius, we have proposed an electronegativity scale of metal ions in aqueous solution with the most common oxidation states and hydration coordination numbers in terms of the effective ionic electrostatic potential. It is found that the metal ions in aqueous solution are poorer electron acceptors compared to those in the gas phase. This solution-phase electronegativity scale shows its efficiency in predicting some important properties of metal ions in aqueous solution such as the aqueous acidities of the metal ions, the stability constants of metal complexes, and the solubility product constants of the metal hydroxides. We have elaborated that the standard reduction potential and the solution-phase electronegativity are two different quantities for describing the processes of metal ions in aqueous solution to soak up electrons with different final states. This work provides a new insight into the chemical behaviors of the metal ions in aqueous solution, indicating a potential application of this electronegativity scale to the design of solution reactions.

Copper(II)-rubeanic acid coprecipitation system for separation-preconcentration of trace metal ions in environmental samples for their flame atomic absorption spectrometric determinations.

PubMed

Soylak, Mustafa; Erdogan, Nilgun D

2006-09-21

A simple and facile preconcentration procedure based on the coprecipitation of trace heavy metal ions with copper(II)-rubeanic acid complex has been developed. The analytical parameters including pH, amounts of rubeanic acid, sample volume, etc. was investigated for the quantitative recoveries of Pb(II), Fe(III), Cd(II), Au(III), Pd(II) and Ni(II). No interferic effects were observed from the concomitant ions. The detection limits for analyte ions by 3 sigma were in the range of 0.14 microg/l for iron-3.4 microg/l for lead. The proposed coprecipitation method was successfully applied to water samples from Palas Lake-Kayseri, soil and sediment samples from Kayseri and Yozgat-Turkey.

Substrate Profile and Metal-ion Selectivity of Human Divalent Metal-ion Transporter-1*

PubMed Central

Illing, Anthony C.; Shawki, Ali; Cunningham, Christopher L.; Mackenzie, Bryan

2012-01-01

Divalent metal-ion transporter-1 (DMT1) is a H+-coupled metal-ion transporter that plays essential roles in iron homeostasis. DMT1 exhibits reactivity (based on evoked currents) with a broad range of metal ions; however, direct measurement of transport is lacking for many of its potential substrates. We performed a comprehensive substrate-profile analysis for human DMT1 expressed in RNA-injected Xenopus oocytes by using radiotracer assays and the continuous measurement of transport by fluorescence with the metal-sensitive PhenGreen SK fluorophore. We provide validation for the use of PhenGreen SK fluorescence quenching as a reporter of cellular metal-ion uptake. We determined metal-ion selectivity under fixed conditions using the voltage clamp. Radiotracer and continuous measurement of transport by fluorescence assays revealed that DMT1 mediates the transport of several metal ions that were ranked in selectivity by using the ratio Imax/K0.5 (determined from evoked currents at −70 mV): Cd2+ > Fe2+ > Co2+, Mn2+ ≫ Zn2+, Ni2+, VO2+. DMT1 expression did not stimulate the transport of Cr2+, Cr3+, Cu+, Cu2+, Fe3+, Ga3+, Hg2+, or VO+. 55Fe2+ transport was competitively inhibited by Co2+ and Mn2+. Zn2+ only weakly inhibited 55Fe2+ transport. Our data reveal that DMT1 selects Fe2+ over its other physiological substrates and provides a basis for predicting the contribution of DMT1 to intestinal, nasal, and pulmonary absorption of metal ions and their cellular uptake in other tissues. Whereas DMT1 is a likely route of entry for the toxic heavy metal cadmium, and may serve the metabolism of cobalt, manganese, and vanadium, we predict that DMT1 should contribute little if at all to the absorption or uptake of zinc. The conclusion in previous reports that copper is a substrate of DMT1 is not supported. PMID:22736759

Complexation of Nickel Ions by Boric Acid or (Poly)borates.

PubMed

Graff, Anais; Barrez, Etienne; Baranek, Philippe; Bachet, Martin; Bénézeth, Pascale

2017-01-01

An experiment based on electrochemical reactions and pH monitoring was performed in which nickel ions were gradually formed by oxidation of a nickel metal electrode in a solution of boric acid. Based on the experimental results and aqueous speciation modeling, the evolution of pH showed the existence of significant nickel-boron complexation. A triborate nickel complex was postulated at high boric acid concentrations when polyborates are present, and the equilibrium constants were determined at 25, 50 and 70 °C. The calculated enthalpy and entropy at 25 °C for the formation of the complex from boric acid and Ni 2+ ions are respectively equal to (65.6 ± 3.1) kJ·mol -1 and (0.5 ± 11.1) J·K -1 ·mol -1 . The results of this study suggest that complexation of nickel ions by borates can significantly enhance the solubility of nickel metal and nickel oxide depending on the concentration of boric acid and pH. First principles calculations were investigated and tend to show that the complex is thermodynamically stable and the nickel cation in solution should interact more strongly with the [Formula: see text] than with boric acid.

Thermometric titration of beta-aryl-alpha-mercaptopropenoic acids and determination of the stoichiometry of their metal complexes.

PubMed

Izquierdo, A; Carrasco, J

1981-05-01

Automatic thermometric titration was applied to some beta-aryl-alpha-mercaptopropenoic acids and the stoichiometry of their complexes with several metal ions was investigated. The heats of neutralization of the mercapto-acids with sodium hydroxide and the heats of their reaction with metal ions were calculated.

Nucleic acid-functionalized transition metal nanosheets for biosensing applications.

PubMed

Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

2017-03-15

In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced recovery of valuable metals from spent lithium-ion batteries through optimization of organic acids produced by Aspergillus niger.

PubMed

Bahaloo-Horeh, Nazanin; Mousavi, Seyyed Mohammad

2017-02-01

In the present study, spent medium bioleaching method was performed using organic acids produced by Aspergillus niger to dissolve Ni, Co, Mn, Li, Cu and Al from spent lithium-ion batteries (LIBs). Response surface methodology was used to investigate the effects and interactions between the effective factors of sucrose concentration, initial pH, and inoculum size to optimize organic acid production. Maximum citric acid, malic acid, and gluconic acid concentrations of 26,478, 1832.53 and 8433.76ppm, respectively, and a minimum oxalic acid concentration of 305.558ppm were obtained under optimal conditions of 116.90 (gl -1 ) sucrose concentration, 3.45% (vv -1 ) inoculum size, and a pH value of 5.44. Biogenically-produced organic acids are used for leaching of spent LIBs at different pulp densities. The highest metal recovery of 100% Cu, 100% Li, 77% Mn, and 75% Al occurred at 2% (wv -1 ) pulp density; 64% Co and 54% Ni recovery occurred at 1% (wv -1 ) pulp density. The bioleaching of metals from spent LIBs can decrease the environmental impact of this waste. The results of this study suggest that the process can be used for large scale industrial purposes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemical rescue of the post-translationally carboxylated lysine mutant of allantoinase and dihydroorotase by metal ions and short-chain carboxylic acids.

PubMed

Ho, Ya-Yeh; Huang, Yen-Hua; Huang, Cheng-Yang

2013-04-01

Bacterial allantoinase (ALLase) and dihydroorotase (DHOase) are members of the cyclic amidohydrolase family. ALLase and DHOase possess similar binuclear metal centers in the active site in which two metals are bridged by a post-translationally carboxylated lysine. In this study, we determined the effects of carboxylated lysine and metal binding on the activities of ALLase and DHOase. Although DHOase is a metalloenzyme, purified DHOase showed high activity without additional metal supplementation in a reaction mixture or bacterial culture. However, unlike DHOase, ALLase had no activity unless some specific metal ions were added to the reaction mixture or culture. Substituting the metal binding sites H59, H61, K146, H186, H242, or D315 with alanine completely abolished the activity of ALLase. However, the K146C, K146D and K146E mutants of ALLase were still active with about 1-6% activity of the wild-type enzyme. These ALLase K146 mutants were found to have 1.4-1.7 mol metal per mole enzyme subunit, which may indicate that they still contained the binuclear metal center in the active site. The activity of the K146A mutant of the ALLase and the K103A mutant of DHOase can be chemically rescued by short-chain carboxylic acids, such as acetic, propionic, and butyric acids, but not by ethanol, propan-1-ol, and imidazole, in the presence of Co2+ or Mn2+ ions. However, the activity was still ~10-fold less than that of wild-type ALLase. Overall, these results indicated that the 20 natural basic amino acid residues were not sufficiently able to play the role of lysine. Accordingly, we proposed that during evolution, the post-translational modification of carboxylated lysine in the cyclic amidohydrolase family was selected for promoting binuclear metal center self-assembly and increasing the nucleophilicity of the hydroxide at the active site for enzyme catalysis. This kind of chemical rescue combined with site-directed mutagenesis may also be used to identify a binuclear metal

Headgroup interactions and ion flotation efficiency in mixtures of a chelating surfactant, different foaming agents, and divalent metal ions.

PubMed

Svanedal, Ida; Boija, Susanne; Norgren, Magnus; Edlund, Håkan

2014-06-10

The correlation between interaction parameters and ion flotation efficiency in mixtures of chelating surfactant metal complexes and different foaming agents was investigated. We have recently shown that chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) forms strong coordination complexes with divalent metal ions, and this can be utilized in ion flotation. Interaction parameters for mixed micelles and mixed monolayer formation for Mg(2+) and Ni(2+) complexes with the chelating surfactant 4-C12-DTPA and different foaming agents were calculated by Rubingh's regular solution theory. Parameters for the calculations were extracted from surface tension measurements and NMR diffusometry. The effects of metal ion coordination on the interactions between 4-C12-DTPA and the foaming agents could be linked to a previously established difference in coordination chemistry between the examined metal ions. As can be expected from mixtures of amphoteric surfactants, the interactions were strongly pH-dependent. Strong correlation was found between interaction parameter β(σ) for mixed monolayer formation and the phase-transfer efficiency of Ni(2+) complexes with 4-C12-DTPA during flotation in a customized flotation cell. In a mixture of Cu(2+) and Zn(2+), the significant difference in conditional stability constants (log K) between the metal complexes was utilized to selectively recover the metal complex with the highest log K (Cu(2+)) by ion flotation. Flotation experiments in an excess concentration of metal ions confirmed the coordination of more than one metal ion to the headgroup of 4-C12-DTPA.

Metal cation dependence of interactions with amino acids: bond dissociation energies of Rb(+) and Cs(+) to the acidic amino acids and their amide derivatives.

PubMed

Armentrout, P B; Yang, Bo; Rodgers, M T

2014-04-24

Metal cation-amino acid interactions are key components controlling the secondary structure and biological function of proteins, enzymes, and macromolecular complexes comprising these species. Determination of pairwise interactions of alkali metal cations with amino acids provides a thermodynamic vocabulary that begins to quantify these fundamental processes. In the present work, we expand a systematic study of such interactions by examining rubidium and cesium cations binding with the acidic amino acids (AA), aspartic acid (Asp) and glutamic acid (Glu), and their amide derivatives, asparagine (Asn) and glutamine (Gln). These eight complexes are formed using electrospray ionization and their bond dissociation energies (BDEs) are determined experimentally using threshold collision-induced dissociation with xenon in a guided ion beam tandem mass spectrometer. Analyses of the energy-dependent cross sections include consideration of unimolecular decay rates, internal energy of the reactant ions, and multiple ion-neutral collisions. Quantum chemical calculations are conducted at the B3LYP, MP2(full), and M06 levels of theory using def2-TZVPPD basis sets, with results showing reasonable agreement with experiment. At 0 and 298 K, most levels of theory predict that the ground-state conformers for M(+)(Asp) and M(+)(Asn) involve tridentate binding of the metal cation to the backbone carbonyl, amino, and side-chain carbonyl groups, although tridentate binding to the carboxylic acid group and side-chain carbonyl is competitive for M(+)(Asn). For the two longer side-chain amino acids, Glu and Gln, multiple structures are competitive. A comparison of these results to those for the smaller alkali cations, Na(+) and K(+), provides insight into the trends in binding energies associated with the molecular polarizability and dipole moment of the side chain. For all four metal cations, the BDEs are inversely correlated with the size of the metal cation and follow the order Asp < Glu

Silver ions-mediated conformational switch: facile design of structure-controllable nucleic acid probes.

PubMed

Wang, Yongxiang; Li, Jishan; Wang, Hao; Jin, Jianyu; Liu, Jinhua; Wang, Kemin; Tan, Weihong; Yang, Ronghua

2010-08-01

Conformationally constraint nucleic acid probes were usually designed by forming an intramolecular duplex based on Watson-Crick hydrogen bonds. The disadvantages of these approaches are the inflexibility and instability in complex environment of the Watson-Crick-based duplex. We report that this hydrogen bonding pattern can be replaced by metal-ligation between specific metal ions and the natural bases. To demonstrate the feasibility of this principle, two linear oligonucleotides and silver ions were examined as models for DNA hybridization assay and adenosine triphosphate detection. The both nucleic acids contain target binding sequences in the middle and cytosine (C)-rich sequences at the lateral portions. The strong interaction between Ag(+) ions and cytosines forms stable C-Ag(+)-C structures, which promises the oligonucleotides to form conformationally constraint formations. In the presence of its target, interaction between the loop sequences and the target unfolds the C-Ag(+)-C structures, and the corresponding probes unfolding can be detected by a change in their fluorescence emission. We discuss the thermodynamic and kinetic opportunities that are provided by using Ag(+) ion complexes instead of traditional Watson-Crick-based duplex. In particular, the intrinsic feature of the metal-ligation motif facilitates the design of functional nucleic acids probes by independently varying the concentration of Ag(+) ions in the medium.

Neutralization by Metal Ions of the Toxicity of Sodium Selenide

PubMed Central

Dauplais, Marc; Lazard, Myriam; Blanquet, Sylvain; Plateau, Pierre

2013-01-01

Inert metal-selenide colloids are found in animals. They are believed to afford cross-protection against the toxicities of both metals and selenocompounds. Here, the toxicities of metal salt and sodium selenide mixtures were systematically studied using the death rate of Saccharomyces cerevisiae cells as an indicator. In parallel, the abilities of these mixtures to produce colloids were assessed. Studied metal cations could be classified in three groups: (i) metal ions that protect cells against selenium toxicity and form insoluble colloids with selenide (Ag+, Cd2+, Cu2+, Hg2+, Pb2+ and Zn2+), (ii) metal ions which protect cells by producing insoluble metal-selenide complexes and by catalyzing hydrogen selenide oxidation in the presence of dioxygen (Co2+ and Ni2+) and, finally, (iii) metal ions which do not afford protection and do not interact (Ca2+, Mg2+, Mn2+) or weakly interact (Fe2+) with selenide under the assayed conditions. When occurring, the insoluble complexes formed from divalent metal ions and selenide contained equimolar amounts of metal and selenium atoms. With the monovalent silver ion, the complex contained two silver atoms per selenium atom. Next, because selenides are compounds prone to oxidation, the stabilities of the above colloids were evaluated under oxidizing conditions. 5,5'-dithiobis-(2-nitrobenzoic acid) (DTNB), the reduction of which can be optically followed, was used to promote selenide oxidation. Complexes with cadmium, copper, lead, mercury or silver resisted dissolution by DTNB treatment over several hours. With nickel and cobalt, partial oxidation by DTNB occurred. On the other hand, when starting from ZnSe or FeSe complexes, full decompositions were obtained within a few tens of minutes. The above properties possibly explain why ZnSe and FeSe nanoparticles were not detected in animals exposed to selenocompounds. PMID:23342137

Modification of hydroxyapatite with ion-selective complexants: 1-hydroxyethane-1,1-diphosphonic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniels, Yasmine; Lyczko, Nathalie; Nzihou, Ange

Hydroxyapatite (HAP) was modified with 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and its effect on divalent metal ion binding was determined. HAP was synthesized from calcium hydroxide and phosphoric acid. After calcination, it was modified with HEDP, and the influence of time and temperature on the modification was investigated. HEDP incorporation increased as its initial solution concentration increased from 0.01 to 0.50 M. Unmodified and modified HAP were characterized using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and specific surface area analysis. Ca/P ratios, acid capacities, and phosphorus elemental analyses gave the effect of modification on compositionmore » and surface characteristics. A high reaction temperature produced new phosphonate bands at 993, 1082, and 1144 cm –1 that indicated the presence of HEDP. HAP modification at a high temperature–long reaction time had the highest HEDP loading and gave the sharpest XRD peaks. The emergence of new HAP–HEDP strands was observed in SEM images for treated samples while EDS showed high phosphorus contents in these strands. Modified HAP had a high acid capacity from the additional P–OH groups in HEDP. The P(O)OH groups maintain their ability to bind metal ions within the HAP matrix: contacting the modified HAP with 10–4 N nitrate solutions of five transition metal ions gives an affinity sequence of Pb(II) > Cd(II) > Zn(II) > Ni(II) > Cu(II). Here, this result is comparable to that of commercially available di(2-ethylhexyl)phosphoric acid, a common solvent extractant, and the trend is consistent with the Misono softness parameter of metal ion polarizabilities.« less

Modification of hydroxyapatite with ion-selective complexants: 1-hydroxyethane-1,1-diphosphonic acid

DOE PAGES

Daniels, Yasmine; Lyczko, Nathalie; Nzihou, Ange; ...

2014-12-29

Hydroxyapatite (HAP) was modified with 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and its effect on divalent metal ion binding was determined. HAP was synthesized from calcium hydroxide and phosphoric acid. After calcination, it was modified with HEDP, and the influence of time and temperature on the modification was investigated. HEDP incorporation increased as its initial solution concentration increased from 0.01 to 0.50 M. Unmodified and modified HAP were characterized using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and specific surface area analysis. Ca/P ratios, acid capacities, and phosphorus elemental analyses gave the effect of modification on compositionmore » and surface characteristics. A high reaction temperature produced new phosphonate bands at 993, 1082, and 1144 cm –1 that indicated the presence of HEDP. HAP modification at a high temperature–long reaction time had the highest HEDP loading and gave the sharpest XRD peaks. The emergence of new HAP–HEDP strands was observed in SEM images for treated samples while EDS showed high phosphorus contents in these strands. Modified HAP had a high acid capacity from the additional P–OH groups in HEDP. The P(O)OH groups maintain their ability to bind metal ions within the HAP matrix: contacting the modified HAP with 10–4 N nitrate solutions of five transition metal ions gives an affinity sequence of Pb(II) > Cd(II) > Zn(II) > Ni(II) > Cu(II). Here, this result is comparable to that of commercially available di(2-ethylhexyl)phosphoric acid, a common solvent extractant, and the trend is consistent with the Misono softness parameter of metal ion polarizabilities.« less

Metal ion influence on eumelanin fluorescence and structure.

PubMed

Sutter, Jens-Uwe; Birch, David J S

2014-04-10

Melanin has long been thought to have an unworkably weak and complex fluorescence, but here we study its intrinsic fluorescence in order to demonstrate how metal ions can be used to control the rate of formation, constituents and structure of eumelanin formed from the well-known laboratory auto-oxidation of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The effect on eumelanin absorption and fluorescence of a range of solvated metal ions is reported including Cu, Zn, Ni, Na and K. Monovalent cations and Zn have little effect, but the effect of transition metal cations can be considerable. For example, at pH 10, copper ions are shown to accelerate the onset of eumelanin formation, but not the rate of formation once it commences, and simplify the usual complex structure and intrinsic fluorescence of eumelanin in a way that is consistent with an increased abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). The presence of a dominant 6 ns fluorescence decay time at 480 nm, when excited at 450 nm describes a distinct photophysical species, which we tentatively assign to small oligomers. Copper is well-known to normally quench fluorescence, but increasing amounts of copper surprisingly leads to an increase in the fluorescence decay time of eumelanin, while reducing the fluorescence intensity, suggesting copper modification of the excited state. Such results have bearing on diverse areas. The most accepted morphology for melanin is that of a graphite-like sheet structure, and one which readily binds metal ions, an interaction that is thought to have an important, though as yet unclear bearing on several areas of medicine including neurology. There is also increasing interest in bio-mimicry by preparing and labelling sheet structures with metal ions for new electronic and photonic materials.

Metal ion influence on eumelanin fluorescence and structure

NASA Astrophysics Data System (ADS)

Sutter, Jens-Uwe; Birch, David J. S.

2014-06-01

Melanin has long been thought to have an unworkably weak and complex fluorescence, but here we study its intrinsic fluorescence in order to demonstrate how metal ions can be used to control the rate of formation, constituents and structure of eumelanin formed from the well-known laboratory auto-oxidation of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The effect on eumelanin absorption and fluorescence of a range of solvated metal ions is reported including Cu, Zn, Ni, Na and K. Monovalent cations and Zn have little effect, but the effect of transition metal cations can be considerable. For example, at pH 10, copper ions are shown to accelerate the onset of eumelanin formation, but not the rate of formation once it commences, and simplify the usual complex structure and intrinsic fluorescence of eumelanin in a way that is consistent with an increased abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). The presence of a dominant 6 ns fluorescence decay time at 480 nm, when excited at 450 nm describes a distinct photophysical species, which we tentatively assign to small oligomers. Copper is well-known to normally quench fluorescence, but increasing amounts of copper surprisingly leads to an increase in the fluorescence decay time of eumelanin, while reducing the fluorescence intensity, suggesting copper modification of the excited state. Such results have bearing on diverse areas. The most accepted morphology for melanin is that of a graphite-like sheet structure, and one which readily binds metal ions, an interaction that is thought to have an important, though as yet unclear bearing on several areas of medicine including neurology. There is also increasing interest in bio-mimicry by preparing and labelling sheet structures with metal ions for new electronic and photonic materials.

Electrochemical sensing of heavy metal ions with inorganic, organic and bio-materials.

PubMed

Cui, Lin; Wu, Jie; Ju, Huangxian

2015-01-15

As heavy metal ions severely harm human health, it is important to develop simple, sensitive and accurate methods for their detection in environment and food. Electrochemical detection featured with short analytical time, low power cost, high sensitivity and easy adaptability for in-situ measurement is one of the most developed methods. This review introduces briefly the recent achievements in electrochemical sensing of heavy metal ions with inorganic, organic and bio-materials modified electrodes. In particular, the unique properties of inorganic nanomaterials, organic small molecules or their polymers, enzymes and nucleic acids for detection of heavy metal ions are highlighted. By employing some representative examples, the design and sensing mechanisms of these electrodes are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

A cross-reactive sensor array for the fluorescence qualitative analysis of heavy metal ions.

PubMed

Kang, Huaizhi; Lin, Liping; Rong, Mingcong; Chen, Xi

2014-11-01

A cross-reactive sensor array using mercaptopropionic acid modified cadmium telluride (CdTe), glutathione modified CdTe, poly(methacrylic acid) modified silver nanoclusters, bovine serum albumin modified gold nanoclusters, rhodamine derivative and calcein blue as fluorescent indicators has been designed for the detection of seven heavy metal ions (Ag(+), Hg(2+), Pb(2+), Cu(2+), Cr(3+), Mn(2+) and Cd(2+)). The discriminatory capacity of the sensor array to different heavy metal ions in different pH solutions has been tested and the results have been analyzed with linear discriminant analysis. Results showed that the sensor array could be used to qualitatively analyze the selected heavy metal ions. The array performance was also evaluated in the identification of known and unknown samples and the preliminary results suggested the promising practicability of the designed sensor assay. Copyright © 2014 Elsevier B.V. All rights reserved.

Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography.

PubMed

Liu, Yong-Qiang; Yu, Hong

2017-04-01

A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg 2+ , Ca 2+ , and Sr 2+ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV-absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg 2+ , Ca 2+ , and Sr 2+ were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg 2+ , Ca 2+ , and Sr 2+ within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and adsorption behavior of aminated electrospun polyacrylonitrile nanofiber mats for heavy metal ion removal.

PubMed

Kampalanonwat, Pimolpun; Supaphol, Pitt

2010-12-01

Polyacrylonitrile (PAN) nanofiber mats were prepared by electrospinning and they were further modified to contain amidino diethylenediamine chelating groups on their surface via heterogeneous reaction with diethylenetriamine (DETA). The obtained aminated PAN (APAN) nanofiber mats were evaluated for their chelating property with four types of metal ions, namely Cu(II), Ag(I), Fe(II), and Pb(II) ions. The amounts of the metal ions adsorbed onto the APAN nanofiber mats were influenced by the initial pH and the initial concentration of the metal ion solutions. Increasing the contact time also resulted in a monotonous increase in the adsorbed amounts of the metal ions, which finally reached equilibria at about 10 h for Cu(II) ions and about 5 h for Ag(I), Fe(II), and Pb(II) ions. The maximal adsorption capacities of the metal ions on the APAN nanofiber mats, as calculated from the Langmuir model, were 150.6, 155.5, 116.5, and 60.6 mg g(-1), respectively. Lastly, the spent APAN nanofiber mats could be facilely regenerated with a hydrochloric acid (HCl) aqueous solution.

Synthesis and characterization of zirconium titanium phosphate and its application in separation of metal ions.

PubMed

Thakkar, Rakesh; Chudasama, Uma

2009-12-15

An advanced inorganic ion exchanger, zirconium titanium phosphate (ZTP) of the class of tetravalent bimetallic acid (TBMA) salt has been synthesized by sol-gel route. ZTP has been characterized for ICP-AES, TGA, FTIR and XRD. Chemical stability of the material in various media-acids, bases and organic solvents has been assessed. Cation exchange capacity (CEC) and effect of calcination (100-500 degrees C) on CEC has also been studied. Distribution behaviour of metal ions Co2+, Ni2+, Cu2+, Zn2+ (d-block), Cd2+, Hg2+, Pb2+, Bi3+ (heavy) and La3+, Ce3+, Th4+, UO(2)2+ (f-block) towards ZTP has been studied and distribution coefficient (K(d)) determined in aqueous as well as various electrolyte media/concentrations. Based on the differential selectivity, breakthrough capacity (BTC) and elution behaviour of various metal ions towards ZTP, a few binary and ternary metal ion separations have been carried out.

New Metal Niobate and Silicotitanate Ion Exchangers: Development and Characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexandra Navrotsky; Mary Lou Balmer; Tina M. Nenoff

2003-12-05

This renewal proposal outlines our current progress and future research plans for ion exchangers: novel metal niobate and silicotitanate ion exchangers and their ultimate deployment in the DOE complex. In our original study several forms (including Cs exchanged) of the heat treated Crystalline Silicotitanates (CSTs) were fully characterized by a combination of high temperature synthesis and phase identification, low temperature synthesis and phase identification, and thermodynamics. This renewal proposal is predicated on work completed in our current EMSP program: we have shown preliminary data of a novel class of niobate-based molecular sieves (Na/Nb/M/O, M = transition metals), which show exceptionallymore » high selectivity for divalent cations under extreme conditions (acid solutions, competing cations), in addition to novel silicotitanate phases which are also selective for divalent cations. Furthermore, these materials are easily converted by a high temperature in-situ heat treatment into a refractory ceramic waste form with low cation leachability. The new waste form is a perovskite phase, which is also a major component of Synroc, a titanate ceramic waste form used for sequestration of HLW wastes from reprocessed, spent nuclear fuel. These new niobate ion exchangers also shown orders of magnitude better selectivity for Sr2+ under acid conditions than any other material. The goal of the program is to reduce the costs associated with divalent cation waste removal and disposal, to minimize the risk of contamination to the environment during ion exchanger processing, and to provide DOE with materials for near-term lab-bench stimulant testing, and eventual deployment. The proposed work will provide information on the structure/property relationship between ion exchanger frameworks and selectivity for specific ions, allowing for the eventual ''tuning'' of framework for specific ion exchange needs. To date, DOE sites have become interested in on-site testing of

Metal Ion Modeling Using Classical Mechanics

PubMed Central

2017-01-01

Metal ions play significant roles in numerous fields including chemistry, geochemistry, biochemistry, and materials science. With computational tools increasingly becoming important in chemical research, methods have emerged to effectively face the challenge of modeling metal ions in the gas, aqueous, and solid phases. Herein, we review both quantum and classical modeling strategies for metal ion-containing systems that have been developed over the past few decades. This Review focuses on classical metal ion modeling based on unpolarized models (including the nonbonded, bonded, cationic dummy atom, and combined models), polarizable models (e.g., the fluctuating charge, Drude oscillator, and the induced dipole models), the angular overlap model, and valence bond-based models. Quantum mechanical studies of metal ion-containing systems at the semiempirical, ab initio, and density functional levels of theory are reviewed as well with a particular focus on how these methods inform classical modeling efforts. Finally, conclusions and future prospects and directions are offered that will further enhance the classical modeling of metal ion-containing systems. PMID:28045509

Electrophoretic studies of polygalacturonate oligomers and their interactions with metal ions.

PubMed

Wiedmer, S K; Cassely, A; Hong, M; Novotny, M V; Riekkola, M L

2000-09-01

Polygalacturonic acid, a linear homopolysaccharide, was investigated by capillary electrophoresis (CE) using linear polyacrylamide-coated capillaries and laser-induced fluorescence (LIF) detection. A successful separation of its fluorescently labeled oligomers was achieved through sieving in polyacrylamide entangled matrices. The reaction conditions for the derivatization of polygalacturonic acid were optimized. In studying the interactions between polygalacturonic acid and various metal ions, the end-label, free-solution electrophoretic (ELFSE) technique, developed earlier in our laboratory (Sudor, J., Novotny, M. V., Anal. Chem. 1995, 67, 4205-4209) was found preferable to the sieving method. ELFSE is fast and convenient in that no polymer solutions are needed for the separation. The investigation showed that for the moderately large oligomers, the strongest binding occurred with calcium and cadmium ions, while the smallest interaction was observed with magnesium ions.

Method and apparatus for ion sequestration and a nanostructured metal phosphate

DOEpatents

Mattigod, Shas V [Richland, WA; Fryxell, Glen E [Kennewic, WA; Li, Xiaohong [Richland, WA; Parker, Kent E [Kennewick, WA; Wellman, Dawn M [West Richland, WA

2010-04-06

A nanostructured substance, a process for sequestration of ionic waste, and an ion-sequestration apparatus are disclosed in the specification. The nanostructured substance can comprise a Lewis acid transition metal bound to a phosphate, wherein the phosphate comprises a primary structural component of the substance and the Lewis acid transition metal is a reducing agent. The nanostructured substance has a Brunner-Emmet-Teller (BET) surface area greater than or equal to approximately 100 m.sup.2/g, and a distribution coefficient for an analyte, K.sub.d, greater than or equal to approximately 5000 ml/g. The process can comprise contacting a fluid and a nanostructured metal phosphate. The apparatus can comprise a vessel and a nanostructured metal phosphate. The vessel defines a volume wherein a fluid contacts the nanostructured metal phosphate.

Biosorption of heavy metal ions to brown algae, Macrocystis pyrifera, Kjellmaniella crassiforia, and Undaria pinnatifida

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seki, Hideshi; Suzuki, Akira

1998-10-01

A fundamental study of the application of brown algae to the aqueous-phase separation of toxic heavy metals was carried out. The biosorption characteristics of cadmium and lead ions were determined with brown algae, Macrocystis pyrifera, Kjellmaniella crassiforia, and Undaria pinnatifida. A metal binding model proposed by the authors was used for the description of metal binding data. The results showed that the biosorption of bivalent metal ions to brown algae was due to bivalent binding to carboxylic groups on alginic acid in brown algae.

Existence of efficient divalent metal ion-catalyzed and inefficient divalent metal ion-independent channels in reactions catalyzed by a hammerhead ribozyme

PubMed Central

Zhou, Jing-Min; Zhou, De-Min; Takagi, Yasuomi; Kasai, Yasuhiro; Inoue, Atsushi; Baba, Tadashi; Taira, Kazunari

2002-01-01

The hammerhead ribozyme is generally accepted as a well characterized metalloenzyme. However, the precise nature of the interactions of the RNA with metal ions remains to be fully defined. Examination of metal ion-catalyzed hammerhead reactions at limited concentrations of metal ions is useful for evaluation of the role of metal ions, as demonstrated in this study. At concentrations of Mn2+ ions from 0.3 to 3 mM, addition of the ribozyme to the reaction mixture under single-turnover conditions enhances the reaction with the product reaching a fixed maximum level. Further addition of the ribozyme inhibits the reaction, demonstrating that a certain number of divalent metal ions is required for proper folding and also for catalysis. At extremely high concentrations, monovalent ions, such as Na+ ions, can also serve as cofactors in hammerhead ribozyme-catalyzed reactions. However, the catalytic efficiency of monovalent ions is extremely low and, thus, high concentrations are required. Furthermore, addition of monovalent ions to divalent metal ion-catalyzed hammerhead reactions inhibits the divalent metal ion-catalyzed reactions, suggesting that the more desirable divalent metal ion–ribozyme complexes are converted to less desirable monovalent metal ion–ribozyme complexes via removal of divalent metal ions, which serve as a structural support in the ribozyme complex. Even though two channels appear to exist, namely an efficient divalent metal ion-catalyzed channel and an inefficient monovalent metal ion-catalyzed channel, it is clear that, under physiological conditions, hammerhead ribozymes are metalloenzymes that act via the significantly more efficient divalent metal ion-dependent channel. Moreover, the observed kinetic data are consistent with Lilley’s and DeRose’s two-phase folding model that was based on ground state structure analyses. PMID:12034824

Potentiometric titration of metal ions in ethanol.

PubMed

Gibson, Graham T T; Mohamed, Mark F; Neverov, Alexei A; Brown, R S

2006-09-18

The potentiometric titrations of Zn2+, Cu2+ and 12 Ln3+ metal ions were obtained in ethanol to determine the titration constants (defined as the at which the [-OEt]/[Mx+]t ratios are 0.5, 1.5, and 2.5) and in two cases (La3+ and Zn2+) a complete speciation diagram. Several simple monobasic acids and aminium ions were also titrated to test the validity of experimental titration measurements and to establish new constants in this medium that will be useful for the preparation of buffers and standard solutions. The dependence of the titration constants on the concentration and type of metal ion and specific counterion effects is discussed. In selected cases, the titration profiles were analyzed using a commercially available fitting program to obtain information about the species present in solution, including La3+ for which a dimer model is proposed. The fitting provides the microscopic values for deprotonation of one to four metal-bound ethanol molecules. Kinetics for the La3+-catalyzed ethanolysis of paraoxon as a function of are presented and analyzed in terms of La3+ speciation as determined by the analysis of potentiometric titration curves. The stability constants for the formation of Zn2+ and Cu2+ complexes with 1,5,9-triazacyclododecane as determined by potentiometric titration are presented.

Liquid metal ion source and alloy

DOEpatents

Clark, Jr., William M.; Utlaut, Mark W.; Behrens, Robert G.; Szklarz, Eugene G.; Storms, Edmund K.; Santandrea, Robert P.; Swanson, Lynwood W.

1988-10-04

A liquid metal ion source and alloy, wherein the species to be emitted from the ion source is contained in a congruently vaporizing alloy. In one embodiment, the liquid metal ion source acts as a source of arsenic, and in a source alloy the arsenic is combined with palladium, preferably in a liquid alloy having a range of compositions from about 24 to about 33 atomic percent arsenic. Such an alloy may be readily prepared by a combustion synthesis technique. Liquid metal ion sources thus prepared produce arsenic ions for implantation, have long lifetimes, and are highly stable in operation.

Cellulose Nanofibrils Aerogel Cross-Linked by Poly(vinyl alcohol) and Acrylic Acid for Efficient and Recycled Adsorption with Heavy Metal Ions.

PubMed

She, Jiarong; Tian, Cuihua; Wu, Yiqiang; Li, Xianjun; Luo, Sha; Qing, Yan; Jiang, Zheng

2018-06-01

Cellulose nanofibrils (CNFs), disintegrated from natural fibers, are promising alternatives in wastewater purification for the porous structure and numerous hydroxyls. The pristine CNFs aerogel has limited mechanical strength and are vulnerable to collapse when exposed to water. In this work, eco-friendly and recycled CNFs aerogel adsorbents were successfully prepared using cellulose nanofibrils (CNFs), which cross-linked by poly(vinyl alcohol) (PVA) and acrylic acid (AA). The combination of PVA and AA endowed CNFs aerogel strong three-dimensional porous structure and desirable adsorption properties. The heavy metal ions were adsorbed on the CNFs-PVA-AA (CPA) adsorbents efficiently and the maximum adsorption capacities for Cu2+ and Pb2+ approached 30.0 mg/g and 131.5 mg/g, respectively. The CPA adsorbent also showed excellent reusability and their adsorption capacities maintained 89% and 88% for Cu2+ and Pb2+ after 5 repeated uses. The adsorption of these heavy metal ions were confirmed to follow pseudo-second-order kinetic and Langmuir isotherm model. The functions of C ═ O and -OH were the major adsorption sites. Chemical adsorption combined with the porous physical adsorption made the CPA to be excellent adsorbent for the removal of heavy metal ions in wastewater.

Studies on the optimum conditions using acid-washed zero-valent iron/aluminum mixtures in permeable reactive barriers for the removal of different heavy metal ions from wastewater.

PubMed

Han, Weijiang; Fu, Fenglian; Cheng, Zihang; Tang, Bing; Wu, Shijiao

2016-01-25

The method of permeable reactive barriers (PRBs) is considered as one of the most practicable approaches in treating heavy metals contaminated surface and groundwater. The mixture of acid-washed zero-valent iron (ZVI) and zero-valent aluminum (ZVAl) as reactive medium in PRBs to treat heavy metal wastewater containing Cr(VI), Cd(2+), Ni(2+), Cu(2+), and Zn(2+) was investigated. The performance of column filled with the mixture of acid-washed ZVI and ZVAl was much better than the column filled with ZVI or ZVAl alone. At initial pH 5.4 and flow rates of 1.0 mL/min, the time that the removal efficiencies of Cr(VI), Cd(2+), Ni(2+), Cu(2+), and Zn(2+) were all above 99.5% can keep about 300 h using 80 g/40 g acid-washed ZVI/ZVAl when treating wastewater containing each heavy metal ions (Cr(VI), Cd(2+), Ni(2+), Cu(2+), and Zn(2+)) concentration of 20.0 mg/L. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize ZVI/ZVAl before and after reaction and the reaction mechanism of the heavy metal ions with ZVI/ZVAl was discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

Synergistic oxygen atom transfer by ruthenium complexes with non-redox metal ions.

PubMed

Lv, Zhanao; Zheng, Wenrui; Chen, Zhuqi; Tang, Zhiming; Mo, Wanling; Yin, Guochuan

2016-07-28

Non-redox metal ions can affect the reactivity of active redox metal ions in versatile biological and heterogeneous oxidation processes; however, the intrinsic roles of these non-redox ions still remain elusive. This work demonstrates the first example of the use of non-redox metal ions as Lewis acids to sharply improve the catalytic oxygen atom transfer efficiency of a ruthenium complex bearing the classic 2,2'-bipyridine ligand. In the absence of Lewis acid, the oxidation of ruthenium(ii) complex by PhI(OAc)2 generates the Ru(iv)[double bond, length as m-dash]O species, which is very sluggish for olefin epoxidation. When Ru(bpy)2Cl2 was tested as a catalyst alone, only 21.2% of cyclooctene was converted, and the yield of 1,2-epoxycyclooctane was only 6.7%. As evidenced by electronic absorption spectra and EPR studies, both the oxidation of Ru(ii) by PhI(OAc)2 and the reduction of Ru(iv)[double bond, length as m-dash]O by olefin are kinetically slow. However, adding non-redox metal ions such as Al(iii) can sharply improve the oxygen transfer efficiency of the catalyst to 100% conversion with 89.9% yield of epoxide under identical conditions. Through various spectroscopic characterizations, an adduct of Ru(iv)[double bond, length as m-dash]O with Al(iii), Ru(iv)[double bond, length as m-dash]O/Al(iii), was proposed to serve as the active species for epoxidation, which in turn generated a Ru(iii)-O-Ru(iii) dimer as the reduced form. In particular, both the oxygen transfer from Ru(iv)[double bond, length as m-dash]O/Al(iii) to olefin and the oxidation of Ru(iii)-O-Ru(iii) back to the active Ru(iv)[double bond, length as m-dash]O/Al(iii) species in the catalytic cycle can be remarkably accelerated by adding a non-redox metal, such as Al(iii). These results have important implications for the role played by non-redox metal ions in catalytic oxidation at redox metal centers as well as for the understanding of the redox mechanism of ruthenium catalysts in the oxygen atom

Reversible photodeposition and dissolution of metal ions

DOEpatents

Foster, Nancy S.; Koval, Carl A.; Noble, Richard D.

1994-01-01

A cyclic photocatalytic process for treating waste water containing metal and organic contaminants. In one embodiment of the method, metal ions are photoreduced onto the photocatalyst and the metal concentrated by resolubilization in a smaller volume. In another embodiment of the method, contaminant organics are first oxidized, then metal ions removed by photoreductive deposition. The present invention allows the photocatalyst to be recycled until nearly complete removal of metal ions and organic contaminants is achieved.

Photocatalytic reduction of heavy metal ions on derivatized titanium dioxide nano-particle surface studied by XAFS

NASA Astrophysics Data System (ADS)

Chen, Lin X.; Rajh, Tijana; Mićić, Olga Wang, Zhiyu; Tiede, David M.; Thurnauer, Marion

1997-12-01

Photoreduction of heavy metal ions, Cu 2- and Hg 2+, on TiO 2 nano-particle surfaces, has been investigated by XAFS measurements. The effects of TiO 2 surface modification reagents on the reaction efficiency have been studied. We observed a significant reaction efficiency enhancement when amino acid alanine was added to a mixture of 0.01 M Cu 2+ and TiO 2 nano-particles. Fifty percent of the adsorbed Cu 2+ has been reduced to Cu 0 after 1-h illumination with a UV-enhanced xenon lamp. Photoreduction of Hg 2+ on TiO 2 colloid surfaces was also investigated without and with thiolactic acid (TLA). In this case, the photoreduction efficiency for Hg 2+ was lowered. Structures of metal ion surroundings in various complexes as well as their role in photoreduction of metal ions are discussed.

Mechanistic Enzyme Models: Pyridoxal and Metal Ions.

ERIC Educational Resources Information Center

Hamilton, S. E.; And Others

1984-01-01

Background information, procedures, and results are presented for experiments on the pyridoxal/metal ion model system. These experiments illustrate catalysis through Schiff's base formation between aldehydes/ketones and primary amines, catalysis by metal ions, and the predictable manner in which metal ions inhibit or catalyze reactions. (JN)

Insufficient acetabular version increases blood metal ion levels after metal-on-metal hip resurfacing.

PubMed

Hart, Alister J; Skinner, John A; Henckel, Johann; Sampson, Barry; Gordon, Fabiana

2011-09-01

Many factors affect the blood metal ion levels after metal-on-metal (MOM) hip arthroplasty. The main surgically adjustable variable is the amount of coverage of the head provided by the cup which is a function of the inclination and version angles. However, most studies have used plain radiographs which have questionable precision and accuracy, particularly for version and large diameter metal heads; further, these studies do not simultaneously assess version and inclination. Thus the relationship between version and blood metal ions levels has not been resolved. We determined whether cup inclination and version influence blood metal ion levels while adjusting for age at assessment, gender, body mass index, horizontal femoral offset, head size, manufacturer hip type, and Oxford hip score. We prospectively followed 100 individuals (51 females, 49 males) with unilateral MOM hip resurfacing who underwent clinical assessment, CT scanning, and blood metal ion measurement. Multiple regression analysis was used to determine which variables were predictors of blood metal ion levels and to model the effect of these variables. Only cup inclination, version angles, and gender influenced blood cobalt or chromium levels. Cobalt and chromium levels positively correlated with inclination angle and negatively correlated with version angle. The effect of changes in version angle was less than for inclination angle. Based on our observations, we developed a formula to predict the effect of these parameters on metal ion levels. Our data suggest insufficient cup version can cause high blood metal ions after MOM hip arthroplasty. We were unable to show that excessive version caused high levels. Level II, prognostic study. See Guidelines for Authors for a complete description of levels of evidence.

Anti-inflammatory drugs interacting with Zn(II), Cd(II) and Pt(II) metal ions.

PubMed

Dendrinou-Samara, C; Tsotsou, G; Ekateriniadou, L V; Kortsaris, A H; Raptopoulou, C P; Terzis, A; Kyriakidis, D A; Kessissoglou, D P

1998-09-01

Complexes of Zn(II), Cd(II) and Pt(II) metal ions with the anti-inflammatory drugs, 1-methyl-5-(p-toluoyl)-1H-pyrrole-2-acetic acid (Tolmetin), alpha-methyl-4-(2-methylpropyl)benzeneacetic acid (Ibuprofen), 6-methoxy-alpha-methylnaphthalene-2-acetic acid (Naproxen) and 1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-acetic acid (indomethacin) have been synthesized and characterized. In the structurally characterized Cd(naproxen)2 complex the anti-inflammatory drugs acts as bidentate chelate ligand coordinatively bound to metal ions through the deprotonated carboxylate group. Crystal data for 1: [C32H26O8Cd], orthorhombic, space group P22(1)2(1), a = 5.693(2) (A), b = 8.760(3) (A), c = 30.74(1) (A), V = 1533(1) A3, Z = 2. Antibacterial and growth inhibitory activity is higher than that of the parent ligands or the platinum(II) diamine compounds.

Magnetic separation of heavy metal ions and evaluation based on surface-enhanced Raman spectroscopy: copper(II) ions as a case study.

PubMed

Yan, Xue; Zhang, Xue-Jiao; Yuan, Ya-Xian; Han, San-Yang; Xu, Min-Min; Gu, Ren'ao; Yao, Jian-Lin

2013-11-01

A new approach was developed for the magnetic separation of copper(II) ions with easy operation and high efficiency. p-Mercaptobenzoic acid served as the modified tag of Fe2O3@Au nanoparticles both for the chelation ligand and Raman reporter. Through the chelation between the copper(II) ions and carboxyl groups on the gold shell, the Fe2O3@Au nanoparticles aggregated to form networks that were enriched and separated from the solution by a magnet. A significant decrease in the concentration of copper(II) ions in the supernatant solution was observed. An extremely sensitive method based on surface-enhanced Raman spectroscopy was employed to detect free copper(II) ions that remained after the magnetic separation, and thus to evaluate the separation efficiency. The results indicated the intensities of the surface-enhanced Raman spectroscopy bands from p-mercaptobenzoic acid were dependent on the concentration of copper(II) ions, and the concentration was decreased by several orders of magnitude after the magnetic separation. The present protocol effectively decreased the total amount of heavy metal ions in the solution. This approach opens a potential application in the magnetic separation and highly sensitive detection of heavy metal ions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of hydroxycinnamic acids on blue color expression of cyanidin derivatives and their metal chelates.

PubMed

Sigurdson, G T; Robbins, R J; Collins, T M; Giusti, M M

2017-11-01

Mechanisms to recreate many anthocyanin blue hues in nature are not fully understood, but interactions with metal ions and phenolic compounds are thought to play important roles. Bluing effects of hydroxycinnamic acids on cyanidin and chelates were investigated by addition of the acids to triglycosylated cyanidin (0-50×[anthocyanin]) and by comparison to hydroxycinnamic acid monoacylated and diacylated Cy fractions by spectrophotometry (380-700nm) and colorimetry in pH 5-8. With no metal ions, λ max and absorbance was greatest for cyanidin with diacylation>monoacylation>increasing [acids]. Hydroxycinnamic acids added to cyanidin solutions weakly impacted color characteristics (ΔE<5); while acylation (covalent acid attachment) resulted in ΔE 5-15. Triglycosylated cyanidin expressed blue color (pH 7-8), suggesting glycosylation pattern also plays a role. Al 3+ chelation increased absorbance 2-42× and λ max ≳40nm (pH 5-6) compared to added hydroxycinnamic acids. Metal chelation and aromatic diacylation resulted in the most blue hues. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catalytic conversion of cellulose to levulinic acid by metal chlorides.

PubMed

Peng, Lincai; Lin, Lu; Zhang, Junhua; Zhuang, Junping; Zhang, Beixiao; Gong, Yan

2010-08-02

The catalytic performance of various metal chlorides in the conversion of cellulose to levulinic acid in liquid water at high temperatures was investigated. The effects of reaction parameters on the yield of levulinic acid were also explored. The results showed that alkali and alkaline earth metal chlorides were not effective in conversion of cellulose, while transition metal chlorides, especially CrCl(3), FeCl(3) and CuCl(2) and a group IIIA metal chloride (AlCl(3)), exhibited high catalytic activity. The catalytic performance was correlated with the acidity of the reaction system due to the addition of the metal chlorides, but more dependent on the type of metal chloride. Among those metal chlorides, chromium chloride was found to be exceptionally effective for the conversion of cellulose to levulinic acid, affording an optimum yield of 67 mol % after a reaction time of 180 min, at 200 degrees C, with a catalyst dosage of 0.02 M and substrate concentration of 50 wt %. Chromium metal, most of which was present in its oxide form in the solid sample and only a small part in solution as Cr3+ ion, can be easily separated from the resulting product mixture and recycled. Finally, a plausible reaction scheme for the chromium chloride catalyzed conversion of cellulose in water was proposed.

Removal of Heavy Metal Ions with Acid Activated Carbons Derived from Oil Palm and Coconut Shells

PubMed Central

Rahman, Mokhlesur M.; Adil, Mohd; Yusof, Alias M.; Kamaruzzaman, Yunus B.; Ansary, Rezaul H.

2014-01-01

In this work, batch adsorption experiments were carried out to investigate the suitability of prepared acid activated carbons in removing heavy metal ions such as nickel(II), lead(II) and chromium(VI). Acid activated carbons were obtained from oil palm and coconut shells using phosphoric acid under similar activation process while the differences lie either in impregnation condition or in both pretreatment and impregnation conditions. Prepared activated carbons were modified by dispersing hydrated iron oxide. The adsorption equilibrium data for nickel(II) and lead(II) were obtained from adsorption by the prepared and commercial activated carbons. Langmuir and Freundlich models fit the data well. Prepared activated carbons showed higher adsorption capacity for nickel(II) and lead(II). The removal of chromium(VI) was studied by the prepared acid activated, modified and commercial activated carbons at different pH. The isotherms studies reveal that the prepared activated carbon performs better in low concentration region while the commercial ones in the high concentration region. Thus, a complete adsorption is expected in low concentration by the prepared activated carbon. The kinetics data for Ni(II), Pb(II) and Cr(VI) by the best selected activated carbon fitted very well to the pseudo-second-order kinetic model. PMID:28788640

Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus niger

NASA Astrophysics Data System (ADS)

Horeh, N. Bahaloo; Mousavi, S. M.; Shojaosadati, S. A.

2016-07-01

In this paper, a bio-hydrometallurgical route based on fungal activity of Aspergillus niger was evaluated for the detoxification and recovery of Cu, Li, Mn, Al, Co and Ni metals from spent lithium-ion phone mobile batteries under various conditions (one-step, two-step and spent medium bioleaching). The maximum recovery efficiency of 100% for Cu, 95% for Li, 70% for Mn, 65% for Al, 45% for Co, and 38% for Ni was obtained at a pulp density of 1% in spent medium bioleaching. The HPLC results indicated that citric acid in comparison with other detected organic acids (gluconic, oxalic and malic acid) had an important role in the effectiveness of bioleaching using A. niger. The results of FTIR, XRD and FE-SEM analysis of battery powder before and after bioleaching process confirmed that the fungal activities were quite effective. In addition, bioleaching achieved higher removal efficiency for heavy metals than the chemical leaching. This research demonstrated the great potential of bio-hydrometallurgical route to recover heavy metals from spent lithium-ion mobile phone batteries.

Selective Metal-Ion-Mediated Vesicle Adhesion Based on Dynamic Self-Organization of a Pyrene-Appended Glutamic Acid.

PubMed

Xing, Pengyao; Wang, Yajie; Yang, Minmin; Zhang, Yimeng; Wang, Bo; Hao, Aiyou

2016-07-13

Vesicles with dynamic membranes provide an ideal model system for investigating biological membrane activities, whereby vesicle aggregation behaviors including adhesion, fusion, fission, and membrane contraction/extension have attracted much attention. In this work we utilize an aromatic amino acid (pyrene-appended glutamic acid, PGlu) to prepare nanovesicles that aggregate to form vesicle clusters selectively induced by Fe(3+) or Cu(2+), and the vesicles transform into irregular nano-objects when interacting with Al(3+). Vesicle clusters have better stability than pristine vesicles, which hinders the spontaneous morphological transformation from vesicles into lamellar nanosheets with long incubation period. The difference between complexation of Fe(3+) and Al(3+) with vesicles was studied by various techniques. On the basis of metal ion-vesicle interactions, this self-assembled nanovesicle system also behaves as an effective fluorescent sensor for Fe(3+) and Al(3+), which cause fluorescence quenching and enhanced excimer emission, respectively.

Accumulation of metal ions by pectinates

NASA Astrophysics Data System (ADS)

Deiana, S.; Deiana, L.; Palma, A.; Premoli, A.; Senette, C.

2009-04-01

The knowledge of the mechanisms which regulate the interactions of metal ions with partially methyl esterified linear polymers of α-1,4 linked D-galacturonic acid units (pectinates), well represented in the root inner and outer apoplasm, is of great relevance to understand the processes which control their accumulation at the soil-root interface as well as their mobilization by plant metabolites. Accumulation of a metal by pectinates can be affected by the presence of other metals so that competition or distribution could be expected depending on the similar or different affinity of the metal ions towards the binding sites, mainly represented by the carboxylate groups. In order to better understand the mechanism of accumulation in the apoplasm of several metal ions, the sorption of Cd(II), Zn(II), Cu(II), Pb(II) and Cr(III) by a Ca-polygalacturonate gel, used as model of the soil-root interface, with a degree of esterification of 18% (PGAE1) and 65% (PGAE2) was studied at pH 3.0, 4.0, 5.0 and 6.0 in the presence of CaCl2 2.5 mM.. The results show that sorption increases with increasing both the initial metal concentration and pH. A similar sorption trend was evidenced for Cu(II) and Pb(II) and for Zn(II) and Cd(II), indicating that the mechanism of sorption for these two ionic couples is quite different. As an example, at pH 6.0 and an initial metal concentration equal to 2.0 mM, the amount of Cu(II) and Pb(II) sorbed was about 1.98 mg-1 of PGAE1 while that of Cd(II) and Zn(II) was about 1.2 mg-1. Cr(III) showed a rather different sorption trend and a much higher amount (2.8 mg-1of PGAE1 at pH 6.0) was recorded. The higher affinity of Cr(III) for the polysaccharidic matrix is attributable to the formation of Cr(III) polynuclear species in solution, as shown by the distribution diagrams obtained through the MEDUSA software. On the basis of these findings, the following affinity towards the PGAE1 can be assessed: Cr(III) > Cu(II) ? Pb(II) > Zn (II) ? Cd

Nanodiamonds act as Trojan horse for intracellular delivery of metal ions to trigger cytotoxicity.

PubMed

Zhu, Ying; Zhang, Yu; Shi, Guosheng; Yang, Jinrong; Zhang, Jichao; Li, Wenxin; Li, Aiguo; Tai, Renzhong; Fang, Haiping; Fan, Chunhai; Huang, Qing

2015-02-05

Nanomaterials hold great promise for applications in the delivery of various molecules with poor cell penetration, yet its potential for delivery of metal ions is rarely considered. Particularly, there is limited insight about the cytotoxicity triggered by nanoparticle-ion interactions. Oxidative stress is one of the major toxicological mechanisms for nanomaterials, and we propose that it may also contribute to nanoparticle-ion complexes induced cytotoxicity. To explore the potential of nanodiamonds (NDs) as vehicles for metal ion delivery, we used a broad range of experimental techniques that aimed at getting a comprehensive assessment of cell responses after exposure of NDs, metal ions, or ND-ion mixture: 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, Trypan blue exclusion text, optical microscope observation, synchrotron-based scanning transmission X-ray microscopy (STXM) and micro X-ray fluorescence (μXRF) microscopy, inductively coupled plasma-mass spectrometry (ICP-MS), reactive oxygen species (ROS) assay and transmission electron microscopy (TEM) observation. In addition, theoretical calculation and molecular dynamics (MD) computation were used to illustrate the adsorption properties of different metal ion on NDs as well as release profile of ion from ND-ion complexes at different pH values. The adsorption capacity of NDs for different metal ions was different, and the adsorption for Cu2+ was the most strong among divalent metal ions. These different ND-ion complexes then had different cytotoxicity by influencing the subsequent cellular responses. Detailed investigation of ND-Cu2+ interaction showed that the amount of released Cu2+ from ND-Cu2+ complexes at acidic lysosomal conditions was much higher than that at neutral conditions, leading to the elevation of intracellular ROS level, which triggered cytotoxicity. By theoretical approaches, we demonstrated that the functional carbon surface and cluster structures of NDs made them

Photocatalytic reduction of heavy metal ions on derivatized titanium dioxide nano-particle surface studied by XAFS.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, L. X.; Rajh, T.; Micic, O.

1997-01-01

Photoreduction of heavy metal ions, Cu{sup 2-} and Hg{sup 2+}, on TiO{sup 2} nano-particle surfaces, has been investigated by XAFS measurements. The effects of TiO{sup 2} surface modification reagents on the reaction efficiency have been studied. We observed a significant reaction efficiency enhancement when amino acid alanine was added to a mixture of 0.01 M Cu{sup 2+} and TiO{sup 2} nano-particles. Fifty percent of the adsorbed Cu{sup 2+} has been reduced to Cu{sup 0} after 1-h illumination with a UV-enhanced xenon lamp. Photoreduction of Hg{sup 2+} on TiO{sup 2} colloid surfaces was also investigated without and with thiolactic acid (TLA).more » In this case, the photoreduction efficiency for Hg{sup 2+} was lowered. Structures of metal ion surroundings in various complexes as well as their role in photoreduction of metal ions are discussed.« less

Biosorption of heavy metal ions on Rhodobacter sphaeroides and Alcaligenes eutrophus H16

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seki, Hideshi; Suzuki, Akira; Mitsueda, Shinichiro

1998-01-15

A fundamental study of the application of bacteria to the recovery of toxic heavy metals from aqueous environments was carried out. The biosorption characteristics of cadmium and lead ions were determined with purple nonsulfur bacteria, Rhodobacter sphaeroides and hydrogen bacteria, Alcaligenes eutrophus H16 that were inactivated by steam sterilization. A simplified version of the metal binding model proposed by Plette et al. was used for the description of meal binding data. The results showed that the biosorption of bivalent metal ions to whole cell bodies of the bacteria was due to monodentate binding to two different types of acidic sites:more » carboxilic and phosphatic-type sites. The number of metal binding sites of A. eutrophus was 2.4-fold larger than that of R. sphaeroides.« less

Sulphur-containing Amino Acids: Protective Role Against Free Radicals and Heavy Metals.

PubMed

Colovic, Mirjana B; Vasic, Vesna M; Djuric, Dragan M; Krstic, Danijela Z

2018-01-30

Sulphur is an abundant element in biological systems, which plays an important role in processes essential for life as a constituent of proteins, vitamins and other crucial biomolecules. The major source of sulphur for humans is plants being able to use inorganic sulphur in the purpose of sulphur-containing amino acids synthesis. Sulphur-containing amino acids include methionine, cysteine, homocysteine, and taurine. Methionine and cysteine are classified as proteinogenic, canonic amino acids incorporated in protein structure. Sulphur amino acids are involved in the synthesis of intracellular antioxidants such as glutathione and N-acetyl cysteine. Moreover, naturally occurring sulphur-containing ligands are effective and safe detoxifying agents, often used in order to prevent toxic metal ions effects and their accumulation in human body. Literature search for peer-reviewed articles was performed using PubMed and Scopus databases, and utilizing appropriate keywords. This review is focused on sulphur-containing amino acids - methionine, cysteine, taurine, and their derivatives - glutathione and N-acetylcysteine, and their defense effects as antioxidant agents against free radicals. Additionally, the protective effects of sulphur-containing ligands against the toxic effects of heavy and transition metal ions, and their reactivation role towards the enzyme inhibition are described. Sulphur-containing amino acids represent a powerful part of cell antioxidant system. Thus, they are essential in the maintenance of normal cellular functions and health. In addition to their worthy antioxidant action, sulphur-containing amino acids may offer a chelating site for heavy metals. Accordingly, they may be supplemented during chelating therapy, providing beneficial effects in eliminating toxic metals. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Effect of humic acid and transition metal ions on the debromination of decabromodiphenyl by nano zero-valent iron: kinetics and mechanisms

NASA Astrophysics Data System (ADS)

Tan, Lei; Liang, Bin; Fang, Zhanqiang; Xie, Yingying; Tsang, Eric Pokeung

2014-12-01

E-waste sites are one of the main sources of the pollutant decabromodiphenyl ether (BDE209); contaminated farmland and water bodies urgently need to be remediated. As a potential in situ remediation technology, nano zero-valent iron (nZVI) technology effectively removes PBDEs. However, the humic acid (HA) and heavy metals in the contaminated sites affect the remediation effects. In this study, we explored the influence of HA and transition metals on the removal of PBDEs by nZVI. The specific surface area and average size of the nZVI particles we prepared were 35 m2/g and 50-80 nm, respectively. The results showed that HA inhibited the removal of PBDEs; as the concentration of HA increased, its inhibitory effect intensified and the k obs decreased. However, the three metal ions (Cu2+, Co2+, and Ni2+) enhanced the removal of PBDEs. The enhancement effect was followed the order Ni2+ > Cu2+ > Co2+. As the concentration of metal ions increased, the promotion effect improved. The synergistic effect of HA and the metal ions was manifested in the combination of the inhibitory effect and the enhancement effect. The values of the first-order kinetic constants ( k obs) under the combined effect were between the values of the rate constants under the individual components. The inhibitory mechanism was the chemisorption of HA, i.e., the benzene carboxylic and phenolic hydroxyl groups in HA occupied the surfactant reactive sites of nZVI, thus inhibiting the removal of BDE209. The promotion mechanism of Cu2+, Co2+, and Ni2+ can be explained by their reduction to zero valence on the nZVI surface; furthermore, Ni2+ strongly affects the debromination and dehydrogenation of BDE209, leading to a stronger promotability than Cu2+or Co2+.

Metal Ion Reactions with Ozone and Atomic Oxygen.

DTIC Science & Technology

1979-04-05

EEEI 3 6 ....... Ii. MICROCOP Y RESOLUTION TEST CHART] / I. ~< 4 . A ’~ N ~ ~’ ~ ~. ~ ~ 4 ~ ~ ~. A ............................. ~ i, .1.’~~ AU 5 <j~1...aluminum-containing compound is ap- plied directly to a surface with high work function. Upon heating the sur- face, Al+ ions are evolved. In the...present experiments the compound was aluminum chloride, prepared by dissolving aluminum metal in hydrochloric *1 acid. The solution was then applied to the

Effect of H+ ion activity and Ca2+ on the toxicity of metals in the environment.

PubMed Central

Hutchinson, T C; Collins, F W

1978-01-01

The role of acidity in determining and restricting plant distribution and performance is discussed. In soils especially, a key effect of H+ ion concentration is on the solubility of potentially toxic heavy metals such as aluminum, managenese, zinc, iron, copper, and nickel. Al has been reported from many studies since the 1920's as the key determining toxic factor in acid soils. Some acid-tolerant species have been shown to be especially tolerant of Al, and mechanisms of tolerance have been suggested. Mn is also a commonly toxic factor at soil pH less than 5.0. Calcium has been shown to alleviate Mn toxicity. Low pH soils are also generally low in Ca, K, Na, and P; all essential major elements for plant growth. In lakes and marine situations acidic waters are uncommon as the waters are buffered. Calcium is again ameliorative of metal toxicities. The pH, redox, and valency state are critical in determining nutrient availability and metal speciation. Recent increases in the H+ ion content of precipitation have caused increased acidities of freshwater lakes in Scandinavia and eastern North America, which have depleted biota, including fish populations. PMID:31277

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Influence of variable chemical conditions on EDTA-enhanced transport of metal ions in mildly acidic groundwater

USGS Publications Warehouse

Kent, D.B.; Davis, J.A.; Joye, J.L.; Curtis, G.P.

2008-01-01

Adsorption of Ni and Pb on aquifer sediments from Cape Cod, Massachusetts, USA increased with increasing pH and metal-ion concentration. Adsorption could be described quantitatively using a semi-mechanistic surface complexation model (SCM), in which adsorption is described using chemical reactions between metal ions and adsorption sites. Equilibrium reactive transport simulations incorporating the SCMs, formation of metal-ion-EDTA complexes, and either Fe(III)-oxyhydroxide solubility or Zn desorption from sediments identified important factors responsible for trends observed during transport experiments conducted with EDTA complexes of Ni, Zn, and Pb in the Cape Cod aquifer. Dissociation of Pb-EDTA by Fe(III) is more favorable than Ni-EDTA because of differences in Ni- and Pb-adsorption to the sediments. Dissociation of Ni-EDTA becomes more favorable with decreasing Ni-EDTA concentration and decreasing pH. In contrast to Ni, Pb-EDTA can be dissociated by Zn desorbed from the aquifer sediments. Variability in adsorbed Zn concentrations has a large impact on Pb-EDTA dissociation.

The effects of heavy metal ions, phthalates and ochratoxin A on oxidation of carcinogenic aristolochic acid I causing Balkan endemic nephropathy.

PubMed

Barta, Frantisek; Levova, Katerina; Hodek, Petr; Schmeiser, Heinz H; Arlt, Volker M; Stiborova, Marie

2015-01-01

Balkan endemic nephropathy (BEN) is a chronic progressive fibrosis associated with upper urothelial carcinoma (UUC). Aetiology of BEN is still not fully explained. Although carcinogenic aristolochic acid I (AAI) was proven as the major cause of BEN/UUC, this nephropathy is considered to be multifactorial. Hence, we investigated whether other factors considered as potential causes of BEN [a mycotoxin ochratoxin A (OTA), Cd, Pb, Se and As ions and organic compounds (i.e. phthalates) released from lignite deposits in BEN areas] can influence detoxication of AAI, whose concentrations are crucial for BEN development. Oxidation of AAI to 8-hydroxyaristolochic acid I (AAIa) in the presence of Cd, Pb, Se, As ions, dibutylphthalate (DBP), butylbenzylphthalate (BBP), bis(2-ethylhexyl)phthalate (DEHP) and OTA by rat liver microsomes was determined by HPLC. Only OTA, cadmium and selenium ions, and BBP inhibited AAI oxidation by rat liver microsomes. These compounds also inhibited activities of CYP1A1 and/or CYP2C6/11 catalysing AAI demethylation in rat livers. Therefore, these CYP inhibitions can be responsible for a decrease in AAIa formation. When the combined effects of these compounds were investigated, the most efficient inhibition was caused by OTA combined with BBP and selenium ions. The results show low effects of BBP, cadmium and selenium ions, and/or their combinations on AAI detoxication. No effects were produced by the other metal ions (Pb, As) and phthalates DBP and DEHP. This finding suggests that they do not influence AAI-mediated BEN development. In contrast, OTA might influence this process, by inhibition of AAI detoxication.

DNA as Sensors and Imaging Agents for Metal Ions

PubMed Central

Xiang, Yu

2014-01-01

Increasing interests in detecting metal ions in many chemical and biomedical fields have created demands for developing sensors and imaging agents for metal ions with high sensitivity and selectivity. This review covers recent progress in DNA-based sensors and imaging agents for metal ions. Through both combinatorial selection and rational design, a number of metal ion-dependent DNAzymes and metal ion-binding DNA structures that can selectively recognize specific metal ions have been obtained. By attaching these DNA molecules with signal reporters such as fluorophores, chromophores, electrochemical tags, and Raman tags, a number of DNA-based sensors for both diamagnetic and paramagnetic metal ions have been developed for fluorescent, colorimetric, electrochemical, and surface Raman detections. These sensors are highly sensitive (with detection limit down to 11 ppt) and selective (with selectivity up to millions-fold) toward specific metal ions. In addition, through further development to simplify the operation, such as the use of “dipstick tests”, portable fluorometers, computer-readable discs, and widely available glucose meters, these sensors have been applied for on-site and real-time environmental monitoring and point-of-care medical diagnostics. The use of these sensors for in situ cellular imaging has also been reported. The generality of the combinatorial selection to obtain DNAzymes for almost any metal ion in any oxidation state, and the ease of modification of the DNA with different signal reporters make DNA an emerging and promising class of molecules for metal ion sensing and imaging in many fields of applications. PMID:24359450

DFT study of the interaction between DOTA chelator and competitive alkali metal ions.

PubMed

Frimpong, E; Skelton, A A; Honarparvar, B

2017-09-01

1, 4, 7, 10-tetraazacyclododecane-1, 4, 7, 10-tetracetic acid (DOTA) is an important chelator for radiolabeling of pharmaceuticals. The ability of alkali metals found in the body to complex with DOTA and compete with radio metal ions can alter the radiolabeling process. Non-covalent interactions between DOTA complexed with alkali metals Li + , Na + , K + and Rb + , are investigated with density functional theory using B3LYP and ωB97XD functionals. Conformational possibilities of DOTA were explored with a varying number of carboxylic pendant arms of DOTA in close proximity to the ions. It is found that the case in which four arms of DOTA are interacting with ions is more stable than other conformations. The objective of this study is to explore the electronic structure properties upon complexation of alkali metals Li + Na + , K + and Rb + with a DOTA chelator. Interaction energies, relaxation energies, entropies, Gibbs free energies and enthalpies show that the stability of DOTA, complexed with alkali metals decreases down the group of the periodic table. Implicit water solvation affects the complexation of DOTA-ions leading to decreases in the stability of the complexes. NBO analysis through the natural population charges and the second order perturbation theory, revealed a charge transfer between DOTA and alkali metals. Conceptual DFT-based properties such as HOMO/LUMO energies, ΔE HOMO-LUMO and chemical hardness and softness indicated a decrease in the chemical stability of DOTA-alkali metal complexes down the alkali metal series. This study serves as a guide to researchers in the field of organometallic chelators, particularly, radiopharmaceuticals in finding the efficient optimal match between chelators and various metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

Pseudo ribbon metal ion beam source.

PubMed

Stepanov, Igor B; Ryabchikov, Alexander I; Sivin, Denis O; Verigin, Dan A

2014-02-01

The paper describes high broad metal ion source based on dc macroparticle filtered vacuum arc plasma generation with the dc ion-beam extraction. The possibility of formation of pseudo ribbon beam of metal ions with the parameters: ion beam length 0.6 m, ion current up to 0.2 A, accelerating voltage 40 kV, and ion energy up to 160 kV has been demonstrated. The pseudo ribbon ion beam is formed from dc vacuum arc plasma. The results of investigation of the vacuum arc evaporator ion-emission properties are presented. The influence of magnetic field strength near the cathode surface on the arc spot movement and ion-emission properties of vacuum-arc discharge for different cathode materials are determined. It was shown that vacuum-arc discharge stability can be reached when the magnetic field strength ranges from 40 to 70 G on the cathode surface.

Separation of metal ions in nitrate solution by ultrasonic atomization

NASA Astrophysics Data System (ADS)

Sato, Masanori; Ikeno, Masayuki; Fujii, Toshitaka

2004-11-01

In the ultrasonic atomization of metal nitrate solutions, the molar ratio of metal ions is changed between solution and mist. Small molar metal ions tend to be transferred to mist by ultrasonic wave acceleration, while large molar ions tend to remain in solution. As a result, metal ions can be separated by ultrasonic atomization. We show experimental data and propose a conceptual mechanism for the ultrasonic separation of metal ions.

Superhydrogels of nanotubes capable of capturing heavy-metal ions.

PubMed

Song, Shasha; Wang, Haiqiao; Song, Aixin; Hao, Jingcheng

2014-01-01

Self-assembly regulated by hydrogen bonds was successfully achieved in the system of lithocholic acid (LCA) mixed with three organic amines, ethanolamine (EA), diethanolamine (DEA), and triethanolamine (TEA), in aqueous solutions. The mixtures of DEA/LCA exhibit supergelation capability and the hydrogels consist of plenty of network nanotubes with uniform diameters of about 60 nm determined by cryogenic TEM. Interestingly, the sample with the same concentration in a system of EA and LCA is a birefringent solution, in which spherical vesicles and can be transformed into nanotubes as the amount of LCA increases. The formation of hydrogels could be driven by the delicate balance of diverse noncovalent interactions, including electrostatic interactions, hydrophobic interactions, steric effects, van der Waals forces, and mainly hydrogen bonds. The mechanism of self-assembly from spherical bilayer vesicles into nanotubes was proposed. The dried hydrogels with nanotubes were explored to exhibit the excellent capability for capturing heavy-metal ions, for example, Cu(2+), Co(2+), Ni(2+), Pb(2+), and Hg(2+). The superhydrogels of nanotubes from the self-assembly of low-molecular-weight gelators mainly regulated by hydrogen bonds used for the removal of heavy-metal ions is simple, green, and high efficiency, and provide a strategic approach to removing heavy-metal ions from industrial sewage. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

PubMed

Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

2016-01-01

Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K < 2) and depends on the charge of the ligand, owing to the ionic nature of the interactions. At the same time, the size of the cation is an important factor that influences the stability: very often, but not always (e.g., for sulfate), it follows the trend Li(+) > Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand).

The use of raw and acid-pretreated bivalve mollusk shells to remove metals from aqueous solutions.

PubMed

Liu, Yang; Sun, Changbin; Xu, Jin; Li, Youzhi

2009-08-30

Heavy metal removal from industrial wastewater is not only to protect living organisms in the environment but also to conserve resources such as metals and water by enabling their reuse. To overcome the disadvantage of high cost and secondary pollution by the conventional physico-chemical treatment techniques, environmentally benign and low-cost adsorbents are in demand. In this study, the use of raw and acid-pretreated bivalve mollusk shells (BMSs) to remove metals from aqueous solutions with single or mixed metal was evaluated at different BMSs doses, pH and temperatures in batch shaking experiments in laboratory conditions. When the BMSs were used to treat CuSO(4)x5H(2)O solution, the copper sorption capacities of the raw and acid-pretreated BMSs were approximately 38.93 mg/g and 138.95 mg/g, respectively. The copper removal efficiency (CRE) of the raw BMSs became greatly enhanced with increasing initial pH, reaching 99.51% at the initial pH 5. Conversely, the CRE of the acid-pretreated BMSs was maintained at 99.48-99.52% throughout the pH range of 1-5. Furthermore, the CRE values of the raw and acid-pretreated BMSs were not greatly changed when the temperature was varied from 15 degrees C to 40 degrees C. In addition, the CRE value of the raw BMSs was maintained for 12 cycles of sorption-desorption with a CRE of 98.4% being observed in the final cycle. Finally, when the BMSs were used to treat electroplating wastewater, the removal efficiencies (REs) of the raw BMSs were 99.97%, 98.99% and 87% for Fe, Zn and Cu, respectively, whereas the REs of the acid-pretreated BMSs were 99.98%, 99.43% and 92.13%, respectively. Ion exchange experiments revealed that one of mechanisms for metal sorption by the BMSs from aqueous solution is related to ion exchange, especially between the metal ions in the treated solution and Ca(2+) from BMSs. Infrared absorbance spectra analysis indicated that the acid pretreatment led to occurrence of the groups (i.e. -OH, -NH, C=O and S

Formation of Metal-Related Ions in Matrix-Assisted Laser Desorption Ionization.

PubMed

Lee, Chuping; Lu, I-Chung; Hsu, Hsu Chen; Lin, Hou-Yu; Liang, Sheng-Ping; Lee, Yuan-Tseh; Ni, Chi-Kung

2016-09-01

In a study of the metal-related ion generation mechanism in matrix-assisted laser desorption ionization (MALDI), crystals of matrix used in MALDI were grown from matrix- and salt-containing solutions. The intensities of metal ion and metal adducts of the matrix ion obtained from unwashed crystals were higher than those from crystals washed with deionized water, indicating that metal ions and metal adducts of the matrix ions are mainly generated from the surface of crystals. The contributions of preformed metal ions and metal adducts of the matrix ions inside the matrix crystals were minor. Metal adducts of the matrix and analyte ion intensities generated from a mixture of dried matrix, salt, and analyte powders were similar to or higher than those generated from the powder of dried droplet crystals, indicating that the contributions of the preformed metal adducts of the matrix and analyte ions were insignificant. Correlation between metal-related ion intensity fluctuation and protonated ion intensity fluctuation was observed, indicating that the generation mechanism of the metal-related ions is similar to that of the protonated ions. Because the thermally induced proton transfer model effectively describes the generation of the protonated ions, we suggest that metal-related ions are mainly generated from the salt dissolution in the matrix melted by the laser. Graphical Abstract ᅟ.

Does Cation Size Affect Occupancy and Electrostatic Screening of the Nucleic Acid Ion Atmosphere?

PubMed Central

2016-01-01

Electrostatics are central to all aspects of nucleic acid behavior, including their folding, condensation, and binding to other molecules, and the energetics of these processes are profoundly influenced by the ion atmosphere that surrounds nucleic acids. Given the highly complex and dynamic nature of the ion atmosphere, understanding its properties and effects will require synergy between computational modeling and experiment. Prior computational models and experiments suggest that cation occupancy in the ion atmosphere depends on the size of the cation. However, the computational models have not been independently tested, and the experimentally observed effects were small. Here, we evaluate a computational model of ion size effects by experimentally testing a blind prediction made from that model, and we present additional experimental results that extend our understanding of the ion atmosphere. Giambasu et al. developed and implemented a three-dimensional reference interaction site (3D-RISM) model for monovalent cations surrounding DNA and RNA helices, and this model predicts that Na+ would outcompete Cs+ by 1.8–2.1-fold; i.e., with Cs+ in 2-fold excess of Na+ the ion atmosphere would contain an equal number of each cation (Nucleic Acids Res.2015, 43, 8405). However, our ion counting experiments indicate that there is no significant preference for Na+ over Cs+. There is an ∼25% preferential occupancy of Li+ over larger cations in the ion atmosphere but, counter to general expectations from existing models, no size dependence for the other alkali metal ions. Further, we followed the folding of the P4–P6 RNA and showed that differences in folding with different alkali metal ions observed at high concentration arise from cation–anion interactions and not cation size effects. Overall, our results provide a critical test of a computational prediction, fundamental information about ion atmosphere properties, and parameters that will aid in the development of

Structures and physical properties of gaseous metal cationized biological ions.

PubMed

Burt, Michael B; Fridgen, Travis D

2012-01-01

Metal chelation can alter the activity of free biomolecules by modifying their structures or stabilizing higher energy tautomers. In recent years, mass spectrometric techniques have been used to investigate the effects of metal complexation with proteins, nucleobases and nucleotides, where small conformational changes can have significant physiological consequences. In particular, infrared multiple photon dissociation spectroscopy has emerged as an important tool for determining the structure and reactivity of gas-phase ions. Unlike other mass spectrometric approaches, this method is able to directly resolve structural isomers using characteristic vibrational signatures. Other activation and dissociation methods, such as blackbody infrared radiative dissociation or collision-induced dissociation can also reveal information about the thermochemistry and dissociative pathways of these biological ions. This information can then be used to provide information about the structures of the ionic complexes under study. In this article, we review the use of gas-phase techniques in characterizing metal-bound biomolecules. Particular attention will be given to our own contributions, which detail the ability of metal cations to disrupt nucleobase pairs, direct the self-assembly of nucleobase clusters and stabilize non-canonical isomers of amino acids.

Separation of metal ions from aqueous solutions

DOEpatents

Almon, Amy C.

1994-01-01

A process and apparatus for quantitatively and selectively separating metal ions from mixtures thereof in aqueous solution. The apparatus includes, in combination, a horizontal electrochemical flow cell containing flow bulk electrolyte solution and an aqueous, metal ion-containing solution, the cell containing a metal mesh working electrode, a counter electrode positioned downstream from the working electrode, an independent variable power supply/potentiostat positioned outside of the flow cell and connected to the electrodes, and optionally a detector such as a chromatographic detector, positioned outside the flow cell. This apparatus and its operation has significant application where trace amounts of metal ions are to be separated.

Primitive Photosynthetic Architectures Based on Self-Organization and Chemical Evolution of Amino Acids and Metal Ions.

PubMed

Liu, Kai; Ren, Xiaokang; Sun, Jianxuan; Zou, Qianli; Yan, Xuehai

2018-06-01

The emergence of light-energy-utilizing metabolism is likely to be a critical milestone in prebiotic chemistry and the origin of life. However, how the primitive pigment is spontaneously generated still remains unknown. Herein, a primitive pigment model based on adaptive self-organization of amino acids (Cystine, Cys) and metal ions (zinc ion, Zn 2+ ) followed by chemical evolution under hydrothermal conditions is developed. The resulting hybrid microspheres are composed of radially aligned cystine/zinc (Cys/Zn) assembly decorated with carbonate-doped zinc sulfide (C-ZnS) nanocrystals. The part of C-ZnS can work as a light-harvesting antenna to capture ultraviolet and visible light, and use it in various photochemical reactions, including hydrogen (H 2 ) evolution, carbon dioxide (CO 2 ) photoreduction, and reduction of nicotinamide adenine dinucleotide (NAD + ) to nicotinamide adenine dinucleotide hydride (NADH). Additionally, guest molecules (e.g., glutamate dehydrogenase, GDH) can be encapsulated within the hierarchical Cys/Zn framework, which facilitates sustainable photoenzymatic synthesis of glutamate. This study helps deepen insight into the emergent functionality (conversion of light energy) and complexity (hierarchical architecture) from interaction and reaction of prebiotic molecules. The primitive pigment model is also promising to work as an artificial photosynthetic microreactor.

Yeast enolase: mechanism of activation by metal ions.

PubMed

Brewer, J M

1981-01-01

Yeast enolase as prepared by current procedures is inherently chemically homogeneous, though deamidation and partial denaturation can produce electrophoretically distinct forms. A true isozyme of the enzyme exists but does not survive the purification procedure. The chemical sequence for both has been established. The enzyme behaves in solution like a compact, nearly spherical molecule of moderate hydration. Strong intramolecular forces maintain the structure of the individual subunits. The enzyme as isolated is dimeric. If dissociated in the presence of magnesium ions and substrate, then the subunits are active, but if the dissociation occurs in the absence of metal ions, they are inactive until they have reassociated and undergone a first order "annealing" process. Magnesium (II) enhances association. The interaction between the subunits is hydrophobic in character. The enzyme can bind up to 2 mol of most metal ions in "conformational" sites which then allows up to 2 mol of substrate or some substrate analogue to bind. This is not sufficient for catalysis, but conformational metal ions do more than just allow substrate binding. A change in the environment of the metal ions occurs on substrate or substrate analogue binding. There is an absolute correlation between the occurrence of a structural change undergone by the 3-amino analogue of phosphoenolpyruvate and whether the metal ions produce any level of enzymatic activity. For catalysis, two more moles of metal ions, called "catalytic", must bind. There is evidence that the enzymatic reaction involves a carbanion mechanism. It is likely that two more moles of metal ion can bind which inhibit the reaction. The requirement for 2 mol of metal ion per subunit which contribute in different ways to catalysis is exhibited by a number of other enzymes.

Efficient biodegradation of acephate by Pseudomonas pseudoalcaligenes PS-5 in the presence and absence of heavy metal ions [Cu(II) and Fe(III)], and humic acid.

PubMed

Singh, Simranjeet; Kumar, Vijay; Upadhyay, Niraj; Singh, Joginder; Singla, Sourav; Datta, Shivika

2017-08-01

The present study was intended to investigate the biodegradation of acephate in aqueous media in the presence and in the absence of metal ions [Fe(III) and Cu(II)], and humic acid (HA). Biodegradations were performed using Pseudomonas pseudoalcaligenes PS-5 (PS-5) isolated from the heavy metal polluted site. Biodegradations were monitored by UV-Visible, FTIR, and electron spray ionization-mass spectrometry (ESI-MS) analyses. ESI-MS analysis revealed that PS-5 degraded acephate to two metabolites showing intense ions at mass-to-charge ratios ( m / z ) 62 and 97. The observed kinetic was the pseudo-first order, and half-life periods ( t 1/2 ) were 2.79 d -1 (of PS-5 + acephate), 3.45 d -1 [of PS-5 + acephate + Fe(III)], 3.16 d -1 [of PS-5 + acephate + Cu(II)], and 5.54 d -1 (of PS-5 + acephate + HA). A significant decrease in degradation rate of acephate was noticed in the presence of HA, and the same was confirmed by UV-Visible and TGA analyses. Strong aggregation behavior of acephate with humic acid in aqueous media was the major cause behind the slow degradation rate of acephate . New results on acephate metabolism by strain PS-5 in the presence and in the absence of metal ions [Fe(III) and Cu(II)] and humic acid were obtained. Results confirmed that Pseudomonas pseudoalcaligenes strain PS-5 was capable of mineralization of the acephate without formation of toxic metabolite methamidophos. More significantly, the Pseudomonas pseudoalcaligenes strain PS-5 could be useful as potential biological agents in effective bioremediation campaign for multi-polluted environments.

Ionic Liquids as Extraction Media for Metal Ions

NASA Astrophysics Data System (ADS)

Hirayama, Naoki

In solvent extraction separation of metal ions, recently, many researchers have investigated possible use of hydrophobic ionic liquids as extraction media instead of organic solvents. Ionic liquids are salts of liquid state around room temperature and can act not only as solvents but also as ion-exchangers. Therefore, the extraction mechanism of metal ions into ionic liquids is complicated. This review presents current overview and perspective on evaluation of nature of hydrophobic ionic liquids as extraction media for metal ions.

Oxidation of cyclohexane catalyzed by metal-ion-exchanged zeolites.

PubMed

Sökmen, Ilkay; Sevin, Fatma

2003-08-01

The ion-exchange rates and capacities of the zeolite NaY for the Cu(II), Co(II), and Pb(II) metal ions were investigated. Ion-exchange equilibria were achieved in approximately 72 h for all the metal ions. The maximum ion exchange of metal ions into the zeolite was found to be 120 mg Pb(II), 110 mg Cu(II), and 100 mg Co(II) per gram of zeolite NaY. It is observed that the exchange capacity of a zeolite varies with the exchanged metal ion and the amount of metal ions exchanged into zeolite decreases in the sequence Pb(II) > Cu(II) > Co(II). Application of the metal-ion-exchanged zeolites in oxidation of cyclohexane in liquid phase with visible light was examined and it is observed that the order of reactivity of the zeolites for the conversion of cyclohexane to cyclohexanone and cyclohexanol is CuY > CoY > PbY. It is found that conversion increases by increase of the empty active sites of a zeolite and the formation of cyclohexanol is favored initially, but the cyclohexanol is subsequently converted to cyclohexanone.

Redox-inactive metal ions promoted the catalytic reactivity of non-heme manganese complexes towards oxygen atom transfer.

PubMed

Choe, Cholho; Yang, Ling; Lv, Zhanao; Mo, Wanling; Chen, Zhuqi; Li, Guangxin; Yin, Guochuan

2015-05-21

Redox-inactive metal ions can modulate the reactivity of redox-active metal ions in a variety of biological and chemical oxidations. Many synthetic models have been developed to help address the elusive roles of these redox-inactive metal ions. Using a non-heme manganese(II) complex as the model, the influence of redox-inactive metal ions as a Lewis acid on its catalytic efficiency in oxygen atom transfer was investigated. In the absence of redox-inactive metal ions, the manganese(II) catalyst is very sluggish, for example, in cyclooctene epoxidation, providing only 9.9% conversion with 4.1% yield of epoxide. However, addition of 2 equiv. of Al(3+) to the manganese(II) catalyst sharply improves the epoxidation, providing up to 97.8% conversion with 91.4% yield of epoxide. EPR studies of the manganese(II) catalyst in the presence of an oxidant reveal a 16-line hyperfine structure centered at g = 2.0, clearly indicating the formation of a mixed valent di-μ-oxo-bridged diamond core, Mn(III)-(μ-O)2-Mn(IV). The presence of a Lewis acid like Al(3+) causes the dissociation of this diamond Mn(III)-(μ-O)2-Mn(IV) core to form monomeric manganese(iv) species which is responsible for improved epoxidation efficiency. This promotional effect has also been observed in other manganese complexes bearing various non-heme ligands. The findings presented here have provided a promising strategy to explore the catalytic reactivity of some di-μ-oxo-bridged complexes by adding non-redox metal ions to in situ dissociate those dimeric cores and may also provide clues to understand the mechanism of methane monooxygenase which has a similar diiron diamond core as the intermediate.

Poly(acrylic acid) modifying bentonite with in-situ polymerization for removing lead ions.

PubMed

He, Y F; Zhang, L; Yan, D Z; Liu, S L; Wang, H; Li, H R; Wang, R M

2012-01-01

In this paper, a new kind of poly(acrylic acid) modified clay adsorbent, the poly(acrylic acid)/bentonite composite (PAA/HB) was prepared by in-situ polymerization, and utilized to remove lead(II) ions from solutions. The maximum adsorption of adsorbent is at pH 5 for metal ions, whereas the adsorption starts at pH 2. The effects of contact time (5-60 min), initial concentration of metal ions (200-1,000 mg/L) and adsorbent dosage (0.04-0.12 g/100 mL) have been reported in this article. The experimental data were investigated by means of kinetic and equilibrium adsorption isotherms. The kinetic data were analyzed by the pseudo-first-order and pseudo-second-order equation. The experimental data fitted the pseudo-second-order kinetic model very well. Langmuir and Freundlich isotherms were tried for the system to better understand the adsorption isotherm process. The maximal adsorption capacity of the lead(II) ions on the PAA/HB, as calculated from the Langmuir model, was 769.2 mg/g. The results in this study indicated that PAA/HB was an attractive candidate for removing lead(II) (99%).

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

NASA Technical Reports Server (NTRS)

Thompson, David W.

1993-01-01

selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

PubMed

Petoral, Rodrigo M; Björefors, Fredrik; Uvdal, Kajsa

2006-11-23

Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.

Ion Implantation Studies of Titanium Metal Surfaces.

DTIC Science & Technology

1981-01-01

sf.Th. 82-0 327 11,y 604.)___ _ 4 . TITLE (and Subtitle) S. TYPE OF REPORT & PERIOD COVERED Final Ion Implantation Studies of Titanium Metal Suf s 6 ...AD-A113 7ag GEORGIA INST OF TECH ATLANTA SCHOOL OF PHYSICS FIG 11/ 6 ION IMPLANTATION STUDOIES OF TITANIUM METAL SURtFACES. (U) 1901 J R STEVENSON. K...LL0 kpproved ror 82 4 ±s~rutic iui.~o 82r-~~ ION IMPLANTATION STUDIES OF TITANIUM METAL SURFACES SECURITY CLASSIFICATION OIOF THIS PAGE (0fen Date

Probing the acidic residue within the integrin binding site of laminin-511 that interacts with the metal ion-dependent adhesion site of α6β1 integrin.

PubMed

Taniguchi, Yukimasa; Li, Shaoliang; Takizawa, Mamoru; Oonishi, Eriko; Toga, Junko; Yagi, Emiko; Sekiguchi, Kiyotoshi

2017-06-03

Laminins are major cell-adhesive proteins of basement membranes that interact with integrins in a divalent cation-dependent manner. Laminin-511 consists of α5, β1, and γ1 chains, of which three laminin globular domains of the α5 chain (α5/LG1-3) and a Glu residue in the C-terminal tail of chain γ1 (γ1-Glu1607) are required for binding to integrins. However, it remains unsettled whether the Glu residue in the γ1 tail is involved in integrin binding by coordinating the metal ion in the metal ion-dependent adhesion site of β1 integrin (β1-MIDAS), or by stabilizing the conformation of α5/LG1-3. To address this issue, we examined whether α5/LG1-3 contain an acidic residue required for integrin binding that is as critical as the Glu residue in the γ1 tail; to achieve this, we undertook exhaustive alanine substitutions of the 54 acidic residues present in α5/LG1-3 of the E8 fragment of laminin-511 (LM511E8). Most of the alanine mutants possessed α6β1 integrin binding activities comparable with wild-type LM511E8. Alanine substitution for α5-Asp3198 and Asp3219 caused mild reduction in integrin binding activity, and that for α5-Asp3218 caused severe reduction, possibly resulting from conformational perturbation of α5/LG1-3. When α5-Asp3218 was substituted with asparagine, the resulting mutant possessed significant binding activity to α6β1 integrin, indicating that α5-Asp3218 is not directly involved in integrin binding through coordination with the metal ion in β1-MIDAS. Given that substitution of γ1-Glu1607 with glutamine nullified the binding activity to α6β1 integrin, these results, taken together, support the possibility that the critical acidic residue coordinating the metal ion in β1-MIDAS is Glu1607 in the γ1 tail, but no such residue is present in α5/LG1-3. Copyright © 2017 Elsevier Inc. All rights reserved.

Zinc-ion-dependent acid phosphatase exhibits magnesium-ion-dependent myo-inositol-1-phosphatase activity.

PubMed

Fujimoto, S; Okano, I; Tanaka, Y; Sumida, Y; Tsuda, J; Kawakami, N; Shimohama, S

1996-06-01

We have purified bovine brain Zn(2+)-dependent acid phosphatase (Zn(2+)-APase), which requires Zn2+ ions to hydrolyze the substrate p-nitrophenyl phosphate (pNPP) in an acidic environment. The substrate specificity and metal requirement of Zn(2+)-APase at a physiological pH was also studied. The enzyme exhibited hydrolytic activity on myo-inositol-1- and -2-monophosphates, 2'-adenosine monophosphate, 2'-guanosine monophosphate, and the alpha- and beta-glycerophosphates, glucose-1-phosphate, and fructose-6-phosphate in 50 mM Tris-HCl buffer (pH 7.4) in the presence of Mg2+ ions, but not on pNPP and phosphotyrosine. Zn2+, Mn2+ and Co2+ ions were less effective for activation. Among the above substrates, myo-inositol-1-phosphate was the most susceptible to hydrolysis by the enzyme in the presence of 3 mM Mg2+ ions. The enzyme exhibited an optimum pH at around 8 for myo-inositol-1-phosphate in the presence of 3 mM Mg2+ ions. The Mg(2+)-dependent myo-inositol-1-phosphatase activity of the enzyme was significantly inhibited by Li+ ions. The Zn(2+)-dependent p-nitrophenyl phosphatase activity and Mg(2+)-dependent myo-inositol-1-phosphatase activity of the purified enzyme fraction exhibited similar behavior on Sephadex G-100 and Mono Q colomns. These findings suggest that Zn(2+)-APase also exhibits Mg(2+)-dependent myo-inositol-1-phosphatase activity under physiological conditions.

Metal ion-dependent DNAzymes and their applications as biosensors.

PubMed

Lan, Tian; Lu, Yi

2012-01-01

Long considered to serve solely as the genetic information carrier, DNA has been shown in 1994 to be able to act as DNA catalysts capable of catalyzing a trans-esterification reaction similar to the action of ribozymes and protein enzymes. Although not yet found in nature, numerous DNAzymes have been isolated through in vitro selection for catalyzing many different types of reactions in the presence of different metal ions and thus become a new class of metalloenzymes. What remains unclear is how DNA can carry out catalysis with simpler building blocks and fewer functional groups than ribozymes and protein enzymes and how DNA can bind metal ions specifically to perform these functions. In the past two decades, many biochemical and biophysical studies have been carried out on DNAzymes, especially RNA-cleaving DNAzymes. Important insights have been gained regarding their metal-dependent activity, global folding, metal binding sites, and catalytic mechanisms for these DNAzymes. Because of their high metal ion selectivity, one of the most important practical applications for DNAzymes is metal ion detection, resulting in highly sensitive and selective fluorescent, colorimetric, and electrochemical sensors for a wide range of metal ions such as Pb(2+), UO2 2 +,[Formula: see text] including paramagnetic metal ions such as Cu(2+). This chapter summarizes recent progresses in in vitro selection of metal ion-selective DNAzymes, their biochemical and biophysical studies and sensing applications.

DUHOCAMIS: a dual hollow cathode ion source for metal ion beams.

PubMed

Zhao, W J; Müller, M W O; Janik, J; Liu, K X; Ren, X T

2008-02-01

In this paper we describe a novel ion source named DUHOCAMIS for multiply charged metal ion beams. This ion source is derived from the hot cathode Penning ion gauge ion source (JINR, Dubna, 1957). A notable characteristic is the modified Penning geometry in the form of a hollow sputter electrode, coaxially positioned in a compact bottle-magnetic field along the central magnetic line of force. The interaction of the discharge geometry with the inhomogeneous but symmetrical magnetic field enables this device to be operated as hollow cathode discharge and Penning discharge as well. The main features of the ion source are the very high metal ion efficiency (up to 25%), good operational reproducibility, flexible and efficient operations for low charged as well as highly charged ions, compact setup, and easy maintenance. For light ions, e.g., up to titanium, well-collimated beams in the range of several tens of milliamperes of pulsed ion current (1 ms, 10/s) have been reliably performed in long time runs.

A vacuum spark ion source: High charge state metal ion beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yushkov, G. Yu., E-mail: gyushkov@mail.ru; Nikolaev, A. G.; Frolova, V. P.

2016-02-15

High ion charge state is often important in ion beam physics, among other reasons for the very practical purpose that it leads to proportionately higher ion beam energy for fixed accelerating voltage. The ion charge state of metal ion beams can be increased by replacing a vacuum arc ion source by a vacuum spark ion source. Since the voltage between anode and cathode remains high in a spark discharge compared to the vacuum arc, higher metal ion charge states are generated which can then be extracted as an ion beam. The use of a spark of pulse duration less thanmore » 10 μs and with current up to 10 kA allows the production of ion beams with current of several amperes at a pulse repetition rate of up to 5 pps. We have demonstrated the formation of high charge state heavy ions (bismuth) of up to 15 + and a mean ion charge state of more than 10 +. The physics and techniques of our vacuum spark ion source are described.« less

Adsorption of endotoxins on Ca2+ -iminodiacetic acid by metal ion affinity chromatography.

PubMed

Lopes, André Moreni; Romeu, Jorge Sánchez; Meireles, Rolando Páez; Perera, Gabriel Marquez; Morales, Rolando Perdomo; Pessoa, Adalberto; Cárdenas, Lourdes Zumalacárregui

2012-11-01

Endotoxins (also known as lipopolysaccharides (LPS)) are undesirable by-products of recombinant proteins, purified from Escherichia coli. LPS can be considered stable under a wide range of temperature and pH, making their removal one of the most difficult tasks in downstream processes during protein purification. The inherent toxicity of LPS makes their removal an important step for the application of these proteins in several biological assays and for a safe parenteral administration. Immobilized metal affinity chromatography (IMAC) enables the affinity interactions between the metal ions (immobilized on the support through the chelating compound) and the target molecules, thus enabling high-efficiency separation of the target molecules from other components present in a mixture. Affinity chromatography is applied with Ca2+ -iminodiacetic acid (IDA) to remove most of the LPS contaminants from the end product (more than 90%). In this study, the adsorption of LPS on an IDA-Ca2+ was investigated. The adsorption Freundlich isotherm of LPS-IDA-Ca2+ provides a theoretical basis for LPS removal. It was found that LPS is bound mainly by interactions between the phosphate group in LPS and Ca2+ ligands on the beads. The factors such as pH (4.0 or 5.5) and ionic strength (1.0 mol/L) are essential to obtain effective removal of LPS for contaminant levels between endotoxin' concentration values less than 100 EU/mL and 100 000 EU/mL. This new protocol represents a substantial advantage in time, effort, and production costs.

Adsorption of humic acids and trace metals in natural waters

NASA Technical Reports Server (NTRS)

Leung, W. H.

1982-01-01

Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

Development of ion-exchange properties of bamboo charcoal modified with concentrated nitric acid

NASA Astrophysics Data System (ADS)

Khandaker, S.; Kuba, T.; Toyohara, Y.; Kamida, S.; Uchikawa, Y.

2017-08-01

The surface chemistry and the structural properties of activated carbon can be altered by the acidic modification. The objective of this study is to investigate the changes occurring in bamboo charcoal (BC) during activation with concentrated nitric acid. Low temperature (500°C) carbonized BC has been prepared and oxidized with 70% concentrated boiling nitric acid (BC-AC). The porous properties of the BC are analyzed with nitrogen adsorption isotherm at 77 K. The surface structure is observed by Field emission scanning electronic microscope (FESEM) and the surface functional groups are examined by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and the pH of the point of zero charge (pHPZC). The results reveal that severe oxidation with HNO3 considerably decreases the surface area of BC with enhanced pore widening and FESEM observation demonstrates the erosive effect of oxidation. The FTIR analysis detects that some absorption bands are assigned for carboxyl, aldehyde and ketone groups on BC-AC. The XPS analysis also clearly shows that the ratio of oxygen and acidic functional groups has been enriched significantly on the BC-AC. The low pHPZC value of BC-AC confirms that the surface is highly acidic for the fixation of acidic functional groups on surface. In general, the existence of the abundant amount of acidic functional groups on adsorbents enhances the sorption of heavy metals ions in aqueous solution. Therefore, it is strongly expected that the modified BC, activated under the proposed conditions would be a promising ion exchanger in aqueous solution and can be applied for the adsorption of different heavy metal ions and radioactive materials from effluent.

Spectroscopic studies of transition-metal ions in molten alkali-metal carboxylates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maroni, V.A.; Maciejewski, M.L.

This paper presents the results of electronic absorption and /sup 13/C-NMR measurements on molten alkali metal formates and acetates and on solutions of selected 3d transition metal ions therein. These studies provide a unique opportunity to explore (1) the highly ordered nature of alkali carboxylates, (2) the ligand field properties of acetate and formate ions, and (3) the coordination chemistry of the 3d transition metals in molten carboxylates. 1 figure, 2 tables.

Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

DOE PAGES

Bang, Suhee; Lee, Yong -Min; Hong, Seungwoo; ...

2014-09-14

Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η 2:η 2-O 2)–M n+ (M n+ = Sr 2+, Ca 2+, Zn 2+, Lu 3+, Y 3+ and Sc 3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca 2+ and Sr 2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities ofmore » complexes formed with stronger Lewis acidities were found to be markedly different. In conclusion, complexes that contain Ca 2+ or Sr 2+ ions were oxidized by an electron acceptor to release O 2, whereas the release of O 2 did not occur for complexes that bind stronger Lewis acids. Furthermore, we discuss these results in the light of the functional role of the Ca 2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex.« less

Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

PubMed Central

Bang, Suhee; Lee, Yong-Min; Hong, Seungwoo; Cho, Kyung-Bin; Nishida, Yusuke; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

2014-01-01

Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η2:η2-O2)–Mn+ (Mn+ = Sr2+, Ca2+, Zn2+, Lu3+, Y3+ and Sc3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca2+ and Sr2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities of complexes formed with stronger Lewis acidities were found to be markedly different. Complexes that contain Ca2+ or Sr2+ ions were oxidized by an electron acceptor to release O2, whereas the release of O2 did not occur for complexes that bind stronger Lewis acids. We discuss these results in the light of the functional role of the Ca2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex. PMID:25242490

Computational Design of Metal Ion Sequestering Agents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hay, Benjamin P.; Rapko, Brian M.

Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach formore » discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort. This project seeks to enhance and strengthen the traditional approach through computer-aided design of new and improved host molecules. Accurate electronic structure calculations are coupled with experimental data to provide fundamental information about ligand structure and the nature of metal-donor group interactions (design criteria). This fundamental information then is used in a molecular mechanics model (MM) that helps us rapidly screen proposed ligand architectures and select the best members from a set of potential candidates. By using combinatorial methods, molecule building software has been developed that generates large numbers of candidate architectures for a given set of donor groups. The specific goals of this project are: • further understand the structural and energetic aspects of individual donor group- metal ion interactions and incorporate this information within the MM framework • further develop and evaluate approaches for correlating ligand structure with reactivity toward metal ions, in other words, screening capability • use molecule structure building software to

Modification of porous starch for the adsorption of heavy metal ions from aqueous solution.

PubMed

Ma, Xiaofei; Liu, Xueyuan; Anderson, Debbie P; Chang, Peter R

2015-08-15

Porous starch xanthate (PSX) and porous starch citrate (PSC) were prepared in anticipation of the attached xanthate and carboxylate groups respectively forming chelation and electrostatic interactions with heavy metal ions in the subsequent adsorption process. The lead(II) ion was selected as the model metal and its adsorption by PSX and PSC was characterized. The adsorption capacity was highly dependent on the carbon disulfide/starch and citric acid/starch mole ratios used during preparation. The adsorption behaviors of lead(II) ion on PSXs and PSCs fit both the pseudo-second-order kinetic model and the Langmuir isotherm model. The maximum adsorption capacity from the Langmuir isotherm equation reached 109.1 and 57.6 mg/g for PSX and PSC when preparation conditions were optimized, and the adsorption times were just 20 and 60 min, respectively. PSX and PSC may be used as effective adsorbents for removal of heavy metals from contaminated liquid. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Utilization of rice husks modified by organomultiphosphonic acids as low-cost biosorbents for enhanced adsorption of heavy metal ions.

PubMed

Xu, Mingyu; Yin, Ping; Liu, Xiguang; Tang, Qinghua; Qu, Rongjun; Xu, Qiang

2013-12-01

Novel biosorbent materials (RH-2 and RH-3) obtained from agricultural waste materials rice husks (RH-1) were successfully developed through fast and facile esterification reactions with hydroxylethylidenediphosphonic acid and nitrilotrimethylenetriphosphonic acid, respectively. The present paper reported the feasibility of using RH-1, RH-2 and RH-3 for removal of heavy metals from simulated wastewater, the results revealed that the adsorption property of functionalized rice husks with organotriphosphonic acid RH-3 for Au(III) was very excellent, especially for gold ions. The combined effect of initial solution pH, RH-3 dosage and initial Au(III) concentration was investigated using response surface methodology (RSM), the results showed that initial Au(III) concentration exerted stronger influence on Au(III) uptake than initial pH and biomass dosage. The analysis of variance (ANOVA) of the quadratic model demonstrated that the model was highly significant, and under the optimum process conditions, the maximum adsorption capacity could reach 3.25 ± 0.07 mmol/g that is higher than other reported adsorbents. Copyright © 2013 Elsevier Ltd. All rights reserved.

The crystallization of metal soaps and fatty acids in oil paint model systems.

PubMed

Hermans, Joen J; Keune, Katrien; van Loon, Annelies; Iedema, Piet D

2016-04-28

The formation and crystallization of metal soaps in oil paint layers is an important issue in the conservation of oil paintings. The chemical reactions and physical processes that are involved in releasing metal ions from pigments and fatty acids from the oil binder to form crystalline metal soap deposits have so far remained poorly understood. We have used a combination of differential scanning calorimetry (DSC) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) on model mixtures of palmitic acid, lead palmitate or zinc palmitate and linseed oil to study the transition from amorphous material to crystalline fatty acid or metal soap. This transition forms the final stage in the cascade of processes leading to metal soap-related oil paint degradation. Palmitic acid as well as the metal soaps showed nearly ideal solubility behavior. However, it was found that, near room temperature, both lead and zinc palmitate are practically insoluble in both liquid and partially polymerized linseed oil. Interestingly, the rate of metal soap and fatty acid crystallization decreased rapidly with the degree of linseed oil polymerization, possibly leading to systems where metal soaps are kinetically trapped in a semi-crystalline state. To explain the various morphologies of metal soap aggregates observed in oil paint layers, it is proposed that factors affecting the probability of crystal nucleation and the rate of crystal growth play a crucial role, like exposure to heat or cleaning solvents and the presence of microcracks.

Study of coagulation processes of selected humic acids under copper ions influence*

NASA Astrophysics Data System (ADS)

Boguta, Patrycja; Sokolowska, Zofia

2013-04-01

Humic acids have limited sorption capacity and big dose of metal or other mineral component which can be sorbed on humic acids, can cause saturation of negative, surface charge of humic acids leading to destabilization of dissolved humic acids compounds. Destabilisation can be observed as coagulation and floculation proces of humic acids. However there are a lot of mechanisms which causing precipitation of humic acids. Thereby, in order to full description of coagulation process, different methods should be applied. Ordinarily, humic acids coagulation is studied by measurement of absorbance, transmittance or carbon loss in solution. Meanwhile, very significant information is also variation of metal content in soil solution and information whether metal goes to precipitate together with humic acids or stays in dissolved form in solution. So, that, from one side, processes of stronger accumulation of metal can lead to soil degradation and micronutrient deficiency for plants. However, there is also possibility to stay metal in solution in toxic and bioavailable form for plants. Main aim of this paper was to study coagulation process of different humic acids extracted from mucking peats under copper ions influence at adjusted pH to 5. In order to this, four peaty-muck soils were taken from selected places in east part of Poland (meadows and river valleys). These soils differed by humification degree, secondary transformation, density and pH. At next step, humic acids were extracted from soils using sodium hydroxide (NaOH) extractant. After exact purification by washing with HF-HCl mixture and water, humic acids were liofilized. Solutions of humic acids were prepared at concentration 40 mg/dm3 with addition of different amount of copper ions to obtain final concentration of Cu(II) ranged from 0-40mg/dm3. After 24 hours solutions were investigated using measurements of absorbance at 470nm (UV-VIS spectrometer Jasco V-530), measurements of organic carbon in solution

Investigation of the binding of Salvianolic acid B to human serum albumin and the effect of metal ions on the binding

NASA Astrophysics Data System (ADS)

Chen, Tingting; Cao, Hui; Zhu, Shajun; Lu, Yapeng; Shang, Yanfang; Wang, Miao; Tang, Yanfeng; Zhu, Li

2011-10-01

The studies on the interaction between HSA and drugs have been an interesting research field in life science, chemistry and clinical medicine. There are also many metal ions present in blood plasma, thus the research about the effect of metal ions on the interaction between drugs and plasma proteins is crucial. In this study, the interaction of Salvianolic acid B (Sal B) with human serum albumin (HSA) was investigated by the steady-state, synchronous fluorescence and circular dichroism (CD) spectroscopies. The results showed that Sal B had a strong ability to quench the intrinsic fluorescence of HSA through a static quenching mechanism. Binding parameters calculated showed that Sal B was bound to HSA with the binding affinities of 10 5 L mol -1. The thermodynamic parameters studies revealed that the binding was characterized by positive enthalpy and positive entropy changes, and hydrophobic interactions were the predominant intermolecular forces to stabilize the complex. The specific binding distance r (2.93 nm) between donor (HSA) and acceptor (Sal B) was obtained according to Förster non-radiative resonance energy transfer theory. The synchronous fluorescence experiment revealed that Sal B cannot lead to the microenvironmental changes around the Tyr and Trp residues of HSA, and the binding site of Sal B on HSA is located in hydrophobic cavity of subdomain IIA. The CD spectroscopy indicated the secondary structure of HSA is not changed in the presence of Sal B. Furthermore, The effect of metal ions (e.g. Zn 2+, Cu 2+, Co 2+, Ni 2+, Fe 3+) on the binding constant of Sal B-HSA complex was also discussed.

Evaluation of a low-cost adsorbent for removal of toxic metal ions from wastewater of an electroplating factory.

PubMed

Sousa, Francisco W; Sousa, Marcelo James; Oliveira, Isadora R N; Oliveira, André G; Cavalcante, Rivelino M; Fechine, Pierre B A; Neto, Vicente O S; de Keukeleire, Denis; Nascimento, Ronaldo F

2009-08-01

In this study, sugar cane residue or bagasse was used for removal of toxic metal ions from wastewater of an electroplating factory located in northeast Brazil. Prior acid treatment increased the adsorption efficacies in batch wise experiments. The microstructure of the material before and after the treatment was investigated by X-ray diffraction, infrared spectroscopy and scanning electron microscopy. Column operations showed that removals of Cu(2+), Ni(2+) and Zn(2+) from wastewater (in the absence of cyanide) were 95.5%, 96.3.0%, and 97.1%, respectively. Regeneration of the adsorbent obtained in acid indicated that the efficiencies decreased only after the fourth cycle of re-use. Acid-treated sugar cane bagasse can be considered a viable alternative to common methods to remove toxic metal ions from aqueous effluents of electroplating industries.

Solution NMR Refinement of a Metal Ion Bound Protein Using Metal Ion Inclusive Restrained Molecular Dynamics Methods

PubMed Central

Chakravorty, Dhruva K.; Wang, Bing; Lee, Chul Won; Guerra, Alfredo J.; Giedroc, David P.; Merz, Kenneth M.

2013-01-01

Correctly calculating the structure of metal coordination sites in a protein during the process of nuclear magnetic resonance (NMR) structure determination and refinement continues to be a challenging task. In this study, we present an accurate and convenient means by which to include metal ions in the NMR structure determination process using molecular dynamics (MD) constrained by NMR-derived data to obtain a realistic and physically viable description of the metal binding site(s). This method provides the framework to accurately portray the metal ions and its binding residues in a pseudo-bond or dummy-cation like approach, and is validated by quantum mechanical/molecular mechanical (QM/MM) MD calculations constrained by NMR-derived data. To illustrate this approach, we refine the zinc coordination complex structure of the zinc sensing transcriptional repressor protein Staphylococcus aureus CzrA, generating over 130 ns of MD and QM/MM MD NMR-data compliant sampling. In addition to refining the first coordination shell structure of the Zn(II) ion, this protocol benefits from being performed in a periodically replicated solvation environment including long-range electrostatics. We determine that unrestrained (not based on NMR data) MD simulations correlated to the NMR data in a time-averaged ensemble. The accurate solution structure ensemble of the metal-bound protein accurately describes the role of conformational dynamics in allosteric regulation of DNA binding by zinc and serves to validate our previous unrestrained MD simulations of CzrA. This methodology has potentially broad applicability in the structure determination of metal ion bound proteins, protein folding and metal template protein-design studies. PMID:23609042

Carboxyl-functionalized nanoparticles with magnetic core and mesopore carbon shell as adsorbents for the removal of heavy metal ions from aqueous solution.

PubMed

Wang, Hui; Yu, Yi-Fei; Chen, Qian-Wang; Cheng, Kai

2011-01-21

This communication demonstrates superparamagnetic nanosized particles with a magnetic core and a porous carbon shell (thickness of 11 nm), which can remove 97% of Pb(2+) ions from an acidic aqueous solution at a Pb(2+) ion concentration of 100 mg L(-1). It is suggested that a weak electrostatic force of attraction between the heavy metal ions and the nanoparticles and the heavy metal ions adsorption on the mesopore carbon shell contribute most to the superior removal property.

Spectroscopic detection of metals ions using a novel selective sensor

NASA Astrophysics Data System (ADS)

Peralta-Domínguez, D.; Ramos-Ortiz, G.; Maldonado, J. L.; Rodriguez, M.; Meneses-Nava, M. A.; Barbosa-Garcia, O.; Santillan, R.; Farfan, N.

2011-09-01

Colorimetric chemosensors are simple, economical and practical optical approach for detecting toxic metal ions (Hg2+, Pb2+, Ni2+, etc.) in the environment. In this work, we present a simple but highly specific organic compound 4-chloro-2-((E)-((E)-3-(4-(dimethylamino)phenyl)allylidene)amino)phenol (L1) that acts as a colorimetric sensor for divalent metal ions in H2O. The mechanism of the interaction between L1 and various metal-ions has been established by UV-vis absorption and emission spectroscopic experiments that indicate favorable coordination of metal ions with L1 in different solvents. Experimental results indicate that the shape of the electronic transition band of L1 (receptor compound) changed after the interaction with divalent metal-ions, such as Hg2+, Pb2+, Mn2+, Co2+, Cu2+, and Ni2+ in aqueous solution. We found that L1 have a considerable selectivity for Ni2+ ions, even in presence of other metals ions when mixtures of DMSO/H2O as are used as solvents. L1, which has been targeted for sensing transition metal ions, exhibits binding-induced color changes from yellow to pink observed even by the naked eye in presence of Ni2+ ions.

Rechargeable dual-metal-ion batteries for advanced energy storage.

PubMed

Yao, Hu-Rong; You, Ya; Yin, Ya-Xia; Wan, Li-Jun; Guo, Yu-Guo

2016-04-14

Energy storage devices are more important today than any time before in human history due to the increasing demand for clean and sustainable energy. Rechargeable batteries are emerging as the most efficient energy storage technology for a wide range of portable devices, grids and electronic vehicles. Future generations of batteries are required to have high gravimetric and volumetric energy, high power density, low price, long cycle life, high safety and low self-discharge properties. However, it is quite challenging to achieve the above properties simultaneously in state-of-the-art single metal ion batteries (e.g. Li-ion batteries, Na-ion batteries and Mg-ion batteries). In this contribution, hybrid-ion batteries in which various metal ions simultaneously engage to store energy are shown to provide a new perspective towards advanced energy storage: by connecting the respective advantages of different metal ion batteries they have recently attracted widespread attention due to their novel performances. The properties of hybrid-ion batteries are not simply the superposition of the performances of single ion batteries. To enable a distinct description, we only focus on dual-metal-ion batteries in this article, for which the design and the benefits are briefly discussed. We enumerate some new results about dual-metal-ion batteries and demonstrate the mechanism for improving performance based on knowledge from the literature and experiments. Although the search for hybrid-ion batteries is still at an early age, we believe that this strategy would be an excellent choice for breaking the inherent disadvantages of single ion batteries in the near future.

Theoretical study of metal noble-gas positive ions

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.

1989-01-01

Theoretical calculations have been performed to determine the spectroscopic constant for the ground and selected low-lying electronic states of the transition-metal noble-gas ions Var(+), FeAr(+), CoAr(+), CuHe(+), CuAr(+), and CuKr(+). Analogous calculations have been performed for the ground states of the alkali noble-gas ions LiAr(+), LiKr(+), NaAr(+), and KAr(+) and the alkaline-earth noble-gas ion MgAr(+) to contrast the difference in binding energies between the simple and transition-metal noble-gas ions. The binding energies increase with increasing polarizability of the noble-gas ions, as expected for a charge-induced dipole bonding mechanism. It is found that the spectroscopic constants of the X 1Sigma(+) states of the alkali noble-gas ions are well described at the self-consistent field level. In contrast, the binding energies of the transition-metal noble-gas ions are substantially increased by electron correlation.

Ligand-enhanced electrokinetic remediation of metal-contaminated marine sediments with high acid buffering capacity.

PubMed

Masi, Matteo; Iannelli, Renato; Losito, Gabriella

2016-06-01

The suitability of electrokinetic remediation for removing heavy metals from dredged marine sediments with high acid buffering capacity was investigated. Laboratory-scale electrokinetic remediation experiments were carried out by applying two different voltage gradients to the sediment (0.5 and 0.8 V/cm) while circulating water or two different chelating agents at the electrode compartments. Tap water, 0.1 M citric acid and 0.1 M ethylenediaminetetraacetic acid (EDTA) solutions were used respectively. The investigated metals were Zn, Pb, V, Ni and Cu. In the unenhanced experiment, the acid front could not propagate due to the high acid buffering capacity of the sediments; the production of OH(-) ions at the cathode resulted in a high-pH environment causing the precipitation of CaCO3 and metal hydroxides. The use of citric acid prevented the formation of precipitates, but solubilisation and mobilisation of metal species were not sufficiently achieved. Metal removal was relevant when EDTA was used as the conditioning agent, and the electric potential was raised up to 0.8 V/cm. EDTA led to the formation of negatively charged complexes with metals which migrated towards the anode compartment by electromigration. This result shows that metal removal from sediments with high acid buffering capacity may be achieved by enhancing the electrokinetic process by EDTA addition when the acidification of the medium is not economically and/or environmentally sustainable.

Metal Ion Speciation and Dissolved Organic Matter Composition in Soil Solutions

NASA Astrophysics Data System (ADS)

Benedetti, M. F.; Ren, Z. L.; Bravin, M.; Tella, M.; Dai, J.

2014-12-01

Knowledge of the speciation of heavy metals and the role of dissolved organic matter (DOM) in soil solution is a key to understand metal mobility and ecotoxicity. In this study, soil column-Donnan membrane technique (SC-DMT) was used to measure metal speciation of Cd, Cu, Ni, Pb, and Zn in eighteen soil solutions, covering a wide range of metal sources and concentrations. DOM composition in these soil solutions was also determined. Our results show that in soil solution Pb and Cu are dominant in complex form, whereas Cd, Ni and Zn mainly exist as free ions; for the whole range of soil solutions, only 26.2% of DOM is reactive and consists mainly of fulvic acid (FA). The metal speciation measured by SC-DMT was compared to the predicted ones obtained via the NICA-Donnan model using the measured FA concentrations. The free ion concentrations predicted by speciation modelling were in good agreement with the measurements. Diffusive gradients in thin-films gels (DGT) were also performed to quantify the labile metal species in the fluxes from solid phase to solution in fourteen soils. The concentrations of metal species detected by DGT were compared with the free ion concentrations measured by DMT and the maximum concentrations calculated based on the predicted metal speciation in SC-DMT soil solutions. It is concluded that both inorganic species and a fraction of FA bound species account for the amount of labile metals measured by DGT, consistent with the dynamic features of this technique. The comparisons between measurements using analytical techniques and mechanistic model predictions provided mutual validation in their performance. Moreover, we show that to make accurate modelling of metal speciation in soil solutions, the knowledge of DOM composition is the crucial information, especially for Cu; like in previous studies the modelling of Pb speciation is not optimal and an updated of Pb generic binding parameters is required to reduce model prediction uncertainties.

Metal Ion-Assembled Micro-Collagen Heterotrimers

PubMed Central

LeBruin, Lyndelle Toni; Banerjee, Sunandan; O'Rourke, Bruce Delany; Case, Martin Ashley

2011-01-01

Collagen mimetic peptides (CMPs) provide critical insight into the assembly, stability and structure of the triple helical collagen protein. The majority of natural fibrous collagens are aab or abc heterotrimers, yet few examples of heterotrimeric CMPs have been reported. Previously CMP heterotrimers have only been accessible by total syntheses or by introducing complementary interstrand electrostatic or steric interactions. Here we describe an abc CMP heterotrimer in which each contributing CMP consists of only three amino acids: glycine, proline and 4-hydroxyproline. Assembly of the heterotrimeric triple helix is directed by a combination of metal-ion coordination to set the relative register of the CMPs, and minimization of valence frustration to direct heterotrimerization. Assembly of the four-component mixture is facile and extremely rapid, and equilibration to the abc heterotrimer occurs within a few hours at modestly elevated temperatures. The melting temperatures of the metal-assembled collagen trimers are higher by some 30 °C than the apopeptide assemblies. Two iterations of the design are described, and the outcomes suggest possibilities for designing self-assembling abc and abb heterotrimers. PMID:21590759

Computational Design of Metal Ion Sequestering Agents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hay, Benjamin P.; Rapko, Brian M.

Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach formore » discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort.« less

Predictivity and fate of metal ion release from metal-on-metal total hip prostheses.

PubMed

Nicolli, Annamaria; Bisinella, Gianluca; Padovani, Giovanni; Vitella, Antonio; Chiara, Federica; Trevisan, Andrea

2014-09-01

Blood metal ion levels in 72 patients with large head metal-on-metal hip arthroplasty were studied to determine the correlation between the values measured in whole blood and urine. Urinary cobalt and chromium levels of 30μg and 21μg, respectively, adjusted to creatinine were found to correspond to the 7μg/l cut-off value that has been accepted in whole blood. Cobalt and chromium levels in whole blood and urine both significantly correlated with increased acetabular component inclination angle over 50 degrees and pain scores. There was no correlation with socket anteversion angle or femoral head diameter. The data support the use of urinary measurement of metal ions adjusted to creatinine to monitor patients with large head metal-on-metal total hip arthroplasty. Copyright © 2014 Elsevier Inc. All rights reserved.

A comparative mass spectrometric study of fatty acids and metals in some seed extracts.

PubMed

Suvar, Sonia Niculina; Bleiziffer, R; Podea, P; Iordache, A; Voica, C; Zgavarogea, R; Culea, M

A major cause of cardiovascular diseases and cancer is diet content, so the optimization of micronutrients in food is very important. Omega-3 fatty acids supplementation for patients had beneficial effects on subjective global assessment score and metabolic profiles. Fatty acids content and the metal ions in different seeds (e.g. linseed, poppy, grape, hemp, nuts, pumpkin, sesame, watermelon, chia) recommended as food supplements, purchased on the Romanian market, were compared. Gas chromatography coupled to mass spectrometry (GC-MS) was used as an excellent technique for fatty acids identification and quantitation, and inductively coupled plasma mass spectrometer (ICP-MS) for analytical measurements of metals.

Selective retention of basic compounds by metal aquo-ion affinity chromatography.

PubMed

Asakawa, Yoshiki; Yamamoto, Eiichi; Asakawa, Naoki

2014-10-01

A novel metal aquo-ion affinity chromatography has been developed for the analysis of basic compounds using heat-treated silica gel containing hydrated metal cations (metal aquo-ions) as the packing material. The packing materials of the metal aquo-ion affinity chromatography were prepared by the immobilization of a single metal component such as Fe(III), Al(III), Ag(I), and Ni(II) on silica gel followed by extensive heat treatment. The immobilized metals form aquo-ions to present cation-exchange ability for basic analytes and the cation-exchange ability for basic analytes depends on pKa of the immobilized metal species. In the present study, to evaluate the retention characteristics of metal aquo-ion affinity chromatography, the on-line solid-phase extraction of drugs was investigated. Obtained data clearly evidence the selective retention capability of metal aquo-ion affinity chromatography for basic analytes with sufficient capacity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for modifying the metal ion sorption capacity of a medium

DOEpatents

Lundquist, Susan H.

2002-01-01

A process for modifying a medium is disclosed that includes treating a medium having a metal ion sorption capacity with a solution that includes: A) an agent capable of forming a complex with metal ions; and B) ions selected from the group consisting of sodium ions, potassium ions, magnesium ions, and combinations thereof, to create a medium having an increased capacity to sorb metal ions relative to the untreated medium.

Do ion levels in hip resurfacing differ from metal-on-metal THA at midterm?

PubMed

Moroni, A; Savarino, L; Hoque, M; Cadossi, M; Baldini, N

2011-01-01

Metal-on-metal Birmingham hip resurfacing (MOM-BHR) is an alternative to metal-on-metal total hip arthroplasty (MOM-THA), especially for young and/or active patients. However, wear resulting in increased serum ion levels is a concern. We asked whether (1) serum chromium (Cr), cobalt (Co), and molybdenum (Mo) concentrations would differ between patients with either MOM-BHR or MOM-THA at 5 years, (2) confounding factors such as gender would influence ion levels; and (3) ion levels would differ at 2 and 5 years for each implant type. Ions were measured in two groups with either MOM-BHR (n = 20) or MOM-THA (n = 35) and a mean 5-year followup, and two groups with either MOM-BHR (n = 15) or MOM-THA (n = 25) and a mean 2-year followup. Forty-eight healthy blood donors were recruited for reference values. At 5 years, there were no differences in ion levels between patients with MOM-BHR or MOM-THA. Gender was a confounding factor, and in the MOM-BHR group at 5 years, Cr concentrations were greater in females compared with those of males. Mean ion levels were similar in patients with 2 and 5 years of followup for each implant type. Ion levels in patients were sevenfold to 10-fold higher than in controls. As the metal ion concentrations in the serum at 5 years were in the range reported in the literature, we do not believe concerns regarding excessive metal ion levels after MOM-BHR are justified. Level III, therapeutic study. See the Guidelines for Authors for a complete description of level of evidence.

Immobilized chiral tropine ionic liquid on silica gel as adsorbent for separation of metal ions and racemic amino acids.

PubMed

Qian, Guofei; Song, Hang; Yao, Shun

2016-01-15

Tropine-type chiral ionic liquid with proline anion was immobilized on silica gel by chemical modification method for the first time, which was proved by elemental, infrared spectrum and thermogravimetric analysis. Secondly, the performance of this kind of ionic liquid-modified silica gel was investigated in the adsorption of some metal ions, which included Cu(2+), Fe(3+), Mn(2+) and Ni(2+). Then the effects of time, initial concentration and temperature on adsorption for Cu(2+) ions were studied in detail, which was followed by the further research of adsorption kinetics and thermodynamics. The adsorption could be better described by pseudo-second-order kinetics model and that the process was spontaneous, exothermic and entropy decreasing. In the mode of 'reuse after adsorption', the ionic liquid-modified silica gel with saturated adsorption of Cu(2+) was finally used in resolution of racemic amino acids for the first time. The static experiment showed that adsorption rate of two enantiomers was obviously different. Inspired by this, the complex was packed in chromatographic column for the separation of racemic amino acids and d-enantiomers were firstly eluted by water or ethanol. Steric hindrance was found as one of key influencing factors for its effect on the stability of the complex. Copyright © 2015 Elsevier B.V. All rights reserved.

Transition metal ion capture using functional mesoporous carbon made with 1,10-phenanthroline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chouyyok, Wilaiwan; Yantasee, Wassana; Shin, Yongsoon

2009-11-01

Functional mesoporous carbon has been built using 1,10-phenanthroline as the fundamental building block, resulting in a nanoporous, high surface area sorbent capable of selectively binding transition metal ions. This material had a specific surface area of 870 m2/g, an average pore size of about 30Å, and contained as much as 8.2 weight percent N. Under acidic conditions, where the 1,10-phenanthroline ligand is protonated, this material was found to be an effective anion exchange material for transition metal anions like PdCl4-2 and H2VO4-1. 1,10-phenanthroline functionalized mesoporous carbon (“Phen-FMC”) was found to have a high affinity for Cu(II), even down to amore » pH of 1. At pHs above 5, Phen-FMC was found to bind a variety of transition metal cations (e.g. Co(II), Ni(II), Zn(II), etc.) from filtered ground water, river water and seawater. Phen-FMC displayed rapid sorption kinetics with Co(II) in filtered river water, reaching equilibrium in less than an hour, and easily lowering the [Co(II)] to sub-ppb levels. Phen-FMC was found to be more effective for transition metal ion capture than ion exchange resin or activated carbon.« less

Oxidative stability of egg and soy lecithin as affected by transition metal ions and pH in emulsion.

PubMed

Wang, Guang; Wang, Tong

2008-12-10

Oxidative stability of egg and soy lecithin in emulsion was evaluated with two transition metal ions, cupric and ferric ion, at two concentration levels (50 and 500 microM). The effect of pH on lipid oxidation was also examined under these two concentrations for each ion. Egg lecithin (EL) had similar peroxide value (PV) development pattern as soy lecithin (SL) when treated with cupric ion under both acidic and neutral pH. Acidic pH of 3 accelerated oxidation of both EL and SL, especially under high concentration of copper. When treated with ferric ion, EL oxidized much faster than SL did. EL had higher value of thiobarbituric acid-reactive substances (TBARS) than SL, possibly because of its higher content of long-chain polyunsaturated fatty acids (PUFA). Acidic pH accelerated TBARS development for both EL and SL, but EL had more significantly increased values. Cupric ion was more powerful than ferric in catalyzing oxidation of both EL and SL under both acidic and neutral pH conditions as measured by PV and TBARS. Linoleic acid may contribute to higher PV production, however, arachidonic acid and docosahexaenoic acid may have contributed more to TBARS production. Overall, SL showed better oxidative stability than EL under the experimental conditions. This study also suggests that using multiple methods is necessary in properly evaluating lipid oxidative stability.

Adsorption of Copper Ion using Acrylic Acid-g-Polyaniline in Aqueous Solution

NASA Astrophysics Data System (ADS)

Kamarudin, Sabariah; Mohammad, Masita

2018-04-01

A conductive polymer, polyaniline (PANI) has unique electrical behaviour, stable in the environment, easy synthesis and have wide application in various fields. Modification of PANI in order to improve its adsorption capacity has been done. In this study, the polyaniline-grafted acrylic acid has been prepared and followed by adsorption of copper ion in aqueous solution. Acrylic acid, PANI and acrylic acid-g-polyaniline (Aag-PANI) were characterized by FTIR and SEM to determine its characteristic. The adsorption capacity was investigated to study the removal capacity of Cu ion from aqueous solution. Two parameters were selected which are pH (2, 4 and 6) and initial metal ion concentration (50 mg/L, 100 mg/L and 200 mg/L). The maximum adsorption capacity for PANI and Aag-PANI are 1.7 mg/g and 64.6 mg/g, respectively, at an initial concentration of 100 mg/L. The Langmuir adsorption isotherm model and Freundlich adsorption isotherm model have been used and showed that it is heterolayer adsorption by follows the Freundlich isotherm model.

Effect of Acid-Base Equilibrium on Absorption Spectra of Humic acid in the Presence of Copper Ions

NASA Astrophysics Data System (ADS)

Lavrik, N. L.; Mulloev, N. U.

2014-03-01

The reaction between humic acid (HA, sample IHSS) and a metal ion (Cu2+) that was manifested as absorption bands in the range 210-350 nm was recorded using absorption spectroscopy. The reaction was found to be more effective as the pH increased. These data were interpreted in the framework of generally accepted concepts about the influence of acid-base equilibrium on the dissociation of salts, according to which increasing the solution pH increases the concentration of HA anions. It was suggested that [HA-Cu2+] complexes formed.

Membrane extraction with thermodynamically unstable diphosphonic acid derivatives

DOEpatents

Horwitz, Earl Philip; Gatrone, Ralph Carl; Nash, Kenneth LaVerne

1997-01-01

Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described.

Role of four conserved aspartic acid residues of EF-loops in the metal ion binding and in the self-assembly of ciliate Euplotes octocarinatus centrin.

PubMed

Liu, Wen; Duan, Lian; Sun, Tijian; Yang, Binsheng

2016-12-01

Ciliate Euplotes octocarinatus centrin (EoCen) is an EF-hand calcium-binding protein closely related to the prototypical calcium sensor protein calmodulin. Four mutants (D37K, D73K, D110K and D146K) were created firstly to elucidate the importance of the first aspartic acid residues (Asp37, Asp73, Asp110 and Asp146) in the beginning of the four EF-loops of EoCen. Aromatic-sensitized Tb 3+ fluorescence indicates that the aspartic acid residues are very important for the metal-binding of EoCen, except for Asp73 (in EF-loop II). Resonance light scattering (RLS) measurements for different metal ions (Ca 2+ and Tb 3+ ) binding proteins suggest that the order of four conserved aspartic acid residues for contributing to the self-assembly of EoCen is Asp37 > Asp146 > Asp110 > Asp73. Cross-linking experiment also exhibits that Asp37 and Asp146 play critical role in the self-assembly of EoCen. Asp37, in site I, which is located in the N-terminal domain, plays the most important role in the metal ion-dependent self-assembly of EoCen, and there is cooperativity between N-terminal and C-terminal domain (especially the site IV). In addition, the dependence of Tb 3+ induced self-assembly of EoCen and the mutants on various factors, including ionic strength and pH, were characterized using RLS. Finally, 2-p-toluidinylnaphthalene-6-sulfonate (TNS) binding, ionic strength and pH control experiments indicate that in the process of EoCen self-assembly, molecular interactions are mediated by both electrostatic and hydrophobic forces, and the hydrophobic interaction has the important status.

Divalent Metal-Ion Complexes with Dipeptide Ligands Having Phe and His Side-Chain Anchors: Effects of Sequence, Metal Ion, and Anchor.

PubMed

Dunbar, Robert C; Berden, Giel; Martens, Jonathan K; Oomens, Jos

2015-09-24

Conformational preferences have been surveyed for divalent metal cation complexes with the dipeptide ligands AlaPhe, PheAla, GlyHis, and HisGly. Density functional theory results for a full set of complexes are presented, and previous experimental infrared spectra, supplemented by a number of newly recorded spectra obtained with infrared multiple photon dissociation spectroscopy, provide experimental verification of the preferred conformations in most cases. The overall structural features of these complexes are shown, and attention is given to comparisons involving peptide sequence, nature of the metal ion, and nature of the side-chain anchor. A regular progression is observed as a function of binding strength, whereby the weakly binding metal ions (Ba(2+) to Ca(2+)) transition from carboxylate zwitterion (ZW) binding to charge-solvated (CS) binding, while the stronger binding metal ions (Ca(2+) to Mg(2+) to Ni(2+)) transition from CS binding to metal-ion-backbone binding (Iminol) by direct metal-nitrogen bonds to the deprotonated amide nitrogens. Two new sequence-dependent reversals are found between ZW and CS binding modes, such that Ba(2+) and Ca(2+) prefer ZW binding in the GlyHis case but prefer CS binding in the HisGly case. The overall binding strength for a given metal ion is not strongly dependent on the sequence, but the histidine peptides are significantly more strongly bound (by 50-100 kJ mol(-1)) than the phenylalanine peptides.

Fulvic acid-sulfide ion competition for mercury ion binding in the Florida everglades

USGS Publications Warehouse

Reddy, M.M.; Aiken, G.R.

2001-01-01

Negatively charged functional groups of fulvic acid compete with inorganic sulfide ion for mercury ion binding. This competition is evaluated here by using a discrete site-electrostatic model to calculate mercury solution speciation in the presence of fulvic acid. Model calculated species distributions are used to estimate a mercury-fulvic acid apparent binding constant to quantify fulvic acid and sulfide ion competition for dissolved inorganic mercury (Hg(II)) ion binding. Speciation calculations done with PHREEQC, modified to use the estimated mercury-fulvic acid apparent binding constant, suggest that mercury-fulvic acid and mercury-sulfide complex concentrations are equivalent for very low sulfide ion concentrations (about 10-11 M) in Everglades' surface water. Where measurable total sulfide concentration (about 10-7 M or greater) is present in Everglades' surface water, mercury-sulfide complexes should dominate dissolved inorganic mercury solution speciation. In the absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominate Everglades' dissolved inorganic mercury speciation.

The effect of platform switching on the levels of metal ion release from different implant–abutment couples

PubMed Central

Alrabeah, Ghada O; Knowles, Jonathan C; Petridis, Haralampos

2016-01-01

The improved peri-implant bone response demonstrated by platform switching may be the result of reduced amounts of metal ions released to the surrounding tissues. The aim of this study was to compare the levels of metal ions released from platform-matched and platform-switched implant–abutment couples as a result of accelerated corrosion. Thirty-six titanium alloy (Ti-6Al-4V) and cobalt–chrome alloy abutments were coupled with titanium cylinders forming either platform-switched or platform-matched groups (n=6). In addition, 18 unconnected samples served as controls. The specimens were subjected to accelerated corrosion by static immersion in 1% lactic acid for 1 week. The amount of metal ions ion of each test tube was measured using inductively coupled plasma mass spectrometry. Scanning electron microscope (SEM) images and energy dispersive spectroscopy X-ray analyses were performed pre- and post-immersion to assess corrosion at the interface. The platform-matched groups demonstrated higher ion release for vanadium, aluminium, cobalt, chrome, and molybdenum compared with the platform-switched groups (P<0.05). Titanium was the highest element to be released regardless of abutment size or connection (P<0.05). SEM images showed pitting corrosion prominent on the outer borders of the implant and abutment platform surfaces. In conclusion, implant–abutment couples underwent an active corrosion process resulting in metal ions release into the surrounding environment. The highest amount of metal ions released was recorded for the platform-matched groups, suggesting that platform-switching concept has a positive effect in reducing the levels of metal ion release from the implant–abutment couples. PMID:27357323

Two distinct modes of metal ion binding in the nuclease active site of a viral DNA-packaging terminase: insight into the two-metal-ion catalytic mechanism

PubMed Central

Zhao, Haiyan; Lin, Zihan; Lynn, Anna Y.; Varnado, Brittany; Beutler, John A.; Murelli, Ryan P.; Le Grice, Stuart F. J.; Tang, Liang

2015-01-01

Many dsDNA viruses encode DNA-packaging terminases, each containing a nuclease domain that resolves concatemeric DNA into genome-length units. Terminase nucleases resemble the RNase H-superfamily nucleotidyltransferases in folds, and share a two-metal-ion catalytic mechanism. Here we show that residue K428 of a bacteriophage terminase gp2 nuclease domain mediates binding of the metal cofactor Mg2+. A K428A mutation allows visualization, at high resolution, of a metal ion binding mode with a coupled-octahedral configuration at the active site, exhibiting an unusually short metal-metal distance of 2.42 Å. Such proximity of the two metal ions may play an essential role in catalysis by generating a highly positive electrostatic niche to enable formation of the negatively charged pentacovalent phosphate transition state, and provides the structural basis for distinguishing Mg2+ from Ca2+. Using a metal ion chelator β-thujaplicinol as a molecular probe, we observed a second mode of metal ion binding at the active site, mimicking the DNA binding state. Arrangement of the active site residues differs drastically from those in RNase H-like nucleases, suggesting a drifting of the active site configuration during evolution. The two distinct metal ion binding modes unveiled mechanistic details of the two-metal-ion catalysis at atomic resolution. PMID:26450964

Technological applications arising from the interactions of DNA bases with metal ions.

PubMed

Park, Ki Soo; Park, Hyun Gyu

2014-08-01

An intense interest has grown in the unique interactions of nucleic acids with metal ions, which lead to the formation of metal-base pairs and the generation of fluorescent nanomaterials. In this review, different types of metal-base pairs, especially those formed from naturally occurring nucleosides, are described with emphasis also being given to recent advances made in employing these complexes to govern enzymatic reactions. The review also contains a comprehensive description of DNA-templated inorganic nanomaterials such as silver nanoclusters which possess excellent fluorescence properties. Finally, a summary is given about how these materials have led to recent advances in the field of nanobiotechnology. Copyright © 2013 Elsevier Ltd. All rights reserved.

Supercritical Fluid Extraction of Toxic Heavy Metals and Uranium from Acidic Solutions with Sulfur-Containing Organophosphorus Reagents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yuehe; Liu, Chongxuan; Wu, Hong

2003-03-02

The feasibility of using sulfur-containing organophosphorus reagents for the chelation-supercritical fluid extraction (SFE) of toxic heavy metals and uranium from acidic media was investigated. The SFE experiments were conducted in a specially-designed flow-through liquid extractor. Effective extraction of the metal ions from various acidic media was demonstrated. The effect of ligand concentration in supercritical CO{sub 2} on the kinetics of metal extraction was studied. A simplified model is used to describe the extraction kinetics and the good agreement of experimental data with the equilibrium-based model is achieved.

Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

DOE PAGES

Demir, Selvan; Brune, Nicholas K.; Van Humbeck, Jeffrey F.; ...

2016-04-08

Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/ activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr 2+, Fe 3+, Nd 3+, and Am 3+, from aqueous solutionsmore » employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Finally, recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity.« less

Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

PubMed Central

2016-01-01

Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

Complexation-induced supramolecular assembly drives metal-ion extraction.

PubMed

Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

2014-09-26

Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyanobacterial megamolecule sacran efficiently forms LC gels with very heavy metal ions.

PubMed

Okajima, Maiko K; Miyazato, Shinji; Kaneko, Tatsuo

2009-08-04

We extracted the megamolecular polysaccharide sacran, which contains carboxylate and sulfate groups, from the jellylike extracellular matrix (ECM) of the cyanobacterium Aphanothece sacrum, which has mineral adsorption bioactivity. We investigated the gelation properties of sacran binding with various heavy metal ions. The sacran chain adsorbed heavier metal ions such as indium, rare earth metals, and lead ions more efficiently to form gel beads. In addition, trivalent metal ions adsorbed onto the sacran chains more efficiently than did divalent ions. The investigation of the metal ion binding ratio on sacran chains demonstrated that sacran adsorbed gadolinium trivalent ions more efficiently than indium trivalent ions. Gel bead formation may be closely correlated to the liquid-crystalline organization of sacran.

Multivalent Ion Transport in Polymers via Metal-Ligand Coordination

NASA Astrophysics Data System (ADS)

Sanoja, Gabriel; Schauser, Nicole; Evans, Christopher; Majumdar, Shubhaditya; Segalman, Rachel

Elucidating design rules for multivalent ion conducting polymers is critical for developing novel high-performance materials for electrochemical devices. Herein, we molecularly engineer multivalent ion conducting polymers based on metal-ligand interactions and illustrate that both segmental dynamics and ion coordination kinetics are essential for ion transport through polymers. We present a novel statistical copolymer, poly(ethylene oxide-stat-imidazole glycidyl ether) (i.e., PEO-stat-PIGE), that synergistically combines the structural hierarchy of PEO with the Lewis basicity of tethered imidazole ligands (xIGE = 0.17) required to coordinate a series of transition metal salts containing bis(trifluoromethylsulfonyl)imide anions. Complexes of PEO-stat-PIGE with salts exhibit a nanostructure in which ion-enriched regions alternate with ion-deficient regions, and an ionic conductivity above 10-5 S/cm. Novel normalization schemes that account for ion solvation kinetics are presented to attain a universal scaling relationship for multivalent ion transport in polymers via metal-ligand coordination. AFOSR MURI program under FA9550-12-1.

Membrane extraction with thermodynamically unstable diphosphonic acid derivatives

DOEpatents

Horwitz, E.P.; Gatrone, R.C.; Nash, K.L.

1997-10-14

Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described. 1 fig.

Evaluation of the factors governing metal biosorption and metal toxicity in acidic soil isolates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pradhan, A.A.

1992-06-09

This research project was designed to determine the feasibility of microbial biosorption processes for removing metal ions from aqueous systems. A culture of acidic soil actinomycetes, grown in an aerobic environment in a completely mixed, semibatch culture reactor, was used for the study. The experiments were based on removal of copper and lead from test solutions. The anionic systems tested were nitrate, sulfate, and chloride. To determine the factors influencing biosorption and to characterize metal uptake by cellular and extracellular components of the microbial system, a dialysis testing procedure was developed. The effectiveness of biosorption was influenced by pH, initialmore » concentration of metals, type of anionic system, and organic content of the system. respirometric runs were carried out to identify potential inhibitory effects of metal accumulation on microbial activities. In general, metal accumulation resulted in a decrease in the microbial oxygen uptake rate. Also, a lag phase was observed before the onset of the respiratory activity particularly at concentrations of copper and lead greater than 100 ppM.« less

Diels-Alder active-template synthesis of rotaxanes and metal-ion-switchable molecular shuttles.

PubMed

Crowley, James D; Hänni, Kevin D; Leigh, David A; Slawin, Alexandra M Z

2010-04-14

A synthesis of [2]rotaxanes in which Zn(II) or Cu(II) Lewis acids catalyze a Diels-Alder cycloaddition to form the axle while simultaneously acting as the template for the assembly of the interlocked molecules is described. Coordination of the Lewis acid to a multidentate endotopic 2,6-di(methyleneoxymethyl)pyridyl- or bipyridine-containing macrocycle orients a chelated dienophile through the macrocycle cavity. Lewis acid activation of the double bond causes it to react with an incoming "stoppered" diene, affording the [2]rotaxane in up to 91% yield. Unusually for an active-template synthesis, the metal binding site "lives on" in these rotaxanes. This was exploited in the synthesis of a molecular shuttle containing two different ligating sites in which the position of the macrocycle could be switched by complexation with metal ions [Zn(II) and Pd(II)] with different preferred coordination geometries.

Environmentally relevant metal and transition metal ions enhance Fc epsilon RI-mediated mast cell activation.

PubMed Central

Walczak-Drzewiecka, Aurelia; Wyczólkowska, Janina; Dastych, Jaroslaw

2003-01-01

Upon contact with allergen, sensitized mast cells release highly active proinflammatory mediators. Allergen-mediated mast cell activation is an important mechanism in the pathogenesis of atopic asthma. Asthmatic patients are especially susceptible to air pollution. Epidemiologic studies found a positive correlation between severity of symptoms among asthmatic patients and the level of particulate matter (PM) in the air. Among the constituents of PM are metals and transition metals, which could mediate some of its adverse effects on human health. We sought to determine the effect of metal and transition metal ions on allergen-mediated mast cell activation. We observed that several metal and transition metal ions activated mast cells and enhanced allergen-mediated mast cell activation. Thus, Al(3+), Cd(2+), and Sr(2+) induced release of granule-associated N-acetyl-ss-d-hexosaminidase, and Al(3+) and Ni(2+) enhanced antigen-mediated release. Metal and transition metal ions also induced significant secretion of interleukin (IL)-4 and increased antigen-mediated IL-4 secretion in mast cells. These effects of metal and transition metal ions on mast cells were observed at concentrations that do not result in direct cytotoxicity and might be relevant for environmental exposure. Thus, metals and transition metals could increase the level of allergen-mediated mast cell activation, which might be one of the mechanisms mediating exacerbation of allergen-driven asthma symptoms by air pollution. PMID:12727598

Correlation of serum metal ion levels with pathological changes of ARMD in failed metal-on-metal-hip-resurfacing arthroplasties.

PubMed

Grammatopoulos, George; Munemoto, Mitsuru; Pollalis, Athanasios; Athanasou, Nicholas A

2017-08-01

Metal-on-metal-hip-resurfacing arthroplasties (MoMHRAs) have been associated with an increased failure rates due to an adverse-response-to-metal-debris (ARMD) associated with a spectrum of pathological features. Serum levels of cobalt (Co) and chromium (Cr) are used to assess MoMHRAs, with regard to ARMD, but it is not certain whether ion levels correlate with pathological changes in periprosthetic tissues. Serum Co and Cr levels were correlated with histological findings in 38 revised MoMHRAs (29 pseudotumour cases and 9 non-pseudotumour cases revised for pain). The extent of necrosis and macrophage infiltrate as well as the aseptic lymphocyte-dominated vasculitis-associated lesion (ALVAL) response was assessed semi-quantitatively; the prosthesis linear wear rate (PLWR) was also determined in ten cases. Cr levels were elevated in 82% and Co levels elevated in 53% of cases; the PLWR correlated with Cr level (rho = 0.8, p = 0.006). Tissue necrosis and macrophage infiltration were noted in all, most of which also exhibited significant ALVAL. Although a discrete correlation was not seen between Co and/or Cr ion levels and the extent of necrosis, degree of macrophage infiltration, or ALVAL score, it was noted that cases with acceptable metal ions levels had high ALVAL score. Histological features of both innate and adaptive immune response to metal wear are seen in periprosthetic tissues in cases with both elevated and non-elevated metal ion levels. MoMHRA failures with acceptable ion levels exhibited a pronounced ALVAL response. Although metal ion levels are elevated in most cases of MoMHRA failure due to ARMD, the finding of a normal metal ion level does not exclude this diagnosis.

Metal-assisted SIMS and cluster ion bombardment for ion yield enhancement

NASA Astrophysics Data System (ADS)

Heile, A.; Lipinsky, D.; Wehbe, N.; Delcorte, A.; Bertrand, P.; Felten, A.; Houssiau, L.; Pireaux, J.-J.; De Mondt, R.; Van Vaeck, L.; Arlinghaus, H. F.

2008-12-01

In addition to structural information, a detailed knowledge of the local chemical environment proves to be of ever greater importance, for example for the development of new types of materials as well as for specific modifications of surfaces and interfaces in multiple fields of materials science or various biomedical and chemical applications. But the ongoing miniaturization and therefore reduction of the amount of material available for analysis constitute a challenge to the detection limits of analytical methods. In the case of time-of-flight secondary ion mass spectrometry (TOF-SIMS), several methods of secondary ion yield enhancement have been proposed. This paper focuses on the investigation of the effects of two of these methods, metal-assisted SIMS and polyatomic primary ion bombardment. For this purpose, thicker layers of polystyrene (PS), both pristine and metallized with different amounts of gold, were analyzed using monoatomic (Ar +, Ga +, Xe +, Bi +) and polyatomic (SF 5+, Bi 3+, C 60+) primary ions. It was found that polyatomic ions generally induce a significant increase of the secondary ion yield. On the other hand, with gold deposition, a yield enhancement can only be detected for monoatomic ion bombardment.

Means for obtaining a metal ion beam from a heavy-ion cyclotron source

DOEpatents

Hudson, E.D.; Mallory, M.L.

1975-08-01

A description is given of a modification to a cyclotron ion source used in producing a high intensity metal ion beam. A small amount of an inert support gas maintains the usual plasma arc, except that it is necessary for the support gas to have a heavy mass, e.g., xenon or krypton as opposed to neon. A plate, fabricated from the metal (or anything that can be sputtered) to be ionized, is mounted on the back wall of the ion source arc chamber and is bombarded by returning energetic low-charged gas ions that fail to cross the initial accelerating gap between the ion source and the accelerating electrode. Some of the atoms that are dislodged from the plate by the returning gas ions become ionized and are extracted as a useful beam of heavy ions. (auth)

Metal hydride compositions and lithium ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Kwo; Nei, Jean

Heterogeneous metal hydride (MH) compositions comprising a main region comprising a first metal hydride and a secondary region comprising one or more additional components selected from the group consisting of second metal hydrides, metals, metal alloys and further metal compounds are suitable as anode materials for lithium ion cells. The first metal hydride is for example MgH.sub.2. Methods for preparing the composition include coating, mechanical grinding, sintering, heat treatment and quenching techniques.

Influence of natural organic matter on the adsorption of metal ion onto clay particles

USGS Publications Warehouse

Schmitt, D.; Taylor, Howard E.; Aiken, G.R.; Roth, D.A.; Frimmel, F.H.

2002-01-01

The influence of natural organic matter (NOM) on the adsorption of Al, Fe, Zn, and Pb onto clay minerals was investigated. Adsorption experiments were carried out at pH = 5 and pH = 7 in the presence and absence of NOM. In general, the presence of NOM decreased the adsorption of metal ions onto the clay particles. Al and Fe were strongly influenced by NOM, whereas Zn and Pb adsorption was only slightly altered. The interaction of the metal ions with the minerals and the influence of NOM on this interaction was investigated by coupling SdFFF with an inductively coupled plasma mass spectrometer (ICPMS) or an inductively coupled plasma atomic emission spectrometer (ICPAES). Quantitative atomization of the clay particles in the ICP was confirmed by comparing elemental content determined by direct injection of the clay into the ICPMS with values from acid digestion. Particle sizes of the clays were found to be between 0.1 and 1 μm by sedimentation field-flow fractionation (SdFFF) with UV detection. Aggregation of particles due to metal adsorption was observed using SdFFF-ICPMS measurements. This aggregation was dependent on the specific metal ion and decreased in the presence of NOM and at higher pH value.

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores

PubMed Central

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D.; Hill, Anita J.; Wang, Huanting

2018-01-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future. PMID:29487910

Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores.

PubMed

Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D; Hill, Anita J; Wang, Huanting

2018-02-01

Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future.

Electrochemical impedance study of the interaction of metal ions with unlabeled PNA.

PubMed

Gao, Lan; Li, Congjuan; Li, Xiaohong; Kraatz, Heinz-Bernhard

2010-09-14

The interactions of the metal ions Mg(2+), Zn(2+), Ni(2+), and Co(2+) with thin films of peptide nucleic acids (PNAs) were studied by electrochemical impedance spectroscopy (EIS), and the results show that Zn(2+), Ni(2+) and Co(2+) interacted favorably with the PNA film involving the backbone and the nucleobases with the exception of Mg(2+) for which the interaction with the backbone appears to be dominant.

Polyatomic ions from a high current ion implanter driven by a liquid metal ion source.

PubMed

Pilz, W; Laufer, P; Tajmar, M; Böttger, R; Bischoff, L

2017-12-01

High current liquid metal ion sources are well known and found their first application as field emission electric propulsion thrusters in space technology. The aim of this work is the adaption of such kind of sources in broad ion beam technology. Surface patterning based on self-organized nano-structures on, e.g., semiconductor materials formed by heavy mono- or polyatomic ion irradiation from liquid metal (alloy) ion sources (LMAISs) is a very promising technique. LMAISs are nearly the only type of sources delivering polyatomic ions from about half of the periodic table elements. To overcome the lack of only very small treated areas by applying a focused ion beam equipped with such sources, the technology taken from space propulsion systems was transferred into a large single-end ion implanter. The main component is an ion beam injector based on high current LMAISs combined with suited ion optics allocating ion currents in the μA range in a nearly parallel beam of a few mm in diameter. Different types of LMAIS (needle, porous emitter, and capillary) are presented and characterized. The ion beam injector design is specified as well as the implementation of this module into a 200 kV high current ion implanter operating at the HZDR Ion Beam Center. Finally, the obtained results of large area surface modification of Ge using polyatomic Bi 2 + ions at room temperature from a GaBi capillary LMAIS will be presented and discussed.

Polyatomic ions from a high current ion implanter driven by a liquid metal ion source

NASA Astrophysics Data System (ADS)

Pilz, W.; Laufer, P.; Tajmar, M.; Böttger, R.; Bischoff, L.

2017-12-01

High current liquid metal ion sources are well known and found their first application as field emission electric propulsion thrusters in space technology. The aim of this work is the adaption of such kind of sources in broad ion beam technology. Surface patterning based on self-organized nano-structures on, e.g., semiconductor materials formed by heavy mono- or polyatomic ion irradiation from liquid metal (alloy) ion sources (LMAISs) is a very promising technique. LMAISs are nearly the only type of sources delivering polyatomic ions from about half of the periodic table elements. To overcome the lack of only very small treated areas by applying a focused ion beam equipped with such sources, the technology taken from space propulsion systems was transferred into a large single-end ion implanter. The main component is an ion beam injector based on high current LMAISs combined with suited ion optics allocating ion currents in the μA range in a nearly parallel beam of a few mm in diameter. Different types of LMAIS (needle, porous emitter, and capillary) are presented and characterized. The ion beam injector design is specified as well as the implementation of this module into a 200 kV high current ion implanter operating at the HZDR Ion Beam Center. Finally, the obtained results of large area surface modification of Ge using polyatomic Bi2+ ions at room temperature from a GaBi capillary LMAIS will be presented and discussed.

Adhesive bonding of ion beam textured metals and fluoropolymers

NASA Technical Reports Server (NTRS)

Mirtich, M. J.; Sovey, J. S.

1978-01-01

An electron bombardment argon ion source was used to ion etch various metals and fluoropolymers. The metal and fluoropolymers were exposed to (0.5 to 1.0) keV Ar ions at ion current densities of (0.2 to 1.5) mA/sq cm for various exposure times. The resulting surface texture is in the form of needles or spires whose vertical dimensions may range from tenths to hundreds of micrometers, depending on the selection of beam energy, ion current density, and etch time. The bonding of textured surfaces is accomplished by ion beam texturing mating pieces of either metals or fluoropolymers and applying a bonding agent which wets in and around the microscopic cone-like structures. After bonding, both tensile and shear strength measurements were made on the samples. Also tested, for comparison's sake, were untextured and chemically etched fluoropolymers. The results of these measurements are presented.

Adhesive bonding of ion beam textured metals and fluoropolymers

NASA Technical Reports Server (NTRS)

Mirtich, M. J.; Sovey, J. S.

1978-01-01

An electron-bombardment argon ion source was used to ion-etch various metals and fluoropolymers. The metal and fluoropolymers were exposed to (0.5 to 1.0)-keV Ar ions at ion current densities of 0.2 to 1.5 mA/sq cm for various exposure times. The resulting surface texture is in the form of needles or spires whose vertical dimensions may range from tenths to hundreds of micrometers, depending on the selection of beam energy, ion current density, and etch time. The bonding of textured surfaces is accomplished by ion-beam texturing mating pieces of either metals or fluoropolymers and applying a bonding agent which wets in and around the microscopic conelike structures. After bonding, both tensile and shear strength measurements were made on the samples. Also tested, for comparison's sake, were untextured and chemically etched fluoropolymers. The results of these measurements are presented in this paper.

Counting the ions surrounding nucleic acids

PubMed Central

2017-01-01

Abstract Nucleic acids are strongly negatively charged, and thus electrostatic interactions—screened by ions in solution—play an important role in governing their ability to fold and participate in biomolecular interactions. The negative charge creates a region, known as the ion atmosphere, in which cation and anion concentrations are perturbed from their bulk values. Ion counting experiments quantify the ion atmosphere by measuring the preferential ion interaction coefficient: the net total number of excess ions above, or below, the number expected due to the bulk concentration. The results of such studies provide important constraints on theories, which typically predict the full three-dimensional distribution of the screening cloud. This article reviews the state of nucleic acid ion counting measurements and critically analyzes their ability to test both analytical and simulation-based models. PMID:28034959

Adsorption preference for divalent metal ions by Lactobacillus casei JCM1134.

PubMed

Endo, Rin; Aoyagi, Hideki

2018-05-09

The removal of harmful metals from the intestinal environment can be inhibited by various ions which can interfere with the adsorption of target metal ions. Therefore, it is important to understand the ion selectivity and adsorption mechanism of the adsorbent. In this study, we estimated the adsorption properties of Lactobacillus casei JCM1134 by analyzing the correlation between its maximum adsorption level (q max ) for seven metals and their ion characteristics. Some metal ions showed altered adsorption levels by L. casei JCM1134 as culture growth time increased. Although it was impossible to identify specific adsorption components, adsorption of Sr and Ba may depend on capsular polysaccharide levels. The maximum adsorption of L. casei JCM1134 (9 h of growth in culture) for divalent metal ions was in the following order: Cu 2+  > Ba 2+  > Sr 2+  > Cd 2+  > Co 2+  > Mg 2+  > Ni 2+ . The q max showed a high positive correlation with the ionic radius. Because this tendency is similar to adsorption occurring through an ion exchange mechanism, it was inferred that an ion exchange mechanism contributed greatly to adsorption by L. casei JCM1134. Because the decrease in the amount of adsorption due to prolonged culture time was remarkable for metals with a large ion radius, it is likely that the adsorption components involved in the ion exchange mechanism decomposed over time. These results and analytical concept may be helpful for designing means to remove harmful metals from the intestinal tract.

Metal ions differentially influence the aggregation and deposition of Alzheimer's beta-amyloid on a solid template.

PubMed

Ha, Chanki; Ryu, Jungki; Park, Chan Beum

2007-05-22

The abnormal deposition and aggregation of beta-amyloid (Abeta) on brain tissues are considered to be one of the characteristic neuropathological features of Alzheimer's disease (AD). Environmental conditions such as metal ions, pH, and cell membranes are associated with Abeta deposition and plaque formation. According to the amyloid cascade hypothesis of AD, the deposition of Abeta42 oligomers as diffuse plaques in vivo is an important earliest event, leading to the formation of fibrillar amyloid plaques by the further accumulation of soluble Abeta under certain environmental conditions. In order to characterize the effect of metal ions on amyloid deposition and plaque growth on a solid surface, we prepared a synthetic template by immobilizing Abeta oligomers onto a N-hydroxysuccinimide ester-activated solid surface. According to our study using ex situ atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR), and thioflavin T (ThT) fluorescence spectroscopy, Cu2+ and Zn2+ ions accelerated both Abeta40 and Abeta42 deposition but resulted only in the formation of "amorphous" aggregates. In contrast, Fe3+ induced the deposition of "fibrillar" amyloid plaques at neutral pH. Under mildly acidic environments, the formation of fibrillar amyloid plaques was not induced by any metal ion tested in this work. Using secondary ion mass spectroscopy (SIMS) analysis, we found that binding Cu ions to Abeta deposits on a solid template occurred by the possible reduction of Cu ions during the interaction of Abeta with Cu2+. Our results may provide insights into the role of metal ions on the formation of fibrillar or amorphous amyloid plaques in AD.

Rapid preparation of biosorbents with high ion exchange capacity from rice straw and bagasse for removal of heavy metals.

PubMed

Rungrodnimitchai, Supitcha

2014-01-01

This work describes the preparation of the cellulose phosphate with high ion exchange capacity from rice straw and bagasse for removal of heavy metals. In this study, rice straw and bagasse were modified by the reaction with phosphoric acid in the presence of urea. The introduced phosphoric group is an ion exchangeable site for heavy metal ions. The reaction by microwave heating yielded modified rice straw and modified bagasse with greater ion exchange capacities (∼3.62 meq/g) and shorter reaction time (1.5-5.0 min) than the phosphorylation by oil bath heating. Adsorption experiments towards Pb²⁺, Cd²⁺, and Cr³⁺ ions of the modified rice straw and the modified bagasse were performed at room temperature (heavy metal concentration 40 ppm, adsorbent 2.0 g/L). The kinetics of adsorption agreed with the pseudo-second-order model. It was shown that the modified rice straw and the modified bagasse could adsorb heavy metal ions faster than the commercial ion exchange resin (Dowax). As a result of Pb²⁺ sorption test, the modified rice straw (RH-NaOH 450W) removed Pb²⁺ much faster in the initial step and reached 92% removal after 20 min, while Dowax (commercial ion exchange resin) took 90 min for the same removal efficiency.

Do ion levels in metal-on-metal hip resurfacing differ from those in metal-on-metal THA at long-term followup?

PubMed

Savarino, Lucia; Cadossi, Matteo; Chiarello, Eugenio; Baldini, Nicola; Giannini, Sandro

2013-09-01

Metal-on-metal hip resurfacing arthroplasty (MOM HR) has become an established alternative to traditional metal-on-metal total hip arthroplasty (MOM THA) for younger, more active patients. Nevertheless, concerns remain regarding wear and corrosion of the bearing surfaces and the resulting systemic metal ion distribution. We therefore asked whether (1) serum ion concentrations in patients with MOM HR at the time of long-term followup were higher than concentrations in a control population with no hip implants; (2) the ion concentrations in patients with MOM HR were different from those in patients with MOM THA; and (3) sex would influence ion levels with regard to implant type. The MOM HR and MOM THA groups consisted of 25 patients (evaluated at a minimum of 96 months) and 16 patients (evaluated at a minimum of 106 months), respectively. Forty-eight healthy donors were recruited for reference values. Cobalt, chromium, nickel, and molybdenum were measured by furnace graphite atomic absorption spectrophotometry. Ion concentrations of cobalt, chromium, and molybdenum in MOM HR were higher than in controls. Chromium and cobalt release were higher in MOM HR than in MOM THA. The sex-based analysis showed the difference was because women had higher concentrations in the MOM HR group than in the MOM THA group, whereas there was no difference between the men in the two groups. In MOM HR, high metal ion release persists for the long term. Consequently, it is important to implement strict biomonitoring for patients who have received these implants. The sustained high levels of chromium in females within the MOM HR group are concerning and merits strong consideration when choosing implants in this patient group.

Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

PubMed

Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

2017-08-16

Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu 2+ cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu 2+ , and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

Crystal structure of a SLC11 (NRAMP) transporter reveals the basis for transition-metal ion transport.

PubMed

Ehrnstorfer, Ines A; Geertsma, Eric R; Pardon, Els; Steyaert, Jan; Dutzler, Raimund

2014-11-01

Members of the SLC11 (NRAMP) family transport iron and other transition-metal ions across cellular membranes. These membrane proteins are present in all kingdoms of life with a high degree of sequence conservation. To gain insight into the determinants of ion selectivity, we have determined the crystal structure of Staphylococcus capitis DMT (ScaDMT), a close prokaryotic homolog of the family. ScaDMT shows a familiar architecture that was previously identified in the amino acid permease LeuT. The protein adopts an inward-facing conformation with a substrate-binding site located in the center of the transporter. This site is composed of conserved residues, which coordinate Mn2+, Fe2+ and Cd2+ but not Ca2+. Mutations of interacting residues affect ion binding and transport in both ScaDMT and human DMT1. Our study thus reveals a conserved mechanism for transition-metal ion selectivity within the SLC11 family.

Detection of heavy-metal ions using liquid crystal droplet patterns modulated by interaction between negatively charged carboxylate and heavy-metal cations.

PubMed

Han, Gyeo-Re; Jang, Chang-Hyun

2014-10-01

Herein, we demonstrated a simple, sensitive, and rapid label-free detection method for heavy-metal (HM) ions using liquid crystal (LC) droplet patterns on a solid surface. Stearic-acid-doped LC droplet patterns were spontaneously generated on an n-octyltrichlorosilane (OTS)-treated glass substrate by evaporating a solution of the nematic LC, 4-cyano-4'-pentylbiphenyl (5CB), dissolved in heptane. The optical appearance of the droplet patterns was a dark crossed texture when in contact with air, which represents the homeotropic orientation of the LC. This was caused by the steric interaction between the LC molecules and the alkyl chains of the OTS-treated surface. The dark crossed appearance of the acid-doped LC patterns was maintained after the addition of phosphate buffered saline (PBS) solution (pH 8.1 at 25°C). The deprotonated stearic-acid molecules self-assembled through the LC/aqueous interface, thereby supporting the homeotropic anchoring of 5CB. However, the optical image of the acid-doped LC droplet patterns incubated with PBS containing HM ions appeared bright, indicating a planar orientation of 5CB at the aqueous/LC droplet interface. This dark to bright transition of the LC patterns was caused by HM ions attached to the deprotonated carboxylate moiety, followed by the sequential interruption of the self-assembly of the stearic acid at the LC/aqueous interface. The results showed that the acid-doped LC pattern system not only enabled the highly sensitive detection of HM ions at a sub-nanomolar concentration but it also facilitated rapid detection (<10 min) with simple procedures. Copyright © 2014 Elsevier B.V. All rights reserved.

Improving the enzymatic hydrolysis of dilute acid pretreated wheat straw by metal ion blocking of non-productive cellulase adsorption on lignin.

PubMed

Akimkulova, Ardak; Zhou, Yan; Zhao, Xuebing; Liu, Dehua

2016-05-01

Eleven salts were selected to screen the possible metal ions for blocking the non-productive adsorption of cellulase onto the lignin of dilute acid pretreated wheat straw. Mg(2+) was screened finally as the promising candidate. The optimal concentration of MgCl2 was 1 mM, but the beneficial action was also dependent on pH, hydrolysis time and cellulase loading. Significant improvement of glucan conversion (19.3%) was observed at low cellulase loading (5 FPU/g solid). Addition of isolated lignins, tannic acid and lignin model compounds to pure cellulose hydrolysis demonstrated that phenolic hydroxyl group (Ph-OH) was the main active site blocked by Mg(2+). The interaction between Mg(2+) and Ph-OH of lignin monomeric moieties followed an order of p-hydroxyphenyl (H)>guaiacyl (G)>syringyl (S). Mg(2+) blocking made the lignin surface less negatively charged, which might weaken the hydrogen bonding and electrostatically attractive interaction between lignin and cellulase enzymes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal ion transport quantified by ICP-MS in intact cells

PubMed Central

Figueroa, Julio A. Landero; Stiner, Cory A.; Radzyukevich, Tatiana L.; Heiny, Judith A.

2016-01-01

The use of ICP-MS to measure metal ion content in biological tissues offers a highly sensitive means to study metal-dependent physiological processes. Here we describe the application of ICP-MS to measure membrane transport of Rb and K ions by the Na,K-ATPase in mouse skeletal muscles and human red blood cells. The ICP-MS method provides greater precision and statistical power than possible with conventional tracer flux methods. The method is widely applicable to studies of other metal ion transporters and metal-dependent processes in a range of cell types and conditions. PMID:26838181

Metal ion transport quantified by ICP-MS in intact cells.

PubMed

Figueroa, Julio A Landero; Stiner, Cory A; Radzyukevich, Tatiana L; Heiny, Judith A

2016-02-03

The use of ICP-MS to measure metal ion content in biological tissues offers a highly sensitive means to study metal-dependent physiological processes. Here we describe the application of ICP-MS to measure membrane transport of Rb and K ions by the Na,K-ATPase in mouse skeletal muscles and human red blood cells. The ICP-MS method provides greater precision and statistical power than possible with conventional tracer flux methods. The method is widely applicable to studies of other metal ion transporters and metal-dependent processes in a range of cell types and conditions.

Predicting high blood metal ion concentrations following hip resurfacing.

PubMed

Matharu, Gulraj S; Berryman, Fiona; Brash, Lesley; Pynsent, Paul B; Treacy, Ronan B C; Dunlop, David J

2015-01-01

To determine whether gender, femoral head size, acetabular inclination, and time since surgery predicted high blood metal ion concentrations following Birmingham Hip Resurfacing (BHR). BHR patients with unilateral bearings at one specialist centre with blood cobalt and chromium concentrations measured up to May 2013 were included. This comprised a mixed (at-risk) group including symptomatic patients and asymptomatic individuals with specific clinical and/or radiological findings. Blood sampling was at a mean of 7.5 years (range 1-15.4 years) postoperatively. Of 319 patients (mean age 49.3 years; 53% male), blood metal ions greater than 7 µg/l were observed in 9% (n = 28). Blood metal ions were significantly higher in females (p<0.001), femoral head sizes ≤48 mm (p<0.01), and cup inclinations >55° (p<0.001). Linear regression demonstrated femoral head size was responsible for the highest proportion of variance in blood metal ions (cobalt p<0.001, R2 = 8%; chromium p<0.001, R2 = 11%). Analysis of femoral head size and inclination together demonstrated 36% of BHRs with head sizes of 38-44 mm and inclination >55° had blood metal ions >7 µg/l. BHR 10-year survival for this at-risk group was 91% (95% confidence intervals 86.0%-95.0%) with 30 hips revised. If blood metal ions are used to screen hip resurfacing patients for adverse reactions to metal debris it is recommended those with small femoral head sizes (38-44 mm) and high acetabular inclinations (>55°) are targeted. These findings require validation in other cohorts as they may not be applicable to all hip resurfacing devices given the differences in radial clearance, coverage arc, and metallurgy.

Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity.

PubMed

Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

2015-11-23

Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment.

Metal Ion Concentrations in Body Fluids after Implantation of Hip Replacements with Metal-on-Metal Bearing – Systematic Review of Clinical and Epidemiological Studies

PubMed Central

Hartmann, Albrecht; Hannemann, Franziska; Lützner, Jörg; Seidler, Andreas; Drexler, Hans; Günther, Klaus-Peter; Schmitt, Jochen

2013-01-01

Introduction The use of metal-on-metal (MoM) total hip arthroplasty (THA) increased in the last decades. A release of metal products (i.e. particles, ions, metallo-organic compounds) in these implants may cause local and/or systemic adverse reactions. Metal ion concentrations in body fluids are surrogate measures of metal exposure. Objective To systematically summarize and critically appraise published studies concerning metal ion concentrations after MoM THA. Methods Systematic review of clinical trials (RCTs) and epidemiological studies with assessment of metal ion levels (cobalt, chromium, titanium, nickel, molybdenum) in body fluids after implantation of metalliferous hip replacements. Systematic search in PubMed and Embase in January 2012 supplemented by hand search. Standardized abstraction of pre- and postoperative metal ion concentrations stratified by type of bearing (primary explanatory factor), patient characteristics as well as study quality characteristics (secondary explanatory factors). Results Overall, 104 studies (11 RCTs, 93 epidemiological studies) totaling 9.957 patients with measurement of metal ions in body fluids were identified and analyzed. Consistently, median metal ion concentrations were persistently elevated after implantation of MoM-bearings in all investigated mediums (whole blood, serum, plasma, erythrocytes, urine) irrespective of patient characteristics and study characteristics. In several studies very high serum cobalt concentrations above 50 µg/L were measured (detection limit typically 0.3 µg/L). Highest metal ion concentrations were observed after treatment with stemmed large-head MoM-implants and hip resurfacing arthroplasty. Discussion Due to the risk of local and systemic accumulation of metallic products after treatment with MoM-bearing, risk and benefits should be carefully balanced preoperatively. The authors support a proposed „time out“ for stemmed large-head MoM-THA and recommend a restricted indication for hip

Ion conducting polymers and polymer blends for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

A stepwise recovery of metals from hybrid cathodes of spent Li-ion batteries with leaching-flotation-precipitation process

NASA Astrophysics Data System (ADS)

Huang, Yanfang; Han, Guihong; Liu, Jiongtian; Chai, Wencui; Wang, Wenjuan; Yang, Shuzhen; Su, Shengpeng

2016-09-01

The recovering of valuable metals in spent lithium-ion battery cathodes brings about economic and environmental benefits. A stepwise leaching-flotation-precipitation process is adopted to separate and recover Li/Fe/Mn from the mixed types of cathode materials (hybrid wastes of LiFePO4 and LiMn2O4). The optimal operating conditions for the stepwise recovery process are determined and analyzed by factorial design, thermodynamics calculation, XRD and SEM characterization in this study. First, Li/Fe/Mn ions are released from the cathode using HCl assisted with H2O2 in the acid leaching step. The leachability of metals follows the series Li > Fe > Mn in the acidic environment. Then Fe3+ ions are selectively floated and recovered as FeCl3 from the leachate in the flotation step. Finally, Mn2+/Mn3+ and Li+ ions are sequentially precipitated and separated as MnO2/Mn2O3 and Li3PO4 using saturated KMnO4 solution and hot saturated Na3PO4 solution, respectively. Under the optimized and advisable conditions, the total recovery of Li, Fe and Mn is respectively 80.93 ± 0.16%, 85.40 ± 0.12% and 81.02 ± 0.08%. The purity for lithium, ferrum and manganese compounds is respectively 99.32 ± 0.07%, 97.91 ± 0.05% and 98.73 ± 0.05%. This stepwise process could provide an alternative way for the effective separation and recovery of metal values from spent Li-ion battery cathodes in industry.

Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution

DOEpatents

Rau, Gregory Hudson

2014-07-01

A system for forming metal hydroxide from a metal carbonate utilizes a water electrolysis cell having an acid-producing anode and a hydroxyl-producing cathode immersed in a water solution of sufficient ionic content to allow an electric current to pass between the hydroxyl-producing cathode and the acid-producing anode. A metal carbonate is placed in close proximity to the acid-producing anode. A direct current electrical voltage is provided across the acid-producing anode and the hydroxyl-producing cathode sufficient to generate acid at the acid-producing anode and hydroxyl ions at the hydroxyl-producing cathode. The acid dissolves at least part of the metal carbonate into metal and carbonate ions allowing the metal ions to travel toward the hydroxyl-producing cathode and to combine with the hydroxyl ions to form the metal hydroxide. The carbonate ions travel toward the acid-producing anode and form carbonic acid and/or water and carbon dioxide.

Non-canonical amino acids bearing thiophene and bithiophene: synthesis by an Ugi multicomponent reaction and studies on ion recognition ability.

PubMed

Esteves, Cátia I C; Raposo, M Manuela M; Costa, Susana P G

2017-05-01

Novel thienyl and bithienyl amino acids with different substituents were obtained by a multicomponent Ugi reaction between a heterocyclic aldehyde, an amine, an acid and an isocyanide. Due to the presence of the sulphur heterocycle at the side chain, these unnatural amino acids are highly emissive and bear extra electron donating atoms so they were tested for their ability to act as fluorescent probes and chemosensors in the recognition of biomedically relevant ions in acetonitrile and acetonitrile/water solutions. The results obtained from spectrophotometric/spectrofluorimetric titrations in the presence of organic and inorganic anions, and alkaline; alkaline-earth and transition metal cations indicated that the bithienyl amino acid bearing a methoxy group is a selective colorimetric chemosensor for Cu 2+ , while the other (bi)thienyl amino acids act as fluorimetric chemosensors with high sensitivity towards Fe 3+ and Cu 2+ in a metal-ligand complex with 1:2 stoichiometry. The photophysical and ion sensing properties of these amino acids confirm their potential as fluorescent probes suitable for incorporation into peptidic frameworks with chemosensory ability.

Metal ion promoted hydrogels for bovine serum albumin adsorption: Cu(II) and Co(II) chelated poly[(N-vinylimidazole)-maleic acid].

PubMed

Pekel, Nursel; Salih, Bekir; Güven, Olgun

2005-05-10

Poly[(N-vinylimidazole)-maleic acid] (poly(VIm-MA)), copolymeric hydrogels were prepared by gamma-irradiating ternary mixtures of N-vinylimidazole-maleic acid-water in a (60)Co-gamma source. Cu(II) and Co(II) ions were chelated within the gels at pH=5.0. The maximum adsorption capacity of the gels were 3.71 mmol/g dry gel for Cu(II) and 1.25 mmol/g dry gel for Co(II) at pH=5.0. The swelling ratios of the gels were 1200% for poly(VIm-MA), 60 and 45% for Cu(II) and Co(II)-chelated poly(VIm-MA) gels at pH=5.0 in acetate buffer solution. These affinity gels with different swelling ratios for plain poly(VIm-MA), Cu(II)-, and Co(II)-chelated poly(VIm-MA), in acetate and phosphate buffers were used in the bovine serum albumin (BSA) adsorption/desorption studies in batch reactor. The maximum BSA adsorption capacities of the gels were 0.38 g/g dry gel for plain, 0.88 g/g dry gel for Cu(II)-chelated poly(VIm-MA) and 1.05 g/g dry gel for Co(II)-chelated poly(VIm-MA) gels. Adsorption capacity of BSA by the gels was reduced dramatically by increasing the ionic strength adjusted with NaCl. More than 95% of BSA were desorbed in 10 h in desorption medium containing 0.1M of EDTA for metal ion-chelated gels at pH=4.7.

ION EXCHANGE SOFTENING: EFFECTS ON METAL CONCENTRATIONS

EPA Science Inventory

A corrosion control pipe loop study to evaluate the effect of ion exchange water softening on metal leaching from household plumbing materials was conducted on two different water qualities having different pH's and hardness levels. The results showed that removing hardness ions ...

Smart textile device using ion polymer metal compound.

PubMed

Nakamura, Taro; Ihara, Tadashi

2013-01-01

We have developed a smart textile device that detects angular displacement of attached surface using ion polymer metal compound. The device was composed of ion polymer metal compound (IPMC) which was fabricated from Nafion resin by heat-press and chemical gold plating. The generated voltage from IPMC was measured as a function of bending angle. Fabricated IPMC device was weaved into a cotton cloth and multidirectional movements were detected.

Metallic glass as a temperature sensor during ion plating

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Spalvins, T.; Buckley, D. H.

1985-01-01

The temperature of the interface and/or a superficial layer of a substrate during ion plating was investigated using a metallic glass of the composition Fe67Co18B14Si1 as the substrate and as the temperature sensor. Transmission electron microscopy and diffraction studies determined the microstructure of the ion-plated gold film and the substrate. Results indicate that crystallization occurs not only in the film, but also in the substrate. The grain size of crystals formed during ion plating was 6 to 60 nm in the gold film and 8 to 100 nm in the substrate at a depth of 10 to 15 micrometers from the ion-plated interface. The temperature rise of the substrate during ion plating was approximately 500 C. Discontinuous changes in metallurgical microstructure, and physical, chemical, and mechanical properties during the amorphous to crystalline transition in metallic glasses make metallic glasses extremely useful materials for temperature sensor applications in coating processes.

Metallic glass as a temperature sensor during ion plating

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Spalvins, T.; Buckley, D. H.

1984-01-01

The temperature of the interface and/or a superficial layer of a substrate during ion plating was investigated using a metallic glass of the composition Fe67Co18B14Si1 as the substrate and as the temperature sensor. Transmission electron microscopy and diffraction studies determined the microstructure of the ion-plated gold film and the substrate. Results indicate that crystallization occurs not only in the film, but also in the substrate. The grain size of crystals formed during ion plating was 6 to 60 nm in the gold film and 8 to 100 nm in the substrate at a depth of 10 to 15 micrometers from the ion-plated interface. The temperature rise of the substrate during ion plating was approximately 500 C. Discontinuous changes in metallurgical microstructure, and physical, chemical, and mechanical properties during the amorphous to crystalline transition in metallic glasses make metallic glasses extremely useful materials for temperature sensor applications in coating processes.

Polyrhodanine modified anodic aluminum oxide membrane for heavy metal ions removal.

PubMed

Song, Jooyoung; Oh, Hyuntaek; Kong, Hyeyoung; Jang, Jyongsik

2011-03-15

Polyrhodanine was immobilized onto the inner surface of anodic aluminum oxide (AAO) membrane via vapor deposition polymerization method. The polyrhodanine modified membrane was applied to remove heavy metal ions from aqueous solution because polyrhodanine could be coordinated with specific metal ions. Several parameters such as initial metal concentration, contact time and metal species were evaluated systematically for uptake efficiencies of the fabricated membrane under continuous flow condition. Adsorption isotherms of Hg(II) ion on the AAO-polyrhodanine membrane were analyzed with Langmuir and Freundlich isotherm models. The adsorption rate of Hg(II) ion on the membrane was obeyed by a pseudo-second order equation, indicating the chemical adsorption. The maximum removal capacity of Hg(II) ion onto the fabricated membrane was measured to be 4.2 mmol/g polymer. The AAO-polyrhodanine membrane had also remarkable uptake performance toward Ag(I) and Pb(II) ions. Furthermore, the polyrhodanine modified membrane could be recycled after recovery process. These results demonstrated that the polyrhodanine modified AAO membrane provided potential applications for removing the hazardous heavy metal ions from wastewater. Copyright © 2011 Elsevier B.V. All rights reserved.

Quantitative and Comprehensive Decomposition of the Ion Atmosphere around Nucleic Acids

PubMed Central

Bai, Yu; Greenfeld, Max; Travers, Kevin; Chu, Vincent B.; Lipfert, Jan; Doniach, Sebastian; Herschlag, Daniel

2011-01-01

The ion atmosphere around nucleic acids critically affects biological and physical processes such as chromosome packing, RNA folding, and molecular recognition. However, the dynamic nature of the ion atmosphere renders it difficult to characterize. The basic thermodynamic description of this atmosphere, a full accounting of the type and number of associated ions, has remained elusive. Here we provide the first complete accounting of the ion atmosphere, using buffer equilibration and atomic emission spectroscopy (BE-AES) to accurately quantitate the cation association and anion depletion. We have examined the influence of ion size and charge on ion occupancy around simple, well-defined DNA molecules. The relative affinity of monovalent and divalent cations correlates inversely with their size. Divalent cations associate preferentially over monovalent cations; e.g., with Na+ in four-fold excess of Mg2+ (20 vs. 5 mM), the ion atmosphere nevertheless has three-fold more Mg2+ than Na+. Further, the dicationic polyamine putrescine2+ does not compete effectively for association relative to divalent metal ions, presumably because of its lower charge density. These and other BE-AES results can be used to evaluate and guide the improvement of electrostatic treatments. As a first step, we compare the BE-AES results to predictions from the widely-used nonlinear Poisson Boltzmann (NLPB) theory and assess the applicability and precision of this theory. In the future, BE-AES in conjunction with improved theoretical models, can be applied to complex binding and folding equilibria of nucleic acids and their complexes, to parse the electrostatic contribution from the overall thermodynamics of important biological processes. PMID:17990882

The impact of auxins used in assisted phytoextraction of metals from the contaminated environment on the alterations caused by lead(II) ions in the organization of model lipid membranes.

PubMed

Hąc-Wydro, Katarzyna; Sroka, Aleksandra; Jabłońska, Klaudia

2016-07-01

Auxins are successfully used to improve phytoextraction efficiency of metal ions from the contaminated environment, however, the mechanism of their activity in this field is not explained. Auxins are known to exert various biochemical alterations in the plant membranes and cells, but their activity involves also direct interactions with lipids leading to changes in membrane organization. Following the suggestion that the auxins-induced modifications in membrane properties alleviate toxic effect of metal ions in this paper we have undertaken the comparative studies on the effect of metal ions and metal ions/auxins mixtures on model membrane systems. The experiments were done on lipid monolayers differing in their composition spread on water subphase and on Pb(2+), Indole-3-acetic acid (IAA), 1-Naphthaleneacetic acid (NAA) and Pb(2+)/IAA and Pb(2+)/NAA water solutions. The analysis of the collected data suggests that metal ions and auxins can change fluidity of the lipid systems and weaken the interactions between monolayer components. This manifested in the increase of the mean area per molecule and the excess area per molecule values for the films on Pb(2+), auxins as well as Pb(2+)/auxin solutions as compared to the values on pure water subphase. However, the presence of auxin in the mixture with lead(II) ions makes the alterations induced by sole metal ions weaker. This effect was more pronounced for the membranes of a higher packing. Thus it was proposed that auxins may enhance phytoextraction of metal ions by weakening their destabilizing effect on membrane. Copyright © 2016 Elsevier B.V. All rights reserved.

Cellular sensing and transport of metal ions: implications in micronutrient homeostasis

PubMed Central

Bird, Amanda J.

2015-01-01

Micronutrients include the transition metal ions zinc, copper, and iron. These metals are essential for life as they serve as cofactors for many different proteins. On the other hand, they can also be toxic to cell growth when in excess. As a consequence, all organisms require mechanisms to tightly regulate the levels of these metal ions. In eukaryotes, one of the primary ways in which metal levels are regulated is through changes in expression of genes required for metal uptake, compartmentalization, storage, and export. By tightly regulating the expression of these genes each organism is able to balance metal levels despite fluctuations in the diet or extracellular environment. The goal of this review is to provide an overview of how gene expression can be controlled at a transcriptional, post-transcriptional, and post-translational level in response to metal ions in lower and higher eukaryotes. Specifically, I review what is know about how these metallo-regulatory factors sense fluctuations in metal ion levels, and how changes in gene expression maintain nutrient homeostasis. PMID:26342943

Effect of ion implantation on the tribology of metal-on-metal hip prostheses.

PubMed

Bowsher, John G; Hussain, Azad; Williams, Paul; Nevelos, Jim; Shelton, Julia C

2004-12-01

Nitrogen ion implantation (which considerably hardens the surface of the bearing) may represent one possible method of reducing the wear of metal-on-metal (MOM) hip bearings. Currently there are no ion-implanted MOM bearings used clinically. Therefore a physiological hip simulator test was undertaken using standard test conditions, and the results compared to previous studies using the same methods. N2-ion implantation of high carbon cast Co-Cr-Mo-on-Co-Cr-Mo hip prostheses increased wear by 2-fold during the aggressive running-in phase compared to untreated bearing surfaces, plus showing no wear reductions during steady-state conditions. Although 2 specimens were considered in the current study, it would appear that ion implantation has no clinical benefit for MOM.

Investigations of Heavy Metal Ion Sorption Using Nanocomposites of Iron-Modified Biochar

NASA Astrophysics Data System (ADS)

Kołodyńska, D.; Bąk, J.; Kozioł, M.; Pylypchuk, L. V.

2017-06-01

Magnetic biochar nanocomposites were obtained by modification of biochar by zero-valent iron. The article provides information on the impact of contact time, initial Cd(II), Co(II), Zn(II), and Pb(II) ion concentrations, dose of the sorbents, solution pH and temperature on the adsorption capacity. On the basis of experiments, it was found that the optimum parameters for the sorption process are phase contact time 360 min (after this time, the equilibrium of all concentrations is reached), the dose of sorbent equal to 5 g/dm3, pH 5 and the temperature 295 K. The values of parameters calculated from the kinetic models and isotherms present the best match to the pseudo second order and Langmuir isotherm models. The calculated thermodynamic parameters ΔH 0, ΔS 0 and ΔG 0 indicate that the sorption of heavy metal ions is an exothermic and spontaneous process as well as favoured at lower temperatures, suggesting the physical character of sorption. The solution of nitric acid(V) at the concentration 0.1 mol/dm3 was the best acidic desorbing agent used for regeneration of metal-loaded magnetic sorbents. The physicochemical properties of synthesized composites were characterized by FTIR, SEM, XRD, XPS and TG analyses. The point characteristics of the double layer for biochar pHPZC and pHIEP were designated.

Light metal production

DOEpatents

Fan, Qinbai

2016-04-19

An electrochemical process for the production of light metals, particularly aluminum. Such a process involves contacting a light metal source material with an inorganic acid to form a solution containing the light metal ions in high concentration. The solution is fed to an electrochemical reactor assembly having an anode side containing an anode and a cathode side containing a cathode, with anode side and the cathode side separated by a bipolar membrane, with the solution being fed to the anode side. Light metal ions are electrochemically transferred through the bipolar membrane to the cathode side. The process further involves reducing the light metal ions to light metal powder. An associated processing system is also provided.

Simultaneous detection and determination of mercury (II) and lead (II) ions through the achievement of novel functional nucleic acid-based biosensors.

PubMed

Khoshbin, Zahra; Housaindokht, Mohammad Reza; Verdian, Asma; Bozorgmehr, Mohammad Reza

2018-09-30

The serious threats of mercury (Hg 2+ ) and lead (Pb 2+ ) ions for the public health makes it important to achieve the detection methods of the ions with high affinity and specificity. Metal ions usually coexist in some environment and foodstuff or clinical samples. Therefore, it is very necessary to develop a fast and simple method for simultaneous monitoring the amount of metal ions, especially when Hg 2+ and Pb 2+ coexist. DNAzyme-based biosensors and aptasensors have been highly regarded for this purpose as two main groups of the functional nucleic acid (FNA)-based biosensors. In this review, we summarize the recent achievements of functional nucleic acid-based biosensors for the simultaneous detection of Hg 2+ and Pb 2+ ions in two main optical and electrochemical groups. The tremendous interest in utilizing the various nanomaterials is also highlighted in the fabrication of the FNA-based biosensors. Finally, some results are presented based on the advantages and disadvantages of the studied FNA-based biosensors to compare their validation. Copyright © 2018 Elsevier B.V. All rights reserved.

Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same

DOEpatents

Alexandratos, Spiro; Shelley, Christopher A.; Horwitz, E. Philip; Chiarizia, Renato

2001-01-01

A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.

Bifunctional phenyl monophosphonic/sulfonic acid ion exchange resin and process for using the same

DOEpatents

Alexandratos, Spiro; Shelley, Christopher A.; Horwitz, E. Philip; Chiarizia, Renato; Gula, Michael J.; Xue, Sui; Harvey, James T.

2002-01-01

A cross-linked water-insoluble ion exchange resin comprised of polymerized monomers having a phenyl ring is disclosed. A contemplated resin contains (i) polymerized phenyl ring-containing monomers having a phosphonic acid ligand linked to the phenyl ring, (ii) about 2 to about 5 millimoles per gram (mmol/g) of phosphorus as phosphonic acid ligands, and (iii) a sufficient amount of a sulfonic acid ligand such that the ratio of mmol/g of phosphonic acid to mmol/g sulfonic acid is up to 3:1. A process for removing polyvalent metal cations from aqueous solution, and a process for removing iron(III) cations from acidic copper(II) cation-containing solutions that utilize the contemplated resin or other resins are disclosed.

Adsorption of heavy metal ions by sawdust of deciduous trees.

PubMed

Bozić, D; Stanković, V; Gorgievski, M; Bogdanović, G; Kovacević, R

2009-11-15

The adsorption of heavy metal ions from synthetic solutions was performed using sawdust of beech, linden and poplar trees. The adsorption depends on the process time, pH of the solution, type of ions, initial concentration of metals and the sawdust concentration in suspension. The kinetics of adsorption was relatively fast, reaching equilibrium for less than 20 min. The adsorption equilibrium follows Langmuir adsorption model. The ion exchange mechanism was confirmed assuming that the alkali-earth metals from the adsorbent are substituted by heavy metal ions and protons. On lowering the initial pH, the adsorption capacity decreased, achieving a zero value at a pH close to unity. The maximum adsorption capacity (7-8 mg g(-1) of sawdust) was achieved at a pH between 3.5 and 5 for all the studied kinds of sawdust. The initial concentration of the adsorbate and the concentration of sawdust strongly affect the process. No influence of particles size was evidenced. A degree of adsorption higher than 80% can be achieved for Cu(2+) ions but it is very low for Fe(2+) ions, not exceeding 10%.

The promise of a specially-designed graft copolymer of acrylic acid onto cellulose as selective sorbent for heavy metal ions.

PubMed

Essawy, Hisham A; Mohamed, Magdy F; Ammar, Nabila S; Ibrahim, Hanan S

2017-10-01

A specially-designed graft copolymer of acrylic acid onto in-situ formed cellulose-fulvate hybrid showed privileged tendency for uptake of Pb(II) during competitive removal from a mixture containing Cd(II) and Ni(II) within 5min at pH 5. This novel trend is attributed mainly to the crowded high content of coordinating centers within the designed graft copolymer along with the acquired superabsorbency. This provides an outstanding tool to separate some metal ions selectively from mixtures containing multiple ions on kinetic basis. Thus, the designed graft copolymer structure exhibited superior efficiency that reached ∼95% for sole removal of Pb(II). Kinetic modeling for Pb(II) individual removal showed excellent fitting with a pseudo second-order model. Intraparticle diffusion model on the other hand ensured governance of boundary layer effect over diffusion during the removal process due to the superabsorbency feature of the graft copolymer. The experimental findings were described with models such as Freundlich, Langmuir, and Dubinin-Radushkevich. The Langmuir and Freundlich models showed convenience with the adsorption isotherm of Pb(II) onto the developed graft copolymer. Copyright © 2017 Elsevier B.V. All rights reserved.

[The role of essential metal ions in the human organism and their oral supplementation to the human body in deficiency states].

PubMed

Lakatos, Béla; Szentmihályi, Klára; Vinkler, Péter; Balla, József; Balla, György

2004-06-20

The role of essential nutrient metal ions (Mg, Fe, Cu, Zn, Mn and Co) often deficient in our foodstuffs, although vitally essential in the function of the human organism as well as the different reasons for these deficiencies both in foods and in the human body have been studied. The most frequent nutritional disease is iron deficient anaemia. Inorganic salts, artificial synthetic monomer organic metal complexes of high stability or organic polymer complexes of high molecular mass are unsatisfactory for supplementation to the human body, owing to poor absorption, low availability and/or harmful side effects. In contrast, we have recently found that mixed metal complexes of oligo/polygalacturonic acids with medium molecular weight prepared from natural pectin of plant origin are efficient for oral supplementation. Sufficient absorption of essential metal ions from metal oligo/polygalacturonate mixed complexes with polynuclear innersphere structure is due to the high ionselectivity and medium stability values. Metal oligo/polygalacturonate mixed complexes contain all deficient essential metal ions in adequate amounts and ratios for higher bioavailability of metal ions and optimal vital function. Therefore, by oral administration of these complexes, metal ion homeostasis and optimal interactions with vitamins and hormones can be ensured. Prelatent or latent macroelement Mg deficiency can often be observed among clinical or ambulance patients. Latent or manifest mesoelement iron deficiency is the most common, however, the occurrence of microelement copper, zinc, manganese and cobalt latent deficiencies is not seldom either. Supplementation studies utilizing essential metal oligo/polygalacturonate complexes led to satisfactory outcome without harmful side effects.

Determination of theoretical capacity of metal ion-doped LiMn 2O 4 as the positive electrode in Li-ion batteries

NASA Astrophysics Data System (ADS)

Todorov, Yanko M.; Hideshima, Yasufumi; Noguchi, Hideyuki; Yoshio, Masaki

The theoretical capacity and cation vacancy of metal ion (M)-doped LiMn 2- xM xO 4 spinel compounds serving as positive electrodes in a 4-V lithium ion batteries are calculated. The capacity depends strongly on the mole fraction of doped metal ion and vacancies. The theoretical capacity increases with increasing oxidation number of the doped metal ion in the 16d site of LiMn 2O 4 at the same doping fraction. The validity of the proposed equation for calculation of the capacity has been initially confirmed using a metal ion with well-known valence, such as the Al ion. The oxidation state of Co, Ni and Cr ions in the spinel structure is found to be trivalent, divalent and trivalent, respectively. Analysis shows that metal ion-doped spinel compounds with low vacancy content promote high capacity.

Oxidation of β-blockers by birnessite: Kinetics, mechanism and effect of metal ions.

PubMed

Chen, Yong; Lu, Xiye; Liu, Lu; Wan, Dong; Chen, Huabin; Zhou, Danna; Sharma, Virender K

2018-03-01

Manganese dioxides are ubiquitous in natural waters, soils, and sediments and play an important role in oxidative transformation of organic pollutants. This work presents the kinetics of the oxidation of selected β-blockers, betaxolol, metoprolol, and atenolol by birnessite (δ-MnO 2 ) as a function of concentration of the β-blocker, dosage of δ-MnO 2 , and solution pH. The values of pseudo-first-order rate constants (k obs ) of β-blockers decreased in the order betaxolol > atenolol > metoprolol, which was positively correlated with their acid dissociation constants (K a ). Effect of series of metal ions (Fe 3+ , Cr 3+ , Al 3+ , Pb 2+ , Cu 2+ , Zn 2+ , Ni 2+ , Cd 2+ , Mg 2+ , and Ca 2+ ) on the degradation of β-blockers by δ-MnO 2 was systematically examined. All of these metal ions inhibited the oxidation reaction under the same constant ionic strength. The inhibition efficiency was positively correlated with the logarithm of stability constant of metal ions in aqueous solution (logK MeOH ). By LC-ESI-MS/MS analyses, the oxidation of β-blockers primarily involved hydroxylation and cleavage of the parent molecules to the short branched chain compounds. An electron transfer mechanism for the oxidation of β-blockers by δ-MnO 2 was proposed. The oxidation was initiated by the electron transfer from the nonbonding electrons on nitrogen (N-electrons) of β-blockers to δ-MnO 2 , followed by transformation of radical intermediates. These findings will help to understand the oxidation processes of β-blockers and predict the effect of metal ions on the removal of pollutants by δ-MnO 2 in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Colorimetric photonic hydrogel aptasensor for the screening of heavy metal ions.

PubMed

Ye, Bao-Fen; Zhao, Yuan-Jin; Cheng, Yao; Li, Ting-Ting; Xie, Zhuo-Ying; Zhao, Xiang-Wei; Gu, Zhong-Ze

2012-09-28

We have developed a robust method for the visual detection of heavy metal ions (such as Hg(2+) and Pb(2+)) by using aptamer-functionalized colloidal photonic crystal hydrogel (CPCH) films. The CPCHs were derived from a colloidal crystal array of monodisperse silica nanoparticles, which were polymerized within the polyacrylamide hydrogel. The heavy metal ion-responsive aptamers were then cross-linked in the hydrogel network. During detection, the specific binding of heavy metal ions and cross-linked single-stranded aptamers in the hydrogel network caused the hydrogel to shrink, which was detected as a corresponding blue shift in the Bragg diffraction peak position of the CPCHs. The shift value could be used to estimate, quantitatively, the amount of the target ion. It was demonstrated that our CPCH aptasensor could screen a wide concentration range of heavy metal ions with high selectivity and reversibility. In addition, these aptasensors could be rehydrated from dried gels for storage and aptamer protection. It is anticipated that our technology may also be used in the screening of a broad range of metal ions in food, drugs and the environment.

Does bearing size influence metal ion levels in large-head metal-on-metal total hip arthroplasty? A comparison of three total hip systems

PubMed Central

2014-01-01

Background The purpose of the study was twofold: first, to determine whether there is a statistically significant difference in the metal ion levels among three different large-head metal-on-metal (MOM) total hip systems. The second objective was to assess whether position of the implanted prostheses, patient demographics or factors such as activity levels influence overall blood metal ion levels and whether there is a difference in the functional outcomes between the systems. Methods In a cross-sectional cohort study, three different metal-on-metal total hip systems were assessed: two monoblock heads, the Durom socket (Zimmer, Warsaw, IN, USA) and the Birmingham socket (Smith and Nephew, Memphis, TN, USA), and one modular metal-on-metal total hip system (Pinnacle, Depuy Orthopedics, Warsaw, IN, USA). Fifty-four patients were recruited, with a mean age of 59.7 years and a mean follow-up time of 41 months (12 to 60). Patients were evaluated clinically, radiologically and biochemically. Statistical analysis was performed on all collected data to assess any differences between the three groups in terms of overall blood metal ion levels and also to identify whether there was any other factor within the group demographics and outcomes that could influence the mean levels of Co and Cr. Results Although the functional outcome scores were similar in all three groups, the blood metal ion levels in the larger monoblock large heads (Durom, Birmingham sockets) were significantly raised compared with those of the Pinnacle group. In addition, the metal ion levels were not found to have a statistically significant relationship to the anteversion or abduction angles as measured on the radiographs. Conclusions When considering a MOM THR, the use of a monoblock large-head system leads to higher elevations in whole blood metal ions and offers no advantage over a smaller head modular system. PMID:24472283

Cytotoxicity and metal ions removal using antibacterial biodegradable hydrogels based on N-quaternized chitosan/poly(acrylic acid).

PubMed

Mohamed, Riham R; Elella, Mahmoud H Abu; Sabaa, Magdy W

2017-05-01

Physically crosslinked hydrogels resulted from interaction between N,N,N-trimethyl chitosan chloride (N-Quaternized Chitosan) (NQC) and poly(acrylic acid) (PAA) were synthesized in different weight ratios (3:1), (1:1) and (1:3) taking the following codes Q3P1, Q1P1 and Q1P3, respectively. Characterization of the mentioned hydrogels was done using several analysis tools including; FTIR, XRD, SEM, TGA, biodegradation in simulated body fluid (SBF) and cytotoxicity against HepG-2 liver cancer cells. FTIR results proved that the prepared hydrogels were formed via electrostatic and H-bonding interactions, while XRD patterns proved that the prepared hydrogels -irrespective to their ratios- were more crystalline than both matrices NQC and PAA. TGA results, on the other hand, revealed that Q1P3 hydrogel was the most thermally stable compared to the other two hydrogels (Q3P1 and Q1P1). Biodegradation tests in SBF proved that these hydrogels were more biodegradable than the native chitosan. Examination of the prepared hydrogels for their potency in heavy metal ions removal revealed that they adsorbed Fe (III) and Cd (II) ions more than chitosan, while they adsorbed Cr (III), Ni (II) and Cu (II) ions less than chitosan. Moreover, testing the prepared hydrogels as antibacterial agents towards several Gram positive and Gram negative bacteria revealed their higher antibacterial activity as compared with NQC when used alone. Evaluating the cytotoxic effect of these hydrogels on an in vitro human liver cancer cell model (HepG-2) showed their good cytotoxic activity towards HepG-2. Moreover, the inhibition rate increased with increasing the hydrogels concentration in the culture medium. Copyright © 2017 Elsevier B.V. All rights reserved.

The Structure of the Metal Transporter Tp34 and its Affinity for Divalent Metal Ions

NASA Astrophysics Data System (ADS)

Knutsen, Gregory; Deka, Ranjit; Brautigam, Chad; Tomchick, Diana; Machius, Mischa; Norgard, Michael

2007-10-01

Tp34 is periplasmic membrane protein of the nonculitvatable spirochete Treponema pallidum, the pathogen of syphillis. It was proposed that Tp34 is a divalent metal transporter, but the identity of the preferred metal ion(s) was unclear. In this study we investigated the ability of divalent metal ions to induce rTp34 dimerization using hydrodynamic techniques and determine the crystal structure of metal bound forms. Using analytical ultracentrifugation sedimentation velocity experiments, we determined that cobalt is superior to nickel at inducing the dimerization of rTp34. rTp34 was crystallized and selected crystals were incubated at a pH 7.5 with CuSO4 and NiSO4. Diffraction experiments were conducted and the processed electron density maps showed that copper was bound to the major metal binding site as well as to three additional minor binding sites. By contrast nickel was only bound to the major metal binding site in one monomer and to three additional minor sites. These results along with previous findings support evidence of Tp34 being involved with metal transport and/or iron utilization.

What are the predictors and prevalence of pseudotumor and elevated metal ions after large-diameter metal-on-metal THA?

PubMed

Bayley, Nick; Khan, Habeeb; Grosso, Paul; Hupel, Thomas; Stevens, David; Snider, Matthew; Schemitsch, Emil; Kuzyk, Paul

2015-02-01

Soft tissue masses, or "pseudotumors," around metal-on-metal total hip arthroplasty (MoM THA) have been reported frequently; however, their prevalence remains unknown. Several risk factors, including elevated metal ion levels, have been associated with the presence of pseudotumor, although this remains controversial. The goals of this study were to (1) determine the prevalence of pseudotumors after large-diameter head MoM THA; (2) identify risk factors associated with pseudotumor formation and elevated metal ion levels; and (3) determine the early failure rate of large-diameter MoM THA. Between December 2005 and November 2012, 258 hips (215 patients) underwent large-diameter head primary MoM THA at our institution. Clinical followup was obtained in 235 hips (91%). Using an inclusion criteria of a minimum followup of 1 year, a subset of 191 hips (mean followup, 4 years; range, 1-7 years) was recruited for high-resolution ultrasound screening for the presence of pseudotumor. Whole blood cobalt and chromium ion levels, UCLA activity level, WOMAC score, patient demographics as well as surgical, implant, and radiographic data were collected. Bivariate correlations and multivariate log-linear regression models were used to compare the presence of pseudotumor and elevated metal ions with all other factors. Ultrasound detected a solid, cystic, or mixed mass in 20% hips (38 of 191). No correlation was found between the presence of pseudotumor and any risk factor that we examined. After controlling for confounding variables, elevated cobalt ions were correlated (p<0.001, R=0.50, R2=0.25) with smaller femoral head size, the presence of bilateral MoM THA, and female sex. Elevated chromium ions were correlated (p<0.001, R=0.59, R2=0.34) with smaller femoral head size, presence of bilateral MoM THA, and lower body mass index. The overall survival of MoM THA was 96% at a mean followup of 4.5 years (range, 2-8 years). With the numbers available, we found no associations between

Multiple functions of the crustacean gill: osmotic/ionic regulation, acid-base balance, ammonia excretion, and bioaccumulation of toxic metals

PubMed Central

Henry, Raymond P.; Lucu, Čedomil; Onken, Horst; Weihrauch, Dirk

2012-01-01

The crustacean gill is a multi-functional organ, and it is the site of a number of physiological processes, including ion transport, which is the basis for hemolymph osmoregulation; acid-base balance; and ammonia excretion. The gill is also the site by which many toxic metals are taken up by aquatic crustaceans, and thus it plays an important role in the toxicology of these species. This review provides a comprehensive overview of the ecology, physiology, biochemistry, and molecular biology of the mechanisms of osmotic and ionic regulation performed by the gill. The current concepts of the mechanisms of ion transport, the structural, biochemical, and molecular bases of systemic physiology, and the history of their development are discussed. The relationship between branchial ion transport and hemolymph acid-base regulation is also treated. In addition, the mechanisms of ammonia transport and excretion across the gill are discussed. And finally, the toxicology of heavy metal accumulation via the gill is reviewed in detail. PMID:23162474

Mesoporous metal oxides and processes for preparation thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suib, Steven L.; Poyraz, Altug Suleyman

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier,more » a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.« less

Effects of the spaces available for cations in strongly acidic cation-exchange resins on the exchange equilibria by quaternary ammonium ions and on the hydration states of metal ions.

PubMed

Watanabe, Yuuya; Ohnaka, Kenji; Fujita, Saki; Kishi, Midori; Yuchi, Akio

2011-10-01

The spaces (voids) available for cations in the five exchange resins with varying exchange capacities and cross-linking degrees were estimated, on the basis of the additivity of molar volumes of the constituents. Tetraalkylammonium ions (NR(4)(+); R: Me, Et, Pr) may completely exchange potassium ion on the resin having a larger void radius. In contrast, the ratio of saturated adsorption capacity to exchange capacity of the resin having a smaller void radius decreased with an increase in size of NR(4)(+) ions, due to the interionic contacts. Alkali metal ions could be exchanged quantitatively. While the hydration numbers of K(+), Rb(+), and Cs(+) were independent of the void radius, those of Li(+) and Na(+), especially Na(+), decreased with a decrease in void radius. Interionic contacts between the hydrated ions enhance the dehydration. Multivalent metal ions have the hydration numbers, comparable to or rather greater than those in water. A greater void volume available due to exchange stoichiometry released the interionic contacts and occasionally promoted the involvement of water molecules other than directly bound molecules. The close proximity between ions in the conventional ion-exchange resins having higher exchange capacities may induce varying interactions.

Metal is not inert: role of metal ions released by biocorrosion in aseptic loosening--current concepts.

PubMed

Cadosch, Dieter; Chan, Erwin; Gautschi, Oliver P; Filgueira, Luis

2009-12-15

Metal implants are essential therapeutic tools for the treatment of bone fractures and joint replacements. The metals and metal alloys used in contemporary orthopedic and trauma surgery are well tolerated by the majority of patients. However, complications resulting from inflammatory and immune reactions to metal implants have been well documented. This review briefly discusses the different mechanisms of metal implant corrosion in the human body, which lead to the release of significant levels of metal ions into the peri-implant tissues and the systemic blood circulation. Additionally, this article reviews the effects of the released ions on bone metabolism and the immune system and discusses their involvement in the pathophysiological mechanisms of aseptic loosening and metal hypersensitivity in patients with metal implants.

Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

NASA Astrophysics Data System (ADS)

Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

2018-03-01

Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd < Ag < Cu series, the increasing chemical activity of metal nanoparticles raises the degree of oxygen sorption due to its chemisorption and subsequent reduction, while the role of the molecular chemisorption stage increases in the Cu < Ag < Pd series. Metal particles or their oxides are shown to act as adsorption sites on the surface and in the pores of the ion-exchanger matrix; the equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

A Water-Stable Metal-Organic Framework for Highly Sensitive and Selective Sensing of Fe3+ Ion.

PubMed

Hou, Bing-Lei; Tian, Dan; Liu, Jiang; Dong, Long-Zhang; Li, Shun-Li; Li, Dong-Sheng; Lan, Ya-Qian

2016-10-17

A new metal-organic framework [Zn 5 (hfipbb) 4 (trz) 2 (H 2 O) 2 ] (NNU-1) [H 2 hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoic acid), Htrz = 1H-1,2,3-triazole] was assembled by hydrothermal synthesis. Single-crystal X-ray diffraction analysis reveals that NNU-1 displays a twofold interpenetrating three-dimensional (3D) framework with a {4 24 ·6 4 }-bcu topology. Interestingly, the 3D framework contains a two-dimensional (2D) layered structure that consists of alternating left- and right-handed double helical chains. On the basis of the hydrophobic -CF 3 groups from H 2 hfipbb ligand, NNU-1 possesses excellent stability in water. It is worth noting that NNU-1 not only shows a highly selective fluorescence quenching effect to Fe 3+ ion in aqueous solution but also resists the interference of other metals including Fe 2+ ion. Accordingly, NNU-1 probably functions as a potential promising fluorescence sensor for detecting Fe 3+ ion with high sensitivity and selectivity.

C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

PubMed

Shul'pin, Georgiy B

2013-09-28

This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2

Ohmic model for electrodeposition of metallic ions

NASA Astrophysics Data System (ADS)

Gliozzi, A. S.; Alexe-Ionescu, A. L.; Barbero, G.

2015-10-01

An ohmic model to describe the electrodeposition of metallic ions on the electrodes is proposed. We assume that the ionic distribution is homogeneous across the electrolytic cell, and that the ionic current is due to the bulk electric field. The nucleation in the electrodeposition is supposed to be well described by a kinetic equation at the electrode, taking into account the neutralization of metallic ions on the electrodes. Two cases are considered. In the first case the characteristic time describing the neutralization of the ions is supposed to be negligible with respect to the flight time of the ions across the cell. In this framework the bulk electric field coincides with the external electric field, and our analysis gives analytical formulae for the surface density of deposited ions and for the electric current in the external circuit. The case where the two characteristic times are comparable, and the effective electric field in the bulk depends on the surface deposition, is considered too. In this case the ordinary differential equations describing the ionic distribution and the adsorption phenomenon have to be solved numerically. The agreement between the presented model and the experimental results published by several groups is reasonably good.

Real-time detection of metal ions using conjugated polymer composite papers.

PubMed

Lee, Ji Eun; Shim, Hyeon Woo; Kwon, Oh Seok; Huh, Yang-Il; Yoon, Hyeonseok

2014-09-21

Cellulose, a natural polymeric material, has widespread technical applications because of its inherent structural rigidity and high surface area. As a conjugated polymer, polypyrrole shows practical potential for a diverse and promising range of future technologies. Here, we demonstrate a strategy for the real-time detection and removal of metal ions with polypyrrole/cellulose (PPCL) composite papers in solution. Simply, the conjugated polymer papers had different chemical/physical properties by applying different potentials to them, which resulted in differentiable response patterns and adsorption efficiencies for individual metal ions. First, large-area PPCL papers with a diameter of 5 cm were readily obtained via vapor deposition polymerization. The papers exhibited both mechanical flexibility and robustness, in which polypyrrole retained its redox property perfectly. The ability of the PPCL papers to recognize metal ions was examined in static and flow cells, in which real-time current change was monitored at five different applied potentials (+1, +0.5, 0, -0.5, and -1 V vs. Ag/AgCl). Distinguishable signals in the PPCL paper responses were observed for individual metal ions through principal component analysis. Particularly, the PPCL papers yielded unique signatures for three metal ions, Hg(ii), Ag(i), and Cr(iii), even in a real sample, groundwater. The sorption of metal ions by PPCL papers was examined in the flow system. The PPCL papers had a greatly superior adsorption efficiency for Hg(ii) compared to that of the other metal ions. With the strong demand for the development of inexpensive, flexible, light-weight, and environmentally friendly devices, the fascinating characteristics of these PPCL papers are likely to provide good opportunities for low-cost paper-based flexible or wearable devices.

Influence of the metal ion on the enzyme activity and kinetics of PepA from Lactobacillus delbrueckii.

PubMed

Ewert, Jacob; Glück, Claudia; Strasdeit, Henry; Fischer, Lutz; Stressler, Timo

2018-03-01

The aminopeptidase A (PepA; EC 3.4.11.7) belongs to the group of metallopeptidases with two bound metal ions per subunit (M1M2(PepA)) and is specific for the cleavage of N-terminal glutamic (Glu) and aspartic acid (Asp) and, in low amounts, serine (Ser) residues. Our group recently characterized the first PepA from a Lactobacillus strain. However, the characterization was performed using synthetic para-nitroaniline substrates and not original peptide substrates, as was done in the current study. Prior to the characterization using original peptide substrates, the PepA purified was converted to its inactive apo-form and eight different metal ions were tested to restore its activity. It was found that five of the metal ions were able to reactivate apo-PepA: Co 2+ , Cu 2+ , Mn 2+ , Ni 2+ and Zn 2+ . Interestingly, depending on the metal ion used for reactivation, the activity and the pH and temperature profile differed. Exemplarily, MnMn(PepA), NiNi(PepA) and ZnZn(PepA) had an activity optimum using MES buffer (50mM, pH 6.0) and 60°C, whereas the activity optimum changed to Na/K-phosphate-buffer (50mM, pH 7.0) and 55°C for CuCu(PepA). However, more important than the changes in optimum pH and temperature, the kinetic properties of PepA were affected by the metal ion used. While all PepA variants could release N-terminal Glu or Asp, only CoCo(PepA), NiNi(PepA) and CuCu(PepA) could release Ser from the particular peptide substrate. In addition, it was found that the enzyme efficiency (V max /K M ) and catalytic mechanism (positive cooperative binding (Hill coefficent; n), substrate inhibition (K IS )) were influenced by the metal ion. Exemplarily, a high cooperativity (n>2),K IS value >20mM and preference for N-terminal Glu were detected for CuCu(PepA). In summary, the results suggested that an exchange of the metal ion can be used for tailoring the properties of PepA for specific hydrolysis requirements. Copyright © 2017 Elsevier Inc. All rights reserved.

Efficient inhibition of heavy metal release from mine tailings against acid rain exposure by triethylenetetramine intercalated montmorillonite (TETA-Mt).

PubMed

Gong, Beini; Wu, Pingxiao; Huang, Zhujian; Li, Yuanyuan; Yang, Shanshan; Dang, Zhi; Ruan, Bo; Kang, Chunxi

2016-11-15

The potential application of triethylenetetramine intercalated montmorillonite (TETA-Mt) in mine tailings treatment and AMD (acid mine drainage) remediation was investigated with batch experiments. The structural and morphological characteristics of TETA-Mt were analyzed with XRD, FTIR, DTG-TG and SEM. The inhibition efficiencies of TETA-Mt against heavy metal release from mine tailings when exposed to acid rain leaching was examined and compared with that of triethylenetetramine (TETA) and Mt. Results showed that the overall inhibition by TETA-Mt surpassed that by TETA or Mt for various heavy metal ions over an acid rain pH range of 3-5.6 and a temperature range of 25-40°C. When mine tailings were exposed to acid rain of pH 4.8 (the average rain pH of the mining site where the mine tailings were from), TETA-Mt achieved an inhibition efficiency of over 90% for Cu(2+), Zn(2+), Cd(2+) and Mn(2+) release, and 70% for Pb(2+) at 25°C. It was shown that TETA-Mt has a strong buffering capacity. Moreover, TETA-Mt was able to adsorb heavy metal ions and the adsorption process was fast, suggesting that coordination was mainly responsible. These results showed the potential of TETA-Mt in AMD mitigation, especially in acid rain affected mining area. Copyright © 2016 Elsevier B.V. All rights reserved.

Water purification from metal ions using carbon nanoparticle-conjugated polymer nanocomposites.

PubMed

Khaydarov, Rashid A; Khaydarov, Renat R; Gapurova, Olga

2010-03-01

The paper deals with a novel method of obtaining nanocarbon-conjugated polymer nanocomposites (NCPC) using nanocarbon colloids (NCC) and polyethylenimine (PEI) for water purification from metal ions. Size of NCC, process of NCPC synthesis, its chemical characteristics, ratio of NCC and PEI in NCPC, speed of coagulation of NCPC, mechanism of interaction of metal ions with NCPC, ability of removing metal ions from water by NCPC against pH have been studied. NCPC has a bonding capacity of 4.0-5.7mmol/g at pH 6 for most of the divalent metal ions. Percent of sorption of Zn(2+), Cd(2+), Cu(2+), Hg(2+), Ni(2+), Cr(6+) ions is higher than 99%. Lifetime of NCPC before coagulation in the treated water is 1s-1000min and depends on the ratio of polymeric molecules and carbon nanoparticle concentrations. Results of laboratory tests of the method are described. Copyright 2009 Elsevier Ltd. All rights reserved.

DNAzyme sensors for detection of metal ions in the environment and imaging them in living cells

PubMed Central

McGhee, Claire E.; Loh, Kang Yong

2017-01-01

The on-site and real-time detection of metal ions is important for environmental monitoring and for understanding the impact of metal ions on human health. However, developing sensors selective for a wide range of metal ions that can work in the complex matrices of untreated samples and cells presents significant challenges. To meet these challenges, DNAzymes, an emerging class of metal ion-dependent enzymes selective for almost any metal ion, have been functionalized with fluorophores, nanoparticles and other imaging agents and incorporated into sensors for the detection of metal ions in environmental samples and for imaging the metal ions in living cells. Herein, we highlight the recent developments of DNAzyme-based fluorescent, colorimetric, SERS, electrochemical and electrochemiluminscent sensors for metal ions for these applications. PMID:28458112

Electrochemical formation of hydroxide for enhancing carbon dioxide and acid gas uptake by a solution

DOEpatents

Rau, Gregory Hudson [Castro Valley, CA

2012-05-15

A system is described for forming metal hydroxide from a metal carbonate utilizing a water electrolysis cell having an acid-producing anode and a hydroxyl-producing cathode immersed in a water solution of sufficient ionic content to allow an electric current to pass between the hydroxyl-producing cathode and the acid-producing anode. A metal carbonate, in particular water-insoluble calcium carbonate or magnesium carbonate, is placed in close proximity to the acid-producing anode. A direct current electrical voltage is provided across the acid-producing anode and the hydroxyl-producing cathode sufficient to generate acid at the acid-producing anode and hydroxyl ions at the hydroxyl-producing cathode. The acid dissolves at least part of the metal carbonate into metal and carbonate ions allowing the metal ions to travel toward the hydroxyl-producing cathode and to combine with the hydroxyl ions to form the metal hydroxide. The carbonate ions travel toward the acid-producing anode and form carbonic acid and/or water and carbon dioxide. Among other uses, the metal hydroxide formed can be employed to absorb acid gases such as carbon dioxide from a gas mixture. The invention can also generate hydrogen and oxidative gases such as oxygen or chlorine.

Liquid metal ion source assembly for external ion injection into an electron string ion source (ESIS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Segal, M. J., E-mail: mattiti@gmail.com; University of Cape Town, Rondebosch, Cape Town 7700; Bark, R. A.

An assembly for a commercial Ga{sup +} liquid metal ion source in combination with an ion transportation and focusing system, a pulse high-voltage quadrupole deflector, and a beam diagnostics system has been constructed in the framework of the iThemba LABS (Cape Town, South Africa)—JINR (Dubna, Russia) collaboration. First, results on Ga{sup +} ion beam commissioning will be presented. Outlook of further experiments for measurements of charge breeding efficiency in the electron string ion source with the use of external injection of Ga{sup +} and Au{sup +} ion beams will be reported as well.

Metal ion binding to iron oxides

NASA Astrophysics Data System (ADS)

Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

2006-06-01

The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

Genome Sequence Analysis of the Naphthenic Acid Degrading and Metal Resistant Bacterium Cupriavidus gilardii CR3

PubMed Central

Xiao, Jingfa; Hao, Lirui; Crowley, David E.; Zhang, Zhewen; Yu, Jun; Huang, Ning; Huo, Mingxin; Wu, Jiayan

2015-01-01

Cupriavidus sp. are generally heavy metal tolerant bacteria with the ability to degrade a variety of aromatic hydrocarbon compounds, although the degradation pathways and substrate versatilities remain largely unknown. Here we studied the bacterium Cupriavidus gilardii strain CR3, which was isolated from a natural asphalt deposit, and which was shown to utilize naphthenic acids as a sole carbon source. Genome sequencing of C. gilardii CR3 was carried out to elucidate possible mechanisms for the naphthenic acid biodegradation. The genome of C. gilardii CR3 was composed of two circular chromosomes chr1 and chr2 of respectively 3,539,530 bp and 2,039,213 bp in size. The genome for strain CR3 encoded 4,502 putative protein-coding genes, 59 tRNA genes, and many other non-coding genes. Many genes were associated with xenobiotic biodegradation and metal resistance functions. Pathway prediction for degradation of cyclohexanecarboxylic acid, a representative naphthenic acid, suggested that naphthenic acid undergoes initial ring-cleavage, after which the ring fission products can be degraded via several plausible degradation pathways including a mechanism similar to that used for fatty acid oxidation. The final metabolic products of these pathways are unstable or volatile compounds that were not toxic to CR3. Strain CR3 was also shown to have tolerance to at least 10 heavy metals, which was mainly achieved by self-detoxification through ion efflux, metal-complexation and metal-reduction, and a powerful DNA self-repair mechanism. Our genomic analysis suggests that CR3 is well adapted to survive the harsh environment in natural asphalts containing naphthenic acids and high concentrations of heavy metals. PMID:26301592

Humic Acid Isolations from Lignite by Ion Exchange Method

NASA Astrophysics Data System (ADS)

Kurniati, E.; Muljani, S.; Virgani, D. G.; Neno, B. P.

2018-01-01

The humic liquid is produced from lignite extraction using alkali solution. Conventional humic acid is obtained by acidifying a humic solution using HCl. The purpose of this research is the formation of solid humic acid from lignite by ion exchange method using cation resin. The results showed that the addition of cation resin was able to reduce the pH from 14 to pH 2 as well as the addition of acid (HCl), indicating the exchange of Na + ions with H + ions. The reduction of pH in the humic solution is influenced by the concentration of sodium ions in the humic solution, the weight of the cation resin, and the ion exchange time. The IR spectra results are in good agreement for humic acid from lignite characterization.

Impact of humic/fulvic acid on the removal of heavy metals from aqueous solutions using nanomaterials: a review.

PubMed

Tang, Wang-Wang; Zeng, Guang-Ming; Gong, Ji-Lai; Liang, Jie; Xu, Piao; Zhang, Chang; Huang, Bin-Bin

2014-01-15

Nowadays nanomaterials have been widely used to remove heavy metals from water/wastewater due to their large surface area and high reactivity. Humic acid (HA) and fulvic acid (FA) exist ubiquitously in aquatic environments and have a variety of functional groups which allow them to complex with metal ions and interact with nanomaterials. These interactions can not only alter the environmental behavior of nanomaterials, but also influence the removal and transportation of heavy metals by nanomaterials. Thus, the interactions and the underlying mechanisms involved warrant specific investigations. This review outlined the effects of HA/FA on the removal of heavy metals from aqueous solutions by various nanomaterials, mainly including carbon-based nanomaterials, iron-based nanomaterials and photocatalytic nanomaterials. Moreover, mechanisms involved in the interactions were discussed and potential environmental implications of HA/FA to nanomaterials and heavy metals were evaluated. © 2013.

Tracking metal ions with polypyrrole thin films adhesively bonded to diazonium-modified flexible ITO electrodes.

PubMed

Lo, Momath; Diaw, Abdou K D; Gningue-Sall, Diariatou; Aaron, Jean-Jacques; Oturan, Mehmet A; Chehimi, Mohamed M

2018-05-09

Adhesively bonded polypyrrole thin films doped with benzene sulfonic acid (BSA) were electrodeposited on aminobenzenediazonium-modified flexible ITO electrodes and further employed for the detection of Pb 2+ , Cu 2+ , and Cd 2+ metal ions in aqueous medium. The aminophenyl (AP) adhesive layer was grafted to ITO by electroreduction of the in situ generated parent diazonium compound. Polypyrrole (PPy) thin films exhibited remarkable adhesion to aminophenyl (ITO-AP). The strongly adherent polypyrrole films exhibited excellent electroactivity in the doped state with BSA which itself served to chelate the metal ions in aqueous medium. The surface of the resulting, modified flexible electrode was characterized by XPS, SEM, and electrochemical methods. The ITO-AP-PPy electrodes were then used for the simultaneous detection of Cu 2+ , Cd 2+ , and Pb 2+ by differential pulse voltammetry (DPV). The detection limits were 11.1, 8.95, and 0.99 nM for Cu 2+ , Cd 2+ , and Pb 2+ , respectively. In addition, the modified electrodes displayed a good reproducibility, making them suitable for the determination of heavy metals in real wastewater samples.

Facile synthesis of Fe3O4@PDA core-shell microspheres functionalized with various metal ions: A systematic comparison of commonly-used metal ions for IMAC enrichment.

PubMed

Jiang, Jiebing; Sun, Xueni; Li, Yan; Deng, Chunhui; Duan, Gengli

2018-02-01

Metal ions differed greatly in affinity towards phosphopeptides, and thus it is essential to systematically compare the phosphopeptides enrichment ability of different metal ions usually used in the IMAC techniques. In this work, for the first time, eight metal ions, including Nb 5+ , Ti 4+ , Zr 4+ , Ga 3+ , Y 3+ , In 3+ , Ce 4+ , Fe 3+ , were immobilized on the polydopamine (PDA)-coated Fe 3 O 4 (denoted as Fe 3 O 4 @PDA-M n+ ), and systematically compared by the real biosamples, in addition to standard phosphopeptides. Fe 3 O 4 microspheres were synthesized via the solvothermal reaction, followed by self-polymerization of dopamine on the surface. Then through taking advantage of the hydroxyl and amino group of PDA, the eight metal ions were easily adhered to the surface of Fe 3 O 4 @PDA. After characterization, the resultant Fe 3 O 4 @PDA-M n+ microspheres were applied to phosphopeptides enrichment based on the binding affinity between metal ions and phosphopeptides. According to the results, different metal ions presented diverse phosphopeptides enrichment efficiency in terms of selectivity, sensitivity and the enrichment ability from real complex samples, and Fe 3 O 4 @PDA-Nb 5+ and Fe 3 O 4 @PDA-Ti 4+ showed obvious advantages of the phosphopeptides enrichment effect after the comparison. This systematic comparison may provide certain reference for the use and development of IMAC materials in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of metal ions sorption of brown peat moss powder

NASA Astrophysics Data System (ADS)

Kelus, Nadezhda; Blokhina, Elena; Novikov, Dmitry; Novikova, Yaroslavna; Chuchalin, Vladimir

2017-11-01

For regularities research of sorptive extraction of heavy metal ions by cellulose and its derivates from aquatic solution of electrolytes it is necessary to find possible mechanism of sorption process and to choice a model describing this process. The present article investigates the regularities of aliovalent metals sorption on brown peat moss powder. The results show that sorption isotherm of Al3+ ions is described by Freundlich isotherm and sorption isotherms of Na+ i Ni2+ are described by Langmuir isotherm. To identify the mechanisms of brown peat moss powder sorption the IR-spectra of the initial brown peat moss powder samples and brown peat moss powder samples after Ni (II) sorption were studied. Metal ion binding mechanisms by brown peat moss powder points to ion exchange, physical adsorption, and complex formation with hydroxyl and carboxyl groups.

Metal ion levels in patients with stainless steel spinal instrumentation.

PubMed

McPhee, I Bruce; Swanson, Cheryl E

2007-08-15

Case-control study. To determine whether metal ion concentrations are elevated in patients with spinal instrumentation. Studies have shown that serum and urinary levels of component metal ions are abnormally elevated in patients with total joint arthroplasties. Little is known of metal ion release and concentrations in patients with spinal instrumentation. The study group consisted of patients who had undergone spinal instrumentation for various spinal disorders with a variety of stainless steel implants, 5 to 25 years previously. A group of volunteers without metal implants were controls. All subjects were tested for serum nickel, blood chromium, and random urine chromium/creatinine ratio estimation. The study group consisted of 32 patients with retained implants and 12 patients whose implants had been removed. There were 26 unmatched controls. There was no difference in serum nickel and blood chromium levels between all 3 groups. The mean urinary chromium/creatinine ratio for patients with implants and those with implants removed was significantly greater than controls (P < 0.001). The difference between study subgroups was not significant (P = 0.16). Of several patient and instrumentation variables, only the number of couplings approached significance for correlation with the urine chromium excretion (P = 0.07). Spinal implants do not raise the levels of serum nickel and blood chromium. There is evidence that metal ions are released from spinal implants and excreted in urine. The excretion of chromium in patients with spinal implants was significantly greater than normal controls although lower where the implants have been removed. The findings are consistent with low-grade release of ions from implants with rapid clearance, thus maintaining normal serum levels. Levels of metal ions in the body fluids probably do not reach a level that causes late side-effect; hence, routine removal of the implants cannot be recommended.

Fatty Acid-Mediated Inhibition of Metal Binding to the Multi-Metal Site on Serum Albumin: Implications for Cardiovascular Disease.

PubMed

Blindauer, Claudia A; Khazaipoul, Siavash; Yu, Ruitao; Stewart, Alan J

2016-01-01

Human serum albumin (HSA) is the major protein in blood plasma and is responsible for circulatory transport of a range of small molecules including fatty acids, metal ions and drugs. We previously identified the major plasma Zn2+ transport site on HSA and revealed that fatty-acid binding (at a distinct site called the FA2 site) and Zn2+ binding are interdependent via an allosteric mechanism. Since binding affinities of long-chain fatty acids exceed those of plasma Zn2+, this means that under certain circumstances the binding of fatty acid molecules to HSA is likely to diminish HSA Zn2+-binding, and hence affects the control of circulatory and cellular Zn2+ dynamics. This relationship between circulatory fatty acid and Zn2+ dynamics is likely to have important physiological and pathological implications, especially since it has been recognised that Zn2+ acts as a signalling agent in many cell types. Fatty acid levels in the blood are dynamic, but most importantly, chronic elevation of plasma fatty acid levels is associated with some metabolic disorders and disease states - including myocardial infarction and other cardiovascular diseases. In this article, we briefly review the metal-binding properties of albumin and highlight the importance of their interplay with fatty acid binding. We also consider the impact of this dynamic link upon levels and speciation of plasma Zn2+, its effect upon cellular Zn2+ homeostasis and its relevance to cardiovascular and circulatory processes in health and disease.

Chemistry of carcinogenic metals.

PubMed Central

Martell, A E

1981-01-01

The periodic distribution of known and suspected carcinogenic metal ions is described, and the chemical behavior of various types of metal ions is explained in terms of the general theory of hard and soft acids and bases. The chelate effect is elucidated, and the relatively high stability of metal chelates in very dilute solutions is discussed. The concepts employed for the chelate effect are extended to explain the high stabilities of macrocyclic and cryptate complexes. Procedures for the use of equilibrium data to determine the speciation of metal ions and complexes under varying solution conditions are described. Methods for assessing the interferences by hydrogen ion, competing metal ions, hydrolysis, and precipitation are explained, and are applied to systems containing iron(III) chelates of fourteen chelating agents designed for effective binding of the ferric ion. The donor groups available for the building up of multidentate ligands are presented, and the ways in which they may be combined to achieve high affinity and selectivity for certain types of metal ions are explained. PMID:6791915

Comparison of metal ion concentrations and implant survival after total hip arthroplasty with metal-on-metal versus metal-on-polyethylene articulations

PubMed Central

Dahlstrand, Henrik; Stark, André; Wick, Marius C; Anissian, Lucas; Hailer, Nils P; Weiss, Rüdiger J

2017-01-01

Background and purpose Large metal-on-metal (MoM) articulations are associated with metal wear and corrosion, leading to increased metal ion concentrations and unacceptable revision rates. There are few comparative studies of 28-mm MoM articulations with conventional metal-on-polyethylene (MoP) couplings. We present a long-term follow-up of a randomized controlled trial comparing MoM versus MoP 28-mm articulations, focused on metal ions and implant survival. Patients and methods 85 patients with a mean age of 65 years at surgery were randomized to a MoM (Metasul) or a MoP (Protasul) bearing. After 16 years, 38 patients had died and 4 had undergone revision surgery. 13 patients were unavailable for clinical follow-up, leaving 30 patients (n = 14 MoM and n = 16 MoP) for analysis of metal ion concentrations and clinical outcome. Results 15-year implant survival was similar in both groups (MoM 96% [95% CI 88–100] versus MoP 97% [95% CI 91–100]). The mean serum cobalt concentration was 4-fold higher in the MoM (1.5 μg/L) compared with the MoP cohort (0.4 μg/L, p < 0.001) and the mean chromium concentration was double in the MoM (2.2 μg/L) compared with the MoP cohort (1.0 μg/L, p = 0.05). Mean creatinine levels were similar in both groups (MoM 93 μmol/L versus MoP 92 μmol/L). Harris hip scores differed only marginally between the MoM and MoP cohorts. Interpretation This is the longest follow-up of a randomized trial on 28-mm MoM articulations, and although implant survival in the 2 groups was similar, metal ion concentrations remained elevated in the MoM cohort even in the long term. PMID:28699417

Cobalt- and Cadmium-Based Metal-Organic Frameworks as High-Performance Anodes for Sodium Ion Batteries and Lithium Ion Batteries.

PubMed

Dong, Caifu; Xu, Liqiang

2017-03-01

Two multifunctional metal-organic frameworks (MOFs) with the same coordination mode, [Co(L)(H 2 O)] n ·2nH 2 O [defined as "Co(L) MOF"] and [Cd(L)(H 2 O)] n ·2nH 2 O [defined as "Cd(L) MOF"] (L = 5-aminoisophthalic acid) have been fabricated via a simple and versatile scalable solvothermal approach at 85 °C for 24 h. The relationship between the structure of the electrode materials (especially the coordination water and different metal ions) and the electrochemical properties of MOFs have been investigated for the first time. And then the possible electrochemical mechanisms of the electrodes have been studied and proposed. In addition, MOFs/RGO hybrid materials were prepared via ball milling, which demonstrated better electrochemical performances than those of individual Co(L) MOF and Cd(L) MOF. For example, when Co(L) MOF/RGO was applied as anode for sodium ion batteries (SIBs), it retained 206 mA h g -1 after 330 cycles at 500 mA g -1 and 1185 mA h g -1 could be obtained after 50 cycles at 100 mA g -1 for lithium-ion batteries (LIBs). The high-discharge capacity, excellent cyclic stability combined with the facile synthesis procedure enable Co(L) MOF- and Cd(L) MOF-based materials to be prospective anode materials for SIBs and LIBs.

Construction of three lanthanide metal-organic frameworks: Synthesis, structure, magnetic properties and highly selective sensing of metal ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiu-Mei, E-mail: zhangxiumeilb@126.com; Li, Peng; Gao, Wei

Three lanthanide metal-organic frameworks (Ln-MOFs), [Ln(TZI)(H{sub 2}O){sub 4}]·3H{sub 2}O (Ln=Gd (1) and Tb (2) and Dy (3), H{sub 3}TZI=5-(1H-tetrazol-5-yl)isophthalic acid), have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction reveals that 1–3 are isostructural and display a 1D double chain based on dinuclear motifs with (μ-COO){sub 2} double bridges. Magnetic studies indicate antiferromagnetic interactions in 1, ferromagnetic interactions in 2 and 3. Furthermore, compound 3 displays a slow relaxation behavior. Compound 2 exhibits intense characteristic green emission of Tb(III) ions in the solid state, which can be observed by the naked eye under UV light. Interestingly, 2 can selectivelymore » sense Pb{sup 2+} and Fe{sup 3+} ions through luminescence enhancement and quenching, respectively. The luminescence quenching mechanisms have been investigated in detail. The study on luminescence Ln-MOFs as a probe for sensing Pb{sup 2+} and Fe{sup 3+} ions is exceedingly rare example. - Graphical abstract: Three Ln-MOFs were successfully synthesized using a 5-(1H-tetrazol-5-yl)isophthalic acid ligand. They displays different magnetic behavior. Especially, the Dy(III) compound slow relaxation behavior. Interestingly, the Tb(III) compound can selectively sense Pb{sup 2+} and Fe{sup 3+} ions through luminescence enhancement and quenching, respectively. - Highlights: • Three Ln-MOFs with tetrazolate dicarboxylate ligand. • Dy(III) compound displays slow relaxation behavior. • The Tb(III) compound shows highly selective luminescence sensing of the Fe{sup 3+} and Pb{sup 2+} ions.« less

Flame Atomic Absorption Spectrometric Determination of Trace Metal Ions in Environmental and Biological Samples After Preconcentration on a Newly Developed Amberlite XAD-16 Chelating Resin Containing p-Aminobenzene Sulfonic Acid.

PubMed

Islam, Aminul; Ahmad, Akil; Laskar, Mohammad Asaduddin

2015-01-01

Amberlite® XAD-16 was functionalized with p-aminobenzene sulfonic acid via an azo spacer in order to prepare a new chelating resin, which was then characterized by water regain value, hydrogen ion capacity, elemental analyses, and IR spectral and thermal studies. The maximum uptake of Cu(II), Ni(II), Zn(II), Co(II), Cr(III), Fe(III), and Pb(II) ions was observed in the pH range 4.0-6.0 with the corresponding half-loading times of 6.5, 7.0, 8.0, 9.0, 11.0, 8.5, and 16.5 min. The sorption data followed Langmuir isotherms and a pseudo-second-order model. Thermodynamic quantities, ΔH and ΔS, based on the variation of the distribution coefficient with temperature were also evaluated. High preconcentration factors of 60-100 up to a low preconcentration limit of 4.0-6.6 μg/L have been achieved for the metal ions. The validity of the method was checked by analyzing standard reference materials and recoveries of trace metals after spiking. The analytical applications of the method were explored by analyzing natural water, mango pulp, mint leaves, and fish.

Multivariate correlations between properties of metal ions and their acute toxicity in mice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turner, J.E.; Williams, M.W.; Hingerty, B.E.

1986-01-01

This paper extends our earlier study of correlations of acute metal-ion toxicity (14-day LD50) in mice and physicochemical properties of the ions. Here we put metal ions into two main groups as defined by Kaiser. Using most of the metals in the periodic system, we find the least redundant linear combinations W/sub i/ of the ionic radius, sum of ionization potentials, atomic weight, Williams softness parameter, and electronegativity for each of Kaiser's two groups. Information is provided so that the W/sub i/ can be evaluated for any metal from these five quantities. For the two groups of metals we thenmore » tested for multivariate correlations between the S/sub i/ having the highest sample variance and our mouse LD50. For our LD50 involving the five metal ions in Kaiser's group (1) the correlation is poor, whereas a good correlation is found for the 14 ions in group (2). 10 refs., 3 tabs.« less

Some aspects of metallic ion chemistry and dynamics in the mesosphere and thermosphere

NASA Technical Reports Server (NTRS)

Mathews, J. D.

1987-01-01

The relationship between the formation of sporadic layers of metallic ion and the dumping of these ions into the upper mesosphere is discussed in terms of the tidal wind, classical (i.e., windshear) and other more complex, perhaps highly nonlinear layer formation mechanisms, and a possible circulation mechanism for these ions. Optical, incoherent scatter radar, rocket, and satellite derived evidence for various layer formation mechanisms and for the metallic ion circulation system is reviewed. The results of simple one dimensional numerical model calculations of sporadic E and intermediate layer formation are presented along with suggestions for more advanced models of intense or blanketing sporadic E. The flux of metallic ions dumped by the tidal wind system into the mesosphere is estimated and compared with estimates of total particle flux of meteoric origin. Possible effects of the metallic ion flux and of meteoric dust on D region ion chemistry are discussed.

Sensing of heavy metal ions by intrinsic TMV coat protein fluorescence.

PubMed

Bayram, Serene S; Green, Philippe; Blum, Amy Szuchmacher

2018-04-15

We propose the use of a cysteine mutant of TMV coat protein as a signal transducer for the selective sensing and quantification of the heavy metal ions, Cd 2+ , Pb 2+ , Zn 2+ and Ni 2+ based on intrinsic tryptophan quenching. TMV coat protein is inexpensive, can be mass-produced since it is expressed and extracted from E-coli. It also displays several different functional groups, enabling a wide repertoire of bioconjugation chemistries; thus it can be easily integrated into functional devices. In addition, TMV-ion interactions have been widely reported and utilized for metallization to generate organic-inorganic hybrid composite novel materials. Building on these previous observations, we herein determine, for the first time, the TMV-ion binding constants assuming the static fluorescence quenching model. We also show that by comparing TMV-ion interactions between native and denatured coat protein, we can distinguish between chemically similar heavy metal ions such as cadmium and zinc ions. Copyright © 2018 Elsevier B.V. All rights reserved.

Sensing of heavy metal ions by intrinsic TMV coat protein fluorescence

NASA Astrophysics Data System (ADS)

Bayram, Serene S.; Green, Philippe; Blum, Amy Szuchmacher

2018-04-01

We propose the use of a cysteine mutant of TMV coat protein as a signal transducer for the selective sensing and quantification of the heavy metal ions, Cd2+, Pb2+, Zn2+ and Ni2+ based on intrinsic tryptophan quenching. TMV coat protein is inexpensive, can be mass-produced since it is expressed and extracted from E-coli. It also displays several different functional groups, enabling a wide repertoire of bioconjugation chemistries; thus it can be easily integrated into functional devices. In addition, TMV-ion interactions have been widely reported and utilized for metallization to generate organic-inorganic hybrid composite novel materials. Building on these previous observations, we herein determine, for the first time, the TMV-ion binding constants assuming the static fluorescence quenching model. We also show that by comparing TMV-ion interactions between native and denatured coat protein, we can distinguish between chemically similar heavy metal ions such as cadmium and zinc ions.

Smart responsive microcapsules capable of recognizing heavy metal ions.

PubMed

Pi, Shuo-Wei; Ju, Xiao-Jie; Wu, Han-Guang; Xie, Rui; Chu, Liang-Yin

2010-09-15

Smart responsive microcapsules capable of recognizing heavy metal ions are successfully prepared with oil-in-water-in-oil double emulsions as templates for polymerization in this study. The microcapsules are featured with thin poly(N-isopropylacrylamide-co-benzo-18-crown-6-acrylamide) (P(NIPAM-co-BCAm)) membranes, and they can selectively recognize special heavy metal ions such as barium(II) or lead(II) ions very well due to the "host-guest" complexation between the BCAm receptors and barium(II) or lead(II) ions. The stable BCAm/Ba(2+) or BCAm/Pb(2+) complexes in the P(NIPAM-co-BCAm) membrane cause a positive shift of the volume phase transition temperature of the crosslinked P(NIPAM-co-BCAm) hydrogel to a higher temperature, and the repulsion among the charged BCAm/Ba(2+) or BCAm/Pb(2+) complexes and the osmotic pressure within the P(NIPAM-co-BCAm) membranes result in the swelling of microcapsules. Induced by recognizing barium(II) or lead(II) ions, the prepared microcapsules with P(NIPAM-co-BCAm) membranes exhibit isothermal and significant swelling not only in outer and inner diameters but also in the membrane thickness. The proposed microcapsules in this study are highly attractive for developing smart sensors and/or carriers for detection and/or elimination of heavy metal ions. Copyright 2010 Elsevier Inc. All rights reserved.

Analysis of Supercritical-Extracted Chelated Metal Ions From Mixed Organic-Inorganic Samples

NASA Technical Reports Server (NTRS)

Sinha, Mahadeva P. (Inventor)

1996-01-01

Organic and inorganic contaminants of an environmental sample are analyzed by the same GC-MS instrument by adding an oxidizing agent to the sample to oxidize metal or metal compounds to form metal ions. The metal ions are converted to chelate complexes and the chelate complexes are extracted into a supercritical fluid such as CO2. The metal chelate extract after flowing through a restrictor tube is directly injected into the ionization chamber of a mass spectrometer, preferably containing a refractory metal filament such as rhenium to fragment the complex to release metal ions which are detected. This provides a fast, economical method for the analysis of metal contaminants in a sample and can be automated. An organic extract of the sample in conventional or supercritical fluid solvents can be detected in the same mass spectrometer, preferably after separation in a supercritical fluid chromatograph.

[Detection of metal ions in hair after metal-metal hip arthroplasty].

PubMed

Hernandez-Vaquero, D; Rodríguez de la Flor, M; Fernandez-Carreira, J M; Sariego-Muñiz, C

2014-01-01

There is an increase in the levels of metals in the serum and urine after the implantation of some models of metal-metal hip prosthesis. It has recently been demonstrated that there is an association between these levels and the levels found in hair. The aim of this study is to determine the presence of metals in hair, and to find out whether these change over time or with the removal of the implant. The levels of chromium, cobalt and molybdenum were determined in the hair of 45 patients at 3, 4, 5, and 6 years after a hip surface replacement. The mean age was 57.5 years, and two were female. Further surgery was required to remove the replacement and implant a new model with metal-polyethylene friction in 11 patients, 5 of them due to metallosis and a periarticular cyst. The mean levels of metals in hair were chromium 163.27 ppm, cobalt 61.98 ppm, and molybdenum 31.36 ppm, much higher than the levels found in the general population. A decrease in the levels of chromium (43.8%), molybdenum (51.1%), and cobalt (91.1%) was observed at one year in the patients who had further surgery to remove the prosthesis. High concentrations of metals in the hair are observed in hip replacements with metal-metal friction, which decrease when that implant is removed. The determination of metal ions in hair could be a good marker of the metal poisoning that occurs in these arthroplasty models. Copyright © 2014 SECOT. Published by Elsevier Espana. All rights reserved.

BIORECOVERY OF METALS FROM ACID MINE DRAINAGE

EPA Science Inventory

Acid mine water is an acidic, metal-bearing wastewater generated by the oxidation of metallic sulfides by certain bacteria in both active and abandoned mining operations. The wastewaters contain substantial quantities of dissolved solids with the particular pollutants dependant u...

Do soft drinks affect metal ions release from orthodontic appliances?

PubMed

Mikulewicz, Marcin; Wołowiec, Paulina; Loster, Bartłomiej W; Chojnacka, Katarzyna

2015-01-01

The effect of orange juice and Coca Cola(®) on the release of metal ions from fixed orthodontic appliances. A continuous flow system designed for in vitro testing of orthodontic appliances was used. Orange juice/Coca Cola(®) was flowing through the system alternately with artificial saliva for 5.5 and 18.5h, respectively. The collected samples underwent a multielemental ICP-OES analysis in order to determine the metal ions release pattern in time. The total mass of ions released from the appliance into orange juice and Coca Cola(®) (respectively) during the experiment was calculated (μg): Ni (15.33; 37.75), Cr (3.604; 1.052), Fe (48.42; ≥ 156.1), Cu (57.87, 32.91), Mn (9.164; 41.16), Mo (9.999; 30.12), and Cd (0.5967; 2.173). It was found that orange juice did not intensify the release of metal ions from orthodontic appliances, whereas Coca Cola(®) caused increased release of Ni ions. Copyright © 2015 Elsevier GmbH. All rights reserved.

Effects of metal ions on the catalytic degradation of dicofol by cellulase.

PubMed

Zhai, Zihan; Yang, Ting; Zhang, Boya; Zhang, Jianbo

2015-07-01

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, Km, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, Vmax, was 0.40 mg/L/min, while that of free cellulase was Km=8.18 mg/L, and Vmax=0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn2+, reversible competition with Cd2+, and irreversible inhibition by Pb2+. Ca2+ promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment. Copyright © 2015. Published by Elsevier B.V.

Application of Sargassum biomass to remove heavy metal ions from synthetic multi-metal solutions and urban storm water runoff.

PubMed

Vijayaraghavan, K; Teo, Ting Ting; Balasubramanian, R; Joshi, Umid Man

2009-05-30

The ability of Sargassum sp. to biosorb four metal ions, namely lead, copper, zinc, and manganese from a synthetic multi-solute system and real storm water runoff has been investigated for the first time. Experiments on synthetic multi-solute systems revealed that Sargassum performed well in the biosorption of all four metal ions, with preference towards Pb, followed by Cu, Zn, and Mn. The solution pH strongly affected the metal biosorption, with pH 6 being identified as the optimal condition for achieving maximum biosorption. Experiments at different biosorbent dosages revealed that good biosorption capacity as well as high metal removal efficiency was observed at 3g/L. The biosorption kinetics was found to be fast with equilibrium being attained within 50 min. According to the Langmuir isotherm model, Sargassum exhibited maximum uptakes of 214, 67.5, 24.2 and 20.2mg/g for lead, copper, zinc, and manganese, respectively in single-solute systems. In multi-metal systems, strong competition between four metal ions in terms of occupancy binding sites was observed, and Sargassum showed preference in the order of Pb>Cu>Zn>Mn. The application of Sargassum to remove four heavy metal ions in real storm water runoff revealed that the biomass was capable of removing the heavy metal ions. However, the biosorption performance was slightly lower compared to that of synthetic metal solutions. Several factors were responsible for this difference, and the most important factor is the presence of other contaminants such as anions, organics, and other trace metals in the runoff.

Influences of hydrological regime on heavy metal and salt ion concentrations in intertidal sediment from Chongming Dongtan, Changjiang River estuary, China

NASA Astrophysics Data System (ADS)

Zhao, Jiale; Gao, Xiaojiang; Yang, Jin

2017-11-01

The tidal flat along the Changjiang (Yangtze) River estuary has long been reclaimed for the agricultural purposes, with the prevailing hydrological conditions during such pedogenic transformations being of great importance to their successful development. In this study, samples of surface sediment from Chongming Dongtan, situated at the mouth of the Changjiang River estuary, were collected and analyzed in order to understand how hydrological management can influence the concentrations of heavy metals and salt ions in pore water, and chemical fractionation of heavy metals during the reclamation process. We performed a series of experiments that simulated three different hydrological regimes: permanent flooding (R1), alternative five-day periods of wetting and drying (R2), continuous field capacity (R3). Our results exhibited good Pearson correlations coefficients between heavy metals and salt ions in the pore water for both R1 and R2. In particular, the concentrations of salt ions in the pore water decreased in all three regimes, but showed the biggest decline in R2. With this R2 experiment, the periodic concentration patterns in the pore water varied for Fe and Mn, but not for Cr, Cu, Pb and Zn. Neither the fractionation of Ni nor the residual fractions of any metals changed significantly in any regime. In R1, the reducible fractions of heavy metals (Cr, Cu, Zn and Pb) in the sediment decreased, while the acid extractable fractions increased. In R2, the acid extractable and the reducible fractions of Cr, Cu, Zn and Pb both decreased, as did the oxidizable fraction of Cu. These data suggest that an alternating hydrological regime can reduce both salinity and the availability of heavy metals in sediments.

Acquisition of Co metal from spent lithium-ion battery using emulsion liquid membrane technology and emulsion stability test

NASA Astrophysics Data System (ADS)

Yuliusman; Wulandari, P. T.; Amiliana, R. A.; Huda, M.; Kusumadewi, F. A.

2018-03-01

Lithium-ion batteries are the most common type to be used as energy source in mobile phone. The amount of lithium-ion battery wastes is approximated by 200 – 500 ton/year. In one lithium-ion battery, there are 5 – 20% of cobalt metal, depend on the manufacturer. One of the way to recover a valuable metal from waste is leaching process then continued with extraction, which is the aim of this study. Spent lithium-ion batteries will be characterized with EDX and AAS, the result will show the amount of cobalt metal with form of LiCoO2 in the cathode. Hydrochloric acid concentration used is 4 M, temperature 80°C, and reaction time 1 hour. This study will discuss the emulsion stability test on emulsion liquid membrane. The purpose of emulsion stability test in this study was to determine optimum concentration of surfactant and extractant to produce a stable emulsion. Surfactant and extractant used were SPAN 80 and Cyanex 272 respectively with both concentrations varied. Membrane and feed phase ratios used in this experiment was 1 : 2. The optimum results of this study were SPAN 80 concentrations of 10% w/v and Cyanex 272 0.7 M.

Effect of detergents, trypsin, and bivalent metal ions on interfacial activation and functioning of phospholipase D.

PubMed

Madyarov, Sh R

2014-07-01

The effects of detergents, trypsin, and bivalent metal ions on production of phosphatidic and lysophosphatidic acids by the action of phospholipase D (PLD) on lecithin and lysolecithin were studied. It was found that these reaction products and dodecyl sulfate ions activate PLD, whereas other anionic detergents are less effective. A protective effect of the functioning enzyme against its hydrolytic inactivation by trypsin was found. Bivalent metal ions can be arranged in the following sequence by their ability to activate PLD in the hydrolysis of lecithin and lysolecithin: Ca2+>Sr2+>Ba2+>Mg2+. These results are considered in relation to a proposed mechanism of activation and functioning of PLD with the participation of clusters of phosphatidates and lysophosphatidates. Such Me2+-induced formation of rafts or microdomains from the products of hydrolysis of phospholipids can rationalize not only PLD activation and self-regulation, but also the action of this mechanism on other components and properties of biomembranes. PLD and other lipolytic enzymes can be classified as lateral vector enzymes.

Cation–Anion Interactions within the Nucleic Acid Ion Atmosphere Revealed by Ion Counting

PubMed Central

Gebala, Magdalena; Giambasu, George M.; Lipfert, Jan; Bisaria, Namita; Bonilla, Steve; Li, Guangchao; York, Darrin M.; Herschlag, Daniel

2016-01-01

The ion atmosphere is a critical structural, dynamic, and energetic component of nucleic acids that profoundly affects their interactions with proteins and ligands. Experimental methods that “count” the number of ions thermodynamically associated with the ion atmosphere allow dissection of energetic properties of the ion atmosphere, and thus provide direct comparison to theoretical results. Previous experiments have focused primarily on the cations that are attracted to nucleic acid polyanions, but have also showed that anions are excluded from the ion atmosphere. Herein, we have systematically explored the properties of anion exclusion, testing the zeroth-order model that anions of different identity are equally excluded due to electrostatic repulsion. Using a series of monovalent salts, we find, surprisingly, that the extent of anion exclusion and cation inclusion significantly depends on salt identity. The differences are prominent at higher concentrations and mirror trends in mean activity coefficients of the electrolyte solutions. Salts with lower activity coefficients exhibit greater accumulation of both cations and anions within the ion atmosphere, strongly suggesting that cation–anion correlation effects are present in the ion atmosphere and need to be accounted for to understand electrostatic interactions of nucleic acids. To test whether the effects of cation–anion correlations extend to nucleic acid kinetics and thermodynamics, we followed the folding of P4–P6, a domain of the Tetrahymena group I ribozyme, via single-molecule fluorescence resonance energy transfer in solutions with different salts. Solutions of identical concentration but lower activity gave slower and less favorable folding. Our results reveal hitherto unknown properties of the ion atmosphere and suggest possible roles of oriented ion pairs or anion-bridged cations in the ion atmosphere for electrolyte solutions of salts with reduced activity. Consideration of these new

Dislocation loop formation by swift heavy ion irradiation of metals.

PubMed

Khara, Galvin S; Murphy, Samuel T; Duffy, Dorothy M

2017-07-19

A coupled two-temperature, molecular dynamics methodology is used to simulate the structural evolution of bcc metals (Fe and W) and fcc metals (Cu and Ni) following irradiation by swift heavy ions. Electronic temperature dependent electronic specific heat capacities and electron-phonon coupling strengths are used to capture the full effects of the variation in the electronic density of states. Tungsten is found to be significantly more resistant to damage than iron, due both to the higher melting temperature and the higher thermal conductivity. Very interesting defect structures, quite different from defects formed in cascades, are found to be created by swift heavy ion irradiation in the bcc metals. Isolated vacancies form a halo around elongated interstitial dislocation loops that are oriented along the ion path. Such configurations are formed by rapid recrystallization of the molten cylindrical region that is created by the energetic ion. Vacancies are created at the recrystallization front, resulting in excess atoms at the core which form interstitial dislocation loops on completion of crystallization. These unique defect structures could, potentially, be used to create metal films with superior mechanical properties and interesting nanostructures.

Dislocation loop formation by swift heavy ion irradiation of metals

NASA Astrophysics Data System (ADS)

Khara, Galvin S.; Murphy, Samuel T.; Duffy, Dorothy M.

2017-07-01

A coupled two-temperature, molecular dynamics methodology is used to simulate the structural evolution of bcc metals (Fe and W) and fcc metals (Cu and Ni) following irradiation by swift heavy ions. Electronic temperature dependent electronic specific heat capacities and electron-phonon coupling strengths are used to capture the full effects of the variation in the electronic density of states. Tungsten is found to be significantly more resistant to damage than iron, due both to the higher melting temperature and the higher thermal conductivity. Very interesting defect structures, quite different from defects formed in cascades, are found to be created by swift heavy ion irradiation in the bcc metals. Isolated vacancies form a halo around elongated interstitial dislocation loops that are oriented along the ion path. Such configurations are formed by rapid recrystallization of the molten cylindrical region that is created by the energetic ion. Vacancies are created at the recrystallization front, resulting in excess atoms at the core which form interstitial dislocation loops on completion of crystallization. These unique defect structures could, potentially, be used to create metal films with superior mechanical properties and interesting nanostructures.

Effects of lability of metal complex on free ion measurement using DMT.

PubMed

Weng, Liping; Van Riemsdijk, Willem H; Temminghoff, Erwin J M

2010-04-01

Very low concentrations of free metal ion in natural samples can be measured using the Donnan membrane technique (DMT) based on ion transport kinetics. In this paper, the possible effects of slow dissociation of metal complexes on the interpretation of kinetic DMT are investigated both theoretically and experimentally. The expressions of the lability parameter, Lgrangian , were derived for DMT. Analysis of new experimental studies using synthetic solution containing NTA as the ligand and Cu(2+) ions shows that when the ionic strength is low (metals. By comparing the fraction of labile species measured using other dynamic sensors (DGT, GIME) in several freshwaters, it is concluded that in most waters ion transport in DMT is controlled by diffusion in the membrane. Only in very soft waters (<0.7 mM Ca+Mg), the dissociation rate of natural metal complex may influence ion transport in DMT. In this case, neglecting this effect may lead to an underestimation of the free metal ion concentration measured.

Phosphonic acid based exchange resins

DOEpatents

Horwitz, E. Philip; Alexandratos, Spiro D.; Gatrone, Ralph C.; Chiarizia, Ronato

1995-01-01

An ion exchange resin for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene.

Fluorescence enhancement of photoswitchable metal ion sensors

NASA Astrophysics Data System (ADS)

Sylvia, Georgina; Heng, Sabrina; Abell, Andrew D.

2016-12-01

Spiropyran-based fluorescence sensors are an ideal target for intracellular metal ion sensing, due to their biocompatibility, red emission frequency and photo-controlled reversible analyte binding for continuous signal monitoring. However, increasing the brightness of spiropyran-based sensors would extend their sensing capability for live-cell imaging. In this work we look to enhance the fluorescence of spiropyran-based sensors, by incorporating an additional fluorophore into the sensor design. We report a 5-membered monoazacrown bearing spiropyran with metal ion specificity, modified to incorporate the pyrene fluorophore. The effect of N-indole pyrene modification on the behavior of the spiropyran molecule is explored, with absorbance and fluorescence emission characterization. This first generation sensor provides an insight into fluorescence-enhancement of spiropyran molecules.

Investigating the features in differential absorbance spectra of NOM associated with metal ion binding: A comparison of experimental data and TD-DFT calculations for model compounds.

PubMed

Yan, Mingquan; Han, Xuze; Zhang, Chenyang

2017-11-01

In this study, seven model compounds containing typical functional groups (phenolic and carboxylic groups) present in nature organic matter (NOM) were used to ascertain the nature of the characteristic bands in differential absorbance spectra (DAS) of NOM that are induced by metal ion binding. Some similarities were found between the DAS of the examined model compounds, caffeic acid, ferulic acid, sinapic acid, terephthalic acid, isophthalic acid, esculetin and myricetin and those of NOM. The binding of Cu(II) with carboxylic group might produce two peaks, A1 and A2, while the binding of Cu(II) with phenolic group might produce all four Gaussian peaks, from A1 to A4 displayed in the DAS of NOM. The UV-visible spectra predicted using time-dependent density functional theory (TD-DFT)-based methods met well with the experimental DAS of model compounds at different stages of Cu(II) binding. It demonstrates that the features in absorbance spectra are chiefly caused by HOMO (Highest Occupied Molecular Orbital) - LUMO (Lowest Unoccupied Molecular Orbital) transitions in the molecule and that the appearance of peaks in DAS reflects the changes of the molecular orbitals around reactive functional groups in a molecule before and after metal ion binding. The basis of the DAS features of NOM that are induced by metal ion binding could be identified primarily by the frontier molecular orbital theory. Copyright © 2017 Elsevier Ltd. All rights reserved.

Study of irradiation damage induced by He2+ ion irradiation in Ni62Ta38 metallic glass and W metal

NASA Astrophysics Data System (ADS)

Zhang, Xiaonan; Mei, Xianxiu; Zhang, Qi; Li, Xiaona; Wang, Yingmin; Wang, Younian

2017-09-01

Metallic glasses are considered to possess good resistant against irradiation due to their inherent structural long-range disorder and a lack of grain boundaries. The He2+ with an energy of 300 keV was used to irradiate Ni62Ta38 binary metallic glass to investigate its resistance against the irradiation, and the irradiated behaviour of the metallic glass was compared with that of W metal. The irradiation fluence range over 2.0 × 1017 ions/cm2-1.6 × 1018 ions/cm2. The TEM results show that nanocrystals of μ-NiTa phase and Ni2Ta phase appeared in Ni62Ta38 metallic glass under the irradiation fluence of 1.6 × 1018 ions/cm2. The SEM results show that the surfaces of Ni62Ta38 metallic glasses maintained flat and smooth, whereas a large area of blisters with peeling formed on the surface of W metal at the irradiation fluence of 1.0 × 1018 ions/cm2. It indicates that the critical irradiation fluence of surface breakage of the Ni62Ta38 metallic glass is higher than that of W metal. After the irradiation, stress was generated in the surface layer of W metal, leading to the increase of the hardness of W metal.

Poultry litter-based activated carbon for removing heavy metal ions in water.

PubMed

Guo, Mingxin; Qiu, Guannan; Song, Weiping

2010-02-01

Utilization of poultry litter as a precursor material to manufacture activated carbon for treating heavy metal-contaminated water is a value-added strategy for recycling the organic waste. Batch adsorption experiments were conducted to investigate kinetics, isotherms, and capacity of poultry litter-based activated carbon for removing heavy metal ions in water. It was revealed that poultry litter-based activated carbon possessed significantly higher adsorption affinity and capacity for heavy metals than commercial activated carbons derived from bituminous coal and coconut shell. Adsorption of metal ions onto poultry litter-based carbon was rapid and followed Sigmoidal Chapman patterns as a function of contact time. Adsorption isotherms could be described by different models such as Langmuir and Freundlich equations, depending on the metal species and the coexistence of other metal ions. Potentially 404 mmol of Cu2+, 945 mmol of Pb2+, 236 mmol of Zn2+, and 250-300 mmol of Cd2+ would be adsorbed per kg of poultry litter-derived activated carbon. Releases of nutrients and metal ions from litter-derived carbon did not pose secondary water contamination risks. The study suggests that poultry litter can be utilized as a precursor material for economically manufacturing granular activated carbon that is to be used in wastewater treatment for removing heavy metals.

A fluorometric paper-based sensor array for the discrimination of heavy-metal ions.

PubMed

Feng, Liang; Li, Hui; Niu, Li-Ya; Guan, Ying-Shi; Duan, Chun-Feng; Guan, Ya-Feng; Tung, Chen-Ho; Yang, Qing-Zheng

2013-04-15

A fluorometric paper-based sensor array has been developed for the sensitive and convenient determination of seven heavy-metal ions at their wastewater discharge standard concentrations. Combining with nine cross-reactive BODIPY fluorescent indicators and array technologies-based pattern-recognition, we have obtained the discrimination capability of seven different heavy-metal ions at their wastewater discharge standard concentrations. After the immobilization of indicators and the enrichment of analytes, identification of the heavy-metal ions was readily acquired using a standard chemometric approach. Clear differentiation among heavy-metal ions as a function of concentration was also achieved, even down to 10(-7)M. A semi-quantitative estimation of the heavy-metal ion concentration was obtained by comparing color changes with a set of known concentrations. The sensor array was tentatively investigated in spiked tap water and sea water, and showed possible feasibility for real sample testing. Copyright © 2013 Elsevier B.V. All rights reserved.

Role of Metal Ions on the Activity of Mycobacterium tuberculosis Pyrazinamidase

PubMed Central

Sheen, Patricia; Ferrer, Patricia; Gilman, Robert H.; Christiansen, Gina; Moreno-Román, Paola; Gutiérrez, Andrés H.; Sotelo, Jun; Evangelista, Wilfredo; Fuentes, Patricia; Rueda, Daniel; Flores, Myra; Olivera, Paula; Solis, José; Pesaresi, Alessandro; Lamba, Doriano; Zimic, Mirko

2012-01-01

Pyrazinamidase of Mycobacterium tuberculosis catalyzes the conversion of pyrazinamide to the active molecule pyrazinoic acid. Reduction of pyrazinamidase activity results in a level of pyrazinamide resistance. Previous studies have suggested that pyrazinamidase has a metal-binding site and that a divalent metal cofactor is required for activity. To determine the effect of divalent metals on the pyrazinamidase, the recombinant wild-type pyrazinamidase corresponding to the H37Rv pyrazinamide-susceptible reference strain was expressed in Escherichia coli with and without a carboxy terminal. His-tagged pyrazinamidase was inactivated by metal depletion and reactivated by titration with divalent metals. Although Co2+, Mn2+, and Zn2+ restored pyrazinamidase activity, only Co2+ enhanced the enzymatic activity to levels higher than the wild-type pyrazinamidase. Cu2+, Fe2+, Fe3+, and Mg2+ did not restore the activity under the conditions tested. Various recombinant mutated pyrazinamidases with appropriate folding but different enzymatic activities showed a differential pattern of recovered activity. X-ray fluorescence and atomic absorbance spectroscopy showed that recombinant wild-type pyrazinamidase expressed in E. coli most likely contained Zn. In conclusion, this study suggests that M. tuberculosis pyrazinamidase is a metalloenzyme that is able to coordinate several ions, but in vivo, it is more likely to coordinate Zn2+. However, in vitro, the metal-depleted enzyme could be reactivated by several divalent metals with higher efficiency than Zn. PMID:22764307

Triboelectrification-Enabled Self-Powered Detection and Removal of Heavy Metal Ions in Wastewater.

PubMed

Li, Zhaoling; Chen, Jun; Guo, Hengyu; Fan, Xing; Wen, Zhen; Yeh, Min-Hsin; Yu, Chongwen; Cao, Xia; Wang, Zhong Lin

2016-04-20

A fundamentally new working principle into the field of self-powered heavy-metal-ion detection and removal using the triboelectrification effect is introduced. The as-developed tribo-nanosensors can selectively detect common heavy metal ions. The water-driven triboelectric nanogenerator is taken as a sustainable power source for heavy-metal-ion removal by recycling the kinetic energy from flowing wastewater. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper Metal-Organic Framework Nanoparticles Stabilized with Folic Acid Improve Wound Healing in Diabetes.

PubMed

Xiao, Jisheng; Zhu, Yunxiao; Huddleston, Samantha; Li, Peng; Xiao, Baixue; Farha, Omar K; Ameer, Guillermo A

2018-02-27

The successful treatment of chronic nonhealing wounds requires strategies that promote angiogenesis, collagen deposition, and re-epithelialization of the wound. Copper ions have been reported to stimulate angiogenesis; however, several applications of copper salts or oxides to the wound bed are required, leading to variable outcomes and raising toxicity concerns. We hypothesized that copper-based metal-organic framework nanoparticles (Cu-MOF NPs), referred to as HKUST-1, which are rapidly degraded in protein solutions, can be modified to slowly release Cu 2+ , resulting in reduced toxicity and improved wound healing rates. Folic acid was added during HKUST-1 synthesis to generate folic-acid-modified HKUST-1 (F-HKUST-1). The effect of folic acid incorporation on NP stability, size, hydrophobicity, surface area, and copper ion release profile was measured. In addition, cytotoxicity and in vitro cell migration processes due to F-HKUST-1 and HKUST-1 were evaluated. Wound closure rates were assessed using the splinted excisional dermal wound model in diabetic mice. The incorporation of folic acid into HKUST-1 enabled the slow release of copper ions, which reduced cytotoxicity and enhanced cell migration in vitro. In vivo, F-HKUST-1 induced angiogenesis, promoted collagen deposition and re-epithelialization, and increased wound closure rates. These results demonstrate that folic acid incorporation into HKUST-1 NPs is a simple, safe, and promising approach to control Cu 2+ release, thus enabling the direct application of Cu-MOF NPs to wounds.

Sorption of heavy metal ions by the nonliving biomass of freshwater macrophytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schneider, I.A.H.; Rubio, J.

1999-07-01

The removal of heavy metal ions by the nonliving biomass of aquatic macrophytes was investigated. The work involved studies of physical and biochemical properties of the materials, batch sorption experiments carried out in agitation flasks, and continuous runs in a packed bed column at laboratory scale. Results showed that the dried biomass of Potamogeton lucens, Salvinia herzogii, and Eichhornia crassipes were excellent biosorbents for Cr(III), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II). The sorption mechanism by these biomaterials was found to proceed mainly by ion exchange reactions between the metal ions and the cationic weak exchanger groups present on the plantmore » surface. Sorption followed the Langmuir isotherm, and maximum metal uptakes values (independent of the metal ion species) were attained at about 1.5 mequiv g{sup {minus}1} for P. lucens, 0.9 mequiv g{sup {minus}1} for S. herzogii, and 0.7 mequiv g{sup {minus}1} for E. crassipes. Advantages and disadvantages found in the use of these natural adsorbents for heavy metals ions present in industrial wastewaters are envisaged.« less

Heavy metal-binding proteins from metal-stimulated bacteria as a novel adsorbent for metal removal technology.

PubMed

Sano, D; Myojo, K; Omura, T

2006-01-01

Water pollution with toxic heavy metals is of growing concern because heavy metals could bring about serious problems for not only ecosystems in the water environment but also human health. Some metal removal technologies have been in practical use, but much energy and troublesome treatments for chemical wastes are required to operate these conventional technologies. In this study, heavy metal-binding proteins (HMBPs) were obtained from metal-stimulated activated sludge culture with affinity chromatography using copper ion as a ligand. Two-dimensional electrophoresis revealed that a number of proteins in activated sludge culture were recovered as HMBPs for copper ion. N-termini of five HMBPs were determined, and two of them were found to be newly discovered proteins for which no amino acid sequences in protein databases were retrieved at more than 80% identities. Metal-coordinating amino acids occupied 38% of residues in one of the N-terminal sequences of the newly discovered HMBPs. Since these HMBPs were expected to be stable under conditions of water and wastewater treatments, it would be possible to utilize HMBPs as novel adsorbents for heavy metal removal if mass volume of HMBPs can be obtained with protein cloning techniques.

Measuring free metal ion concentrations in situ in natural waters using the Donnan Membrane Technique.

PubMed

Kalis, Erwin J J; Weng, Liping; Dousma, Freerk; Temminghoff, Erwin J M; Van Riemsdijk, Willem H

2006-02-01

Metal toxicity is not related to the total but rather to the free or labile metal ion concentration. One of the techniques that can be used to measure several free metal ion concentrations simultaneously is the Donnan Membrane Technique (DMT) in combination with the inductively coupled plasma-mass spectrometer (ICP-MS). However, free metal ion concentrations in natural waters are commonly below the detection limit of ICP-MS. We decreased the detection limit by making use of a ligand, and we developed a field DMT cell that can be applied in situ in natural waters. A kinetic approach can be used to calculate free metal ion concentrations when the equilibrium time becomes too large. The field DMT measured in situ in natural waters a free metal ion concentration ranging from 0.015% (Cu) to 13% (Zn) of a total metal concentration ranging from 0.06 nM (Cd) to 237 nM (Zn). The free metal ion concentrations were difficult to predict using an equilibrium speciation model, probably due to the uncertainty in the nature of the dissolved organic matter or the presence of other reactive colloids. It is shown that DMT can follow changes in the free metal ion concentration on times scales less than a day under certain conditions.

Barcoded materials based on photoluminescent hybrid system of lanthanide ions-doped metal organic framework and silica via ion exchange.

PubMed

Shen, Xiang; Yan, Bing

2016-04-15

A multicolored photoluminescent hybrid system based on lanthanide ions-doped metal organic frameworks/silica composite host has potential in display and barcode applications. By controlling the stoichiometry of the lanthanides via cation exchange, proportional various lanthanide ions are successfully introduced into metal organic frameworks, whose emission intensity is correspondingly proportional to its amount. The resulting luminescent barcodes depend on the lanthanide ions ratios and compositions. Subsequently, the lanthanide ions located in the channels of metal organic frameworks are protected from any interaction with the environment after the modification of silica on the surface. The optical and thermal stability of the hybrid materials are improved for technological application. Copyright © 2016 Elsevier Inc. All rights reserved.

Functional nucleic acids as in vivo metabolite and ion biosensors.

PubMed

Alsaafin, Alaa; McKeague, Maureen

2017-08-15

Characterizing the role of metabolites, metals, and proteins is required to understand normal cell function, and ultimately, elucidate the mechanism of disease. Metabolite concentration and transformation results collected from cell lysates or fixed-cells conceal important dynamic information and differences between individual cells that often have profound functional consequences. Functional nucleic acid-based biosensors are emerging tools that are capable of monitoring ions and metabolites in cell populations or whole animals. Functional nucleic acids (FNAs) are a class of biomolecules that can exhibit either ligand binding or enzymatic activity. Unlike their protein analogues or the use of instrument-based analysis, FNA-based biosensors are capable of entering cells without disruption to the cellular environment and can report on the concentration, dynamics, and spatial localization of molecules in cells. Here, we review the types of FNAs that have been used as in vivo biosensors, and how FNAs can be coupled to transduction systems and delivered inside cells. We also provide examples from the literature that demonstrate their impact in practical applications. Finally, we comment on the critical limitations that need to be addressed to enable their use for single-cell dynamic tracking of metabolites and ions in vivo. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

Flame-ion chemistry of the lanthanide metals Ce, Pr and Nd

NASA Astrophysics Data System (ADS)

Patterson, Patricia M.; Goodings, John M.

1996-01-01

A pair of premixed, H2---O2---Ar flames of fuel-rich (FR) and fuel-lean (FL) composition, both at atmospheric pressure and 2425 K, were doped with about 10-6 mol fraction of the lanthanide metals La, Ce, Pr and Nd; from a previous study, La was used as a benchmark. The metals produce solid particles in the flames and gaseous metallic species. The latter include metallic atoms A near the flame reaction zone, but only the monoxide AO, the oxide hydroxide OAOH and, in some cases, the dioxide AO2 further downstream at equilibrium. Metallic ions (< 1% of the total metal) were observed by sampling the flames through a nozzle into a mass spectrometer. All of the observed ions can be represented by four hydrate series: (a) major signals of AO+·nH2O (n = 0-3) for La, Ce, Pr and Nd; (b) small signals of AO2H+·nH2O (n = 0-2) for Ce, Pr and Nd; (c) still smaller signals of AO2+·nH2O (n = 0, 1) for Ce, Pr and Nd in the FL flame only; and (d) tiny signals of AOH+·nH2O (n = 0, 1) for Pr and Nd in the FR flame only. The actual structures of some of these ions may not correspond to simple hydrates: e.g. AO+·H2O = A(OH)2+ = protonated OAOH; AO2H+·H2O = A(OH)3+, etc. Since hydrogen flames contain essentially no natural ionization, a major objective was to consider probable ionization mechanisms for the metals. The primary reactions include both chemi-ionization, and thermal (collisional) ionization of AO whose ionization energy is low (about 5 eV). Some of the ions are formed by secondary ion/molecule reactions including three-body hydration, proton transfer, electron (charge) transfer, H atom abstraction by radicals and oxidation. In addition, the chemical ionization of the metallic species by H3O+ was investigated. The flame-ion chemistry of these metals is discussed in detail.

Metal resistance sequences and transgenic plants

DOEpatents

Meagher, Richard Brian; Summers, Anne O.; Rugh, Clayton L.

1999-10-12

The present invention provides nucleic acid sequences encoding a metal ion resistance protein, which are expressible in plant cells. The metal resistance protein provides for the enzymatic reduction of metal ions including but not limited to divalent Cu, divalent mercury, trivalent gold, divalent cadmium, lead ions and monovalent silver ions. Transgenic plants which express these coding sequences exhibit increased resistance to metal ions in the environment as compared with plants which have not been so genetically modified. Transgenic plants with improved resistance to organometals including alkylmercury compounds, among others, are provided by the further inclusion of plant-expressible organometal lyase coding sequences, as specifically exemplified by the plant-expressible merB coding sequence. Furthermore, these transgenic plants which have been genetically modified to express the metal resistance coding sequences of the present invention can participate in the bioremediation of metal contamination via the enzymatic reduction of metal ions. Transgenic plants resistant to organometals can further mediate remediation of organic metal compounds, for example, alkylmetal compounds including but not limited to methyl mercury, methyl lead compounds, methyl cadmium and methyl arsenic compounds, in the environment by causing the freeing of mercuric or other metal ions and the reduction of the ionic mercury or other metal ions to the less toxic elemental mercury or other metals.

ETMB-RBF: discrimination of metal-binding sites in electron transporters based on RBF networks with PSSM profiles and significant amino acid pairs.

PubMed

Ou, Yu-Yen; Chen, Shu-An; Wu, Sheng-Cheng

2013-01-01

Cellular respiration is the process by which cells obtain energy from glucose and is a very important biological process in living cell. As cells do cellular respiration, they need a pathway to store and transport electrons, the electron transport chain. The function of the electron transport chain is to produce a trans-membrane proton electrochemical gradient as a result of oxidation-reduction reactions. In these oxidation-reduction reactions in electron transport chains, metal ions play very important role as electron donor and acceptor. For example, Fe ions are in complex I and complex II, and Cu ions are in complex IV. Therefore, to identify metal-binding sites in electron transporters is an important issue in helping biologists better understand the workings of the electron transport chain. We propose a method based on Position Specific Scoring Matrix (PSSM) profiles and significant amino acid pairs to identify metal-binding residues in electron transport proteins. We have selected a non-redundant set of 55 metal-binding electron transport proteins as our dataset. The proposed method can predict metal-binding sites in electron transport proteins with an average 10-fold cross-validation accuracy of 93.2% and 93.1% for metal-binding cysteine and histidine, respectively. Compared with the general metal-binding predictor from A. Passerini et al., the proposed method can improve over 9% of sensitivity, and 14% specificity on the independent dataset in identifying metal-binding cysteines. The proposed method can also improve almost 76% sensitivity with same specificity in metal-binding histidine, and MCC is also improved from 0.28 to 0.88. We have developed a novel approach based on PSSM profiles and significant amino acid pairs for identifying metal-binding sites from electron transport proteins. The proposed approach achieved a significant improvement with independent test set of metal-binding electron transport proteins.

ETMB-RBF: Discrimination of Metal-Binding Sites in Electron Transporters Based on RBF Networks with PSSM Profiles and Significant Amino Acid Pairs

PubMed Central

Ou, Yu-Yen; Chen, Shu-An; Wu, Sheng-Cheng

2013-01-01

Background Cellular respiration is the process by which cells obtain energy from glucose and is a very important biological process in living cell. As cells do cellular respiration, they need a pathway to store and transport electrons, the electron transport chain. The function of the electron transport chain is to produce a trans-membrane proton electrochemical gradient as a result of oxidation–reduction reactions. In these oxidation–reduction reactions in electron transport chains, metal ions play very important role as electron donor and acceptor. For example, Fe ions are in complex I and complex II, and Cu ions are in complex IV. Therefore, to identify metal-binding sites in electron transporters is an important issue in helping biologists better understand the workings of the electron transport chain. Methods We propose a method based on Position Specific Scoring Matrix (PSSM) profiles and significant amino acid pairs to identify metal-binding residues in electron transport proteins. Results We have selected a non-redundant set of 55 metal-binding electron transport proteins as our dataset. The proposed method can predict metal-binding sites in electron transport proteins with an average 10-fold cross-validation accuracy of 93.2% and 93.1% for metal-binding cysteine and histidine, respectively. Compared with the general metal-binding predictor from A. Passerini et al., the proposed method can improve over 9% of sensitivity, and 14% specificity on the independent dataset in identifying metal-binding cysteines. The proposed method can also improve almost 76% sensitivity with same specificity in metal-binding histidine, and MCC is also improved from 0.28 to 0.88. Conclusions We have developed a novel approach based on PSSM profiles and significant amino acid pairs for identifying metal-binding sites from electron transport proteins. The proposed approach achieved a significant improvement with independent test set of metal-binding electron transport proteins

Removal of heavy metals from acid mine drainage using chicken eggshells in column mode.

PubMed

Zhang, Ting; Tu, Zhihong; Lu, Guining; Duan, Xingchun; Yi, Xiaoyun; Guo, Chuling; Dang, Zhi

2017-03-01

Chicken eggshells (ES) as alkaline sorbent were immobilized in a fixed bed to remove typical heavy metals from acid mine drainage (AMD). The obtained breakthrough curves showed that the breakthrough time increased with increasing bed height, but decreased with increasing flow rate and increasing particle size. The Thomas model and bed depth service time model could accurately predict the bed dynamic behavior. At a bed height of 10 cm, a flow rate of 10 mL/min, and with ES particle sizes of 0.18-0.425 mm, for a multi-component heavy metal solution containing Cd 2+ , Pb 2+ and Cu 2+ , the ES capacities were found to be 1.57, 146.44 and 387.51 mg/g, respectively. The acidity of AMD effluent clearly decreased. The ES fixed-bed showed the highest removal efficiency for Pb with a better adsorption potential. Because of the high concentration in AMD and high removal efficiency in ES fixed-bed of iron ions, iron floccules (Fe 2 (OH) 2 CO 3 ) formed and obstructed the bed to develop the overall effectiveness. The removal process was dominated by precipitation under the alkaline reaction of ES, and the co-precipitation of heavy metals with iron ions. The findings of this work will aid in guiding and optimizing pilot-scale application of ES to AMD treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Further insights into the metal ion binding abilities and the metalation pathway of a plant metallothionein from Musa acuminata

PubMed Central

Cabral, Augusto C. S.; Jakovleska, Jovana; Deb, Aniruddha; Penner-Hahn, James E.; Pecoraro, Vincent L.

2017-01-01

The superfamily of metallothioneins (MTs) combines a diverse group of metalloproteins, sharing the characteristics of rather low molecular weight and high cysteine content. The latter provides MTs with the capability to coordinate thiophilic metal ions, in particular those with a d10 electron configuration. The sub-family of plant MT3 proteins is only poorly characterized and there is a complete lack of three-dimensional structure information. Building upon our previous results on the Musa acuminata MT3 (musMT3) protein, the focus of the present work is to understand the metal cluster formation process, the role of the single histidine residue present in musMT3, and the metal ion binding affinity. We concentrate our efforts on the coordination of ZnII and CdII ions, using CoII as a spectroscopic probe for ZnII binding. The overall protein-fold is analysed with a combination of limited proteolytic digestion, mass spectrometry, and dynamic light scattering. Histidine coordination of metal ions is probed with extended X-ray absorption fine structure spectroscopy and CoII titration experiments. Initial experiments with isothermal titration calorimetry provide insights into the thermodynamics of metal ion binding. PMID:29218632

Highly Acidic Ambient Particles, Soluble Metals, and Oxidative Potential: A Link between Sulfate and Aerosol Toxicity.

PubMed

Fang, Ting; Guo, Hongyu; Zeng, Linghan; Verma, Vishal; Nenes, Athanasios; Weber, Rodney J

2017-03-07

Soluble transition metals in particulate matter (PM) can generate reactive oxygen species in vivo by redox cycling, leading to oxidative stress and adverse health effects. Most metals, such as those from roadway traffic, are emitted in an insoluble form, but must be soluble for redox cycling. Here we present the mechanism of metals dissolution by highly acidic sulfate aerosol and the effect on particle oxidative potential (OP) through analysis of size distributions. Size-segregated ambient PM were collected from a road-side and representative urban site in Atlanta, GA. Elemental and organic carbon, ions, total and water-soluble metals, and water-soluble OP were measured. Particle pH was determined with a thermodynamic model using measured ionic species. Sulfate was spatially uniform and found mainly in the fine mode, whereas total metals and mineral dust cations were highest at the road-side site and in the coarse mode, resulting in a fine mode pH < 2 and near neutral coarse mode. Soluble metals and OP peaked at the intersection of these modes demonstrating that sulfate plays a key role in producing highly acidic fine aerosols capable of dissolving primary transition metals that contribute to aerosol OP. Sulfate-driven metals dissolution may account for sulfate-health associations reported in past studies.

Modeling the adsorption of metal ions (Cu 2+, Ni 2+, Pb 2+) onto ACCs using surface complexation models

NASA Astrophysics Data System (ADS)

Faur-Brasquet, Catherine; Reddad, Zacaria; Kadirvelu, Krishna; Le Cloirec, Pierre

2002-08-01

Activated carbon cloths (ACCs), whose efficiency has been demonstrated for microorganics adsorption from water, were here studied in the removal of metal ions from aqueous solution. Two ACCs are investigated, they are characterized in terms of porosity parameters (BET specific surface area, percentage of microporosity) and chemical characteristics (acidic surface groups, acidity constants, point of zero charge). A first part consists in the experimental study of three metal ions removal (Cu 2+, Ni 2+ and Pb 2+) in a batch reactor. Isotherms modeling by Freundlich and Brunauer-Emmett-Teller (BET) equations enables the following adsorption order: Cu 2+>Ni 2+>Pb 2+ to be determined for adsorption capacities on a molar basis. It may be related to adsorbates characteristics in terms of electronegativity and ionic radius. The influence of adsorbent's microporosity is also shown. Adsorption experiments carried out for pH values ranging from 2 to 10 demonstrate: (i) an adsorption occurring below the precipitation pH; (ii) the strong influence of pH, with a decrease of electrostatic repulsion due to the formation of less charged hydrolyzed species coupled with a decrease of activated carbon surface charge as pH increases. The second part focuses on the modeling of adsorption versus the pH experimental data by the diffuse layer model (DLM) using Fiteql software. The model is efficient to describe the system behavior in the pH range considered. Regarding complexation constants, they show the following affinity for ACC: Pb 2+>Cu 2+>Ni 2+. They are related to initial concentrations used for the three metal ions.

BODIPY-based fluorometric sensor array for the highly sensitive identification of heavy-metal ions.

PubMed

Niu, Li-Ya; Li, Hui; Feng, Liang; Guan, Ying-Shi; Chen, Yu-Zhe; Duan, Chun-Feng; Wu, Li-Zhu; Guan, Ya-Feng; Tung, Chen-Ho; Yang, Qing-Zheng

2013-05-02

A BODIPY(4,4-difluoro-4-bora-3a,4a-diaza-s-indacene)-based fluorometric sensor array has been developed for the highly sensitive detection of eight heavy-metal ions at micromolar concentration. The di-2-picolyamine (DPA) derivatives combine high affinities for a variety of heavy-metal ions with the capacity to perturb the fluorescence properties of BODIPY, making them perfectly suitable for the design of fluorometric sensor arrays for heavy-metal ions. 12 cross-reactive BODIPY fluorescent indicators provide facile identification of the heavy-metal ions using a standard chemometric approach (hierarchical clustering analysis); no misclassifications were found over 45 trials. Clear differentiation among heavy-metal ions as a function of concentration was also achieved, even down to 10(-7)M. A semi-quantitative interpolation of the heavy-metal concentration is obtained by comparing the total Euclidean distance of the measurement with a set of known concentrations in the library. Copyright © 2013 Elsevier B.V. All rights reserved.

Characterization of Lactobacillus brevis L62 strain, highly tolerant to copper ions.

PubMed

Mrvčić, Jasna; Butorac, Ana; Solić, Ema; Stanzer, Damir; Bačun-Družina, Višnja; Cindrić, Mario; Stehlik-Tomas, Vesna

2013-01-01

Lactic acid bacteria (LAB) as starter culture in food industry must be suitable for large-scale industrial production and possess the ability to survive in unfavorable processes and storage conditions. Approaches taken to address these problems include the selection of stress-resistant strains. In food industry, LAB are often exposed to metal ions induced stress. The interactions between LAB and metal ions are very poorly investigated. Because of that, the influence of non-toxic, toxic and antioxidant metal ions (Zn, Cu, and Mn) on growth, acid production, metal ions binding capacity of wild and adapted species of Leuconostoc mesenteroides L3, Lactobacillus brevis L62 and Lactobacillus plantarum L73 were investigated. The proteomic approach was applied to clarify how the LAB cells, especially the adapted ones, protect themselves and tolerate high concentrations of toxic metal ions. Results have shown that Zn and Mn addition into MRS medium in the investigated concentrations did not have effect on the bacterial growth and acid production, while copper ions were highly toxic, especially in static conditions. Leuc. mesenteroides L3 was the most efficient in Zn binding processes among the chosen LAB species, while L. plantarum L73 accumulated the highest concentration of Mn. L. brevis L62 was the most copper resistant species. Adaptation had a positive effect on growth and acid production of all species in the presence of copper. However, the adapted species incorporated less metal ions than the wild species. The exception was adapted L. brevis L62 that accumulated high concentration of copper ions in static conditions. The obtained results showed that L. brevis L62 is highly tolerant to copper ions, which allows its use as starter culture in fermentative processes in media with high concentration of copper ions.

Liquid metal ion source and alloy for ion emission of multiple ionic species

DOEpatents

Clark, Jr., William M.; Utlaut, Mark W.; Wysocki, Joseph A.; Storms, Edmund K.; Szklarz, Eugene G.; Behrens, Robert G.; Swanson, Lynwood W.; Bell, Anthony E.

1987-06-02

A liquid metal ion source and alloy for the simultaneous ion evaporation of arsenic and boron, arsenic and phosphorus, or arsenic, boron and phosphorus. The ionic species to be evaporated are contained in palladium-arsenic-boron and palladium-arsenic-boron-phosphorus alloys. The ion source, including an emitter means such as a needle emitter and a source means such as U-shaped heater element, is preferably constructed of rhenium and tungsten, both of which are readily fabricated. The ion sources emit continuous beams of ions having sufficiently high currents of the desired species to be useful in ion implantation of semiconductor wafers for preparing integrated circuit devices. The sources are stable in operation, experience little corrosion during operation, and have long operating lifetimes.

Metal ion reactive thin films using spray electrostatic LbL assembly.

PubMed

Krogman, Kevin C; Lyon, Katharine F; Hammond, Paula T

2008-11-20

By using the spray-layer-by-layer (Spray-LbL) technique, the number of metal counterions trapped within LbL coatings is significantly increased by kinetically freezing the film short of equilibrium, potentially limiting interchain penetration and forcing chains to remain extrinsically compensated to a much greater degree than observed in the traditional dipped LbL technique. The basis for the enhanced entrapment of metal ions such as Cu2+, Fe2+, and Ag+ is addressed, including the equilibrium driving force for extrinsic compensation by soft versus hard metal ions and the impact of Spray-LbL on the kinetics of polymer-ion complexation. These polymer-bound metal-ion coatings are also demonstrated to be effective treatments for air filtration, functionalizing existing filters with the ability to strongly bind toxic industrial compounds such as ammonia or cyanide gases, as well as chemical warfare agent simulants such as chloroethyl ethyl sulfide. On the basis of results reported here, future work could extend this method to include other toxic soft-base ligands such as carbon monoxide, benzene, or organophosphate nerve agents.

Analytical strategies based on quantum dots for heavy metal ions detection.

PubMed

Vázquez-González, Margarita; Carrillo-Carrion, Carolina

2014-01-01

Heavy metal contamination is one of the major concerns to human health because these substances are toxic and retained by the ecological system. Therefore, in recent years, there has been a pressing need for fast and reliable methods for the analysis of heavy metal ions in environmental and biological samples. Quantum dots (QDs) have facilitated the development of sensitive sensors over the past decade, due to their unique photophysical properties, versatile surface chemistry and ligand binding ability, and the possibility of the encapsulation in different materials or attachment to different functional materials, while retaining their native luminescence property. This paper comments on different sensing strategies with QD for the most toxic heavy metal ions (i.e., cadmium, Cd2+; mercury, Hg2+; and lead, Pb2+). Finally, the challenges and outlook for the QD-based sensors for heavy metals ions are discussed.

Combining the Power of Irmpd with Ion-Molecule Reactions: the Structure and Reactivity of Radical Ions of Cysteine and its Derivatives

NASA Astrophysics Data System (ADS)

Lesslie, Michael; Osburn, Sandra; Berden, Giel; Oomens, J.; Ryzhov, Victor

2015-06-01

Most of the work on peptide radical cations has involved protons as the source of charge. Nonetheless, using metal ions as charge sources often offers advantages like stabilization of the structure via multidentate coordination and the elimination of the "mobile proton". Moreover, characterization of metal-bound amino acids is of general interest as the interaction of peptide side chains with metal ions in biological systems is known to occur extensively. In the current study, we generate thiyl radicals of cysteine and homocysteine in the gas phase complexed to alkali metal ions. Subsequently, we utilize infrared multiple-photon dissociation (IRMPD) and ion-molecule reactions (IMR) to characterize the structure and reactivity of these radical ions. Our group has worked extensively with the cysteine-based radical cations and anions, characterizing the gas-phase reactivity and rearrangement of the amino acid and several of its derivatives. In a continuation of this work, we are perusing the effects of metal ions as the charge bearing species on the reactivity of the sulfur radical. Our S-nitroso chemistry can easily be used in conjunction with metal ion coordination to produce initial S-based radicals in peptide radical-metal ion complexes. In all cases we have been able to achieve radical formation with significant yield to study reactivity. Ion-molecule reactions of metallated radicals with allyl iodide, dimethyl disulfide, and allyl bromide have all shown decreasing reactivity going down group 1A. Recently, we determined the experimental IR spectra for the homocysteine radical cation with Li+, Na+, and K+ as the charge bearing species at the FELIX facility. For comparison, the protonated IR spectrum of homocysteine has previously been obtained by our group. A preliminary match of the IR spectra has been confirmed. Finally, calculations are underway to determine the bond distances of all the metal adduct structures.

Ultrahigh-current-density metal-ion implantation and diamondlike-hydrocarbon films for tribological applications

NASA Astrophysics Data System (ADS)

Wilbur, P. J.

1993-09-01

The metal-ion-implantation system used to implant metals into substrates are described. The metal vapor required for operation is supplied by drawing sufficient electron current from the plasma discharge to an anode-potential crucible so a solid, pure metal placed in the crucible will be heated to the point of vaporization. The ion-producing, plasma discharge is initiated within a graphite-ion-source body, which operates at high temperature, by using an argon flow that is turned off once the metal vapor is present. Extraction of ion beams several cm in diameter at current densities ranging to several hundred micro-A/sq cm on a target 50 cm downstream of the ion source were demonstrated using Mg, Ag, Cr, Cu, Si, Ti, V, B, and Zr. These metals were implanted into over 100 substrates (discs, pins, flats, wires). A model describing thermal stresses induced in materials (e.g. ceramic plates) during high-current-density implantation is presented. Tribological and microstructural characteristics of iron and 304-stainless-steel samples implanted with Ti or B are examined. Diamondlike-hydrocarbon coatings were applied to steel surfaces and found to exhibit good tribological performance.