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Sample records for additional metal ions

  1. Low coefficient of thermal expansion polyimides containing metal ion additives

    SciTech Connect

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

    1992-07-01

    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 CTE's of conventional polyimides range from 30 to 60 ppm/C. Approaches that have been reported to lower their CTE's include linearizing the polymer molecular structure and orienting the polyimide film. This current study involves the incorporation of metal ion-containing additives into polyimides and has resulted in significantly lowered CTE's. 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% to over 100% depending on the choice of additive and its concentration.

  2. 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.

  3. Metal-Ion Additives Reduce Thermal Expansion Of Polyimides

    NASA Technical Reports Server (NTRS)

    Stoakley, Diane M.; St. Clair, Anne K.; Emerson, Burt R., Jr.; Willis, George L.

    1994-01-01

    Polyimides widely used as high-performance polymers because of their excellent thermal stability and toughness. However, their coefficients of thermal expansion (CTE's) greater than those of metals, ceramics, and glasses. Decreasing CTE's of polyimides increase usefulness for aerospace and electronics applications in which dimensional stability required. Additives containing metal ions reduce coefficients of thermal expansion of polyimides. Reductions range from 11 to over 100 percent.

  4. Metal ion adsorption to complexes of humic acid and metal oxides: Deviations from the additivity rule

    SciTech Connect

    Vermeer, A.W.P.; McCulloch, J.K.; Van Riemsdijk, W.H.; Koopal, L.K.

    1999-11-01

    The adsorption of cadmium ions to a mixture of Aldrich humic acid and hematite is investigated. The actual adsorption to the humic acid-hematite complex is compared with the sum of the cadmium ion adsorptivities to each of the isolated components. It is shown that the sum of the cadmium ion adsorptivities is not equal to the adsorption to the complex. In general, the adsorption of a specific metal ion to the complex can be understood and qualitatively predicted using the adsorptivities to each of the pure components and taking into account the effect of the pH on the interaction between humic acid and iron oxide on the metal ion adsorption. Due to the interaction between the negatively charged humic acid and the positively charged iron oxide, the adsorption of metal ions on the mineral oxide in the complex will increase as compared to that on the isolated oxide, whereas the adsorption to the humic acid will decrease as compared to that on the isolated humic acid. As a result, the overall adsorption of a specific metal ion to the complex will be smaller than predicted by the additivity rule when this metal ion has a more pronounced affinity for the humic acid than for the mineral oxide, whereas it will be larger than predicted by the additivity rule when the metal ion has a higher affinity for the oxide than for the humic acid.

  5. Generation of reactive oxygen species by interaction between antioxidants used as food additive and metal ions.

    PubMed

    Iwasaki, Yusuke; Oda, Momoko; Tsukuda, Yuri; Nagamori, Yuki; Nakazawa, Hiroyuki; Ito, Rie; Saito, Koichi

    2014-01-01

    Food additives, such as preservatives, sweeteners, coloring agents, and flavoring agents, are widely used in food manufacturing. However, their combined effects on the human body are not known. The purpose of this study was to examine whether combinations of antioxidants and metal ions generate reactive oxygen species (ROS) under in vitro conditions using electron spin resonance (ESR). Among the metal ions examined, only iron and copper generated ROS in the presence of antioxidants. Moreover, certain phenolic antioxidants having pro-oxidant activity induced DNA oxidation and degradation via the generation of high levels of ROS in the presence of copper ion, resulting in complete degradation of DNA in vitro. PMID:25212818

  6. Development of high capacity, high rate lithium ion batteries utilizing metal fiber conductive additives

    NASA Astrophysics Data System (ADS)

    Ahn, Soonho; Kim, Youngduk; Kim, Kyung Joon; Kim, Tae Hyung; Lee, Hyungkeun; Kim, Myung H.

    As lithium ion cells dominate the battery market, the performance improvement is an utmost concern among developers and researchers. Conductive additives are routinely employed to enhance electrode conductivity and capacity. Carbon particulates—graphite or carbon black powders—are conventional and popular choices as conductive fillers. However, percolation requirements of particles demand significant volumetric content of impalpable, and thereby high area conductive fillers. As might be expected, the electrode active surface area escalates unnecessarily, resulting in overall increase in reaction with electrolytes and organic solvents. The increased reactions usually manifest as an irreversible loss of anode capacity, gradual oxidation and consumption of electrolyte on the cathode—which causes capacity decline during cycling—and an increased threat to battery safety by gas evolution and exothermic solvent oxidation. In this work we have utilized high aspect ratio, flexible, micronic metal fibers as low active area and high conductivity additives. The metal fibers appear well dispersed within the electrode and to satisfy percolation requirements very efficiently at very low volumetric content compared to conventional carbon-based conductive additives. Results from 18650-type cells indicate significant enhancements in electrode capacity and high rate capability while the irreversible capacity loss is negligible.

  7. Toward improving the graphene-semiconductor composite photoactivity via the addition of metal ions as generic interfacial mediator.

    PubMed

    Zhang, Nan; Yang, Min-Quan; Tang, Zi-Rong; Xu, Yi-Jun

    2014-01-28

    We report a simple and general approach to improve the transfer efficiency of photogenerated charge carriers across the interface between graphene (GR) and semiconductor CdS by introducing a small amount of metal ions (Ca(2+), Cr(3+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+)) as "mediator" into their interfacial layer matrix, while the intimate interfacial contact between GR and CdS is maintained. This simple strategy can not only significantly improve the visible-light-driven photoactivity of GR-CdS semiconductor composites for targeting selective photoredox reaction, including aerobic oxidation of alcohol and anaerobic reduction of nitro compound, but also drive a balance between the positive effect of GR on retarding the recombination of electron-hole pairs photogenerated from semiconductor and the negative "shielding effect" of GR resulting from the high weight addition of GR. Our current work highlights that the significant issue on improving the photoactivity of GR-semiconductor composites via strengthening interfacial contact is not just a simple issue of tighter connection between GR and the semiconductor, but it is also the optimization of the atomic charge carrier transfer pathway across the interface between GR and the semiconductor. PMID:24304042

  8. Photoelectrochemical detection of metal ions.

    PubMed

    Zhao, Wei-Wei; Xu, Jing-Juan; Chen, Hong-Yuan

    2016-07-21

    Depending on the situation, metal ions may either play beneficial roles or be harmful to human health and ecosystems. Sensitive and accurate detection of metal ions is thus a critical issue in the field of analytical sciences and great efforts have been devoted to the development of various metal ion sensors. Photoelectrochemical (PEC) detection is an emerging technique for the bio/chemical detection of metal ions, and features a fast response, low cost and high sensitivity. Using representative examples, this review will first introduce the fundamentals and summarize recent progress in the PEC detection of metal ions. In addition, interesting strategies for the design of particular PEC metal ion sensors are discussed. Challenges and opportunities in this field are also presented. PMID:27297834

  9. Addition of metal ions to a (hemi)cellulolytic enzymatic cocktail produced in-house improves its activity, thermostability, and efficiency in the saccharification of pretreated sugarcane bagasse.

    PubMed

    Vasconcellos, V M; Tardioli, P W; Giordano, R L C; Farinas, C S

    2016-05-25

    High activity and stability are essential for (hemi)cellulolytic enzymes used in biomass conversion, while non-productive binding of cellulases to lignin reduces saccharification efficiency and needs to be avoided. One potential strategy is the addition of inexpensive metal ions. This paper describes the influence of divalent metal ions on the activity, thermostability, and saccharification efficiency of (hemi)cellulolytic enzymes produced in-house by Aspergillus niger under solid-state fermentation (SSF). The use of Mn(2+) provided the best (hemi)cellulolytic activity and stability, with an increase in endoglucanase activity of up to 57%. The use of Mn(2+) was then investigated in the saccharification of sugarcane bagasse submitted to acid, steam-explosion, and hydrothermal pretreatments. The addition of Mn(2+) ions at 10mM in the saccharification of acid-pretreated bagasse resulted in a 34% increase in glucose release. These positive effects appeared to be due to a reduction in non-productive enzyme adsorption. The findings suggest that the addition of inexpensive metal ions can help to improve activity, thermostability, and saccharification efficiency of (hemi)cellulolytic enzymes. PMID:26709004

  10. Metal Ion Sources for Ion Beam Implantation

    SciTech Connect

    Zhao, W. J.; Zhao, Z. Q.; Ren, X. T.

    2008-11-03

    In this paper a theme touched upon the progress of metal ion sources devoted to metal ion beam implantation (MIBI) will be reviewed. A special emphasis will be given to some kinds of ion sources such as ECR, MEVVA and Cluster ion sources. A novel dual hollow cathode metal ion source named DUHOCAMIS will be introduced and discussed.

  11. Metal Ions in Unusual Valency States.

    ERIC Educational Resources Information Center

    Sellers, Robin M.

    1981-01-01

    Discusses reactivity of metal ions with the primary products of water radiolysis, hyper-reduced metal ions, zero-valent metal ions, unstable divalent ions from the reduction of bivalent ions, hyper-oxidized metal ions, and metal complexes. (CS)

  12. Protein-Transition Metal Ion Networks

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Proteins obtained from agricultural sources were blended with divalent metal ions. Feather keratin, egg albumin, and wheat gluten showed increases of 2-3 times in modulus with addition of divalent transition metal ions Cu2+ and Zn2+. Increasing concentrations of ions resulted in increased stiffnes...

  13. Antileishmanial Activity of Disulfiram and Thiuram Disulfide Analogs in an Ex Vivo Model System Is Selectively Enhanced by the Addition of Divalent Metal Ions

    PubMed Central

    Peniche, Alex G.; Renslo, Adam R.; Melby, Peter C.

    2015-01-01

    Current treatments for cutaneous and visceral leishmaniasis are toxic, expensive, difficult to administer, and limited in efficacy and availability. Disulfiram has primarily been used to treat alcoholism. More recently, it has shown some efficacy as therapy against protozoan pathogens and certain cancers, suggesting a wide range of biological activities. We used an ex vivo system to screen several thiuram disulfide compounds for antileishmanial activity. We found five compounds (compound identifier [CID] 7188, 5455, 95876, 12892, and 3117 [disulfiram]) with anti-Leishmania activity at nanomolar concentrations. We further evaluated these compounds with the addition of divalent metal salts based on studies that indicated these salts could potentiate the action of disulfiram. In addition, clinical studies suggested that zinc has some efficacy in treating cutaneous leishmaniasis. Several divalent metal salts were evaluated at 1 μM, which is lower than the normal levels of copper and zinc in plasma of healthy individuals. The leishmanicidal activity of disulfiram and CID 7188 were enhanced by several divalent metal salts at 1 μM. The in vitro therapeutic index (IVTI) of disulfiram and CID 7188 increased 12- and 2.3-fold, respectively, against L. major when combined with ZnCl2. The combination of disulfiram with ZnSO4 resulted in a 1.8-fold increase in IVTI against L. donovani. This novel combination of thiuram disulfides and divalent metal ions salts could have application as topical and/or oral therapies for treatment of cutaneous and visceral leishmaniasis. PMID:26239994

  14. Antileishmanial Activity of Disulfiram and Thiuram Disulfide Analogs in an Ex Vivo Model System Is Selectively Enhanced by the Addition of Divalent Metal Ions.

    PubMed

    Peniche, Alex G; Renslo, Adam R; Melby, Peter C; Travi, Bruno L

    2015-10-01

    Current treatments for cutaneous and visceral leishmaniasis are toxic, expensive, difficult to administer, and limited in efficacy and availability. Disulfiram has primarily been used to treat alcoholism. More recently, it has shown some efficacy as therapy against protozoan pathogens and certain cancers, suggesting a wide range of biological activities. We used an ex vivo system to screen several thiuram disulfide compounds for antileishmanial activity. We found five compounds (compound identifier [CID] 7188, 5455, 95876, 12892, and 3117 [disulfiram]) with anti-Leishmania activity at nanomolar concentrations. We further evaluated these compounds with the addition of divalent metal salts based on studies that indicated these salts could potentiate the action of disulfiram. In addition, clinical studies suggested that zinc has some efficacy in treating cutaneous leishmaniasis. Several divalent metal salts were evaluated at 1 μM, which is lower than the normal levels of copper and zinc in plasma of healthy individuals. The leishmanicidal activity of disulfiram and CID 7188 were enhanced by several divalent metal salts at 1 μM. The in vitro therapeutic index (IVTI) of disulfiram and CID 7188 increased 12- and 2.3-fold, respectively, against L. major when combined with ZnCl2. The combination of disulfiram with ZnSO4 resulted in a 1.8-fold increase in IVTI against L. donovani. This novel combination of thiuram disulfides and divalent metal ions salts could have application as topical and/or oral therapies for treatment of cutaneous and visceral leishmaniasis. PMID:26239994

  15. Metal ion-containing epoxies

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

    A variety of metallic and organometallic complexes to be used as potential additives for an epoxy used by the aerospace industry as a composite matrix resin were investigated. A total of 9 complexes were screened for compatibility and for their ability to accelerate or inhibit the cure of a highly crosslinkable epoxy resin. Methods for combining the metallic complexes with the resin were investigated, gel times recorded, and cure exotherms studied by differential scanning calorimetry. Glass transition temperatures of cured metal ion containing epoxy castings were determined by thermomechanical analysis. Thermal stabilities of the castings were determined by thermogravimetric analysis. Mechanical strength and stiffness of these doped epoxies were also measured.

  16. Ion beam modification of metals

    NASA Astrophysics Data System (ADS)

    Dearnaley, G.

    1990-04-01

    Energetic ions beams may be used in various ways to modify and so improve the tribological properties of metals. These methods include: — ion implantation of selected additive species; — ion beam mixing of thin deposited coatings; — ion-beam-assisted deposition of thicker overlay coatings. The first of these techniques has been widely used to modify the electronic properties of semiconductors, but has since been extended for the treatment of all classes of material. Tool steels can be strengthened by the ion implantation of nitrogen or titanium, to produce fine dispersions of hard second-phase precipitates. Solid solution strengthening, by combinations of substitutional and interstitial species, such as yttrium and nitrogen, has also been successful. Both ion beam mixing (IBM) and ion-beam-assisted deposition (IBAD) use a combination of coating and ion bombardment. In the first case, the objective is to intermix the coating and substrate by the aid of radiation-enhanced diffusion. In the latter case, the coating is densified and modified during deposition and the process can be continued in order to build up overlay coatings several μm in thickness. The surface can then be tailored, for instance to provide a hard and adherent ceramic such as silicon nitride, boron nitride or titanium nitride. It is an advantage that all the above processes can be applied at relatively low temperatures, below about 200° C, thereby avoiding distortion of precision components. Ion implantation is also being successfully applied for the reduction of corrosion, especially at high temperatures or in the atmosphere and to explore the mechanisms of oxidation. Ion-assisted coatings, being compact and adherent, provide a more substantial protection against corrosion: silicon nitride and boron nitride are potentially useful in this respect. Examples will be given of the successful application of these methods for the surface modification of metals and alloys, and developments in the

  17. Metal Additive Manufacturing: A Review

    NASA Astrophysics Data System (ADS)

    Frazier, William E.

    2014-06-01

    This paper reviews the state-of-the-art of an important, rapidly emerging, manufacturing technology that is alternatively called additive manufacturing (AM), direct digital manufacturing, free form fabrication, or 3D printing, etc. A broad contextual overview of metallic AM is provided. AM has the potential to revolutionize the global parts manufacturing and logistics landscape. It enables distributed manufacturing and the productions of parts-on-demand while offering the potential to reduce cost, energy consumption, and carbon footprint. This paper explores the material science, processes, and business consideration associated with achieving these performance gains. It is concluded that a paradigm shift is required in order to fully exploit AM potential.

  18. The relaxation of intrinsic compressive stress in complementary metal-oxide-semiconductor transistors by additional N ion implantation treatment with atomic force microscope-Raman stress extraction

    NASA Astrophysics Data System (ADS)

    Liao, M.-H.; Chen, C.-H.; Chang, L.-C.; Yang, C.; Kao, S.-C.

    2012-05-01

    Based on the stress extraction and measurement by atomic force microscope-Raman technique with the nanometer level space resolution, the high compressive stress about 550 MPa on the Si active region (OD) is observed for the current complementary metal-oxide-semiconductor (CMOS) transistor. During the thermal budget for the standard manufacture process of the current CMOS transistor, the difference of thermal expansion coefficients between Si and Shallow Trench Isolation (STI) oxide results in this high compressive stress in Si OD and further degrades the electron carrier mobility seriously. In order to relax this intrinsic processed compressive stress in Si OD and try to recover this performance loss, the novel process is proposed in this work in addition to the usage of one-side pad SiN layer. With this novel process of additional N-ion implantation (IMP) treatment in STI oxide, it can be found that the less compressive stress about 438 MPa in Si OD can be achieved by the smaller difference of thermal expansion coefficients between Si and N-doped SiO2 STI oxide. The formation of Si-N bonding in N-doped SiO2 STI region can be monitored by Fourier transform infrared spectroscopy spectra and thermal expansion coefficients for Si, SiO2, and SiN are 2.6 ppm/K, 0.4 ppm/K, and 2.87 ppm/K, respectively. The effective relaxation of intrinsic processed compressive stress in Si OD about 112 MPa (from 550 MPa to 438 MPa) by this proposed additional N IMP treatment contributes ˜14% electron carrier mobility enhancement/recovery. The experimental electrical data agree well with the theoretical piezoelectricity calculation for the strained-Si theory.

  19. Immobilized metal ion affinity chromatography.

    PubMed

    Yip, T T; Hutchens, T W

    1992-01-01

    Immobilized metal ion affinity chromatography (IMAC) (1,2) is also referred to as metal chelate chromatography, metal ion interaction chromatography, and ligand-exchange chromatography. We view this affinity separation technique as an intermediate between highly specific, high-affinity bioaffinity separation methods, and wider spectrum, low-specificity adsorption methods, such as ion exchange. The IMAC stationary phases are designed to chelate certain metal ions that have selectivity for specific groups (e.g., His residues) in peptides (e.g., 3-7) and on protein surfaces (8-13). The number of stationary phases that can be synthesized for efficient chelation of metal ions is unlimited, but the critical consideration is that there must be enough exposure of the metal ion to interact with the proteins, preferably in a biospecific manner. Several examples are presented in Fig. 1. The challenge to produce new immobilized chelating groups, including protein surface metal-binding domains (14,15) is being explored continuously. Table 1 presents a list of published procedures for the synthesis and use of stationary phases with immobilized chelating groups. This is by no means exhaustive, and is intended only to give an idea of the scope and versatility of IMAC. Fig. 1 Schematic illustration of several types of immobilized metal-chelating groups, including, iminodiacetate (IDA), tris(carboxymethyl) ethylenediamine (TED), and the metal-binding peptides (GHHPH)(n)G (where n = 1,2,3, and 5) (14,15). Table 1 Immobilized Chelating Groups and Metal Ions Used for Immobilized Metal Ion Affinity Chromatography Chelating group Suitable metal ions Reference Commercial source Immodiacetate Transitional1,2 Pharmacia LKB Pierce Sigma Boehringer Mannheim TosoHaas 2-Hydroxy-3[N-(2- pyrtdylmethyl) glycme]propyl Transitional3 Not available ?-Alky1 mtrilo triacetic acid Transitional4 Not available Carboxymethylated asparhc acid Ca(II)13 Not available Tris (carboxy- methyl) ethylene Diamme

  20. Additively Manufactured Metals in Oxygen Systems Project

    NASA Technical Reports Server (NTRS)

    Tylka, Jonathan

    2015-01-01

    Metals produced by additive manufacturing methods, such as Powder Bed Fusion Technology, are now mature enough to be considered for qualification in human spaceflight oxygen systems. The mechanical properties of metals produced through AM processes are being systematically studied. However, it is unknown whether AM metals in oxygen applications may present an increased risk of flammability or ignition as compared to wrought metals of the same metallurgical composition due to increased porosity. Per NASA-STD-6001B materials to be used in oxygen system applications shall be based on flammability and combustion test data, followed by a flammability assessment. Without systematic flammability and ignition testing in oxygen there is no credible method for NASA to accurately evaluate the risk of using AM metals in oxygen systems.

  1. Behavior of metal ions in bioelectrochemical systems: A review

    NASA Astrophysics Data System (ADS)

    Lu, Zhihao; Chang, Dingming; Ma, Jingxing; Huang, Guangtuan; Cai, Lankun; Zhang, Lehua

    2015-02-01

    Bioelectrochemical systems (BESs) have been focused on by many researchers to treat wastewater and recover energy or valuable chemicals from wastes. In BESs, metal ions play an important role in the conductivity of solution, reactors' internal resistance, power generation, chemical production and activity of microorganisms. Additionally, the metal ions are also involved in anodic or cathodic reaction processes directly or indirectly in BESs. This paper reviews the behavior of metal ions in BESs, including (1) increase of the conductivity of electrolyte and decrease of internal resistance, (2) transfer for desalination, (3) enhancement or inhibition of the biocatalysis in anode, (4) improvement of cathodic performance by metal ions through electron acceptance or catalysis in cathodic process and (5) behavior of metal ions on membranes. Moreover, the perspectives of BESs removing heavy metal ions in wastewater or solid waste are discussed to realize recovery, reduction and detoxification simultaneously.

  2. The role of metal ion-ligand interactions during divalent metal ion adsorption.

    PubMed

    Eldridge, Daniel S; Crawford, Russell J; Harding, Ian H

    2015-09-15

    A suite of seven different divalent metal ions (Ca(II), Cd(II), Cu(II), Mg(II), Ni(II), Pb(II), Zn(II)) was adsorbed from solution onto two Fe2O3 samples, quartz SiO2 and three different amphoteric polystyrene latices (containing amine and carboxyl functional groups). For the metal oxides, a high correlation was observed between the pH at which 50% of the metal was removed from solution (pH50) and the first hydrolysis constant for the metal ion (pK1). For the polystyrene latices, a much higher correlation was observed between the pH50 and pKc (equilibrium constant describing metal-carboxyl affinity) as opposed to pK1. These observations provide evidence of a strong relationship that exists between a metal's affinity for a particular ligand in solution and for that metal ion's affinity for the same ligand present as part of an adsorbing surface. The isoelectric point of the amphoteric latex surface can be increased by decreasing the carboxyl content of the latex surface. For all 7 metal ions, this resulted in a substantial decrease, for any given pH, in adsorption. We suggest that this may be partly due to the decreased carboxyl content, but is dominantly attributable to the presence of less favorable electrostatic conditions. This, in turn, demonstrates that electrostatics play a controlling role in metal ion adsorption onto amphoteric latex surfaces and, in addition to the nature of the metal ion, also controls the pH at which adsorption takes place. PMID:26001134

  3. 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)

  4. 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.

  5. Metrology Needs for Metal Additive Manufacturing Powders

    NASA Astrophysics Data System (ADS)

    Slotwinski, John A.; Garboczi, Edward J.

    2015-03-01

    Additive manufacturing (AM) processes can produce highly complex and customized parts without the need for dedicated tooling and can produce parts directly from the part design information. These types of processes are poised to revolutionize the manufacturing industry, yet several challenges are currently preventing more widespread adoption of AM technologies. Among these challenges are metrology issues associated with the measurement and characterization of the metal powders used for AM systems. This article will describe the technical challenges and needs for characterizing metal AM powders, recent research efforts to address those needs, and current work to standardize characterization methods in ASTM and ISO, such as the recently released ASTM F3049, Standard Guide for Characterizing Properties of Metal Powders Used for Additive Manufacturing Processes.

  6. 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.

  7. 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

  8. Interplay of metal ions and urease.

    PubMed

    Carter, Eric L; Flugga, Nicholas; Boer, Jodi L; Mulrooney, Scott B; Hausinger, Robert P

    2009-01-01

    Urease, the first enzyme to be crystallized, contains a dinuclear nickel metallocenter that catalyzes the decomposition of urea to produce ammonia, a reaction of great agricultural and medical importance. Several mechanisms of urease catalysis have been proposed on the basis of enzyme crystal structures, model complexes, and computational efforts, but the precise steps in catalysis and the requirement of nickel versus other metals remain unclear. Purified bacterial urease is partially activated via incubation with carbon dioxide plus nickel ions; however, in vitro activation also has been achieved with manganese and cobalt. In vivo activation of most ureases requires accessory proteins that function as nickel metallochaperones and GTP-dependent molecular chaperones or play other roles in the maturation process. In addition, some microorganisms control their levels of urease by metal ion-dependent regulatory mechanisms. PMID:20046957

  9. Metal ions, Alzheimer's disease and chelation therapy.

    PubMed

    Budimir, Ana

    2011-03-01

    In the last few years, various studies have been providing evidence that metal ions are critically involved in the pathogenesis of major neurological diseases (Alzheimer, Parkinson). Metal ion chelators have been suggested as potential therapies for diseases involving metal ion imbalance. Neurodegeneration is an excellent target for exploiting the metal chelator approach to therapeutics. In contrast to the direct chelation approach in metal ion overload disorders, in neurodegeneration the goal seems to be a better and subtle modulation of metal ion homeostasis, aimed at restoring ionic balance. Thus, moderate chelators able to coordinate deleterious metals without disturbing metal homeostasis are needed. To date, several chelating agents have been investigated for their potential to treat neurodegeneration, and a series of 8-hydroxyquinoline analogues showed the greatest potential for the treatment of neurodegenerative diseases. PMID:21406339

  10. 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.

  11. Microstructural Control of Additively Manufactured Metallic Materials

    NASA Astrophysics Data System (ADS)

    Collins, P. C.; Brice, D. A.; Samimi, P.; Ghamarian, I.; Fraser, H. L.

    2016-07-01

    In additively manufactured (AM) metallic materials, the fundamental interrelationships that exist between composition, processing, and microstructure govern these materials’ properties and potential improvements or reductions in performance. For example, by using AM, it is possible to achieve highly desirable microstructural features (e.g., highly refined precipitates) that could not otherwise be achieved by using conventional approaches. Simultaneously, opportunities exist to manage macro-level microstructural characteristics such as residual stress, porosity, and texture, the last of which might be desirable. To predictably realize optimal microstructures, it is necessary to establish a framework that integrates processing variables, alloy composition, and the resulting microstructure. Although such a framework is largely lacking for AM metallic materials, the basic scientific components of the framework exist in literature. This review considers these key components and presents them in a manner that highlights key interdependencies that would form an integrated framework to engineer microstructures using AM.

  12. Metal Ion Sensors Based on DNAzymes and Related DNA Molecules

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao-Bing; Kong, Rong-Mei; Lu, Yi

    2011-07-01

    Metal ion sensors are an important yet challenging field in analytical chemistry. Despite much effort, only a limited number of metal ion sensors are available for practical use because sensor design is often a trial-and-error-dependent process. DNAzyme-based sensors, in contrast, can be developed through a systematic selection that is generalizable for a wide range of metal ions. Here, we summarize recent progress in the design of DNAzyme-based fluorescent, colorimetric, and electrochemical sensors for metal ions, such as Pb2+, Cu2+, Hg2+, and UO22+. In addition, we also describe metal ion sensors based on related DNA molecules, including T-T or C-C mismatches and G-quadruplexes.

  13. Metal Ion Sensors Based on DNAzymes and Related DNA Molecules

    PubMed Central

    Kong, Rong-Mei

    2011-01-01

    Metal ion sensors are an important yet challenging field in analytical chemistry. Despite much effort, only a limited number of metal ion sensors are available for practical use because sensor design is often a trial-and-error-dependent process. DNAzyme-based sensors, in contrast, can be developed through a systematic selection that is generalizable for a wide range of metal ions. Here, we summarize recent progress in the design of DNAzyme-based fluorescent, colorimetric, and electrochemical sensors for metal ions, such as Pb2+, Cu2+, Hg2+, and UO22+ In addition, we also describe metal ion sensors based on related DNA molecules, including T-T or C-C mismatches and G-quadruplexes. PMID:21370984

  14. Metal hydrides for lithium-ion batteries.

    PubMed

    Oumellal, Y; Rougier, A; Nazri, G A; Tarascon, J-M; Aymard, L

    2008-11-01

    Classical electrodes for Li-ion technology operate via an insertion/de-insertion process. Recently, conversion electrodes have shown the capability of greater capacity, but have so far suffered from a marked hysteresis in voltage between charge and discharge, leading to poor energy efficiency and voltages. Here, we present the electrochemical reactivity of MgH(2) with Li that constitutes the first use of a metal-hydride electrode for Li-ion batteries. The MgH(2) electrode shows a large, reversible capacity of 1,480 mAh g(-1) at an average voltage of 0.5 V versus Li(+)/Li(o) which is suitable for the negative electrode. In addition, it shows the lowest polarization for conversion electrodes. The electrochemical reaction results in formation of a composite containing Mg embedded in a LiH matrix, which on charging converts back to MgH(2). Furthermore, the reaction is not specific to MgH(2), as other metal or intermetallic hydrides show similar reactivity towards Li. Equally promising, the reaction produces nanosized Mg and MgH(2), which show enhanced hydrogen sorption/desorption kinetics. We hope that such findings can pave the way for designing nanoscale active metal elements with applications in hydrogen storage and lithium-ion batteries. PMID:18849978

  15. 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.

  16. Metal assisted focused-ion beam nanopatterning

    NASA Astrophysics Data System (ADS)

    Kannegulla, Akash; Cheng, Li-Jing

    2016-09-01

    Focused-ion beam milling is a versatile technique for maskless nanofabrication. However, the nonuniform ion beam profile and material redeposition tend to disfigure the surface morphology near the milling areas and degrade the fidelity of nanoscale pattern transfer, limiting the applicability of the technique. The ion-beam induced damage can deteriorate the performance of photonic devices and hinders the precision of template fabrication for nanoimprint lithography. To solve the issue, we present a metal assisted focused-ion beam (MAFIB) process in which a removable sacrificial aluminum layer is utilized to protect the working material. The new technique ensures smooth surfaces and fine milling edges; in addition, it permits direct formation of v-shaped grooves with tunable angles on dielectric substrates or metal films, silver for instance, which are rarely achieved by using traditional nanolithography followed by anisotropic etching processes. MAFIB was successfully demonstrated to directly create nanopatterns on different types of substrates with high fidelity and reproducibility. The technique provides the capability and flexibility necessary to fabricate nanophotonic devices and nanoimprint templates.

  17. Metal assisted focused-ion beam nanopatterning.

    PubMed

    Kannegulla, Akash; Cheng, Li-Jing

    2016-09-01

    Focused-ion beam milling is a versatile technique for maskless nanofabrication. However, the nonuniform ion beam profile and material redeposition tend to disfigure the surface morphology near the milling areas and degrade the fidelity of nanoscale pattern transfer, limiting the applicability of the technique. The ion-beam induced damage can deteriorate the performance of photonic devices and hinders the precision of template fabrication for nanoimprint lithography. To solve the issue, we present a metal assisted focused-ion beam (MAFIB) process in which a removable sacrificial aluminum layer is utilized to protect the working material. The new technique ensures smooth surfaces and fine milling edges; in addition, it permits direct formation of v-shaped grooves with tunable angles on dielectric substrates or metal films, silver for instance, which are rarely achieved by using traditional nanolithography followed by anisotropic etching processes. MAFIB was successfully demonstrated to directly create nanopatterns on different types of substrates with high fidelity and reproducibility. The technique provides the capability and flexibility necessary to fabricate nanophotonic devices and nanoimprint templates. PMID:27479713

  18. Versatile high current metal ion implantation facility

    SciTech Connect

    Brown, I.G.; Dickinson, M.R.; Galvin, J.E.; Godechot, X.; MacGill, R.A.

    1991-06-01

    A metal ion implantation facility has been developed with which high current beams of practically all the solid metals of the periodic table can be produced. A multi-cathode, broad beam, metal vapor vacuum arc ion source is used to produce repetitively pulsed metal ion beams at an extraction voltage of up to 100 kV, corresponding to an ion energy of up to several hundred keV because of the ion-charge state multiplicity, and with a beam current of up to several amperes peak pulsed and several tens of mA time averaged delivered onto a downstream target. Implantation is done in a broad-beam mode, with a direct line-of-sight from ion source to target. Here we summarize some of the features of the ion source and the implantation facility that has been built up around it. 28 refs., 5 figs.

  19. COMPUTATIONAL DESIGN OF METAL ION SEQUESTERING AGENTS

    EPA Science Inventory

    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...

  20. Pseudo ribbon metal ion beam source

    SciTech Connect

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

    2014-02-15

    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.

  1. 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.

  2. 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

  3. Sequence-selective metal ion binding to DNA oligonucleotides.

    PubMed

    Frøystein, N A; Davis, J T; Reid, B R; Sletten, E

    1993-07-01

    Metal ion titrations of several DNA oligonucleotides, 10 dodecamers and one decamer have been monitored by 1H NMR spectroscopy in order to elucidate metal ion binding patterns. Also, the effects of paramagnetic impurities on resonance linewidths and NOESY cross-peak intensities have been reversed by EDTA back-titration experiments. 1H 1D NMR spectra were recorded after successive additions of aliquots of different metal salts to oligonucleotide samples. Paramagnetic manganese(II) salts were used in most cases, but a few samples were also titrated with diamagnetic zinc(II). From this study, we conclude that there exists a sequence-selective metal ion binding pattern. The metal ions bind predominantly to 5'-G in the contexts 5'-GC and 5'-GA. The order of preference seems to be GG > or = GA > GT > > GC. No evidence of metal ion binding to 5'-G in 5'-GC steps or to non-G residues was found. The H6 or H8 resonances on preceding (5'-) bases were affected by the adjacent bound paramagnetic metal ion, but no effect was observed on the protons of the succeeding (3'-) base. The metal binding site in the duplexes is most likely at G-N7, as manifested by the pronounced paramagnetic line broadening or diamagnetic shift of the G-H8 signal. This sequence selectivity may be qualitatively explained by a sequence-dependent variation in the molecular electrostatic potentials of guanine residues (MEPs) along the oligonucleotide chain. PMID:8363924

  4. Metallic ion production with the dione EBIS

    NASA Astrophysics Data System (ADS)

    Visentin, B.; Courtois, A.; Gobin, R.; Harrault, F.; Leroy, P. A.

    1997-01-01

    We report the first quantitative results obtained with metallic elements injected from an Hollow Cathode ion source into the Dioné EBIS. These results are concerned with the charge state distribution of gold ions, with a maximum for Au47+ of (1,3 × 107 ions), and the highest charge state detectable on a wire profiler of Au63+. The Au50+ ions have been captured in Mimas storage synchrotron, and an Fe20+ ion beam has been accelerated in the Saturne synchrotron. The Hollow Cathode ion source lifetime has been tested on a long term basis (Au1+ injected into Dioné during six weeks, 24 hours per day). This source, able to produce metallic ions with any buffer gas (Ne, Ar, Kr, Xe, or N) and is also used to inject gaseous ions into Dioné.

  5. Structural Metals in the Group I Intron: A Ribozyme with a Multiple Metal Ion Core

    SciTech Connect

    Stahley,M.; Adams, P.; Wang, J.; Strobel, S.

    2007-01-01

    Metal ions play key roles in the folding and function for many structured RNAs, including group I introns. We determined the X-ray crystal structure of the Azoarcus bacterial group I intron in complex with its 5' and 3' exons. In addition to 222 nucleotides of RNA, the model includes 18 Mg2+ and K+ ions. Five of the metals bind within 12 Angstroms of the scissile phosphate and coordinate the majority of the oxygen atoms biochemically implicated in conserved metal-RNA interactions. The metals are buried deep within the structure and form a multiple metal ion core that is critical to group I intron structure and function. Eight metal ions bind in other conserved regions of the intron structure, and the remaining five interact with peripheral structural elements. Each of the 18 metals mediates tertiary interactions, facilitates local bends in the sugar-phosphate backbone or binds in the major groove of helices. The group I intron has a rich history of biochemical efforts aimed to identify RNA-metal ion interactions. The structural data are correlated to the biochemical results to further understand the role of metal ions in group I intron structure and function.

  6. Chemical Shuttle Additives in Lithium Ion Batteries

    SciTech Connect

    Patterson, Mary

    2013-03-31

    The goals of this program were to discover and implement a redox shuttle that is compatible with large format lithium ion cells utilizing LiNi{sub 1/3}Mn{sub 1/3}Co{sub 1/3}O{sub 2} (NMC) cathode material and to understand the mechanism of redox shuttle action. Many redox shuttles, both commercially available and experimental, were tested and much fundamental information regarding the mechanism of redox shuttle action was discovered. In particular, studies surrounding the mechanism of the reduction of the oxidized redox shuttle at the carbon anode surface were particularly revealing. The initial redox shuttle candidate, namely 2-(pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole (BDB) supplied by Argonne National Laboratory (ANL, Lemont, Illinois), did not effectively protect cells containing NMC cathodes from overcharge. The ANL-RS2 redox shuttle molecule, namely 1,4-bis(2-methoxyethoxy)-2,5-di-tert-butyl-benzene, which is a derivative of the commercially successful redox shuttle 2,5-di-tert-butyl-1,4-dimethoxybenzene (DDB, 3M, St. Paul, Minnesota), is an effective redox shuttle for cells employing LiFePO{sub 4} (LFP) cathode material. The main advantage of ANL-RS2 over DDB is its larger solubility in electrolyte; however, ANL-RS2 is not as stable as DDB. This shuttle also may be effectively used to rebalance cells in strings that utilize LFP cathodes. The shuttle is compatible with both LTO and graphite anode materials although the cell with graphite degrades faster than the cell with LTO, possibly because of a reaction with the SEI layer. The degradation products of redox shuttle ANL-RS2 were positively identified. Commercially available redox shuttles Li{sub 2}B{sub 12}F{sub 12} (Air Products, Allentown, Pennsylvania and Showa Denko, Japan) and DDB were evaluated and were found to be stable and effective redox shuttles at low C-rates. The Li{sub 2}B{sub 12}F{sub 12} is suitable for lithium ion cells utilizing a high voltage cathode (potential that is higher

  7. Biosorption of metal ions from aqueous solutions

    SciTech Connect

    Chen, Jiaping; Yiacoumi, Sotira

    1997-01-01

    Copper biosorption from aqueous solutions by calcium alginate is reported in this paper. The experimental section includes potentiometric titrations of biosorbents, batch equilibrium and kinetic studies of copper biosorption, as well as fixed-bed biosorption experiments. The potentiometric titration results show that the surface charge increases with decreasing pH. The biosorption of copper strongly depends on solution pH; the metal ion binding increases from 0 to 90 percent in pH ranging from 1.5 to 5.0. In addition, a decrease in ionic strength results in an increase of copper ion removal. Kinetic studies indicate that mass transfer plays an important role in the biosorption rate. Furthermore, a fixed-bed biosorption experiment shows that calcium alginate has a significant capacity for copper ion removal. The two-pK Basic Stem model successfully represents the surface charge and equilibrium biosorption experimental data. The calculation results demonstrate that the copper removal may result from the binding of free copper and its hydroxide with surface functional groups of the biosorbents.

  8. Uptake of metal ions on humic acids

    SciTech Connect

    Pehlivan, E.; Arslan, G.

    2006-09-15

    The kinetics, the sorption capacities, pH and temperature dependence of sorption of humic acids (HAs) of Turkish brown coals with respect to Zn(II), Cu(II), Ni(II), Co(II) and Pb(II) ions were investigated, and the roles of the carboxylic and phenolic groups in the adsorption of metals ion on HAs were searched in this work. These metal ions are able to form complex compounds with carboxylic and phenolic groups of HAs. Adsorption equilibrium was achieved in between 50 and 60 min for all studied cations. HAs extracted from different brown coals have been characterized by chemical and physical methods. The chemical properties of HAs showed differences depending on the source from which they were obtained. The sorption of metals on the surface of HAs depends strongly on the pH, and sorption decreases with decreasing pH. Maximum removal of metal ions was demonstrated at pH values of 4.1-5.0. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The {Delta}G{sup 0} became negative as the temperature increased, and so the equilibrium constant decreased slightly. The investigation proved that the HAs are suitable materials for the studied heavy metal ion removal from aqueous solution and could be considered as potential material for purification of effluent polluted with toxic metal ions.

  9. 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 ...

  10. Metal-ion recycle technology for metal electroplating waste waters

    SciTech Connect

    Sauer, N.N.; Smith, B.F.

    1993-06-01

    As a result of a collaboration with Boeing Aerospace, the authors have begun a program to identify suitable treatments or to develop new treatments for electroplating baths. The target baths are mixed-metal or alloy baths that are being integrated into the Boeing electroplating complex. These baths, which are designed to replace highly toxic chromium and cadmium baths, contain mixtures of two metals, either nickel-tungsten, nickel-zinc, or zinc-tin. This report reviews the literature and details currently available on emerging technologies that could affect recovery of metals from electroplating baths under development by Boeing Aerospace. This literature survey summarizes technologies relevant to the recovery of metals from electroplating processes. The authors expanded the scope to investigate single metal ion recovery technologies that could be applied to metal ion recovery from alloy baths. This review clearly showed that the electroplating industry has traditionally relied on precipitation and more recently on electrowinning as its waste treatment methods. Despite the almost ubiquitous use of precipitation to remove contaminant metal ions from waste electroplating baths and rinse waters, this technology is clearly no longer feasible for the electroplating industry for several reasons. First, disposal of unstabilized sludge is no longer allowed by law. Second, these methods are no longer adequate as metal-removal techniques because they cannot meet stringent new metal discharge limits. Third, precious resources are being wasted or discarded because these methods do not readily permit recovery of the target metal ions. As a result, emerging technologies for metal recovery are beginning to see application to electroplating waste recycle. This report summarizes current research in these areas. Included are descriptions of various membrane technologies, such as reverse osmosis and ultrafiltration, ion exchange and chelating polymer technology, and electrodialysis.

  11. Upgraded vacuum arc ion source for metal ion implantation

    SciTech Connect

    Nikolaev, A. G.; Oks, E. M.; Savkin, K. P.; Yushkov, G. Yu.; Brown, I. G.

    2012-02-15

    Vacuum arc ion sources have been made and used by a large number of research groups around the world over the past twenty years. The first generation of vacuum arc ion sources (dubbed ''Mevva,'' for metal vapor vacuum arc) was developed at Lawrence Berkeley National Laboratory in the 1980s. This paper considers the design, performance parameters, and some applications of a new modified version of this kind of source which we have called Mevva-V.Ru. The source produces broad beams of metal ions at an extraction voltage of up to 60 kV and a time-averaged ion beam current in the milliampere range. Here, we describe the Mevva-V.Ru vacuum arc ion source that we have developed at Tomsk and summarize its beam characteristics along with some of the applications to which we have put it. We also describe the source performance using compound cathodes.

  12. Metal-air cell with performance enhancing additive

    SciTech Connect

    Friesen, Cody A; Buttry, Daniel

    2015-11-10

    Systems and methods drawn to an electrochemical cell comprising a low temperature ionic liquid comprising positive ions and negative ions and a performance enhancing additive added to the low temperature ionic liquid. The additive dissolves in the ionic liquid to form cations, which are coordinated with one or more negative ions forming ion complexes. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. The ion complexes improve oxygen reduction thermodynamics and/or kinetics relative to the ionic liquid without the additive.

  13. CONTROL ROD ALLOY CONTAINING NOBLE METAL ADDITIONS

    DOEpatents

    Anderson, W.K.; Ray, W.E.

    1960-05-01

    Silver-base alloys suitable for use in the fabrication of control rods for neutronic reactors are given. The alloy consists of from 0.5 wt.% to about 1.5 wt.% of a noble metal of platinum, ruthenium, rhodium, osmium, or palladium, up to 10 wt.% of cadmium, from 2 to 20 wt.% indium, the balance being silver.

  14. Bioavailability of Metal Ions and Evolutionary Adaptation

    PubMed Central

    Hong Enriquez, Rolando P.; Do, Trang N.

    2012-01-01

    The evolution of life on earth has been a long process that began nearly 3.5 × 109 years ago. In their initial moments, evolution was mainly influenced by anaerobic environments; with the rise of O2 and the corresponding change in bioavailability of metal ions, new mechanisms of survival were created. Here we review the relationships between ancient atmospheric conditions, metal ion bioavailability and adaptation of metals homeostasis during early evolution. A general picture linking geochemistry, biochemistry and homeostasis is supported by the reviewed literature and is further illustrated in this report using simple database searches. PMID:25371266

  15. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Rapko, Brian M.

    2006-06-01

    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 for 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.

  16. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Rapko, Brian M.

    2005-06-15

    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 for 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.

  17. Metal ion coupled protein folding and allosteric motions

    NASA Astrophysics Data System (ADS)

    Wang, Wei

    2014-03-01

    Many proteins need the help of cofactors for their successful folding and functioning. Metal ions, i.e., Zn2+, Ca2+, and Mg2+ etc., are typical biological cofactors. Binding of metal ions can reshape the energy landscapes of proteins, thereby modifying the folding and allosteric motions. For example, such binding may make the intrinsically disordered proteins have funneled energy landscapes, consequently, ensures their spontaneous folding. In addition, the binding may activate certain biological processes by inducing related conformational changes of regulation proteins. However, how the local interactions involving the metal ion binding can induce the global conformational motions of proteins remains elusive. Investigating such question requires multiple models with different details, including quantum mechanics, atomistic models, and coarse grained models. In our recent work, we have been developing such multiscale methods which can reasonably model the metal ion binding induced charge transfer, protonation/deprotonation, and large conformational motions of proteins. With such multiscale model, we elucidated the zinc-binding induced folding mechanism of classical zinc finger and the calcium-binding induced dynamic symmetry breaking in the allosteric motions of calmodulin. In addition, we studied the coupling of folding, calcium binding and allosteric motions of calmodulin domains. In this talk, I will introduce the above progresses on the metal ion coupled protein folding and allosteric motions. We thank the finacial support from NSFC and the 973 project.

  18. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Rapko, Brian M.

    2005-06-15

    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 for 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 generate

  19. Ion exchange properties of novel hydrous metal oxide materials

    SciTech Connect

    Gardner, T.J.; McLaughlin, L.I.

    1996-12-31

    Hydrous metal oxide (HMO) materials are inorganic ion exchangers which have many desirable characteristics for catalyst support applications, including high cation exchange capacity, anion exchange capability, high surface area, ease of adjustment of acidity and basicity, bulk or thin film preparation, and similar chemistry for preparation of various transition metal oxides. Cation exchange capacity is engineered into these materials through the uniform incorporation of alkali cations via manipulation of alkoxide chemistry. Specific examples of the effects of Na stoichiometry and the addition of SiO{sub 2} to hydrous titanium oxide (HTO) on ion exchange behavior will be given. Acid titration and cationic metal precursor complex exchange will be used to characterize the ion exchange behavior of these novel materials.

  20. Effect of metal ions on positron annihilation characteristics in metal ion containing epoxies

    NASA Technical Reports Server (NTRS)

    Singh, J. J.; St. Clair, A. K.; Stoakley, D. M.; Holt, W. H.; Mock, W., Jr.

    1984-01-01

    In the course of developing improved moisture-resistant epoxy resins, two different types of epoxy resins containing variable mole ratios of chromium ions per polymer repeat unit were developed. Positron annihilation characteristics have been investigated in these resins as a function of their metal ion content. In both cases, the presence of metal ions reduces the lifetime as well as the intensity of the long life component. The long life component intensity reduction is considerably more pronounced than the lifetime reduction. These results have been discussed in terms of increased unpaired electron density at Ps formation sites due to the presence of chromium ions in the matrix.

  1. IMMUNOASSAYS FOR METAL IONS. (R824029)

    EPA Science Inventory

    Abstract

    Antibodies that recognize chelated forms of metal ions have been used to construct immunoassays for Cd(II), Hg(II), Pb(II), and Ni(II). In this paper, the format of these immunoassays is described and the binding properties of three monoclonal antibodies direc...

  2. 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.

  3. Ion Mobility Spectrometry of Heavy Metals.

    PubMed

    Ilbeigi, Vahideh; Valadbeigi, Younes; Tabrizchi, Mahmoud

    2016-07-19

    A simple, fast, and inexpensive method was developed for detecting heavy metals via the ion mobility spectrometry (IMS) in the negative mode. In this method, Cl(-) ion produced by the thermal ionization of NaCl is employed as the dopant or the ionizing reagent to ionize heavy metals. In practice, a solution of mixed heavy metals and NaCl salts was directly deposited on a Nichrome filament and electrically heated to vaporize the salts. This produced the IMS spectra of several heavy-metal salts, including CdCl2, ZnSO4, NiCl2, HgSO4, HgCl2, PbI2, and Pb(Ac)2. For each heavy metal (M), one or two major peaks were observed, which were attributed to M·Cl(-) or [M·NaCl]Cl(-)complexes. The method proved to be useful for the analysis of mixed heavy metals. The absolute detection limits measured for ZnSO4 and HgSO4 were 0.1 and 0.05 μg, respectively. PMID:27321408

  4. A review on electrolyte additives for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Sheng Shui

    This paper reviews electrolyte additives used in Li-ion batteries. According to their functions, the additives can be divided into these categories: (1) solid electrolyte interface (SEI) forming improver, (2) cathode protection agent, (3) LiPF 6 salt stabilizer, (4) safety protection agent, (5) Li deposition improver, and (6) other agents such as solvation enhancer, Al corrosion inhibitor, and wetting agent. The function and mechanism of each category additives are generally described and discussed.

  5. 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.

  6. Bending Electrostriction in Polyurethanes Containing Ions as Contaminants or Additives

    NASA Astrophysics Data System (ADS)

    Watanabe, Masashi; Kato, Takahiro; Suzuki, Makoto; Amaike, Yoichi; Hirai, Toshihiro

    1999-08-01

    We demonstrated that the bending electrostriction in polyurethane films is controlled by the ions contained as contaminants or additives. The sample film used in this investigation was composed of a segmented polyester-polyurethane and was coated with a thin gold electrode on each surface by ion-sputtering. Although the application of an electric field (2 MV/m) can caused bending deformation of the film, removal of the ionic contaminants from the polyurethane by electrodialysis reduced the degree of deformation. On the other hand, the addition of a small amount of lithium bromide changed the bending direction.

  7. Ion irradiation effects on metallic nanocrystals

    NASA Astrophysics Data System (ADS)

    Kluth, P.; Johannessen, B.; Giulian, R.; Schnohr, C. S.; Foran, G. J.; Cookson, D. J.; Byrne, A. P.; Ridgway, M. C.

    We have investigated structural and morphological properties of metallic nanocrystals (NCs) exposed to ion irradiation. NCs were characterized by transmission electron microscopy in combination with advanced synchrotron-based analytical techniques, in particular X-ray absorption spectroscopy and small-angle X-ray scattering. A number of different effects were observed depending on the irradiation conditions. At energies where nuclear stopping is predominant, structural disorder/amorphization followed by inverse Ostwald ripening/dissolution due to ion beam mixing was observed for Au and Cu NCs embedded in SiO2. The ion-irradiation-induced crystalline to amorphous transition in the NCs, which cannot be achieved in the corresponding bulk metals, was attributed to their initially higher structural energy as compared to bulk material and possibly preferential nucleation of the amorphous phase at the NC/SiO2 interface. At very high irradiation energies (swift heavy ion irradiation), where the energy loss is nearly entirely due to electronic stopping, a size-dependent shape transformation of the NCs from spheres to rod like shapes was apparent in Au NCs. Our preliminary results are in good agreement with considerations on melting of the NCs in the ion track as one mechanism involved in the shape transformation.

  8. 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.

  9. Ion irradiation effects on metallic nanocrystals

    SciTech Connect

    Kluth, P.; Johannessen, B.; Giulian, R.; Schnohr, C.S.; Foran, G.J.; Cookson, D.J.; Byrne, A.P.; Ridgway, M.C.

    2008-04-02

    We have investigated structural and morphological properties of metallic nanocrystals (NCs) exposed to ion irradiation. NCs were characterized by transmission electron microscopy in combination with advanced synchrotron-based analytical techniques, in particular X-ray absorption spectroscopy and small-angle X-ray scattering. A number of different effects were observed depending on the irradiation conditions. At energies where nuclear stopping is predominant, structural disorder/amorphization followed by inverse Ostwald ripening/dissolution due to ion beam mixing was observed for Au and Cu NCs embedded in SiO{sub 2}. The ion-irradiation-induced crystalline to amorphous transition in the NCs, which cannot be achieved in the corresponding bulk metals, was attributed to their initially higher structural energy as compared to bulk material and possibly preferential nucleation of the amorphous phase at the NC/SiO{sub 2} interface. At very high irradiation energies (swift heavy ion irradiation), where the energy loss is nearly entirely due to electronic stopping, a size-dependent shape transformation of the NCs from spheres to rod like shapes was apparent in Au NCs. Our preliminary results are in good agreement with considerations on melting of the NCs in the ion track as one mechanism involved in the shape transformation.

  10. View of building 11050, showing metal clad addition on east ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    View of building 11050, showing metal clad addition on east elevation, looking southwest. - Naval Ordnance Test Station Inyokern, China Lake Pilot Plant, Machine Shop, C Street, China Lake, Kern County, CA

  11. Effects of transition metal ion coordination on the collision-induced dissociation of polyalanines.

    PubMed

    Watson, Heather M; Vincent, John B; Cassady, Carolyn J

    2011-11-01

    Transition metal-polyalanine complexes were analyzed in a high-capacity quadrupole ion trap after electrospray ionization. Polyalanines have no polar amino acid side chains to coordinate metal ions, thus allowing the effects metal ion interaction with the peptide backbone to be explored. Positive mode mass spectra produced from peptides mixed with salts of the first row transition metals Cr(III), Fe(II), Fe(III), Co(II), Ni(II), Cu(I), and Cu(II) yield singly and doubly charged metallated ions. These precursor ions undergo collision-induced dissociation (CID) to give almost exclusively metallated N-terminal product ions whose types and relative abundances depend on the identity of the transition metal. For example, Cr(III)-cationized peptides yield CID spectra that are complex and have several neutral losses, whereas Fe(III)-cationized peptides dissociate to give intense non-metallated products. The addition of Cu(II) shows the most promise for sequencing. Spectra obtained from the CID of singly and doubly charged Cu-heptaalanine ions, [M + Cu - H](+) and [M + Cu](2+) , are complimentary and together provide cleavage at every residue and no neutral losses. (This contrasts with [M + H](+) of heptaalanine, where CID does not provide backbone ions to sequence the first three residues.) Transition metal cationization produces abundant metallated a-ions by CID, unlike protonated peptides that produce primarily b- and y-ions. The prominence of metallated a-ions is interesting because they do not always form from b-ions. Tandem mass spectrometry on metallated (Met = metal) a- and b-ions indicate that [b(n)  + Met - H](2+) lose CO to form [a(n)  + Met - H](2+), mimicking protonated structures. In contrast, [a(n)  + Met - H](2+) eliminate an amino acid residue to form [a(n-1)  + Met - H](2+), which may be useful in sequencing. PMID:22124980

  12. Complexing of metal ions by humic substances

    SciTech Connect

    Bryan, N.D.; Zhang, Y.; Jones, M.N.

    1995-12-31

    The interaction of metal ions with humic substances is being studied using two different techniques. UV-scanning ultracentrifugation is being used to determine molecular weights and to investigate changes in aggregation brought about by metal ion complexation. The relationship between cation charge and conformation of the humic ligands is also being investigated. The complexation of actinide elements (U, Np, Pu, Am) by humic substances from soils contaminated by both natural processes and by low-level effluent releases is also being studied. Gel permeation chromatography has been used to show both that different fractions of humic substances vary greatly in their effectiveness as ligands and that different actinide elements associate with different fractions. These studies have also shown that uranium desorption is kinetically controlled by humic substances.

  13. Cyanoethylated Compounds as Additives in Lithium/Lithium Ion Batteries

    SciTech Connect

    Nagasubramanian, Ganesan

    1998-05-08

    The power loss of lithium/lithium ion battery cells is significantly reduced, especially at low temperatures, when about 1% by weight of an additive is incorporated in the electrolyte layer of the cells. The usable additives are organic solvent soluble cyanoethylated polysaccharides and poly(vinyl alcohol). The power loss decrease results primarily from the decrease in the charge transfer resistance at the interface between the electrolyte and the cathode.

  14. 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. PMID:16961382

  15. Transparent monolithic metal ion containing nanophase aerogels

    SciTech Connect

    Risen, W. M., Jr.; Hu, X.; Ji, S.; Littrell, K.

    1999-12-01

    The formation of monolithic and transparent transition metal containing aerogels has been achieved through cooperative interactions of high molecular weight functionalized carbohydrates and silica precursors, which strongly influence the kinetics of gelation. After initial gelation, subsequent modification of the ligating character of the system, coordination of the group VIII metal ions, and supercritical extraction afford the aerogels. The structures at the nanophase level have been probed by photon and electron transmission and neutron scattering techniques to help elucidate the basis for structural integrity together with the small entity sizes that permit transparency in the visible range. They also help with understanding the chemical reactivities of the metal-containing sites in these very high surface area materials. These results are discussed in connection with new reaction studies.

  16. On the Metal Ion Selectivity of Oxoacid Extractants

    SciTech Connect

    Hay, Benjamin; Chagnes, Alexandre; Cote, Gerard

    2013-01-01

    Relationships between metal chelate stability, ligand basicity, and metal ion acidity are reviewed and the general applicability is illustrated by linear correlations between aqueous stability constants and ligand pKa values for 35 metals with 26 ligands. The results confirm that most individual ligands of this type exhibit a stability ordering that correlates with the Lewis acidity of the metal ion. It is concluded that the general metal ion selectivity exhibited by liquid-liquid oxoacid extractants such as carboxylic acids, -diketones, and alkylphosphoric acids reflects the intrinsic affinity of the metal ion for the negative oxygen donor ligand.

  17. Ab Initio Calculations Applied to Problems in Metal Ion Chemistry

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry; Arnold, James O. (Technical Monitor)

    1994-01-01

    Electronic structure calculations can provide accurate spectroscopic data (such as molecular structures) vibrational frequencies, binding energies, etc.) that have been very useful in explaining trends in experimental data and in identifying incorrect experimental measurements. In addition, ab initio calculations. have given considerable insight into the many interactions that make the chemistry of transition metal systems so diverse. In this review we focus on cases where calculations and experiment have been used to solve interesting chemical problems involving metal ions. The examples include cases where theory was used to differentiate between disparate experimental values and cases where theory was used to explain unexpected experimental results.

  18. Liquid metal alloy ion source based metal ion injection into a room-temperature electron beam ion source

    SciTech Connect

    Thorn, A.; Ritter, E.; Zschornack, G.; Ullmann, F.; Pilz, W.; Bischoff, L.

    2012-02-15

    We have carried out a series of measurements demonstrating the feasibility of using the Dresden electron beam ion source (EBIS)-A, a table-top sized, permanent magnet technology based electron beam ion source, as a charge breeder. Low charged gold ions from an AuGe liquid metal alloy ion source were injected into the EBIS and re-extracted as highly charged ions, thereby producing charge states as high as Au{sup 60+}. The setup, the charge breeding technique, breeding efficiencies as well as acceptance and emittance studies are presented.

  19. Applications of Metal Additive Manufacturing in Veterinary Orthopedic Surgery

    NASA Astrophysics Data System (ADS)

    Harrysson, Ola L. A.; Marcellin-Little, Denis J.; Horn, Timothy J.

    2015-03-01

    Veterinary medicine has undergone a rapid increase in specialization over the last three decades. Veterinarians now routinely perform joint replacement, neurosurgery, limb-sparing surgery, interventional radiology, radiation therapy, and other complex medical procedures. Many procedures involve advanced imaging and surgical planning. Evidence-based medicine has also become part of the modus operandi of veterinary clinicians. Modeling and additive manufacturing can provide individualized or customized therapeutic solutions to support the management of companion animals with complex medical problems. The use of metal additive manufacturing is increasing in veterinary orthopedic surgery. This review describes and discusses current and potential applications of metal additive manufacturing in veterinary orthopedic surgery.

  20. Epitaxy and Microstructure Evolution in Metal Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Basak, Amrita; Das, Suman

    2016-07-01

    Metal additive manufacturing (AM) works on the principle of incremental layer-by-layer material consolidation, facilitating the fabrication of objects of arbitrary complexity through the controlled melting and resolidification of feedstock materials by using high-power energy sources. The focus of metal AM is to produce complex-shaped components made of metals and alloys to meet demands from various industrial sectors such as defense, aerospace, automotive, and biomedicine. Metal AM involves a complex interplay between multiple modes of energy and mass transfer, fluid flow, phase change, and microstructural evolution. Understanding the fundamental physics of these phenomena is a key requirement for metal AM process development and optimization. The effects of material characteristics and processing conditions on the resulting epitaxy and microstructure are of critical interest in metal AM. This article reviews various metal AM processes in the context of fabricating metal and alloy parts through epitaxial solidification, with material systems ranging from pure-metal and prealloyed to multicomponent materials. The aim is to cover the relationships between various AM processes and the resulting microstructures in these material systems.

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

    NASA Astrophysics Data System (ADS)

    Segal, M. J.; Bark, R. A.; Thomae, R.; Donets, E. E.; Donets, E. D.; Boytsov, A.; Ponkin, D.; Ramsdorf, A.

    2016-02-01

    An assembly for a commercial Ga+ 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+ 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+ and Au+ ion beams will be reported as well.

  2. Liquid metal alloy ion sources—An alternative for focussed ion beam technology

    NASA Astrophysics Data System (ADS)

    Bischoff, Lothar; Mazarov, Paul; Bruchhaus, Lars; Gierak, Jacques

    2016-06-01

    Today, Focused Ion Beam (FIB) processing is nearly exclusively based on gallium Liquid Metal Ion Sources (LMIS). But, many applications in the μm- or nm range could benefit from ion species other than gallium: local ion implantation, ion beam mixing, ion beam synthesis, or Focused Ion Beam Lithography (IBL). Therefore, Liquid Metal Alloy Ion Sources (LMAIS) represent a promising alternative to expand the remarkable application fields for FIB. Especially, the IBL process shows potential advantages over, e.g., electron beam or other lithography techniques: direct, resistless, and three-dimensional patterning, enabling a simultaneous in-situ process control by cross-sectioning and inspection. Taking additionally into account that the used ion species influences significantly the physical and chemical nature of the resulting nanostructures—in particular, the electrical, optical, magnetic, and mechanic properties leading to a large potential application area which can be tuned by choosing a well suited LMAIS. Nearly half of the elements of the periodic table are recently available in the FIB technology as a result of continuous research in this area during the last forty years. Key features of a LMAIS are long life-time, high brightness, and stable ion current. Recent developments could make these sources feasible for nano patterning issues as an alternative technology more in research than in industry. The authors will review existing LMAIS, LMIS other than Ga, and binary and ternary alloys. These physical properties as well as the fabrication technology and prospective domains for modern FIB applications will similarly be reviewed. Other emerging ion sources will be also presented and their performances discussed.

  3. 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.

  4. Enhancing toxic metal removal from acidified sludge with nitrite addition.

    PubMed

    Du, Fangzhou; Freguia, Stefano; Yuan, Zhiguo; Keller, Jürg; Pikaar, Ilje

    2015-05-19

    The production of sludge (biosolids) during wastewater treatment is a major issue for water utilities. A main issue limiting its beneficial reuse on agricultural lands is the presence of toxic metals. The currently used metal reduction technologies achieve insufficient removal of metals that are bound to the organic fraction of the sludge. In this study, we propose and demonstrate a novel method that involves the addition of nitrite during sludge acidification to enhance metal removal. Using waste activated sludge collected from three full-scale wastewater treatment plants, we found that acidification to pH 2.0 achieved good Zn solubilization of around 70%, but only 3-7% of Cu was being dissolved. Nitrite addition to the acidified sludge at a concentration of 20 mg NO2(-)-N/L (equals to 19.2 mg HNO2-N/L), substantially enhanced Cu removal to 45-64%, while Zn removal was also increased to over 81%. Metal distribution analysis using sequential chemical extraction revealed that the improvement of Cu and Zn removal was mainly due to the release of the organically bound metal fraction. We hypothesize that free nitrous acid (HNO2, FNA) may assist in the (partial) disruption of extracellular polymeric substances (EPS) and the subsequent release and solubilization of fixed metals. PMID:25872418

  5. Rational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Raymond, Kenneth N.

    2000-09-30

    The discriminate bonding of metal ions is a challenge to the synthetic chemist and a phenomenon of considerable practical importance.1 An important feature of many technical applications is the specific or preferential binding of a single metal ion in the presence of many metals. Examples range from large-volume uses (e.g. ferric EDTA as a plant food, calcium complexing agents as water softeners or anticaking formulations) to very high technology applications (technetium complexation in radiopharmaceuticals, synthetic metalloenzymes). We are interested in efficient and discriminate binding of actinides for waste stream remediation. Actinides represent a major and long-lived contaminant in nuclear waste. While the separation of actinides from other radioactive components of waste, such as Sr and Cs, is relatively well established, the separation of actinides from each other and in complex solutions (e.g. those found in tank wastes) is not as well resolved. The challenge of designing metal-specific (actinide) ligands is facilitated by examples from nature. Bacteria synthesize Fe(III)-specific ligands, called siderophores, to sequester Fe(III) from the environment and return it to the cell. The similarities between Fe(III) and Pu(IV) (their charge-to-size ratios and acidity), make the siderophores prototypical for designing actinide-specific ligands. The chelating groups present in siderophores are usually hydroxamic acids and catecholamides. We have developed derivatives of these natural products which have improved properties. The catechol derivatives are the 2,3-dihydroxyterephthalamides (TAMs), and 3,4-dihydroxysulfonamides (SFAMs), and the hydroxamic acid derivatives are three isomers of hydroxypyridinones, 1,2- HOPO, 3,2-HOPO, and 3,4-HOPO. All of these ligands are attached to molecular backbones by amides and a very important feature of HOPO and CAM ligands is a strong hydrogen bonds formed between the amide proton and the adjacent phenolic oxygen in the metal

  6. 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

  7. Antifungal Properties of Electrically Generated Metallic Ions

    PubMed Central

    Berger, T. J.; Spadaro, J. A.; Bierman, Richard; Chapin, S. E.; Becker, R. O.

    1976-01-01

    A qualitative and quantitative investigation was undertaken to study the susceptibility of unicellular eucaryotic organisms (yeasts) to metallic cations generated by low levels of direct current. Results were characteristic of effects obtained previously using clinical and standard bacteria test organisms. The present study demonstrated that anodic silver (Ag+) at low direct currents had inhibitory and fungicidal properties. Broth dilution susceptibility tests were made on several species of Candida and one species of Torulopsis. Growth in all isolates was inhibited by concentrations of electrically generated silver ions between 0.5 and 4.7 μg/ml, and silver exhibited fungicidal properties at concentrations as low as 1.9 μg/ml. The inhibitory and fungicidal concentrations of electrically generated silver ions are lower than those reported for other silver compounds. Images PMID:1034467

  8. Metal Ion Intercalated graphitic as Transparent Electrodes

    NASA Astrophysics Data System (ADS)

    Wan, Jiayu; Bao, Wenzhong; Gu, Feng; Fuhrer, Michael; Hu, Liangbing; UMD Team

    To best utilize the performance of graphene based transparent electrodes, we novelized Li-ion intercalation in graphene, and achieved highest performance of carbon based transparent electrodes. Transmission as high as 91.7% with a sheet resistance of 3.0 ohm/sq is achieved for 19-layer LiC6, significantly higher than any other continuous transparent electrodes. The unconventional modification of ultrathin graphite optoelectronic properties is explained by the suppression of interband optical transitions and a small intraband Drude conductivity near the interband edge. To achieve low cost, large scale graphene-based transparent electrodes, we further developed Na-ion intercalated printed reduced graphene oxide (RGO) film. The larger layer-layer distance of RGO allows Na-ion intercalation, leading to simultaneously much higher DC conductivity and higher optical transmittance. Typical increase of transmittance from 36% to 79% and decrease of sheet resistance from 83 kohms/sq to 311 ohms/sq in the printed network was observed. This study demonstrated the great potential of metal-ion intercalation to improve the performance of graphene-based materials for transparent conductor applications.

  9. Metal ions potentiate microglia responsiveness to endotoxin.

    PubMed

    Rachmawati, Dessy; Peferoen, Laura A N; Vogel, Daphne Y S; Alsalem, Inás W A; Amor, Sandra; Bontkes, Hetty J; von Blomberg, B Mary E; Scheper, Rik J; van Hoogstraten, Ingrid M W

    2016-02-15

    Oral metal exposure has been associated with diverse adverse reactions, including neurotoxicity. We showed previously that dentally applied metals activate dendritic cells (MoDC) via TLR4 (Ni, Co, Pd) and TLR3 (Au). It is still unknown whether the low levels of dental metals reaching the brain can trigger local innate cells or prime them to become more responsive. Here we tested whether dentally applied metals (Cr, Fe, Co, Ni, Cu, Zn, Au, Hg) activate primary human microglia in vitro and, as a model, monocytic THP-1-cells, in high non-toxic as well as near-physiological concentrations. In addition the effects of 'near-physiological' metal exposure on endotoxin (LPS) responsiveness of these cells were evaluated. IL-8 and IL-6 production after 24h was used as read out. In high, non-toxic concentrations all transition metals except Cr induced IL-8 and IL-6 production in microglia, with Ni and Co providing the strongest stimulation. When using near-physiological doses (up to 10× the normal plasma concentration), only Zn and Cu induced significant IL-8 production. Of note, the latter metals also markedly potentiated LPS responsiveness of microglia and THP-1 cells. In conclusion, transition metals activate microglia similar to MoDCs. In near-physiological concentrations Zn and Cu are the most effective mediators of innate immune activation. A clear synergism between innate responses to Zn/Cu and LPS was observed, shedding new light on the possible relation between oral metal exposure and neurotoxicity. PMID:26857501

  10. Interaction of lactic acid bacteria with metal ions: opportunities for improving food safety and quality.

    PubMed

    Mrvčić, Jasna; Stanzer, Damir; Solić, Ema; Stehlik-Tomas, Vesna

    2012-09-01

    Certain species of lactic acid bacteria (LAB), as well as other microorganisms, can bind metal ions to their cells surface or transport and store them inside the cell. Due to this fact, over the past few years interactions of metal ions with LAB have been intensively investigated in order to develop the usage of these bacteria in new biotechnology processes in addition to their health and probiotic aspects. Preliminary studies in model aqueous solutions yielded LAB with high absorption potential for toxic and essential metal ions, which can be used for improving food safety and quality. This paper provides an overview of results obtained by LAB application in toxic metal ions removing from drinking water, food and human body, as well as production of functional foods and nutraceutics. The biosorption abilities of LAB towards metal ions are emphasized. The binding mechanisms, as well as the parameters influencing the passive and active uptake are analyzed. PMID:22806724

  11. Metal ion cooperativity in ribozyme cleavage of RNA

    PubMed Central

    Brännvall, Mathias; Kirsebom, Leif A.

    2001-01-01

    Combinations of chemical and genetic approaches were used to study the function of divalent metal ions in cleavage of RNA by the ribozyme RNase P RNA. We show that different divalent metal ions have differential effects on cleavage site recognition and rescue of cleavage activity by mixing divalent metal ions that do not promote cleavage by themselves. We conclude that efficient and correct cleavage is the result of cooperativity between divalent metal ions bound at different sites in the RNase P RNA-substrate complex. Complementation of a mutant RNase P RNA phenotype as a result of divalent metal ion replacement is demonstrated also. This finding together with other data indicate that one of the metal ions involved in this cooperativity is positioned near the cleavage site. The possibility that the Mg2+/Ca2+ ratio might regulate the activity of biocatalysts that depend on RNA for activity is discussed. PMID:11606743

  12. Characterization of Metal Powders Used for Additive Manufacturing

    PubMed Central

    Slotwinski, JA; Garboczi, EJ; Stutzman, PE; Ferraris, CF; Watson, SS; Peltz, MA

    2014-01-01

    Additive manufacturing (AM) techniques1 can produce complex, high-value metal parts, with potential applications as critical parts, such as those found in aerospace components. The production of AM parts with consistent and predictable properties requires input materials (e.g., metal powders) with known and repeatable characteristics, which in turn requires standardized measurement methods for powder properties. First, based on our previous work, we assess the applicability of current standardized methods for powder characterization for metal AM powders. Then we present the results of systematic studies carried out on two different powder materials used for additive manufacturing: stainless steel and cobalt-chrome. The characterization of these powders is important in NIST efforts to develop appropriate measurements and standards for additive materials and to document the property of powders used in a NIST-led additive manufacturing material round robin. An extensive array of characterization techniques was applied to these two powders, in both virgin and recycled states. The physical techniques included laser diffraction particle size analysis, X-ray computed tomography for size and shape analysis, and optical and scanning electron microscopy. Techniques sensitive to structure and chemistry, including X-ray diffraction, energy dispersive analytical X-ray analysis using the X-rays generated during scanning electron microscopy, and X-Ray photoelectron spectroscopy were also employed. The results of these analyses show how virgin powder changes after being exposed to and recycled from one or more Direct Metal Laser Sintering (DMLS) additive manufacturing build cycles. In addition, these findings can give insight into the actual additive manufacturing process. PMID:26601040

  13. Fluorescence enhancement aided by metal ion displacement.

    PubMed

    Susini, Vanessa; Ienco, Andrea; Lucia Rossi, Veronica; Paolicchi, Aldo; Sanesi, Antonio

    2016-06-15

    Immunosensors are one of the most common platform used in clinical laboratories, in particular the class based on Enzyme Linked Fluorescent Assays (ELFA) takes advantage of the amplification step of the enzyme, usually the alkaline phosphatase, that catalyzes the hydrolysis of a fluorescent substrate leading it to fluoresce. Anyway, they suffer in sensitivity if compared to molecular diagnostic or more modern in vitro diagnostic devices. In our work, a simple and effective mechanism to enhance the fluorescent signal, and hence the sensitivity of the system, is presented. It is based on the metal ion displacement principle in which a second fluorophore, in our case Calcein Blue, quenched by a cobalt ion is add to the first one (4-MUP), and, in presence of inorganic phosphate, it will be progressively activated by the inorganic phosphate itself leading to the metal displacement. In this way Calcein Blue, newly free to fluoresce, contributes to global fluorescent signal generated by 4-MU. We have tested our proof of principle on a currently used immunoanalyzer, that is VIDAS® system (bioMérieux, Marcy l'Etoile, France) obtaining a fluorescence enhancement of about 50% for each concentration of hydrolyzed 4-MUP tested. PMID:26851581

  14. Accelerating Industrial Adoption of Metal Additive Manufacturing Technology

    NASA Astrophysics Data System (ADS)

    Vartanian, Kenneth; McDonald, Tom

    2016-03-01

    While metal additive manufacturing (AM) technology has clear benefits, there are still factors preventing its adoption by industry. These factors include the high cost of metal AM systems, the difficulty for machinists to learn and operate metal AM machines, the long approval process for part qualification/certification, and the need for better process controls; however, the high AM system cost is the main barrier deterring adoption. In this paper, we will discuss an America Makes-funded program to reduce AM system cost by combining metal AM technology with conventional computerized numerical controlled (CNC) machine tools. Information will be provided on how an Optomec-led team retrofitted a legacy CNC vertical mill with laser engineered net shaping (LENS®—LENS is a registered trademark of Sandia National Labs) AM technology, dramatically lowering deployment cost. The upgraded system, dubbed LENS Hybrid Vertical Mill, enables metal additive and subtractive operations to be performed on the same machine tool and even on the same part. Information on the LENS Hybrid system architecture, learnings from initial system deployment and continuing development work will also be provided to help guide further development activities within the materials community.

  15. Porosity Measurements and Analysis for Metal Additive Manufacturing Process Control

    PubMed Central

    Slotwinski, John A; Garboczi, Edward J; Hebenstreit, Keith M

    2014-01-01

    Additive manufacturing techniques can produce complex, high-value metal parts, with potential applications as critical metal components such as those found in aerospace engines and as customized biomedical implants. Material porosity in these parts is undesirable for aerospace parts - since porosity could lead to premature failure - and desirable for some biomedical implants - since surface-breaking pores allows for better integration with biological tissue. Changes in a part’s porosity during an additive manufacturing build may also be an indication of an undesired change in the build process. Here, we present efforts to develop an ultrasonic sensor for monitoring changes in the porosity in metal parts during fabrication on a metal powder bed fusion system. The development of well-characterized reference samples, measurements of the porosity of these samples with multiple techniques, and correlation of ultrasonic measurements with the degree of porosity are presented. A proposed sensor design, measurement strategy, and future experimental plans on a metal powder bed fusion system are also presented. PMID:26601041

  16. Porosity Measurements and Analysis for Metal Additive Manufacturing Process Control.

    PubMed

    Slotwinski, John A; Garboczi, Edward J; Hebenstreit, Keith M

    2014-01-01

    Additive manufacturing techniques can produce complex, high-value metal parts, with potential applications as critical metal components such as those found in aerospace engines and as customized biomedical implants. Material porosity in these parts is undesirable for aerospace parts - since porosity could lead to premature failure - and desirable for some biomedical implants - since surface-breaking pores allows for better integration with biological tissue. Changes in a part's porosity during an additive manufacturing build may also be an indication of an undesired change in the build process. Here, we present efforts to develop an ultrasonic sensor for monitoring changes in the porosity in metal parts during fabrication on a metal powder bed fusion system. The development of well-characterized reference samples, measurements of the porosity of these samples with multiple techniques, and correlation of ultrasonic measurements with the degree of porosity are presented. A proposed sensor design, measurement strategy, and future experimental plans on a metal powder bed fusion system are also presented. PMID:26601041

  17. Separation of traces of metal ions from sodium matrices

    NASA Technical Reports Server (NTRS)

    Korkisch, J.; Orlandini, K. A.

    1969-01-01

    Method for isolating metal ion traces from sodium matrices consists of two extractions and an ion exchange step. Extraction is accomplished by using 2-thenoyltrifluoracetone and dithizone followed by cation exchange.

  18. Comet Encke: Meteor metallic ion identification by mass spectrometer

    NASA Technical Reports Server (NTRS)

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

    1973-01-01

    Positive metallic ions have been measured in the earth's atmosphere between 85 and 120 km, during the period of the beta Taurids meteor shower, which is associated with Comet Encke. The ions originate during and following ablation of extraterrestrial debris by the earth's atmosphere. The enhancement of metal ion density during meteor showers is primary evidence for their extraterrestrial origin. The present results were obtained from a rocket-borne ion mass spectrometer.

  19. Effects of different additives with assistance of microwave heating for heavy metal stabilization in electronic industry sludge.

    PubMed

    Jothiramalingam, R; Lo, Shang-Lien; Chen, Ching-lung

    2010-01-01

    Electronic industrial wastewater sludge in Taiwan is normally passed through an acid-extraction process to reclaim most of the copper ions, the remaining residue may still need to be treated by various stabilization technologies using suitable additives. Cement solidification is used as the common method to stabilize the industrial wastewater sludge in Taiwan. However, this method has the disadvantage of an increase in waste volume. In the present study selective additives such as sodium sulfide, barium manganate and different phase of alumina were tested as a possible alternate additive to stabilize the heavy metal ion in the treated solid waste sludge via microwave heating treatment. The effects of additive amount, power of microwave irradiation and reaction time have been studied. Heavy metal leaching capacity is determined by using standard toxicity characteristic leaching procedure test and elemental content in the leachate is analyzed by inductively coupled plasma analysis. Sodium sulfide is effectively stabilizing the leaching copper ion with high selectivity in the presence of microwave irradiation and finally stabilized in the form of copper sulfide, which is a significant reaction to stabilize the copper ion leaching in the waste sludge. Complete stabilization of heavy metal ion and copper ion content (<5mgL(-1)) in industrial sludge is achieved by heating the microwave treated barium manganate and alumina additives by adopting suitable reaction conditions. Hybrid microwave and conventional heating process with minor amount of additive providing the efficient heavy metal stabilization for treated electronic industry waste sludge. PMID:19945139

  20. Plasma immersion ion implantation for reducing metal ion release

    SciTech Connect

    Diaz, C.; Garcia, J. A.; Maendl, S.; Pereiro, R.; Fernandez, B.; Rodriguez, R. J.

    2012-11-06

    Plasma immersion ion implantation of Nitrogen and Oxygen on CoCrMo alloys was carried out to improve the tribological and corrosion behaviors of these biomedical alloys. In order to optimize the implantation results we were carried experiments at different temperatures. Tribocorrosion tests in bovine serum were used to measure Co, Cr and Mo releasing by using Inductively Coupled Plasma Mass Spectrometry analysis after tests. Also, X-ray Diffraction analysis were employed in order to explain any obtained difference in wear rate and corrosion tests. Wear tests reveals important decreases in rate of more than one order of magnitude for the best treatment. Moreover decreases in metal release were found for all the implanted samples, preserving the same corrosion resistance of the unimplanted samples. Finally this paper gathers an analysis, in terms of implantation parameters and achieved properties for industrial implementation of these treatments.

  1. In situ combustion with metallic additives SUPRI TR 87

    SciTech Connect

    Holt, R.J.

    1992-07-01

    In-situ combustion is the most energy efficient of the thermal oil recovery methods. In this process, a portion of a reservoir's oil is burned in-situ as fuel to drive the recovery process. In light oil reservoirs, too little fuel may be deposited, making sustained combustion difficult. In heavy oil reservoirs, too much fuel may be deposited leading to high air injection requirements and unfavorable economics. This study has been designed to attack these problems. Water soluble metallic additives are investigated as agents to modify fuel deposition and combustion performance. This report describes seven combustion tube runs using two cradle oils and two metallic additives. The oils are 12{degrees} and 34{degrees} API, both from Cymric (California). The metallic additives tested are ionic nitrate (Fe(NO{sub 3}){sub 3}9H{sub 2}O) and zinc nitrate (Zn(NO{sub 3}){sub 2}6H{sub 2}O). Iron and tin additives improved the combustion efficiency in all cases. Fluctuations in the produced gas compositions were observed in all control runs, but nearly disappeared with the iron and tin additives. The combustion front velocities were also increased by iron and tin. Changes were also observed in the apparent hydrogen to carbon (H/C) ratio of the fuel, heat of combustion, air requirements, and amount of fuel deposited. Iron and tin caused increases in fuel concentration while causing a decrease in air requirement. The increase in fuel concentration varied between the oils, however, tin and iron were consistently more effective than zinc. A particularly interesting result occurred with the Cymric light oil. In the control runs, a sustained combustion front was not achieved, while in the iron additive runs, stable, sustained combustion was achieved. Iron and tin salts are suitable additives to increase fuel deposition when that is needed. Additives suitable for use as a fuel reducing agent have not yet been found. 26 refs., 23 figs, 6 tabs.

  2. In situ combustion with metallic additives SUPRI TR 87

    SciTech Connect

    Holt, R.J.

    1992-07-01

    In-situ combustion is the most energy efficient of the thermal oil recovery methods. In this process, a portion of a reservoir`s oil is burned in-situ as fuel to drive the recovery process. In light oil reservoirs, too little fuel may be deposited, making sustained combustion difficult. In heavy oil reservoirs, too much fuel may be deposited leading to high air injection requirements and unfavorable economics. This study has been designed to attack these problems. Water soluble metallic additives are investigated as agents to modify fuel deposition and combustion performance. This report describes seven combustion tube runs using two cradle oils and two metallic additives. The oils are 12{degrees} and 34{degrees} API, both from Cymric (California). The metallic additives tested are ionic nitrate (Fe(NO{sub 3}){sub 3}9H{sub 2}O) and zinc nitrate (Zn(NO{sub 3}){sub 2}6H{sub 2}O). Iron and tin additives improved the combustion efficiency in all cases. Fluctuations in the produced gas compositions were observed in all control runs, but nearly disappeared with the iron and tin additives. The combustion front velocities were also increased by iron and tin. Changes were also observed in the apparent hydrogen to carbon (H/C) ratio of the fuel, heat of combustion, air requirements, and amount of fuel deposited. Iron and tin caused increases in fuel concentration while causing a decrease in air requirement. The increase in fuel concentration varied between the oils, however, tin and iron were consistently more effective than zinc. A particularly interesting result occurred with the Cymric light oil. In the control runs, a sustained combustion front was not achieved, while in the iron additive runs, stable, sustained combustion was achieved. Iron and tin salts are suitable additives to increase fuel deposition when that is needed. Additives suitable for use as a fuel reducing agent have not yet been found. 26 refs., 23 figs, 6 tabs.

  3. Developing gradient metal alloys through radial deposition additive manufacturing.

    PubMed

    Hofmann, Douglas C; Roberts, Scott; Otis, Richard; Kolodziejska, Joanna; Dillon, R Peter; Suh, Jong-ook; Shapiro, Andrew A; Liu, Zi-Kui; Borgonia, John-Paul

    2014-01-01

    Interest in additive manufacturing (AM) has dramatically expanded in the last several years, owing to the paradigm shift that the process provides over conventional manufacturing. Although the vast majority of recent work in AM has focused on three-dimensional printing in polymers, AM techniques for fabricating metal alloys have been available for more than a decade. Here, laser deposition (LD) is used to fabricate multifunctional metal alloys that have a strategically graded composition to alter their mechanical and physical properties. Using the technique in combination with rotational deposition enables fabrication of compositional gradients radially from the center of a sample. A roadmap for developing gradient alloys is presented that uses multi-component phase diagrams as maps for composition selection so as to avoid unwanted phases. Practical applications for the new technology are demonstrated in low-coefficient of thermal expansion radially graded metal inserts for carbon-fiber spacecraft panels. PMID:24942329

  4. The metallurgy and processing science of metal additive manufacturing

    SciTech Connect

    Sames, William J.; List, III, Frederick Alyious; Pannala, Sreekanth; Dehoff, Ryan R.; Babu, Sudarsanam Suresh

    2016-01-01

    Here, additive Manufacturing (AM), widely known as 3D printing, is a method of manufacturing that forms parts from powder, wire, or sheets in a process that proceeds layer-by-layer.Many techniques (using many different names) have been developed to accomplish this via melting or solid - state joining. In this review, these techniques for producing metal parts are explored, with a focus on the science of metal AM: processing defects, heat transfer, solidification, solid- state precipitation, mechanical properties, and post-processing metallurgy. The various metal AM techniques are compared, with analysis of the strengths and limitations of each. Few alloys have been developed for commercial production, but recent development efforts are presented as a path for the ongoing development of new materials for AM processes.

  5. Developing Gradient Metal Alloys through Radial Deposition Additive Manufacturing

    PubMed Central

    Hofmann, Douglas C.; Roberts, Scott; Otis, Richard; Kolodziejska, Joanna; Dillon, R. Peter; Suh, Jong-ook; Shapiro, Andrew A.; Liu, Zi-Kui; Borgonia, John-Paul

    2014-01-01

    Interest in additive manufacturing (AM) has dramatically expanded in the last several years, owing to the paradigm shift that the process provides over conventional manufacturing. Although the vast majority of recent work in AM has focused on three-dimensional printing in polymers, AM techniques for fabricating metal alloys have been available for more than a decade. Here, laser deposition (LD) is used to fabricate multifunctional metal alloys that have a strategically graded composition to alter their mechanical and physical properties. Using the technique in combination with rotational deposition enables fabrication of compositional gradients radially from the center of a sample. A roadmap for developing gradient alloys is presented that uses multi-component phase diagrams as maps for composition selection so as to avoid unwanted phases. Practical applications for the new technology are demonstrated in low-coefficient of thermal expansion radially graded metal inserts for carbon-fiber spacecraft panels. PMID:24942329

  6. The metallurgy and processing science of metal additive manufacturing

    DOE PAGESBeta

    Sames, William J.; List, III, Frederick Alyious; Pannala, Sreekanth; Dehoff, Ryan R.; Babu, Sudarsanam Suresh

    2016-03-07

    Here, additive Manufacturing (AM), widely known as 3D printing, is a method of manufacturing that forms parts from powder, wire, or sheets in a process that proceeds layer-by-layer.Many techniques (using many different names) have been developed to accomplish this via melting or solid - state joining. In this review, these techniques for producing metal parts are explored, with a focus on the science of metal AM: processing defects, heat transfer, solidification, solid- state precipitation, mechanical properties, and post-processing metallurgy. The various metal AM techniques are compared, with analysis of the strengths and limitations of each. Few alloys have been developedmore » for commercial production, but recent development efforts are presented as a path for the ongoing development of new materials for AM processes.« less

  7. Epoxy nanocomposites with two-dimensional transition metal dichalcogenide additives.

    PubMed

    Eksik, Osman; Gao, Jian; Shojaee, S Ali; Thomas, Abhay; Chow, Philippe; Bartolucci, Stephen F; Lucca, Don A; Koratkar, Nikhil

    2014-05-27

    Emerging two-dimensional (2D) materials such as transition metal dichalcogenides offer unique and hitherto unavailable opportunities to tailor the mechanical, thermal, electronic, and optical properties of polymer nanocomposites. In this study, we exfoliated bulk molybdenum disulfide (MoS2) into nanoplatelets, which were then dispersed in epoxy polymers at loading fractions of up to 1% by weight. We characterized the tensile and fracture properties of the composite and show that MoS2 nanoplatelets are highly effective at enhancing the mechanical properties of the epoxy at very low nanofiller loading fractions (below 0.2% by weight). Our results show the potential of 2D sheets of transition metal dichalcogenides as reinforcing additives in polymeric composites. Unlike graphene, transition metal dichalcogenides such as MoS2 are high band gap semiconductors and do not impart significant electrical conductivity to the epoxy matrix. For many applications, it is essential to enhance mechanical properties while also maintaining the electrical insulation properties and the high dielectric constant of the polymer material. In such applications, conductive carbon based fillers such as graphene cannot be utilized. This study demonstrates that 2D transition metal dichalcogenide additives offer an elegant solution to such class of problems. PMID:24754702

  8. A biosystem for removal of metal ions from water

    SciTech Connect

    Kilbane, J.J. II.

    1990-01-01

    The presence of heavy metal ions in ground and surface waters constitutes a potential health risk and is an environmental concern. Moreover, processes for the recovery of valuable metal ions are of interest. Bioaccumulation or biosorption is not only a factor in assessing the environmental risk posed by metal ions; it can also be used as a means of decontamination. A biological system for the removal and recovery of metal ions from contaminated water is reported here. Exopolysaccharide-producing microorganisms, including a methanotrophic culture, are demonstrated to have superior metal binding ability, compared with other microbial cultures. This paper describes a biosorption process in which dried biomass obtained from exopolysaccharide-producing microorganisms is encapsulated in porous plastic beads and is used for metal ion binding and recovery. 22 refs., 13 figs.

  9. Fluorescence imaging of metal ions implicated in diseases.

    PubMed

    Qian, Xuhong; Xu, Zhaochao

    2015-07-21

    Metal ions play an important role in various biological processes, their abnormal homeostasis in cells is related to many diseases, such as neurodegenerative disease, cancer and diabetes. Fluorescent imaging offers a unique route to detect metal ions in cells via a contactless and damage-free way with high spatial and temporal fidelity. Consequently, it represents a promising method to advance the understanding of physiological and pathological functions of metal ions in cell biology. In this highlight article, we will discuss recent advances in fluorescent imaging of metal ions by small-molecule sensors for understanding the role of metals in related diseases. We will also discuss challenges and opportunities for the design of small-molecule sensors for fluorescent detection of cellular metal ions as a potential method for disease diagnosis. PMID:25556818

  10. Metal Ion Capture Mechanism of a Copper Metallochaperone.

    PubMed

    Chakravorty, Dhruva K; Li, Pengfei; Tran, Trang T; Bayse, Craig A; Merz, Kenneth M

    2016-01-26

    A novel cation-π interaction between the bound Cu(+) metal ion and Trp44 in the periplasmic Cu(+)/Ag(+) metallochaperone Escherichia coli CusF protects Cu(+) from the oxidative influence of the periplasm. In a popular model of metal ion transfer, a conformational change in the metal binding loop disrupts the cation-π interaction and moves Trp44 aside to provide access to the occluded metal ion binding site in an "open" conformation. In this study, our molecular dynamics simulations support this putative mechanism of metal ion transfer. We find that the apoprotein undergoes a transition back and forth from the crystallographically observed "closed" state to the hypothesized open conformation over multiple microseconds. In agreement with nuclear magnetic resonance data, our simulations show that similar transitions are prohibited in Cu(+)·CusF, suggesting that the conformational transitions are gated by a metal ion-mediated second-shell hydrogen bond between metal binding residue His36 and Asp37 of the metal binding loop region. Ab initio quantum mechanical calculations indicate that metal ion binding strengthens this interaction significantly, much like what is found in the case of other metalloproteins. The study builds toward a common evolutionary role of metal ion-mediated second-shell hydrogen bonds in metalloprotein structure and function. PMID:26690586

  11. Applications for Gradient Metal Alloys Fabricated Using Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Hofmann, Douglas C.; Borgonia, John Paul C.; Dillon, Robert P.; Suh, Eric J.; Mulder, jerry L.; Gardner, Paul B.

    2013-01-01

    Recently, additive manufacturing (AM) techniques have been developed that may shift the paradigm of traditional metal production by allowing complex net-shaped hardware to be built up layer-by-layer, rather than being machined from a billet. The AM process is ubiquitous with polymers due to their low melting temperatures, fast curing, and controllable viscosity, and 3D printers are widely available as commercial or consumer products. 3D printing with metals is inherently more complicated than with polymers due to their higher melting temperatures and reactivity with air, particularly when heated or molten. The process generally requires a high-power laser or other focused heat source, like an electron beam, for precise melting and deposition. Several promising metal AM techniques have been developed, including laser deposition (also called laser engineered net shaping or LENS® and laser deposition technology (LDT)), direct metal laser sintering (DMLS), and electron beam free-form (EBF). These machines typically use powders or wire feedstock that are melted and deposited using a laser or electron beam. Complex net-shape parts have been widely demonstrated using these (and other) AM techniques and the process appears to be a promising alternative to machining in some cases. Rather than simply competing with traditional machining for cost and time savings, the true advantage of AM involves the fabrication of hardware that cannot be produced using other techniques. This could include parts with "blind" features (like foams or trusses), parts that are difficult to machine conventionally, or parts made from materials that do not exist in bulk forms. In this work, the inventors identify that several AM techniques can be used to develop metal parts that change composition from one location in the part to another, allowing for complete control over the mechanical or physical properties. This changes the paradigm for conventional metal fabrication, which relies on an

  12. Molecular Turnstiles Regulated by Metal Ions.

    PubMed

    Wang, Guangxia; Xiao, Hongmei; He, Jiaojiao; Xiang, Junfeng; Wang, Ying; Chen, Xuebo; Che, Yanke; Jiang, Hua

    2016-04-15

    A family of novel molecular turnstiles 1-3 composed of two stators with pyridyl binding sites and a different-sized triptycene rotor was synthesized. The molecular turnstiles behave in an open state at room temperature in the absence of metal ions but display significantly different closed states in the presence of Ag(+) and Pd(2+). The Ag(+)-mediated turnstiles 1-3Ag exhibited closed states but unreadable bistability at ambient temperature because the Ag(+)-mediated macrocyclic framework is not able to restrict the rotations of the rotors; while temperature was decreased, the macrocyclic frameworks became stable enough to halt the rotations of the rotors, eventually leading to the readable closed states for 1-3Ag. In contrast, Pd(2+)-mediated macrocyclic frameworks are stable, giving rise to a detectable closed state of turnstiles 1-3Pd in a wide range of temperatures. These findings have also been supported by DFT calculations. PMID:26986992

  13. Metal Additive Manufacturing: A Review of Mechanical Properties

    NASA Astrophysics Data System (ADS)

    Lewandowski, John J.; Seifi, Mohsen

    2016-07-01

    This article reviews published data on the mechanical properties of additively manufactured metallic materials. The additive manufacturing techniques utilized to generate samples covered in this review include powder bed fusion (e.g., EBM, SLM, DMLS) and directed energy deposition (e.g., LENS, EBF3). Although only a limited number of metallic alloy systems are currently available for additive manufacturing (e.g., Ti-6Al-4V, TiAl, stainless steel, Inconel 625/718, and Al-Si-10Mg), the bulk of the published mechanical properties information has been generated on Ti-6Al-4V. However, summary tables for published mechanical properties and/or key figures are included for each of the alloys listed above, grouped by the additive technique used to generate the data. Published values for mechanical properties obtained from hardness, tension/compression, fracture toughness, fatigue crack growth, and high cycle fatigue are included for as-built, heat-treated, and/or HIP conditions, when available. The effects of test orientation/build direction on properties, when available, are also provided, along with discussion of the potential source(s) (e.g., texture, microstructure changes, defects) of anisotropy in properties. Recommendations for additional work are also provided.

  14. Computational scheme for the prediction of metal ion binding by a soil fulvic acid

    USGS Publications Warehouse

    Marinsky, J.A.; Reddy, M.M.; Ephraim, J.H.; Mathuthu, A.S.

    1995-01-01

    The dissociation and metal ion binding properties of a soil fulvic acid have been characterized. Information thus gained was used to compensate for salt and site heterogeneity effects in metal ion complexation by the fulvic acid. An earlier computational scheme has been modified by incorporating an additional step which improves the accuracy of metal ion speciation estimates. An algorithm is employed for the prediction of metal ion binding by organic acid constituents of natural waters (once the organic acid is characterized in terms of functional group identity and abundance). The approach discussed here, currently used with a spreadsheet program on a personal computer, is conceptually envisaged to be compatible with computer programs available for ion binding by inorganic ligands in natural waters.

  15. Synthetic metallic dialkydithiocarbamates as antiwear and extreme-pressure additives for lubricating oils: Role of metal on their effectiveness

    SciTech Connect

    Tuli, D.K.; Sarin, R.; Gupta, A.K.

    1995-04-01

    Dialkydithiocarbamates of five metals have been synthesized in pure form by following a simple general method. The alkyl chain in each of these compounds has been kept the same so as to observe the performance variations due to metal ions. The EP properties expressed as load wear index and weld load indicated the highest performance by Bi followed by Pb, Sb, Zn and Mo. The antiwear properties in terms of wear scar diameter, relative anti-wear effectiveness and mean average wear scar diameter show a performance order of Bi > Pb > Sb > Zn > Mo. The large ionic radius metals (Bi, Pb & Sb) had the best overall load-carrying performance and their effectiveness increased substantially when the additive concentration was more than 0.004 gm atom/Kg. The results suggest that Bi has good potential to replace toxic Pb and Sb from existing lubrication systems. 18 refs., 7 refs., 1 tab.

  16. Electron Capture Dissociation of Trivalent Metal Ion-Peptide Complexes

    NASA Astrophysics Data System (ADS)

    Flick, Tawnya G.; Donald, William A.; Williams, Evan R.

    2013-02-01

    With electrospray ionization from aqueous solutions, trivalent metal ions readily adduct to small peptides resulting in formation of predominantly (peptide + MT - H)2+, where MT = La, Tm, Lu, Sm, Ho, Yb, Pm, Tb, or Eu, for peptides with molecular weights below ~1000 Da, and predominantly (peptide + MT)3+ for larger peptides. ECD of (peptide + MT - H)2+ results in extensive fragmentation from which nearly complete sequence information can be obtained, even for peptides for which only singly protonated ions are formed in the absence of the metal ions. ECD of these doubly charged complexes containing MT results in significantly higher electron capture efficiency and sequence coverage than peptide-divalent metal ion complexes that have the same net charge. Formation of salt-bridge structures in which the metal ion coordinates to a carboxylate group are favored even for (peptide + MT)3+. ECD of these latter complexes for large peptides results in electron capture by the protonation site located remotely from the metal ion and predominantly c/ z fragments for all metals, except Eu3+, which undergoes a one electron reduction and only loss of small neutral molecules and b/ y fragments are formed. These results indicate that solvation of the metal ion in these complexes is extensive, which results in the electrochemical properties of these metal ions being similar in both the peptide environment and in bulk water.

  17. Cleaning Process Development for Metallic Additively Manufactured Parts

    NASA Technical Reports Server (NTRS)

    Tramel, Terri L.; Welker, Roger; Lowery, Niki; Mitchell, Mark

    2014-01-01

    Additive Manufacturing of metallic components for aerospace applications offers many advantages over traditional manufacturing techniques. As a new technology, many aspects of its widespread utilization remain open to investigation. Among these are the cleaning processes that can be used for post finishing of parts and measurements to verify effectiveness of the cleaning processes. Many cleaning and drying processes and measurement methods that have been used for parts manufactured using conventional techniques are candidates that may be considered for cleaning and verification of additively manufactured parts. Among these are vapor degreasing, ultrasonic immersion and spray cleaning, followed by hot air drying, vacuum baking and solvent displacement drying. Differences in porosity, density, and surface finish of additively manufactured versus conventionally manufactured parts may introduce new considerations in the selection of cleaning and drying processes or the method used to verify their effectiveness. This presentation will review the relative strengths and weaknesses of different candidate cleaning and drying processes as they may apply to additively manufactured metal parts for aerospace applications. An ultrasonic cleaning technique for exploring the cleanability of parts will be presented along with an example using additively manufactured Inconel 718 test specimens to illustrate its use. The data analysis shows that this ultrasonic cleaning approach results in a well-behaved ultrasonic cleaning/extraction behavior. That is, it does not show signs of accelerated cavitation erosion of the base material, which was later confirmed by neutron imaging. In addition, the analysis indicated that complete cleaning would be achieved by ultrasonic immersion cleaning at approximately 5 minutes, which was verified by subsequent cleaning of additional parts.

  18. Molecular designs for controlling the local environments around metal ions.

    PubMed

    Cook, Sarah A; Borovik, A S

    2015-08-18

    -oxyl radical. We therefore probed the amount of spin density on the oxido ligand of our complexes using EPR spectroscopy in conjunction with oxygen-17 labeling. Our findings showed that there is a significant amount of spin on the oxido ligand, yet the M-oxo bonds are best described as highly covalent and there is no indication that an oxyl radical is formed. These results offer the intriguing possibility that high-spin M-oxo complexes are involved in O-O bond formation in biology. Ligand redesign to incorporate H-bond accepting units (sulfonamido groups) simultaneously provided a metal ion binding pocket, adjacent H-bond acceptors, and an auxiliary binding site for a second metal ion. These properties allowed us to isolate a series of heterobimetallic complexes of Fe(III) and Mn(III) in which a group II metal ion was coordinated within the secondary coordination sphere. Examination of the influence of the second metal ion on the electron transfer properties of the primary metal center revealed unexpected similarities between Ca(II) and Sr(II) ions, a result with relevance to the OEC. In addition, the presence of a second metal ion was found to prevent intramolecular oxidation of the ligand with an O atom transfer reagent. PMID:26181849

  19. Multiply stripped ion generation in the metal vapor vacuum arc

    SciTech Connect

    Brown, I.G.; Feinberg, B.; Galvin, J.E.

    1986-08-01

    We consider the charge state distribution of ions produced in the metal vapor vacuum arc plasma discharge. A high current metal ion source, the MEVVA ion source, in which the ion beam is extracted from a metal vapor vacuum arc plasma, has been used to obtain the spectra of multiple charged ions produced within the cathode spots. A computer calculation of the charge state distribution that evolves within the spots via stepwide ionization of ions by electron impact provides a theoretical basis for comparison of the data. In this paper we report on the measured charge state distributions for a wide variety of metallic species and compare these results with the predictions of this theory. 55 refs.

  20. Structural insights into protein-metal ion partnerships.

    PubMed

    Barondeau, David P; Getzoff, Elizabeth D

    2004-12-01

    New metalloprotein structures continue to provide discoveries regarding protein-metal ion partnerships. Many recent structures reveal metal ion sites that control or are controlled by protein conformational change, including modulation by alternative splice variants and striking conformational changes. Only a few novel catalytic metal centers have been revealed recently, such as the surprising Ni-hook superoxide dismutase catalytic site and the cubane-like Mn(3)CaO(4) photosynthetic oxygen-evolving center. However, important new variations on old heme themes, breakthroughs in the fields of metal ion regulation and metallochaperones, and captivating insights into partnerships between proteins and minerals have also been described. Very high resolution metal site structures and metalloprotein design will be increasingly important in order to leverage the wealth of native metalloprotein structures into a deep understanding of metal ion site specificity and activity. PMID:15582401

  1. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    NASA Astrophysics Data System (ADS)

    Vora, Hitesh D.; Rajamure, Ravi Shanker; Roy, Anurag; Srinivasan, S. G.; Sundararajan, G.; Banerjee, Rajarshi; Dahotre, Narendra B.

    2016-07-01

    Various physical and chemical properties of surface and subsurface regions of Al can be improved by the formation of transition metal intermetallic phases (Al x TM y ) via coating of the transition metal (TM). The lower equilibrium solid solubility of TM in Al (<1 at.%) is a steep barrier to the formation of solid solutions using conventional alloying methods. In contrast, as demonstrated in the present work, surface engineering via a laser-aided additive manufacturing approach can effectively synthesize TM intermetallic coatings on the surface of Al. The focus of the present work included the development of process control to achieve thermodynamic and kinetic conditions necessary for desirable physical, microstructural and compositional attributes. A multiphysics finite element model was developed to predict the temperature profile, cooling rate, melt depth, dilution of W in Al matrix and corresponding micro-hardness in the coating, and the interface between the coating and the base material and the base material.

  2. Laser Assisted Additively Manufactured Transition Metal Coating on Aluminum

    NASA Astrophysics Data System (ADS)

    Vora, Hitesh D.; Rajamure, Ravi Shanker; Roy, Anurag; Srinivasan, S. G.; Sundararajan, G.; Banerjee, Rajarshi; Dahotre, Narendra B.

    2016-05-01

    Various physical and chemical properties of surface and subsurface regions of Al can be improved by the formation of transition metal intermetallic phases (Al x TM y ) via coating of the transition metal (TM). The lower equilibrium solid solubility of TM in Al (<1 at.%) is a steep barrier to the formation of solid solutions using conventional alloying methods. In contrast, as demonstrated in the present work, surface engineering via a laser-aided additive manufacturing approach can effectively synthesize TM intermetallic coatings on the surface of Al. The focus of the present work included the development of process control to achieve thermodynamic and kinetic conditions necessary for desirable physical, microstructural and compositional attributes. A multiphysics finite element model was developed to predict the temperature profile, cooling rate, melt depth, dilution of W in Al matrix and corresponding micro-hardness in the coating, and the interface between the coating and the base material and the base material.

  3. Alkali metal ion battery with bimetallic electrode

    SciTech Connect

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  4. A self-sputtering ion source: A new approach to quiescent metal ion beams

    SciTech Connect

    Oks, Efim M.; Anders, Andre

    2009-09-03

    A new metal ion source is presented based on sustained self-sputtering plasma in a magnetron discharge. Metals exhibiting high self-sputtering yield like Cu, Ag, Zn, and Bi can be used in a high-power impulse magnetron sputtering (HIPIMS) discharge such that the plasma almost exclusively contains singly charged metal ions of the target material. The plasma and extracted ion beam are quiescent. The ion beams consist mostly of singly charged ions with a space-charge limited current density which reached about 10 mA/cm2 at an extraction voltage of 45 kV and a first gap spacing of 12 mm.

  5. A self-sputtering ion source: A new approach to quiescent metal ion beams

    SciTech Connect

    Oks, Efim

    2010-02-15

    A new metal ion source is presented based on sustained self-sputtering plasma in a magnetron discharge. Metals exhibiting high self-sputtering yield such as Cu, Ag, Zn, and Bi can be used in a high-power impulse magnetron sputtering discharge such that the plasma almost exclusively contains singly charged metal ions of the target material. The plasma and extracted ion beam are quiescent. The ion beams consist mostly of singly charged ions with a space-charge limited current density which reached about 10 mA/cm{sup 2} at an extraction voltage of 45 kV and a first gap spacing of 12 mm.

  6. Development of a lithium liquid metal ion source for MeV ion beam analysis

    SciTech Connect

    Read, P.M.; Maskrey, J.T.; Alton, G.D.

    1988-01-01

    Lithium liquid metal ion sources are an attractive complement to the existing gaseous ion sources that are extensively used for ion beam analysis. This is due in part to the high brightness of the liquid metal ion source and in part to the availability of a lithium ion beam. High brightness is of particular importance to MeV ion microprobes which are now approaching current density limitations on targets determined by the ion source. The availability of a lithium beam provides increased capabilities for hydrogen profiling and high resolution Rutherford backscattering spectrometry. This paper describes the design and performance of a lithium liquid metal ion source suitable for use on a 5MV Laddertron accelerator. Operational experience with the source and some of its uses for ion beam analysis are discussed. 8 refs., 2 figs.

  7. Metal ion adsorption at the ionic liquid-mica interface

    NASA Astrophysics Data System (ADS)

    McDonald, Samila; Elbourne, Aaron; Warr, Gregory G.; Atkin, Rob

    2015-12-01

    Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete with the IL cation and adsorb to mica charge sites. In this work amplitude modulated atomic force microscopy (AM-AFM) has been used to probe metal ion adsorption at the interface of mica with propylammonium nitrate (PAN), a room temperature IL. Lithium, sodium, potassium, magnesium and calcium nitrate salts were added to PAN at a concentration of ~60 mM. Aluminum nitrate was also investigated, but only at 5 mM because its solubility in PAN is much lower. The AM-AFM images obtained when the metal ions were present are strikingly different to that of pure PAN, indicating that the ions compete effectively with the propylammonium cation and adsorb to negatively charged sites on the mica surface despite their much lower concentration. This is a consequence of electrostatic attractions between the mica charge sites and the metal ions being significantly stronger than for the propylammonium cation; compared to the metal ions the propylammonium charged group is relatively constrained sterically. A distinct honeycomb pattern is noted for the PAN + Al3+ system, less obviously for the divalent ions and not at all for monovalent ions. This difference is attributed to the strength of electrostatic interactions between metal ions and mica charge sites increasing with the ion charge, which means that divalent and (particularly) trivalent ions are located more precisely above the charged sites of the mica lattice. The images obtained allow important distinctions between metal ion adsorption at mica-water and mica-PAN interfaces to be made.Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete

  8. Metal ion effects on enolase activity

    SciTech Connect

    Lee, M.E.; Nowak, T.

    1986-05-01

    Most metal binding studies with yeast enolase suggest that two metals per monomer are required for catalytic activity. The functions of metal I and metal II have not been unequivocally defined. In a series of kinetic experiments where the concentration of MgII is kept constant at subsaturating levels (1mM), the addition of MnII or of ZnII gives a hyperbolic decrease in activity. The final velocity of these mixed metal systems is the same velocity obtained with either only MnII or ZnII respectively. The concentration of MnII (40 ..mu..M) or of Zn (2..mu..M) which gives half maximal effect in the presence of (1mM) MgII is approximately the same as the Km' value for MnII (9..mu..M) or ZnII (3..mu..M) respectively. Direct binding of MnII to enolase in the absence and presence of MgII shows that MnII and MgII compete for the same metal site on enolase. In the presence of 2-phosphoglycerate (2-PGA) and MgII, only a single site is occupied by MnII. Results suggest MnII at site I and MgII at site II. PRR and high resolution /sup 1/H and /sup 31/P NMR studies of enzyme-ligand complexes containing MnII and MgII and MnII are consistent with this model. /sub 31/P measurements allow a measure of the equilibrium constant (0.36) for enolase. Saturation transfer measurements yield net rate constants (k/sub f/ = 0.49s/sup -1/; k/sub r/ = 1.3s/sup -1/) for the overall reaction. These values are smaller than k/sub cat/ (38s/sup -1/) measured under analogous conditions. The cation at site I appears to determine catalytic activity.

  9. Impregnated-electrode-type liquid metal ion source

    NASA Astrophysics Data System (ADS)

    Ishikawa, J.; Gotoh, Y.; Tsuji, H.; Takagi, T.

    We have developed an impregnated-electrode-type liquid metal ion source whose tip is a sintered-porous structure made of a refractory metal such as tungsten. By this structure the ratio of the liquid metal surface area facing the vacuum to the volume is low, which decreases useless metal evaporation from the surface. The maximum vapour pressure of the metal in operation for this ion source is 10 -1-10 0 Torr, which is 2-3 orders of magnitude higher than that for the needle type. Therefore, useful metal ions such as Ga +, Au +, Ag +, In +, Si 2+, Ge 2+, and Sb 2+ can be extracted from single element metals or alloys. The porous structure of the tip has also an effect on the positive control of the liquid metal flow rate to the tip head. Thus, a stable operation with a high current of a few hundreds of μA can be obtained together with a low current high brightness ion beam. Therefore, this ion source is suitable not only for microfocusing but also for a general use as a metal ion source.

  10. 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.

  11. 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

  12. Catalysis using hydrous metal oxide ion exchangers

    DOEpatents

    Dosch, R.G.; Stephens, H.P.; Stohl, F.V.

    1983-07-21

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  13. Catalysis using hydrous metal oxide ion exchanges

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.; Stohl, Frances V.

    1985-01-01

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  14. Inhibition of hot salt corrosion by metallic additives

    NASA Technical Reports Server (NTRS)

    Deadmore, D. L.; Lowell, C. E.

    1978-01-01

    The effectiveness of several potential fuel additives in reducing the effects of sodium sulfate-induced hot corrosion was evaluated in a cyclic Mach 0.3 burner rig. The potential inhibitors examined were salts of Al, Si, Cr, Fe, Zn, Mg, Ca, and Ba. The alloys tested were IN-100, U-700, IN-738, IN-792, Mar M-509, and 304 stainless steel. Each alloy was exposed for 100 cycles of 1 hour each at 900 C in combustion gases doped with the corrodant and inhibitor salts and the extent of attack was determined by measuring maximum metal thickness loss. The most effective and consistent inhibitor additive was Ba (NO3)2 which reduced the hot corrosion attack to nearly that of simple oxidation.

  15. Requirement for transient metal ions revealed through computational analysis for DNA polymerase going in reverse

    PubMed Central

    Perera, Lalith; Freudenthal, Bret D.; Beard, William A.; Shock, David D.; Pedersen, Lee G.; Wilson, Samuel H.

    2015-01-01

    DNA polymerases facilitate faithful insertion of nucleotides, a central reaction occurring during DNA replication and repair. DNA synthesis (forward reaction) is “balanced,” as dictated by the chemical equilibrium by the reverse reaction of pyrophosphorolysis. Two closely spaced divalent metal ions (catalytic and nucleotide-binding metals) provide the scaffold for these reactions. The catalytic metal lowers the pKa of O3′ of the growing primer terminus, and the nucleotide-binding metal facilitates substrate binding. Recent time-lapse crystallographic studies of DNA polymerases have identified an additional metal ion (product metal) associated with pyrophosphate formation, leading to the suggestion of its possible involvement in the reverse reaction. Here, we establish a rationale for a role of the product metal using quantum mechanical/molecular mechanical calculations of the reverse reaction in the confines of the DNA polymerase β active site. Additionally, site-directed mutagenesis identifies essential residues and metal-binding sites necessary for pyrophosphorolysis. The results indicate that the catalytic metal site must be occupied by a magnesium ion for pyrophosphorolysis to occur. Critically, the product metal site is occupied by a magnesium ion early in the pyrophosphorolysis reaction path but must be removed later. The proposed dynamic nature of the active site metal ions is consistent with crystallographic structures. The transition barrier for pyrophosphorolysis was estimated to be significantly higher than that for the forward reaction, consistent with kinetic activity measurements of the respective reactions. These observations provide a framework to understand how ions and active site changes could modulate the internal chemical equilibrium of a reaction that is central to genome stability. PMID:26351676

  16. Bioinorganic Chemistry of the Alkali Metal Ions.

    PubMed

    Kim, Youngsam; Nguyen, Thuy-Tien T; Churchill, David G

    2016-01-01

    The common Group 1 alkali metals are indeed ubiquitous on earth, in the oceans and in biological systems. In this introductory chapter, concepts involving aqueous chemistry and aspects of general coordination chemistry and oxygen atom donor chemistry are introduced. Also, there are nuclear isotopes of importance. A general discussion of Group 1 begins from the prevalence of the ions, and from a comparison of their ionic radii and ionization energies. While oxygen and water molecule binding have the most relevance to biology and in forming a detailed understanding between the elements, there is a wide range of basic chemistry that is potentially important, especially with respect to biological chelation and synthetic multi-dentate ligand design. The elements are widely distributed in life forms, in the terrestrial environment and in the oceans. The details about the workings in animal, as well as plant life are presented in this volume. Important biometallic aspects of human health and medicine are introduced as well. Seeing as the elements are widely present in biology, various particular endogenous molecules and enzymatic systems can be studied. Sodium and potassium are by far the most important and central elements for consideration. Aspects of lithium, rubidium, cesium and francium chemistry are also included; they help in making important comparisons related to the coordination chemistry of Na(+) and K(+). Physical methods are also introduced. PMID:26860297

  17. Metal ion adsorption at the ionic liquid-mica interface.

    PubMed

    McDonald, Samila; Elbourne, Aaron; Warr, Gregory G; Atkin, Rob

    2016-01-14

    Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete with the IL cation and adsorb to mica charge sites. In this work amplitude modulated atomic force microscopy (AM-AFM) has been used to probe metal ion adsorption at the interface of mica with propylammonium nitrate (PAN), a room temperature IL. Lithium, sodium, potassium, magnesium and calcium nitrate salts were added to PAN at a concentration of ∼60 mM. Aluminum nitrate was also investigated, but only at 5 mM because its solubility in PAN is much lower. The AM-AFM images obtained when the metal ions were present are strikingly different to that of pure PAN, indicating that the ions compete effectively with the propylammonium cation and adsorb to negatively charged sites on the mica surface despite their much lower concentration. This is a consequence of electrostatic attractions between the mica charge sites and the metal ions being significantly stronger than for the propylammonium cation; compared to the metal ions the propylammonium charged group is relatively constrained sterically. A distinct honeycomb pattern is noted for the PAN + Al(3+) system, less obviously for the divalent ions and not at all for monovalent ions. This difference is attributed to the strength of electrostatic interactions between metal ions and mica charge sites increasing with the ion charge, which means that divalent and (particularly) trivalent ions are located more precisely above the charged sites of the mica lattice. The images obtained allow important distinctions between metal ion adsorption at mica-water and mica-PAN interfaces to be made. PMID:26661934

  18. Progress in metal ion separation and preconcentration : an overview.

    SciTech Connect

    Bond, A. H.

    1998-05-19

    A brief historical perspective covering the most mature chemically-based metal ion separation methods is presented, as is a summary of the recommendations made in the 1987 National Research Council (NRC) report entitled ''Separation and Purification: Critical Needs and Opportunities''. A review of Progress in Metal Ion Separation and Preconcentration shows that advances are occurring in each area of need cited by the NRC. Following an explanation of the objectives and general organization of this book, the contents of each chapter are briefly summarized and some future research opportunities in metal ion separations are presented.

  19. Separation of platinum group metal ions by Donnan dialysis

    SciTech Connect

    Brajter, K.; Slonawska, K.; Cox, J.A.

    1985-10-01

    Separations of metal ions on the basis of Donnan dialysis across anion-exchange membranes should be possible if the receiver electrolyte composition favors the formation of selected anionic complexes of the sample metal ions. Moreover, such a separation has the possibility of being better suited from some applications than batch or column experiments with anion-exchange resins. The above hypothesis are tested on the platinum-group metal ions, Pt(IV), Rh(III), Pd(II), Ir(III), and Ir(IV). 13 references, 4 tables.

  20. An Animal Model Using Metallic Ions to Produce Autoimmune Nephritis.

    PubMed

    Ramírez-Sandoval, Roxana; Luévano-Rodríguez, Nayeli; Rodríguez-Rodríguez, Mayra; Pérez-Pérez, María Elena; Saldívar-Elias, Sergio; Gurrola-Carlos, Reinaldo; Avalos-Díaz, Esperanza; Bollain-y-Goytia, Juan José; Herrera-Esparza, Rafael

    2015-01-01

    Autoimmune nephritis triggered by metallic ions was assessed in a Long-Evans rat model. The parameters evaluated included antinuclear autoantibody production, kidney damage mediated by immune complexes detected by immunofluorescence, and renal function tested by retention of nitrogen waste products and proteinuria. To accomplish our goal, the animals were treated with the following ionic metals: HgCl2, CuSO4, AgNO3, and Pb(NO3)2. A group without ionic metals was used as the control. The results of the present investigation demonstrated that metallic ions triggered antinuclear antibody production in 60% of animals, some of them with anti-DNA specificity. Furthermore, all animals treated with heavy metals developed toxic glomerulonephritis with immune complex deposition along the mesangium and membranes. These phenomena were accompanied by proteinuria and increased concentrations of urea. Based on these results, we conclude that metallic ions may induce experimental autoimmune nephritis. PMID:26064998

  1. An Animal Model Using Metallic Ions to Produce Autoimmune Nephritis

    PubMed Central

    Ramírez-Sandoval, Roxana; Luévano-Rodríguez, Nayeli; Rodríguez-Rodríguez, Mayra; Pérez-Pérez, María Elena; Saldívar-Elias, Sergio; Gurrola-Carlos, Reinaldo; Avalos-Díaz, Esperanza; Bollain-y-Goytia, Juan José

    2015-01-01

    Autoimmune nephritis triggered by metallic ions was assessed in a Long-Evans rat model. The parameters evaluated included antinuclear autoantibody production, kidney damage mediated by immune complexes detected by immunofluorescence, and renal function tested by retention of nitrogen waste products and proteinuria. To accomplish our goal, the animals were treated with the following ionic metals: HgCl2, CuSO4, AgNO3, and Pb(NO3)2. A group without ionic metals was used as the control. The results of the present investigation demonstrated that metallic ions triggered antinuclear antibody production in 60% of animals, some of them with anti-DNA specificity. Furthermore, all animals treated with heavy metals developed toxic glomerulonephritis with immune complex deposition along the mesangium and membranes. These phenomena were accompanied by proteinuria and increased concentrations of urea. Based on these results, we conclude that metallic ions may induce experimental autoimmune nephritis. PMID:26064998

  2. Standard addition method for free acid determination in solutions with hydrolyzable ions

    SciTech Connect

    Baumann, E.W.

    1981-01-01

    The free acid content of solutions containing hydrolyzable ions has been determined potentiometrically by a standard addition method. Two increments of acid are added to the sample in a 1M potassium thiocyanate solution. The sample concentration is calculated by solution of three simultaneous Nernst equations. The method has been demonstrated for solutions containing Al/sup 3 +/, Cr/sup 3 +/, Fe/sup 3 +/, Ni/sup 2 +/, Th/sup 4 +/, or UO/sub 2//sup 2 +/ with a metal-to-acid ratio of < 2.5. The method is suitable for determination of 10 ..mu..moles acid in 10 mL total volume. The accuracy is verifiable by reasonable agreement of the Nerst slopes found in the presence and absence of hydrolyzable ions. The relative standard deviation is < 2.5 percent.

  3. Cooperative adsorption of critical metal ions using archaeal poly-γ-glutamate.

    PubMed

    Hakumai, Yuichi; Oike, Shota; Shibata, Yuka; Ashiuchi, Makoto

    2016-06-01

    Antimony, beryllium, chromium, cobalt (Co), gallium (Ga), germanium, indium (In), lithium, niobium, tantalum, the platinoids, the rare-earth elements (including dysprosium, Dy), and tungsten are generally regarded to be critical (rare) metals, and the ions of some of these metals are stabilized in acidic solutions. We examined the adsorption capacities of three water-soluble functional polymers, namely archaeal poly-γ-glutamate (L-PGA), polyacrylate (PAC), and polyvinyl alcohol (PVA), for six valuable metal ions (Co(2+), Ni(2+), Mn(2+), Ga(3+), In(3+), and Dy(3+)). All three polymers showed apparently little or no capacity for divalent cations, whereas L-PGA and PAC showed the potential to adsorb trivalent cations, implying the beneficial valence-dependent selectivity of anionic polyelectrolytes with multiple carboxylates for metal ions. PVA did not adsorb metal ions, indicating that the crucial role played by carboxyl groups in the adsorption of crucial metal ions cannot be replaced by hydroxyl groups under the conditions. In addition, equilibrium studies using the non-ideal competitive adsorption model indicated that the potential for L-PGA to be used for the removal (or collection) of water-soluble critical metal ions (e.g., Ga(3+), In(3+), and Dy(3+)) was far superior to that of any other industrially-versatile PAC materials. PMID:27013333

  4. 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. PMID:26996438

  5. Metal ion levels: how can they help us?

    PubMed

    Griffin, William L

    2014-04-01

    Ion levels have been shown to reliably predict abnormal function of the bearing surface with increased wear, but ion levels should not be used alone as a trigger for when to proceed with revision surgery with metal-metal articulations. Risk stratification strategies help determine which patients should be monitored more closely with serial ion levels, cross-sectional imaging with a MARS MRI, or proceed on to revision. Based on the current data available, an ion level greater than 4.5 ppb (Cr or Co) may serve as a threshold for when abnormal wear is occurring, and is suggested as a trigger for a MARS MRI scan. PMID:24655610

  6. Comparison of synovial fluid, urine, and serum ion levels in metal-on-metal total hip arthroplasty at a minimum follow-up of 18 years.

    PubMed

    Lass, Richard; Grübl, Alexander; Kolb, Alexander; Stelzeneder, David; Pilger, Alexander; Kubista, Bernd; Giurea, Alexander; Windhager, Reinhard

    2014-09-01

    Diagnosis of adverse reactions to metal debris in metal-on-metal hip arthroplasty is a multifactorial process. Systemic ion levels are just one factor in the evaluation and should not be relied upon solely to determine the need for revision surgery. Furthermore, the correlation between cobalt or chromium serum, urine, or synovial fluid levels and adverse local tissue reactions is still incompletely understood. The hypothesis was that elevated serum and urine metal-ion concentrations are associated with elevated local metal-ion concentrations in primary total hip arthroplasties (THA) and with failure of metal-on-metal articulations in the long-term. In our present study, we evaluated these concentrations in 105 cementless THA with metal-on-metal articulating surfaces with small head diameter at a minimum of 18 years postoperatively. Spearman correlation showed a high correlation between the joint fluid aspirate concentration of cobalt and chromium with the serum cobalt (r = 0.81) and chromium level (r = 0.77) in patients with the THA as the only source of metal-ions. In these patients serum metal-ion analysis is a valuable method for screening. In patients with more than one source of metal or renal insufficiency additional investigations, like joint aspirations are an important tool for evaluation of wear and adverse tissue reactions in metal-on-metal THA. PMID:24841922

  7. Understanding composite explosive energetics: I, The role of metallic additives

    SciTech Connect

    Tao, W.C.; Tarver, C.M.; Breithaupt, D.R.; McGuire, R.R.; Ornellas, D.L.

    1990-01-01

    Composite explosives (CE) have found major applications in air blast, cratering, fragmentation, underwater applications, and other commercial and military systems in which prompt delivery of the available energy is not a primary requirement. In direct metal acceleration applications, composite explosives have not generally been effective because their potential energy is transformed to kinetic energy over time periods extending to tens of microseconds. We are interested in defining the rate determining steps and understanding the chemical interactions between different components in the composite explosive formulation in order to determine the partitioning of the available energy. In this study, we investigate the role of the metallic additive in a bicomponent composite explosive consisting of PETN and aluminum. Of specific interests are the early time performance of and the extent of aluminum reaction in the composite formulation. For formulations loaded with 5 wt% and 10 wt% of 5 micron spherical aluminum, we found that 100% of the aluminum reacted within the first microsecond of volume expansion. The extent of aluminum reaction with the PETN detonation products is reduced to about 65% for composite formulations loaded with 20 wt% aluminum. It is evident from the results of a series of scaling experiments that the detonation behavior of the PETN-aluminum bicomponent composite explosive is nonideal. 6 refs., 11 figs., 2 tabs.

  8. Effects of metal ions on fibroblasts and spiral ganglion cells.

    PubMed

    Paasche, G; Ceschi, P; Löbler, M; Rösl, C; Gomes, P; Hahn, A; Rohm, H W; Sternberg, K; Lenarz, T; Schmitz, K-P; Barcikowski, S; Stöver, T

    2011-04-01

    Degeneration of spiral ganglion cells (SGC) after deafness and fibrous tissue growth around the electrode carrier after cochlear implantation are two of the major challenges in current cochlear implant research. Metal ions are known to possess antimicrobial and antiproliferative potential. The use of metal ions could therefore provide a way to reduce tissue growth around the electrode array after cochlear implantation. Here, we report on in vitro experiments with different concentrations of metal salts with antiproliferative and toxic effects on fibroblasts, PC-12 cells, and freshly isolated spiral ganglion cells, the target cells for electrical stimulation by a cochlear implant. Standard cell lines (NIH/3T3 and L-929 fibroblasts and PC-12 cells) and freshly isolated SGC were incubated with concentrations of metal ions between 0.3 μmol/liter and 10 mmol/liter for 48 hr. Cell survival was investigated by neutral red uptake, CellQuantiBlue assay, or counting of stained surviving neurons. Silver ions exhibited distinct thresholds for proliferating and confluent cells. For zinc ions, the effective concentration was lower for fibroblasts than for PC-12 cells. SGC showed comparable thresholds for reduced cell survival not only for silver and zinc ions but also for copper(II) ions, indicating that these ions might be promising for reducing tissue growth on the surface of CI electrode arrays. These effects were also observed when combinations of two of these ions were investigated. PMID:21312225

  9. Percolation of gallium dominates the electrical resistance of focused ion beam deposited metals

    SciTech Connect

    Faraby, H.; DiBattista, M.; Bandaru, P. R.

    2014-04-28

    Metal deposition through focused ion beam (FIB) based systems is thought to result in material composed of the primary metal from the metallo-organic precursor in addition to carbon, oxygen, and gallium. We determined, through electrical resistance and chemical composition measurements on a wide range of FIB deposited platinum and tungsten lines, that the gallium ion (Ga{sup +}) concentration in the metal lines plays the dominant role in controlling the electrical resistivity. Effective medium theory, based on McLachlan's formalisms, was used to describe the relationship between the Ga{sup +} concentration and the corresponding resistivity.

  10. Extracting metal ions with diphosphonic acid, or derivative thereof

    DOEpatents

    Horwitz, Earl P.; Gatrone, Ralph C.; Nash, Kenneth L.

    1994-01-01

    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.

  11. Extracting metal ions with diphosphonic acid, or derivative thereof

    DOEpatents

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

    1994-07-26

    Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulfur 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.

  12. 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.

  13. 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.

  14. Predicting the relative toxicity of metal ions using ion characteristics: Microtox{reg_sign} bioluminescence assay

    SciTech Connect

    McCloskey, J.T.; Newman, M.C.; Clark, S.B.

    1996-10-01

    Quantitative structure-activity relationships have been used to predict the relative toxicity of organic compounds. Although not as common, ion characteristics have also proven useful for predicting the relative toxicity of metal ions. The purpose of this study was to determine if the relative toxicity of metal ions using the Microtox{reg_sign} bioassay was predictable using ion characteristics. Median effect concentrations (EC50s) were determined for 20 metals in a NaNO{sub 3} medium, which reflected freshwater speciation conditions, using the Microtox bacterial assay. The log of EC50 values was modeled using several ion characteristics, and Akaike`s Information Criterion was calculated to determine which ion characteristics provided the best fit. Whether modeling total ion or free ion EC50 values, the one variable which best modeled EC50s was the softness index, while a combination of {chi}{sub m}{sup 2}r ({chi}{sub m} = electronegativity, r = Pauling ionic radius) and {vert_bar}log K{sub OH}{vert_bar} was the best two-variable model. Other variables, including {Delta}E{sub 0} and {chi}{sub m}{sup 2}r (one-variable models) and (AN/{Delta}IP, {Delta}E{sub 0}) and ({chi}{sub m}{sup 2}r, Z{sup 2}/r) (two-variable models), also gave adequate fits. Modeling with speciated (free ion) versus unspeciated (total ion) EC50 values did not improve fits. Modeling mono-, di-, and trivalent metal ions separately improved the models. The authors conclude that ion characteristics can be used to predict the relative toxicity of metal ions whether in freshwater (NaNO{sub 3} medium) or saltwater (NaCl medium) speciation conditions and that this approach can be applied to metal ions varying widely in both valence and binding tendencies.

  15. An Engineered Palette of Metal Ion Quenchable Fluorescent Proteins

    PubMed Central

    Yu, Xiaozhen; Strub, Marie-Paule; Barnard, Travis J.; Noinaj, Nicholas; Piszczek, Grzegorz; Buchanan, Susan K.; Taraska, Justin W.

    2014-01-01

    Many fluorescent proteins have been created to act as genetically encoded biosensors. With these sensors, changes in fluorescence report on chemical states in living cells. Transition metal ions such as copper, nickel, and zinc are crucial in many physiological and pathophysiological pathways. Here, we engineered a spectral series of optimized transition metal ion-binding fluorescent proteins that respond to metals with large changes in fluorescence intensity. These proteins can act as metal biosensors or imaging probes whose fluorescence can be tuned by metals. Each protein is uniquely modulated by four different metals (Cu2+, Ni2+, Co2+, and Zn2+). Crystallography revealed the geometry and location of metal binding to the engineered sites. When attached to the extracellular terminal of a membrane protein VAMP2, dimeric pairs of the sensors could be used in cells as ratiometric probes for transition metal ions. Thus, these engineered fluorescent proteins act as sensitive transition metal ion-responsive genetically encoded probes that span the visible spectrum. PMID:24752441

  16. 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. PMID:24109750

  17. An optical dosimeter for monitoring heavy metal ions in water

    NASA Astrophysics Data System (ADS)

    Mignani, Anna G.; Regan, Fiona; Leamy, D.; Mencaglia, A. A.; Ciaccheri, L.

    2005-05-01

    This work presents an optochemical dosimeter for determining and discriminating nickel, copper, and cobalt ions in water that can be used as an early warning system for water pollution. An inexpensive fiber optic spectrophotometer monitors the sensor's spectral behavior under exposure to water solutions of heavy metal ions in the 1-10 mg/l concentration range. The Principal Component Analysis (PCA) method quantitatively determines the heavy metals and discriminates their type and combination.

  18. Metal ion implantation for large scale surface modification

    SciTech Connect

    Brown, I.G.

    1992-10-01

    Intense energetic beams of metal ions can be produced by using a metal vapor vacuum arc as the plasma discharge from which the ion beam is formed. We have developed a number of ion sources of this kind and have built a metal ion implantation facility which can produce repetitively pulsed ion beams with mean ion energy up to several hundred key, pulsed beam current of more than an ampere, and time averaged current of several tens of milliamperes delivered onto a downstream target. We've also done some preliminary work on scaling up this technology to very large size. For example, a 50-cm diameter (2000 cm[sup 2]) set of beam formation electrodes was used to produce a pulsed titanium beam with ion current over 7 amperes at a mean ion energy of 100 key. Separately, a dc embodiment has been used to produce a dc titanium ion beam with current over 600 mA, power supply limited in this work, and up to 6 amperes of dc plasma ion current was maintained for over an hour. In a related program we've developed a plasma immersion method for applying thin metallic and compound films in which the added species is atomically mixed to the substrate. By adding a gas flow to the process, well-bonded compound films can also be formed; metallic films and multilayers as well as oxides and nitrides with mixed transition zones some hundreds of angstroms thick have been synthesized. Here we outline these parallel metal-plasma-based research programs and describe the hardware that we've developed and some of the surface modification research that we've done with it.

  19. Production of negative hydrogen ions on metal grids

    SciTech Connect

    Oohara, W.; Maetani, Y.; Takeda, Takashi; Takeda, Toshiaki; Yokoyama, H.; Kawata, K.

    2015-03-15

    Negative hydrogen ions are produced on a nickel grid with positive-ion irradiation. In order to investigate the production mechanism, a copper grid without the chemisorption of hydrogen atoms and positive helium ions without negative ionization are used for comparison. Positive hydrogen ions reflected on the metal surface obtain two electrons from the surface and become negatively ionized. It is found that the production yield of negative ions by desorption ionization of chemisorbed hydrogen atoms seems to be small, and the production is a minor mechanism.

  20. Polaronic Transport in Phosphate Glasses Containing Transition Metal Ions

    NASA Astrophysics Data System (ADS)

    Henderson, Mark

    The goal of this dissertation is to characterize the basic transport properties of phosphate glasses containing various amounts of TIs and to identify and explain any electronic phase transitions which may occur. The P2 O5-V2O5-WO3 (PVW) glass system will be analyzed to find the effect of TI concentration on conduction. In addition, the effect of the relative concentrations of network forming ions (SiO2 and P2O5) on transport will be studied in the P2O5-SiO2-Fe2O 3 (PSF) system. Also presented is a numerical study on a tight-binding model adapted for the purposes of modelling Gaussian traps, mimicking TI's, which are arranged in an extended network. The results of this project will contribute to the development of fundamental theories on the electronic transport in glasses containing mixtures of transition oxides as well as those containing multiple network formers without discernible phase separation. The present study on the PVW follows up on previous investigation into the effect on mixed transition ions in oxide glasses. Past research has focused on glasses containing transition metal ions from the 3d row. The inclusion of tungsten, a 5d transition metal, adds a layer of complexity through the mismatch of the energies of the orbitals contributing to localized states. The data have indicated that a transition reminiscent of a metal-insulator transition (MIT) occurs in this system as the concentration of tungsten increases. As opposed to some other MIT-like transitions found in phosphate glass systems, there seems to be no polaron to bipolaron conversion. Instead, the individual localization parameter for tungsten noticeably decreases dramatically at the transition point as well as the adiabaticity. Another distinctive feature of this project is the study of the PSF system, which contains two true network formers, phosphorous pentoxide (P2O 5) and silicon dioxide (SiO2). It is not usually possible to do a reliable investigation of the conduction properties of

  1. A new paradigm of DNA synthesis: three-metal-ion catalysis.

    PubMed

    Yang, Wei; Weng, Peter J; Gao, Yang

    2016-01-01

    Enzyme catalysis has been studied for over a century. How it actually occurs has not been visualized until recently. By combining in crystallo reaction and X-ray diffraction analysis of reaction intermediates, we have obtained unprecedented atomic details of the DNA synthesis process. Contrary to the established theory that enzyme-substrate complexes and transition states have identical atomic composition and catalysis occurs by the two-metal-ion mechanism, we have discovered that an additional divalent cation has to be captured en route to product formation. Unlike the canonical two metal ions, which are coordinated by DNA polymerases, this third metal ion is free of enzyme coordination. Its location between the α- and β-phosphates of dNTP suggests that the third metal ion may drive the phosphoryltransfer from the leaving group opposite to the 3'-OH nucleophile. Experimental data indicate that binding of the third metal ion may be the rate-limiting step in DNA synthesis and the free energy associated with the metal-ion binding can overcome the activation barrier to the DNA synthesis reaction. PMID:27602203

  2. Functional Identification of Catalytic Metal Ion Binding Sites within RNA

    PubMed Central

    2005-01-01

    The viability of living systems depends inextricably on enzymes that catalyze phosphoryl transfer reactions. For many enzymes in this class, including several ribozymes, divalent metal ions serve as obligate cofactors. Understanding how metal ions mediate catalysis requires elucidation of metal ion interactions with both the enzyme and the substrate(s). In the Tetrahymena group I intron, previous work using atomic mutagenesis and quantitative analysis of metal ion rescue behavior identified three metal ions (MA, MB, and MC) that make five interactions with the ribozyme substrates in the reaction's transition state. Here, we combine substrate atomic mutagenesis with site-specific phosphorothioate substitutions in the ribozyme backbone to develop a powerful, general strategy for defining the ligands of catalytic metal ions within RNA. In applying this strategy to the Tetrahymena group I intron, we have identified the pro-SP phosphoryl oxygen at nucleotide C262 as a ribozyme ligand for MC. Our findings establish a direct connection between the ribozyme core and the functionally defined model of the chemical transition state, thereby extending the known set of transition-state interactions and providing information critical for the application of the recent group I intron crystallographic structures to the understanding of catalysis. PMID:16092891

  3. Towards metals analysis using corona discharge ionization ion mobility spectrometry.

    PubMed

    Jafari, Mohammad T; Saraji, Mohammad; Sherafatmand, Hossein

    2016-02-25

    For the first time, the capability of corona discharge ionization ion mobility spectrometry (CD-IMS) in the determination of metal complex was evaluated. The extreme simplicity of dispersive liquid-liquid microextraction (DLLME) coupled to the high sensitivity of CD-IMS measurement could make this combination really useful for simple, rapid, and sensitive determination of metals in different samples. In this regard, mercury, as a model metal, was complexed with diethyldithiocarbamate (DEDTC), and then extracted into the carbon tetrachloride using DLLME. Some parameters affecting the extraction efficiency, including the type and volume of the extraction solvent, the type and volume of the disperser solvent, the concentration of the chelating agent, salt addition and, pH were exhaustively investigated. Under the optimized condition, the enrichment factor was obtained to be 142. The linear range of 0.035-10.0 μg mL(-1) with r(2) = 0.997 and the detection limit of 0.010 μg mL(-1) were obtained. The relative standard deviation values were calculated to be lower than 4% and 8% for intra-day and inter-day, respectively. Finally, the developed method was successfully applied for the extraction and determination of mercury in various real samples. The satisfactory results revealed the capability of the proposed method in trace analysis without tedious derivatization or hydride generation. PMID:26851088

  4. Implantation of nitrogen, carbon, and phosphorus ions into metals

    SciTech Connect

    Guseva, M.I.; Gordeeva, G.V.

    1987-01-01

    The application of ion implantation for alloying offers a unique opportunity to modify the chemical composition, phase constitution, and microstructure of the surface layers of metals. The authors studied ion implantation of nitrogen and carbon into the surface layers of metallic targets. The phase composition of the implanted layers obtained on the Kh18N10T stainless steel, the refractory molybdenum alloy TsM-6, niobium, and nickel was determined according to the conventional method of recording the x-ray diffraction pattern of the specimens using monochromatic FeK/sub alpha/-radiation on a DRON-2,0 diffractometer. The targets were bombarded at room temperature in an ILU-3 ion accelerator. The implantation of metalloid ions was also conducted with the targets being bombarded with 100-keV phosphorus ions and 40-keV carbon ions.

  5. Quantum ion-acoustic wave oscillations in metallic nanowires

    SciTech Connect

    Moradi, Afshin

    2015-05-15

    The low-frequency electrostatic waves in metallic nanowires are studied using the quantum hydrodynamic model, in which the electron and ion components of the system are regarded as a two-species quantum plasma system. The Poisson equation as well as appropriate quantum boundary conditions give the analytical expressions of dispersion relations of the surface and bulk quantum ion-acoustic wave oscillations.

  6. Selective fluorescence sensors for detection of nitroaniline and metal Ions based on ligand-based luminescent metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Yu, Zongchao; Wang, Fengqin; Lin, Xiangyi; Wang, Chengmiao; Fu, Yiyuan; Wang, Xiaojun; Zhao, Yongnan; Li, Guodong

    2015-12-01

    Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)-based metal-organic frameworks, Zn3L3(DMF)2 (1) and Zn3L3(DMA)2(H2O)3 (2) (L=4,4‧-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe3+ and Al3+ by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significant fluorescence quenching effect for Fe3+. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity.

  7. Plasma spectroscopy of metal ions for hyper-electron cyclotron resonance ion source.

    PubMed

    Muto, Hideshi; Ohshiro, Yukimitsu; Yamaka, Shoichi; Watanabe, Shin-ichi; Oyaizu, Michihiro; Kubono, Shigeru; Yamaguchi, Hidetoshi; Kase, Masayuki; Hattori, Toshiyuki; Shimoura, Susumu

    2014-02-01

    In this research, the optical line spectra of metal ions from ECR plasma were observed using a grating monochromator with a photomultiplier. The light intensity of line spectrum from the ECR plasma had a strong correlation with ion beam intensity measured by a magnetic mass analyzer. This correlation is a significant information for the beam tuning process, because it allows to conduct the extraction of the desired metal ion species from the ECR plasma. Separation of ion species of the same charge to mass ratio with an electromagnetic mass analyzer is known to be an exceptionally complex process, but this research provides a new approach for its simplification. In this paper the grating monochromator method for metal ion beam tuning such as (40)Ca(12+), (56)Fe(15+), and (85)Rb(20+) of hyper-ECR ion source as an injector for RIKEN Azimuthal Varying Field cyclotron is described. PMID:24593484

  8. Intercalation of Coordinatively Unsaturated Fe(III) Ion within Interpenetrated Metal-Organic Framework MOF-5.

    PubMed

    Holmberg, Rebecca J; Burns, Thomas; Greer, Samuel M; Kobera, Libor; Stoian, Sebastian A; Korobkov, Ilia; Hill, Stephen; Bryce, David L; Woo, Tom K; Murugesu, Muralee

    2016-06-01

    Coordinatively unsaturated Fe(III) metal sites were successfully incorporated into the iconic MOF-5 framework. This new structure, Fe(III) -iMOF-5, is the first example of an interpenetrated MOF linked through intercalated metal ions. Structural characterization was performed with single-crystal and powder XRD, followed by extensive analysis by spectroscopic methods and solid-state NMR, which reveals the paramagnetic ion through its interaction with the framework. EPR and Mössbauer spectroscopy confirmed that the intercalated ions were indeed Fe(III) , whereas DFT calculations were employed to ascertain the unique pentacoordinate architecture around the Fe(III) ion. Interestingly, this is also the first crystallographic evidence of pentacoordinate Zn(II) within the MOF-5 SBU. This new MOF structure displays the potential for metal-site addition as a framework connector, thus creating further opportunity for the innovative development of new MOF materials. PMID:27061210

  9. Theory of ion-stimulated electron emission from simple metals: Explicit calculations

    SciTech Connect

    Gaspar, J.A. |; Eguiluz, A.G. |; Mills, D.L.

    1995-05-15

    We apply a description of ion-stimulated electron emission from metals developed earlier by one of us [D. L. Mills, Surf. Sci. 294, 161 (1993)] to ions which strike aluminum metal at both grazing and normal incidence. The electronic response of the substrate is modeled within the jellium picture. For grazing incidence, we employ realistic ion trajectories which allow penetration of the ions into the metal. The substrate response is described microscopically, so a proper description of short-wavelength aspects is incorporated fully in our calculations. Response functions employed are those for a jellium slab, so that electron emission mediated by bulk plasmons is described. Our results reproduce very well the experimental data reported by Rau, for the case of grazing incidence. In addition, we present calculations for the case of normal incidence.

  10. Adaptation of intertidal biofilm communities is driven by metal ion and oxidative stresses

    PubMed Central

    Zhang, Weipeng; Wang, Yong; Lee, On On; Tian, Renmao; Cao, Huiluo; Gao, Zhaoming; Li, Yongxin; Yu, Li; Xu, Ying; Qian, Pei-Yuan

    2013-01-01

    Marine organisms in intertidal zones are subjected to periodical fluctuations and wave activities. To understand how microbes in intertidal biofilms adapt to the stresses, the microbial metagenomes of biofilms from intertidal and subtidal zones were compared. The genes responsible for resistance to metal ion and oxidative stresses were enriched in both 6-day and 12-day intertidal biofilms, including genes associated with secondary metabolism, inorganic ion transport and metabolism, signal transduction and extracellular polymeric substance metabolism. In addition, these genes were more enriched in 12-day than 6-day intertidal biofilms. We hypothesize that a complex signaling network is used for stress tolerance and propose a model illustrating the relationships between these functions and environmental metal ion concentrations and oxidative stresses. These findings show that bacteria use diverse mechanisms to adapt to intertidal zones and indicate that the community structures of intertidal biofilms are modulated by metal ion and oxidative stresses. PMID:24212283

  11. Comparative study of metal and non-metal ion implantation in polymers: Optical and electrical properties

    NASA Astrophysics Data System (ADS)

    Resta, V.; Quarta, G.; Farella, I.; Maruccio, L.; Cola, A.; Calcagnile, L.

    2014-07-01

    The implantation of 1 MeV metal (63Cu+, 107Ag+, 197Au+) and non-metal (4He+, 12C+) ions in a polycarbonate (PC) matrix has been studied in order to evaluate the role of ion species in the modification of optical and electrical properties of the polymer. When the ion fluence is above ∼1 × 1013 ions cm-2, the threshold for latent tracks overlapping is overcome and π-bonded carbon clusters grow and aggregate forming a network of conjugated Cdbnd C bonds. For fluences around 1 × 1017 ions cm-2, the aggregation phenomena induce the formation of amorphous carbon and/or graphite like structures. At the same time, nucleation of metal nanoparticles (NPs) from implanted species can take place when the supersaturation threshold is overcome. The optical absorption of the samples increases in the visible range and the optical band gap redshifts from 3.40 eV up to 0.70 eV mostly due to the carbonization process and the formation of C0x clusters and cluster aggregates. Specific structures in the extinction spectra are observed when metal ions are selected in contrast to the non-metal ion implanted PC, thus revealing the possible presence of noble metal based NPs interstitial to the C0x cluster network. The corresponding electrical resistance decreases much more when metal ions are implanted with at least a factor of 2 orders of magnitude difference than the non-metal ions based samples. An absolute value of ∼107 Ω/sq has been measured for implantation with metals at doses higher than 5 × 1016 ions cm-2, being 1017 Ω/sq the corresponding sheet resistance for pristine PC.

  12. Removal of metal ions from aqueous solution

    SciTech Connect

    Jackson, P.J.; Delhaize, E.; Robinson, N.J.; Unkefer, C.J.; Furlong, C.

    1990-03-20

    This patent describes a method of removing heavy metals from aqueous solution, a composition of matter used in effecting the removal, and apparatus used in effecting the removal. One or more of the polypeptides, poly ({gamma}-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly ({gamma}-glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  13. Removal of metal ions from aqueous solution

    DOEpatents

    Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

    1990-01-01

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  14. Removal of metal ions from aqueous solution

    SciTech Connect

    Jackson, P.J.; Delhaize, E.; Robinson, N.J.; Unkefer, C.J.; Furlong, C.

    1988-08-26

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly ({gamma}-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly ({gamma}-glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  15. Removal of metal ions from aqueous solution

    SciTech Connect

    Jackson, P.J.; Delhaize, E.; Robinson, N.J.; Unkefer, C.J.; Furlong, C.

    1990-11-13

    A method is disclosed of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly ([gamma]glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly ([gamma]glutamylcysteinyl)glycines having a particular number of monomer repeat unit for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form. 1 fig.

  16. Removal of metal ions from aqueous solution

    SciTech Connect

    Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

    1990-11-13

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat unit for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heayv metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  17. In Vivo Metal Ion Imaging Using Fluorescent Sensors.

    PubMed

    Van de Bittner, Genevieve C; Hirayama, Tasuku

    2016-01-01

    In vivo imaging in living animals provides the ability to monitor alterations of signaling molecules, ions, and other biological components during various life stages and in disease. The data gained from in vivo imaging can be used for biological discovery or to determine elements of disease progression and can inform the development and translation of therapeutics. Herein, we present theories behind small-molecule, fluorescent, metal ion sensors as well as the methods for their successful application to in vivo metal ion imaging, including ex vivo validation. PMID:27283424

  18. 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

  19. Metal ion implantation in inert polymers for strain gauge applications

    NASA Astrophysics Data System (ADS)

    Di Girolamo, Giovanni; Massaro, Marcello; Piscopiello, Emanuela; Tapfer, Leander

    2010-10-01

    Metal ion implantation in inert polymers may produce ultra-thin conducting films below the polymer surface. These subsurface films are promising structures for strain gauge applications. To this purpose, polycarbonate substrates were irradiated at room temperature with low-energy metal ions (Cu + and Ni +) and with fluences in the range between 1 × 10 16 and 1 × 10 17 ions/cm 2, in order to promote the precipitation of dispersed metal nanoparticles or the formation of a continuous thin film. The nanoparticle morphology and the microstructural properties of polymer nanocomposites were investigated by glancing-incidence X-ray diffraction and transmission electron microscopy (TEM) measurements. At lower fluences (<5 × 10 16 ions/cm 2) a spontaneous precipitation of spherical-shaped metal nanoparticles occurred below the polymer top-surface (˜50 nm), whereas at higher fluences the aggregation of metal nanoparticles produced the formation of a continuous polycrystalline nanofilm. Furthermore, a characteristic surface plasmon resonance peak was observed for nanocomposites produced at lower ion fluences, due to the presence of Cu nanoparticles. A reduced electrical resistance of the near-surface metal-polymer nanocomposite was measured. The variation of electrical conductivity as a function of the applied surface load was measured: we found a linear relationship and a very small hysteresis.

  20. The use of divalent metal ions by type II topoisomerases.

    PubMed

    Deweese, Joseph E; Osheroff, Neil

    2010-07-01

    Type II topoisomerases are essential enzymes that regulate DNA under- and overwinding and remove knots and tangles from the genetic material. In order to carry out their critical physiological functions, these enzymes utilize a double-stranded DNA passage mechanism that requires them to generate a transient double-stranded break. Consequently, while necessary for cell survival, type II topoisomerases also have the capacity to fragment the genome. This feature of the prokaryotic and eukaryotic enzymes, respectively, is exploited to treat a variety of bacterial infections and cancers in humans. All type II topoisomerases require divalent metal ions for catalytic function. These metal ions function in two separate active sites and are necessary for the ATPase and DNA cleavage/ligation activities of the enzymes. ATPase activity is required for the strand passage process and utilizes the metal-dependent binding and hydrolysis of ATP to drive structural rearrangements in the protein. Both the DNA cleavage and ligation activities of type II topoisomerases require divalent metal ions and appear to utilize a novel variant of the canonical two-metal-ion phosphotransferase/hydrolase mechanism to facilitate these reactions. This article will focus primarily on eukaryotic type II topoisomerases and the roles of metal ions in the catalytic functions of these enzymes. PMID:20703329

  1. The Use of Divalent Metal Ions by Type II Topoisomerases

    PubMed Central

    Deweese, Joseph E.; Osheroff, Neil

    2010-01-01

    Type II topoisomerases are essential enzymes that regulate DNA under- and overwinding and remove knots and tangles from the genetic material. In order to carry out their critical physiological functions, these enzymes utilize a double-stranded DNA passage mechanism that requires them to generate a transient double-stranded break. Consequently, while necessary for cell survival, type II topoisomerases also have the capacity to fragment the genome. This feature of the prokaryotic and eukaryotic enzymes, respectively, is exploited to treat a variety of bacterial infections and cancers in humans. All type II topoisomerases require divalent metal ions for catalytic function. These metal ions function in two separate active sites and are necessary for the ATPase and DNA cleavage/ligation activities of the enzymes. ATPase activity is required for the strand passage process and utilizes the metal-dependent binding and hydrolysis of ATP to drive structural rearrangements in the protein. Both the DNA cleavage and ligation activities of type II topoisomerases require divalent metal ions and appear to utilize a novel variant of the canonical two-metal-ion phosphotransferase/hydrolase mechanism to facilitate these reactions. This article will focus primarily on eukaryotic type II topoisomerases and the roles of metal ions in the catalytic functions of these enzymes. PMID:20703329

  2. Luminometric Label Array for Quantification and Identification of Metal Ions.

    PubMed

    Pihlasalo, Sari; Montoya Perez, Ileana; Hollo, Niklas; Hokkanen, Elina; Pahikkala, Tapio; Härmä, Harri

    2016-05-17

    Quantification and identification of metal ions has gained interest in drinking water and environmental analyses. We have developed a novel label array method for the quantification and identification of metal ions in drinking water. This simple ready-to-go method is based on the nonspecific interactions of multiple unstable lanthanide chelates and nonantenna ligands with sample leading to a luminescence signal profile, unique to the sample components. The limit of detection at ppb concentration level and average coefficient of variation of 10% were achieved with the developed label array. The identification of 15 different metal ions including different oxidation states Cr(3+)/Cr(6+), Cu(+)/Cu(2+), Fe(2+)/Fe(3+), and Pb(2+)/Pb(4+) was demonstrated. Moreover, a binary mixture of Cu(2+) and Fe(3+) and ternary mixture of Cd(2+), Ni(2+), and Pb(2+) were measured and individual ions were distinguished. PMID:27086705

  3. Ion beam induced nanosized Ag metal clusters in glass

    NASA Astrophysics Data System (ADS)

    Mahnke, H.-E.; Schattat, B.; Schubert-Bischoff, P.; Novakovic, N.

    2006-04-01

    Silver metal clusters have been formed in soda lime glass by high-energy heavy-ion irradiation at ISL. The metal cluster formation was detected with X-ray absorption spectroscopy (EXAFS) in fluorescence mode, and the shape of the clusters was imaged with transmission electron microscopy. While annealing in reducing atmosphere alone, leads to the formation of metal clusters in Ag-containing glasses, where the Ag was introduced by ion-exchange, such clusters are not very uniform in size and are randomly distributed over the Ag-containing glass volume. Irradiation with 600-MeV Au ions followed by annealing, however, results in clusters more uniform in size and arranged in chains parallel to the direction of the ion beam.

  4. Hall transport of divalent metal ion modified DNA lattices

    SciTech Connect

    Dugasani, Sreekantha Reddy; Lee, Keun Woo; Yoo, Sanghyun; Gnapareddy, Bramaramba; Bashar, Saima; Park, Sung Ha; Kim, Si Joon; Jung, Joohye; Jung, Tae Soo; Kim, Hyun Jae

    2015-06-29

    We investigate the Hall transport characteristics of double-crossover divalent metal ion (Cu{sup 2+}, Ni{sup 2+}, Zn{sup 2+}, and Co{sup 2+})-modified DNA (M-DNA) lattices grown on silica via substrate-assisted growth. The electronic characteristics of the M-DNA lattices are investigated by varying the concentration of the metal ions and then conducting Hall measurements, including resistivity, Hall mobility, carrier concentration, and magneto resistance. The tendency of the resistivity and Hall mobility was to initially decrease as the ion concentration increased, until reaching the saturation concentration (C{sub s}) of each metal ion, and then to increase as the ion concentration increased further. On the other hand, the carrier concentration revealed the opposite tendency as the resistivity and Hall mobility. The specific binding (≤C{sub s}) and the nonspecific aggregates (>C{sub s}) of the ions into the DNA lattices were significantly affected by the Hall characteristics. The numerical ranges of the Hall parameters revealed that the M-DNA lattices with metal ions had semiconductor-like characteristics. Consequently, the distinct characteristics of the electrical transport through M-DNA lattices will provide useful information on the practical use of such structures in physical devices and chemical sensors.

  5. 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)

  6. Process for improving moisture resistance of epoxy resins by addition of chromium ions

    NASA Technical Reports Server (NTRS)

    St.clair, A. K.; Stoakley, D. M.; St.clair, T. L.; Singh, J. J. (Inventor)

    1985-01-01

    A process for improving the moisture resistance properties of epoxidized TGMDA and DGEBA resin system by chemically incorporating chromium ions is described. The addition of chromium ions is believed to prevent the absorption of water molecules.

  7. 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. PMID:25169678

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

    NASA Astrophysics Data System (ADS)

    Yushkov, G. Yu.; Nikolaev, A. G.; Oks, E. M.; Frolova, V. P.

    2016-02-01

    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 than 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.

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

    PubMed

    Yushkov, G Yu; Nikolaev, A G; Oks, E M; Frolova, V P

    2016-02-01

    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 than 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. PMID:26931966

  10. 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

    Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on

  11. 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. PMID:22936101

  12. Decreased fluidity of cell membranes causes a metal ion deficiency in recombinant Saccharomyces cerevisiae producing carotenoids.

    PubMed

    Liu, Peitong; Sun, Liang; Sun, Yuxia; Shang, Fei; Yan, Guoliang

    2016-04-01

    The genome-wide transcriptional responses of S. cerevisiae to heterologous carotenoid biosynthesis were investigated using DNA microarray analysis. The results show that the genes involved in metal ion transport were specifically up-regulated in the recombinant strain, and metal ions, including Cu(2+), Fe(2+), Mn(2+), and Mg(2+), were deficient in the recombinant strain compared to the ion content of the parent strain. The decrease in metal ions was ascribed to a decrease in cell membrane (CM) fluidity caused by lower levels of unsaturated fatty acids and ergosterol. This was confirmed by the observation that metal ion levels were restored when CM fluidity was increased by supplying linoleic acid. In addition, a 24.3 % increase in the β-carotene concentration was observed. Collectively, our results suggest that heterologous production of carotenoids in S. cerevisiae can induce cellular stress by rigidifying the CM, which can lead to a deficiency in metal ions. Due to the importance of CM fluidity in cellular physiology, maintaining normal CM fluidity might be a potential approach to improving carotenoid production in genetically engineered S. cerevisiae. PMID:26749524

  13. Asparagus cochinchinensis Extract Alleviates Metal Ion-Induced Gut Injury in Drosophila: An In Silico Analysis of Potential Active Constituents

    PubMed Central

    Zhang, Weiyu; Jin, Li Hua

    2016-01-01

    Metal ions and sulfate are components of atmospheric pollutants that have diverse ways of entering the human body. We used Drosophila as a model to investigate the effect of Asparagus cochinchinensis (A. cochinchinensis) extracts on the gut and characterized gut homeostasis following the ingestion of metal ions (copper, zinc, and aluminum). In this study, we found that the aqueous A. cochinchinensis extract increased the survival rate, decreased epithelial cell death, and attenuated metal ion-induced gut morphological changes in flies following chronic exposure to metal ions. In addition, we screened out, by network pharmacology, six natural products (NPs) that could serve as putative active components of A. cochinchinensis that prevented gut injury. Altogether, the results of our study provide evidence that A. cochinchinensis might be an effective phytomedicine for the treatment of metal ion-induced gut injury. PMID:27123034

  14. Asparagus cochinchinensis Extract Alleviates Metal Ion-Induced Gut Injury in Drosophila: An In Silico Analysis of Potential Active Constituents.

    PubMed

    Zhang, Weiyu; Jin, Li Hua

    2016-01-01

    Metal ions and sulfate are components of atmospheric pollutants that have diverse ways of entering the human body. We used Drosophila as a model to investigate the effect of Asparagus cochinchinensis (A. cochinchinensis) extracts on the gut and characterized gut homeostasis following the ingestion of metal ions (copper, zinc, and aluminum). In this study, we found that the aqueous A. cochinchinensis extract increased the survival rate, decreased epithelial cell death, and attenuated metal ion-induced gut morphological changes in flies following chronic exposure to metal ions. In addition, we screened out, by network pharmacology, six natural products (NPs) that could serve as putative active components of A. cochinchinensis that prevented gut injury. Altogether, the results of our study provide evidence that A. cochinchinensis might be an effective phytomedicine for the treatment of metal ion-induced gut injury. PMID:27123034

  15. Enhanced metal removal from wastewater by coagulant addition

    SciTech Connect

    Karthikeyan, K.G.; Elliott, H.A.; Cannon, F.S.

    1996-11-01

    Besides metallurgical industries, metal-containing wastewaters are generated in the manufacturing/processing of batteries, petroleum, photographic materials, paints, inks, leather, and wood. The toxic nature of the heavy metals has resulted in the promulgation of standards requiring very low concentration of metals in the treated effluent. To comply with the strict regulatory requirements, it is necessary to treat the wastewaters (both industrial and municipal) before discharging them into natural water bodies. The objective of this study was to compare the pH-dependent Cu and Cd removal profiles for simple precipitation, adsorption, and coprecipitation in the presence of freshly-formed hydrous oxides of Fe and Al. Because of the significantly different pH at which hydrolysis/precipitation occurs, Cu and Cd were chosen as representative heavy metals. The results have been interpreted in the context of investing the use of coagulants to achieve low metal concentrations in wastewater effluents.

  16. Does Ion Release Differ Between Hip Resurfacing and Metal-on-metal THA?

    PubMed Central

    Moroni, Antonio; Cadossi, Matteo; Baldini, Nicola; Giannini, Sandro

    2008-01-01

    Modern metal-on-metal hip resurfacing was introduced as a bone-preserving method of joint reconstruction for young and active patients; however, the large diameter of the bearing surfaces is of concern for potential increased metal ion release. We hypothesized there were no differences in serum concentrations of chromium, cobalt, and molybdenum between patients who had metal-on-metal hip resurfacing (Group A; average head diameter, 48 mm; median followup, 24 months) and patients who had 28-mm metal-on-metal THA (Group B; median followup, 25 months). Serum concentrations also were compared with concentrations in healthy subjects. We identified no differences in ion levels between Groups A and B. A distinction was made according to gender. Women showed a higher chromium release in Group A whereas men had a higher cobalt release in Group B. Values obtained from Group A were higher than those of the control subjects. Our data suggest metal-on-metal bearings for THA should not be rejected because of concern regarding potential increased metal ion release; however, patients with elevated ion levels, even without loosening or toxicity, could be at higher risk and should be followed up periodically. Level of Evidence: Level III, therapeutic study. See the Guidelines for Authors for a complete description of levels of evidence. PMID:18196364

  17. Colored thin films for specific metal ion detection.

    PubMed

    Schauer, Caroline L; Chen, Mu-San; Price, Ronald R; Schoen, Paul E; Ligler, Frances S

    2004-08-15

    This paper describes the investigation of chitosan and poly(allylamine) (PAH) for the creation of a multi-film, color-based dipstick for the detection of metal ions in solution. Thin, colored films of chitosan and PAH cross-linked with hexamethylene 1,6-di(aminocarboxysulfonate) (HDACS) are created where color is due to film thickness and optical interference effects. The films are investigated for their ability to selectively detect aqueous metal ions via changes in thickness and/or color. Chitosan-HDACS films were selective for Cr(VI) over all other metal ions tested including Cr(acac)3 and Cr(NO3)3 x 9H2O, and PAH-HDACS films were selective for Cu(II) and Cu(I) salts over all other metal ions tested. The irreversible, selective changes due to metal ion solutions were not caused by varying the pH. Potomac River water was also tested using the two films, with results indicating the presence of Cu(II) in the aqueous sample. PMID:15382871

  18. Membranes Remove Metal Ions Fron Industrial Liquids

    NASA Technical Reports Server (NTRS)

    Hsu, W. P. L.; May, C.

    1983-01-01

    Use of membrane films affords convenient and economical alternative for removing and recovering metal cations present in low concentrations from large quantities of liquid solutions. Possible applications of membrane films include use in analytical chemistry for determination of small amounts of toxic metallic impurities in lakes, streams, and municipal effluents. Also suitable for use as absorber of certain pollutant gases and odors present in confined areas.

  19. 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.

  20. Additive-free thick graphene film as an anode material for flexible lithium-ion batteries.

    PubMed

    Rana, Kuldeep; Kim, Seong Dae; Ahn, Jong-Hyun

    2015-04-28

    This work demonstrates a simple route to develop mechanically flexible electrodes for Li-ion batteries (LIBs) that are usable as lightweight effective conducting networks for both cathodes and anodes. Removing electrochemically dead elements, such as binders, conducting agents and metallic current collectors, from the battery components will allow remarkable progress in this area. To investigate the feasibility of using thick, additive-free graphene films as anodes for flexible LIBs, we have synthesized and tested thick, additive-free, freestanding graphene films as anodes, first in a coin cell and further in a flexible full cell. As an anode material in a half cell, it showed a discharge capacity of about 350 mA h g(-1) and maintained nearly this capacity over 50 cycles at various current rates. This film was also tested as an anode material in a full cell with a LiCoO2 cathode and showed good electrochemical performance. Because the graphene-based flexible film showed good performance in half- and full coin cells, we used this film as a flexible anode for flexible LIBs. No conducting agent or binder was used in the anode side, which helped in realizing the flexible LIBs. Using this, we demonstrate a thin, lightweight and flexible lithium ion battery with good electrochemical performance in both its flat and bent states. PMID:25587843

  1. 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.

  2. Localized ion milling of metallic and ceramic TEM specimens

    SciTech Connect

    Fisher, A.T.; Bentley, J.

    1986-01-01

    The utility of localized ion milling in the preparation of metallic and ceramic specimens for TEM and AEM is being evaluated from the standpoint of optimizing procedures and identifying limitations and milling characteristics. The equipment used was a Gatan model 645 precision ion milling system (PIMS). This device is a scanning ion beam instrument with which selected areas of a sample can be imaged by either secondary electron or secondary ion signals and selectively ion milled in a small region within the imaged area. The 1 to 10 keV ion beam can be focussed to a 2 ..mu..m spot. Specimens are thinned without removing them from the electron microscope specimen holder.

  3. Reducing hazardous heavy metal ions using mangium bark waste.

    PubMed

    Khabibi, Jauhar; Syafii, Wasrin; Sari, Rita Kartika

    2016-08-01

    The objective of this study was to evaluate the characteristics of mangium bark and its biosorbent ability to reduce heavy metal ions in standard solutions and wastewater and to assess changes in bark characteristics after heavy metal absorption. The experiments were conducted to determine heavy metal absorption from solutions of heavy metals alone and in mixtures as well as from wastewater. The results show that mangium bark can absorb heavy metals. Absorption percentages and capacities from single heavy metal solutions showed that Cu(2+) > Ni(2+) > Pb(2+) > Hg(2+), while those from mixture solutions showed that Hg(2+) > Cu(2+) > Pb(2+) > Ni(2+). Wastewater from gold mining only contained Cu, with an absorption percentage and capacity of 42.87 % and 0.75 mg/g, respectively. The highest absorption percentage and capacity of 92.77 % and 5.18 mg/g, respectively, were found for Hg(2+) in a mixture solution and Cu(2+) in single-metal solution. The Cu(2+) absorption process in a single-metal solution changed the biosorbent characteristics of the mangium bark, yielding a decreased crystalline fraction; changed transmittance on hydroxyl, carboxyl, and carbonyl groups; and increased the presence of Cu. In conclusion, mangium bark biosorbent can reduce hazardous heavy metal ions in both standard solutions and wastewater. PMID:27179811

  4. Metal plasma immersion ion implantation and deposition: A review

    SciTech Connect

    Anders, A.

    1996-09-01

    Metal Plasma Immersion Ion Implantation and Deposition (MePIIID) is a hybrid process combining cathodic arc deposition and plasma immersion ion implantation. The properties of metal plasma produced by vacuum arcs are reviewed and the consequences for MePIIID are discussed. Different version of MePIIID are described and compared with traditional methods of surface modification such as ion beam assisted deposition (IBAD). MePIIID is a very versatile approach because of the wide range of ion species and energies used. In one extreme case, films are deposited with ions in the energy range 20--50 eV, and at the other extreme, ions can be implanted with high energy (100 keV or more) without film deposition. Novel features of the technique include the use of improved macroparticle filters; the implementation of several plasma sources for multi-element surface modification; tuning of ion energy during implantation and deposition to tailor the substrate-film intermixed layer and structure of the growing film; simultaneous pulsing of the plasma potential (positive) and substrate bias (negative) with a modified Marx generator; and the use of high ion charge states.

  5. Mechanism of Metal Ion Activation of the Diphtheria Toxin Repressor DtxR

    NASA Astrophysics Data System (ADS)

    D'Aquino, J. Alejandro; Ringe, Dagmar

    2006-08-01

    The diphtheria toxin repressor, DtxR, is a metal ion-activated transcriptional regulator that has been linked to the virulence of Corynebacterium diphtheriae. Structure determination has shown that there are two metal ion binding sites per repressor monomer, and site-directed mutagenesis has demonstrated that binding site 2 (primary) is essential for recognition of the target DNA repressor, leaving the role of binding site 1 (ancillary) unclear (1 - 3). Calorimetric techniques have demonstrated that while binding site 1 (ancillary) has high affinity for metal ion with a binding constant of 2 × 10-7, binding site 2 (primary) is a low affinity binding site with a binding constant of 6.3 × 10-4. These two binding sites act independently and their contribution can be easily dissected by traditional mutational analysis. Our results clearly demonstrate that binding site 1 (ancillary) is the first one to be occupied during metal ion activation, playing a critical role in stabilization of the repressor. In addition, structural data obtained for the mutants Ni-DtxR(H79A,C102D), reported here and the previously reported DtxR(H79A) (4) has allowed us to propose a mechanism of metal ion activation for DtxR.

  6. Comet Encke: Meteor metallic ion identification by mass spectrometer

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

    Metal ions including Na-40(+), Mg-24(+), Si-28(+), K-39(+), Ca-40(+), Sc-45(+), Cr-52(+), Fe-56(+), and Ni-58(+) were detected in the upper atmosphere during the beta Taurids meteor shower. Abundances of these ions relative to Si(+) show agreement in most instances with chondrites. A notable exception is 45(+), which is Sc(+), is 100 times more abundant than neutral scandium found in chondrites.

  7. Comet encke: meteor metallic ion identification by mass spectrometer.

    PubMed

    Goldberg, R A; Aikin, A C

    1973-04-20

    Metal ions including 23(+) (Na(+)), 24(+) (Mg(+)) 28(+) (Si(+)), 39(+) (K(+)), 40(+) (Ca(+)), 45(+) (Sc(+)), 52(+) Cr(+)). 56(+) (Fe(+)), and 58(+) (Ni(+)) have been detected in the upper atmosphere during the period of the Beta Taurids meteor shower. The abundances of these ions relative to Si(+) show, agreement in most instances with abundances in chondrites. A notable exception is 45(+), which, if it is Sc(+), is 100 times more abundant than neutral scandium found in chondrites. PMID:17816288

  8. The properties of high-intensity impregnated-electrode-type liquid-metal ion sources

    NASA Astrophysics Data System (ADS)

    Ishikawa, Junzo

    1989-04-01

    The impregnated-electrode-type liquid-metal ion source has a porous tip structure produced by sintering tungsten powders. Thus, stable operation over a wide range of emission currents (a few to several hundred μA) is possible, since the liquid-metal flow rate can be controlled. In addition, various liquid metals at relatively high vapor pressure (maximum pressure: 0.3 Torr) can be ionized. This type is therefore suitable for general use as a metal ion source. With the newly designed double lens system to overcome large beam divergence, more than 200 μA of lithium ion current was transported over a distance of 0.4 m within an optical column 2 cm in diameter. After mass separation, more than 70 μA of Li + was obtained. Using multipoint emission to further intensify the current, a germanium ion current of mA order was obtained just after the extractor. This ion source can also be used for mufocusing applications, one of which is a new technique of direct deposition by focused ion beam.

  9. Adsorbent for metal ions and method of making and using

    DOEpatents

    White, Lloyd R.; Lundquist, Susan H.

    2000-01-01

    A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions.

  10. Adsorbent for metal ions and method of making and using

    DOEpatents

    White, L.R.; Lundquist, S.H.

    1999-08-10

    A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions. 2 figs.

  11. Adsorbent for metal ions and method of making and using

    DOEpatents

    White, Lloyd R.; Lundquist, Susan H.

    1999-01-01

    A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, can be used free flowing, in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove Cs ions from aqueous solutions.

  12. 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. PMID:20656104

  13. Immobilized materials for removal of toxic metal ions from surface/groundwaters and aqueous waste streams.

    PubMed

    Zawierucha, Iwona; Kozlowski, Cezary; Malina, Grzegorz

    2016-04-20

    Heavy metals from industrial processes are of special concern because they produce chronic poisoning in the aquatic environment. More strict environmental regulations on the discharge of toxic metals require the development of various technologies for their removal from polluted streams (i.e. industrial wastewater, mine waters, landfill leachate, and groundwater). The separation of toxic metal ions using immobilized materials (novel sorbents and membranes with doped ligands), due to their high selectivity and removal efficiency, increased stability, and low energy requirements, is promising for improving the environmental quality. This critical review is aimed at studying immobilized materials as potential remediation agents for the elimination of numerous toxic metal (e.g. Pb, Cd, Hg, and As) ions from polluted streams. This study covers the general characteristics of immobilized materials and separation processes, understanding of the metal ion removal mechanisms, a review of the application of immobilized materials for the removal of toxic metal ions, as well as the impacts of various parameters on the removal efficiency. In addition, emerging trends and opportunities in the field of remediation technologies using these materials are addressed. PMID:27044908

  14. Metal ion-humic acid nanoparticle interactions: role of both complexation and condensation mechanisms.

    PubMed

    Town, Raewyn M; van Leeuwen, Herman P

    2016-07-21

    Purely Donnan type models for electrostatic binding by humic acid (HA) nanoparticles are shown to be physically incomplete. To describe the extent of ion binding by HA, such models need to invoke parameters that are not consistent with experimental observations. These disparate parameters include anomalously high Donnan potentials, as well as intrinsic affinity constants for electrostatically associating ions such as Ca(2+). In contrast, the recently introduced counterion condensation - Donnan model (CCD) provides a physicochemically realistic description of the electrostatic contribution to metal ion binding by humic acid nanoparticles. The extent of Ca(2+)-HA association can be adequately described solely in terms of electrostatics only, including counterion condensation in the intraparticulate double layer in addition to Donnan partitioning in the remainder of the particle body. The binding of Cd(ii), Pb, (ii) and Cu(ii) by HA also involves inner-sphere complex formation leading to intraparticulate metal species distributions with major proportions of condensed and complexed ions. PMID:27327433

  15. Data mining of metal ion environments present in protein structures.

    PubMed

    Zheng, Heping; Chruszcz, Maksymilian; Lasota, Piotr; Lebioda, Lukasz; Minor, Wladek

    2008-09-01

    Analysis of metal-protein interaction distances, coordination numbers, B-factors (displacement parameters), and occupancies of metal-binding sites in protein structures determined by X-ray crystallography and deposited in the PDB shows many unusual values and unexpected correlations. By measuring the frequency of each amino acid in metal ion-binding sites, the positive or negative preferences of each residue for each type of cation were identified. Our approach may be used for fast identification of metal-binding structural motifs that cannot be identified on the basis of sequence similarity alone. The analysis compares data derived separately from high and medium-resolution structures from the PDB with those from very high-resolution small-molecule structures in the Cambridge Structural Database (CSD). For high-resolution protein structures, the distribution of metal-protein or metal-water interaction distances agrees quite well with data from CSD, but the distribution is unrealistically wide for medium (2.0-2.5A) resolution data. Our analysis of cation B-factors versus average B-factors of atoms in the cation environment reveals substantial numbers of structures contain either an incorrect metal ion assignment or an unusual coordination pattern. Correlation between data resolution and completeness of the metal coordination spheres is also found. PMID:18614239

  16. Data mining of metal ion environments present in protein structures

    PubMed Central

    Zheng, Heping; Chruszcz, Maksymilian; Lasota, Piotr; Lebioda, Lukasz; Minor, Wladek

    2010-01-01

    Analysis of metal-protein interaction distances, coordination numbers, B-factors (displacement parameters), and occupancies of metal binding sites in protein structures determined by X-ray crystallography and deposited in the PDB shows many unusual values and unexpected correlations. By measuring the frequency of each amino acid in metal ion binding sites, the positive or negative preferences of each residue for each type of cation were identified. Our approach may be used for fast identification of metal-binding structural motifs that cannot be identified on the basis of sequence similarity alone. The analysis compares data derived separately from high and medium resolution structures from the PDB with those from very high resolution small-molecule structures in the Cambridge Structural Database (CSD). For high resolution protein structures, the distribution of metal-protein or metal-water interaction distances agrees quite well with data from CSD, but the distribution is unrealistically wide for medium (2.0 – 2.5 Å) resolution data. Our analysis of cation B-factors versus average B-factors of atoms in the cation environment reveals substantial numbers of structures contain either an incorrect metal ion assignment or an unusual coordination pattern. Correlation between data resolution and completeness of the metal coordination spheres is also found. PMID:18614239

  17. Roxarsone desorption from the surface of goethite by competitive anions, phosphate and hydroxide ions: Significance of the presence of metal ions.

    PubMed

    Wang, Ling-Yuan; Wang, Shao-Wei; Chen, Wan-Ru

    2016-06-01

    Aromatic organoarsenical roxarsone (ROX) is a common additive for livestock feed. This arsenic containing pollutant could be discharged into the environment through agricultural application of animal manure, and pose potential threats to both humans and the wider environment. In this study, the influence of pH, competing anions and metal ions on the adsorption and desorption of ROX on goethite were investigated in order to understand their mobility in the environment. Both hydroxide ions and phosphate are common substances in the environment, and both are potential competing anions for ROX. Our results showed the addition of phosphate desorbed more ROX than the addition of hydroxide ions. As pH increased, the effect of phosphate did not show much difference to that of hydroxide ion. The results indicate that the presence of phosphate will greatly increase the mobility of ROX at low pH. Six common metal ions, including Zn(2+), Cu(2+), Fe(3+), Mn(2+), Mg(2+), and Ca(2+), were tested and all spiked metal ions enhanced the stability of ROX adsorption on the surface of goethite, and led to less desorption when phosphate was added. The results demonstrate that metal ions may form complex/surface precipitation with ROX to enhance its adsorption. The effect from Fe(3+), Zn(2+) and Cu(2+) was more pronounced than other metal ions, which might result from the fact that these three metal ions tend to associate with hydroxide ions and decrease the pH. The results of this research may shed light on the environmental fate and transportation of aromatic organoarsenicals in soil. PMID:26999752

  18. How do energetic ions damage metallic surfaces?

    SciTech Connect

    Osetskiy, Yury N.; Calder, Andrew F.; Stoller, Roger E.

    2015-02-20

    Surface modification under bombardment by energetic ions observed under different conditions in structural and functional materials and can be either unavoidable effect of the conditions or targeted modification to enhance materials properties. Understanding basic mechanisms is necessary for predicting properties changes. The mechanisms activated during ion irradiation are of atomic scale and atomic scale modeling is the most suitable tool to study these processes. In this paper we present results of an extensive simulation program aimed at developing an understanding of primary surface damage in iron by energetic particles. We simulated 25 keV self-ion bombardment of Fe thin films with (100) and (110) surfaces at room temperature. A large number of simulations, ~400, were carried out allow a statistically significant treatment of the results. The particular mechanism of surface damage depends on how the destructive supersonic shock wave generated by the displacement cascade interacts with the free surface. Three basic scenarios were observed, with the limiting cases being damage created far below the surface with little or no impact on the surface itself, and extensive direct surface damage on the timescale of a few picoseconds. In some instances, formation of large <100> vacancy loops beneath the free surface was observed, which may explain some earlier experimental observations.

  19. How do energetic ions damage metallic surfaces?

    DOE PAGESBeta

    Osetskiy, Yury N.; Calder, Andrew F.; Stoller, Roger E.

    2015-02-20

    Surface modification under bombardment by energetic ions observed under different conditions in structural and functional materials and can be either unavoidable effect of the conditions or targeted modification to enhance materials properties. Understanding basic mechanisms is necessary for predicting properties changes. The mechanisms activated during ion irradiation are of atomic scale and atomic scale modeling is the most suitable tool to study these processes. In this paper we present results of an extensive simulation program aimed at developing an understanding of primary surface damage in iron by energetic particles. We simulated 25 keV self-ion bombardment of Fe thin films withmore » (100) and (110) surfaces at room temperature. A large number of simulations, ~400, were carried out allow a statistically significant treatment of the results. The particular mechanism of surface damage depends on how the destructive supersonic shock wave generated by the displacement cascade interacts with the free surface. Three basic scenarios were observed, with the limiting cases being damage created far below the surface with little or no impact on the surface itself, and extensive direct surface damage on the timescale of a few picoseconds. In some instances, formation of large <100> vacancy loops beneath the free surface was observed, which may explain some earlier experimental observations.« less

  20. Removal and recovery of toxic metal ions from aqueous waste sites using polymer pendant ligands

    SciTech Connect

    Fish, D.

    1996-10-01

    The purpose of this project is to investigate the use of polymer pendant ligand technology to remove and recover toxic metal ions from DOE aqueous waste sites. Polymer pendant lgiands are organic ligands, anchored to crosslinked, modified divinylbenzene-polystyrene beads, that can selectively complex metal ions. The metal ion removal step usually occurs through a complexation or ion exchange phenomena, thus recovery of the metal ions and reuse of the beads is readily accomplished.

  1. 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. PMID:18315181

  2. DUHOCAMIS: A dual hollow cathode ion source for metal ion beams

    SciTech Connect

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

    2008-02-15

    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.

  3. Reducing of internal resistance lithium ion battery using glucose addition

    NASA Astrophysics Data System (ADS)

    Salim, Andri Pratama; Hafidlullah, Noor; Purwanto, Agus

    2016-02-01

    There are two indicators of battery performance, i.e : capacity and the internal resistance of battery. In this research, the affect of glucose addition to decrease the internal resistance of lithium battery was investigated. The ratio of glucose addition were varied at weight ratio 1%, 3%, and 5% and one mixtures without glucose addition. Lithium ferri phosphate (LiFePO4), polyvinylidene fluoride (PVDF), acetylene black (AB) and glucose were materials that used in this study. Both of mixtures were mixed in the vacuum mixer until became homogeneous. The slurry was coated on an aluminium foil sheet and the coated thickness was 200 µm. The performance of battery lithium was examined by Eight Channel Battery Analyzer and the Internal resistance was examined by Internal Resistance of Battery Meter. The result from all analyzer were showed that the internal resistance reduced as well as the battery capacity. The best internal resistance value is owned by mixtures with 3wt% ratio glucose addition. It has an internal resistance value about 64 miliohm.

  4. Depth resolution improvement in secondary ion mass spectrometry analysis using metal cluster complex ion bombardment

    SciTech Connect

    Tomita, M.; Kinno, T.; Koike, M.; Tanaka, H.; Takeno, S.; Fujiwara, Y.; Kondou, K.; Teranishi, Y.; Nonaka, H.; Fujimoto, T.; Kurokawa, A.; Ichimura, S.

    2006-07-31

    Secondary ion mass spectrometry analyses were carried out using a metal cluster complex ion of Ir{sub 4}(CO){sub 7}{sup +} as a primary ion beam. Depth resolution was evaluated as a function of primary ion species, energy, and incident angle. The depth resolution obtained using cluster ion bombardment was considerably better than that obtained by oxygen ion bombardment under the same experimental condition due to reduction of atomic mixing in the depth. The authors obtained a depth resolution of {approx}1 nm under 5 keV, 45 deg. condition. Depth resolution was degraded by ion-bombardment-induced surface roughness at 5 keV with higher incident angles.

  5. Importance of diffuse metal ion binding to RNA.

    PubMed

    Tan, Zhi-Jie; Chen, Shi-Jie

    2011-01-01

    RNAs are highly charged polyanionic molecules. RNA structure and function are strongly correlated with the ionic condition of the solution. The primary focus of this article is on the role of diffusive ions in RNA folding. Due to the long-range nature of electrostatic interactions, the diffuse ions can contribute significantly to RNA structural stability and folding kinetics. We present an overview of the experimental findings as well as the theoretical developments on the diffuse ion effects in RNA folding. This review places heavy emphasis on the effect of magnesium ions. Magnesium ions play a highly efficient role in stabilizing RNA tertiary structures and promoting tertiary structural folding. The highly efficient role goes beyond the mean-field effect such as the ionic strength. In addition to the effects of specific ion binding and ion dehydration, ion-ion correlation for the diffuse ions can contribute to the efficient role of the multivalent ions such as the magnesium ions in RNA folding. PMID:22010269

  6. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    ERIC Educational Resources Information Center

    Duong, Hung Tuan

    2009-01-01

    The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

  7. Sensing Metal Ions with DNA Building Blocks: Fluorescent Pyridobenzimidazole Nucleosides

    PubMed Central

    Kim, Su Jeong; Kool, Eric T.

    2008-01-01

    We describe novel fluorescent N-deoxyribosides (1 and 2) having 2-pyrido-2-benzimidazole and 2-quino-2-benzimidazole as aglycones. The compounds were prepared from the previously unknown heterocyclic precursors and Hoffer’s chlorosugar, yielding alpha anomers as the chief products. X-ray crystal structures confirmed the geometry, and showed that the pyridine and benzimidazole ring systems deviated from coplanarity in the solid state by 154° and 140°, respectively. In methanol the compounds 1 and 2 had absorption maxima at 360 and 370 nm respectively, and emission maxima at 494 and 539 nm. Experiments revealed varied fluorescence responses of the nucleosides to a panel of seventeen monovalent, divalent and trivalent metal ions in methanol. One or both of the nucleosides showed significant changes with ten of the metal ions. The most pronounced spectral changes for ligand-nucleoside 1 included red shifts in fluorescence (Au+, Au3+), strong quenching (Cu2+, Ni2+, Pt2+), and in substantial enhancements in emission intensity coupled with redshifts (Ag+, Cd2+, Zn2+). The greatest spectral changes for ligand-nucleoside 2 included a redshift in fluorescence (Ag+), a blueshift (Cd2+), strong quenching (Pd2+, Pt2+), and in substantial enhancements in emission intensity coupled with a blueshift (Zn2+). The compounds could be readily incorporated into oligodeoxynucleotides, where an initial study revealed that they retained sensitivity to metal ions in aqueous solution, and demonstrated possible cooperative sensing behavior with several ions. The two free nucleosides alone can act as differential sensors for at multiple metal ions, and they are potentially useful monomers for contributing metal ion sensing capability to DNAs. PMID:16669686

  8. In vivo response of heme-oxygenase-1 to metal ions released from metal-on-metal hip prostheses.

    PubMed

    Beraudi, Alina; Bianconi, Eva; Catalani, Simona; Canaider, Silvia; De Pasquale, Dalila; Apostoli, Pietro; Bordini, Barbara; Stea, Susanna; Toni, Aldo; Facchin, Federica

    2016-07-01

    Metal ion release and accumulation is considered to be a factor responsible for the high failure rates of metal-on-metal (MoM) hip implants. Numerous studies have associated the presence of these ions, besides other factors, including a hypoxia‑like response and changes in pH due to metal corrosion leading to the induction of the oxidative stress response. The aim of the present study was to verify whether, in patients with a MoM hip prosthesis, mRNA and protein expression of HMOX‑1 was modulated by the presence of metal ions and whether patients without prostheses exhibit a different expression pattern of this enzyme. The study was conducted on 22 matched pairs of patients with and without prostheses, for a total of 44 samples. Ion dosage was determined using inductively coupled plasma mass spectrometry equipped with dynamic cell reaction. HMOX‑1 gene expression was quantified by reverse transcription-quantitative polymerase chain reaction and HMOX‑1 protein expression was analyzed using an enzyme-linked immunosorbent assay. The results demonstrated that although there were significant differences in the metallic ion concentrations amongst the two groups of patients, there was no correlation between circulating levels of cobalt (Co) and chromium (Cr), and HMOX‑1 gene and protein expression. Additionally, there was no significant difference in the protein expression levels of HMOX‑1 between the two groups. In conclusion, it was demonstrated that circulating Co and Cr ions released by articular prosthetics do not induce an increase in HMOX‑1 mRNA and protein expression at least 3.5 years after the implant insertion. The present study suggests that involvement of HMOX‑1 may be excluded from future studies and suggests that other antioxidant enzymes, including superoxide dismutase, glutathione peroxidase and reductase should be investigated. PMID:27176599

  9. Metallic ions in cometary comae and plasma tails

    NASA Astrophysics Data System (ADS)

    Ip, W.-H.; Axford, W. I.

    1986-06-01

    A surprising result of the International Cometary Explorer (ICE) observations of the comet Giacobini-Zinner was the detection of ions of mass 23-24 AMU with a relatively high abundance. According to the experiments, these ions may be either Na(+) or C2(+), if not both. It is suggested here that the detected ions may indeed be in part Na(+) and/or Mg(+), and that these and other metallic ions, especially Si(+) and Fe(+), may be an important component of the cometary ionosphere and central plasma tail. The reasons are similar in principle to those which account for the prevalence of such ions in sporadic E layers in the terrestrial ionosphere, notably the comparatively short timescales for ionization of their neutral parent atoms and the large difference between the rates of dissociative and radiative recombination.

  10. Metal ions affecting the gastrointestinal system including the liver.

    PubMed

    Naughton, Declan P; Nepusz, Tamás; Petroczi, Andrea

    2011-01-01

    In the present context, metal ions can be categorized into several classes including those that are essential for life and those that have no known biological function and thus can be considered only as potentially hazardous. Many complexities arise with regard to metal toxicity and there is a paucity of studies relating to many metals which are frequent components of the diet. For many people ingestion of mineral supplements is considered a risk-free health choice despite growing evidence to the contrary. Numerous approaches have been developed to assess risk associated with ingestion of metal ions. These include straightforward estimation of safe limits such as oral reference dose which are often based on data derived from animal experiments. More convoluted approaches such as the Target Hazard Quotient involve assessment of hazard with frequent exposure over long durations such as a lifetime. The latter calculation also affords facile consideration of the effects of many metals together. In many cases, rigorous data are unavailable, hence, large factors of uncertainty are employed to relate risk to humans. Owing to the nature of metal toxicity, data pertaining to the gastrointestinal tract and liver are often acquired from diseases of metal homeostasis or episodes of considerable metal overload. Whilst these studies provide evidence for mechanisms of metal-induced toxicity such as enhancing oxidative stress, extrapolation of these results to healthy individuals or patients with chronic inflammatory diseases is not straightforward. In summary, the diverse nature of metals and their effects on human tissues along with a paucity of studies on the full range of their effects, warrant further in-depth studies on the association of metals to ageing, chronic inflammatory diseases, and cancer. PMID:21473378

  11. 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. PMID:27306427

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Adsorption characteristics of metal ions on chitosan chemically modified by D-galactose

    SciTech Connect

    Kondo, Kazuo; Sumi, Hisaharu; Matsumoto, Michiaki

    1996-07-01

    The adsorption characteristics of metal ions on chitosan chemically modified by D-galactose were examined. The pH dependency on the distribution ratio was found to be affected by the valency of the metal ion, and the apparent adsorption equilibrium constants of the metal ions were determined. The order of adsorption of the metal ions is Ga > In > Nd > Eu for the trivalent metal ions and Cu > Ni > Co for the divalent metal ions. It is believed that amino and hydroxyl groups in the chitosan act as a chelating ligand.

  15. Metal ion bombardment of onion skin cell wall

    SciTech Connect

    Sangyuenyongpipat, S.; Vilaithong, T.; Yu, L.D.; Verdaguer, A.; Ratera, I.; Ogletree, D.F.; Monteiro, O.R.; Brown, I.G.

    2004-05-10

    Ion bombardment of living cellular material is a novel subfield of ion beam surface modification that is receiving growing attention from the ion beam and biological communities. Although it has been demonstrated that the technique is sound, in that an adequate fraction of the living cells can survive both the vacuum environment and energetic ion bombardment, there remains much uncertainty about the process details. Here we report on our observations of onion skin cells that were subjected to ion implantation, and propose some possible physical models that tend to support the experimental results. The ion beams used were metallic (Mg, Ti, Fe, Ni, Cu), mean ion energy was typically 30keV, and the implantation fluence was in the range 1014 1016 ions/cm2. The cells were viewed using Atomic Force Microscopy, revealing the formation of microcrater-like structures due to ion bombardment. The implantation depth profile was measured with Rutherford backscattering spectrometry and compared to the results of the TRIM, T-DYN and PROFILE computer codes.

  16. Laser-driven ion sources for metal ion implantation for the reduction of dry friction

    SciTech Connect

    Boody, F. P.; Juha, L.; Kralikova, B.; Krasa, J.; Laska, L.; Masek, K.; Pfeifer, M.; Rohlena, K.; Skala, J.; Straka, P.; Perina, V.; Woryna, E.; Giersch, D.; Hoepfl, R.; Kelly, J. C.; Hora, H.

    1997-04-15

    The anomalously high ion currents and very high ionization levels of laser-produced plasmas give laser-driven ion sources significant advantages over conventional ion sources. In particular, laser-driven ion sources should provide higher currents of metal ions at lower cost, for implantation into solids in order to improve their material properties such as friction. The energy and charge distributions for Pb and Sn ions produced by ablation of solid targets with {approx}25 J, {approx}300 ps iodine laser pulses, resulting in up to 48-times ionized MeV ions, as well as the optimization of focus position, are presented. Implantation of these ions into Ck-45 steel, without electrostatic acceleration, produced profiles with two regions. Almost all of the ions were implanted in a near surface region a few nm deep. However, a small but significant number of ions were implanted as deep as could be measured with Rutherford backscattering (RBS), here 150 nm for Sn and 250 nm for Pb. For the implanted ion densities and profiles achieved, no change in the coefficient of friction was measured for either ion.

  17. A nanoporous metal recuperated MnO2 anode for lithium ion batteries.

    PubMed

    Guo, Xianwei; Han, Jiuhui; Zhang, Ling; Liu, Pan; Hirata, Akihiko; Chen, Luyang; Fujita, Takeshi; Chen, Mingwei

    2015-10-01

    Lithium-ion batteries (LIBs) have been intensively studied to meet the increased demands for the high energy density of portable electronics and electric vehicles. The low specific capacity of the conventional graphite based anodes is one of the key factors that limit the capacity of LIBs. Transition metal oxides, such as NiO, MnO2 and Fe3O4, are known to be promising anode materials that are expected to improve the specific capacities of LIBs for several times. However, the poor electrical conductivity of these oxides significantly restricts the lithium ion storage and charge/discharge rate. Here we report that dealloyed nanoporous metals can realize the intrinsic lithium storage performance of the oxides by forming oxide/metal composites. Without any organic binder, conductive additive and additional current collector, the hybrid electrodes can be directly used as anodes and show highly reversible specific capacity with high-rate capability and long cyclic stability. PMID:26350685

  18. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, Toshifumi; Kukacka, Lawrence E.; Horn, William H.

    1985-01-01

    Quick setting polymer concrete compositions with excellent structural properties are disclosed; these polymer concrete compositions are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate, which may be wet, and with a source of bivalent metallic ions.

  19. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1981-11-04

    Quick setting polymer concrete compositions which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  20. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1983-05-13

    Quick setting polymer concrete compositions are described which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  1. Principles Governing Metal Ion Selectivity in Ion Channel Proteins

    NASA Astrophysics Data System (ADS)

    Lim, Carmay

    2014-03-01

    Our research interests are to (i) unravel the principles governing biological processes and use them to identify novel drug targets and guide drug design, and (ii) develop new methods for studying macromolecular interactions. This talk will provide an overview of our work in these two areas and an example of how our studies have helped to unravel the principles underlying the conversion of Ca2+-selective to Na+-selective channels. Ion selectivity of four-domain voltage-gated Ca2+(Cav) and sodium (Nav) channels, which is controlled by the selectivity filter (SF, the narrowest region of an open pore), is crucial for electrical signaling. Over billions of years of evolution, mutation of the Glu from domain II/III in the EEEE/DEEA SF of Ca2+-selective Cav channels to Lys made these channels Na+-selective. This talk will delineate the physical principles why Lys is sufficient for Na+/Ca2+selectivity and why the DEKA SF is more Na+-selective than the DKEA one.

  2. Flue gas desulfurization/denitrification using metal-chelate additives

    DOEpatents

    Harkness, John B. L.; Doctor, Richard D.; Wingender, Ronald J.

    1986-01-01

    A method of simultaneously removing SO.sub.2 and NO from oxygen-containing flue gases resulting from the combustion of carbonaceous material by contacting the flue gas with an aqueous scrubber solution containing an aqueous sulfur dioxide sorbent and an active metal chelating agent which promotes a reaction between dissolved SO.sub.2 and dissolved NO to form hydroxylamine N-sulfonates. The hydroxylamine sulfonates are then separated from the scrubber solution which is recycled.

  3. Flue gas desulfurization/denitrification using metal-chelate additives

    DOEpatents

    Harkness, J.B.L.; Doctor, R.D.; Wingender, R.J.

    1985-08-05

    A method of simultaneously removing SO/sub 2/ and NO from oxygen-containing flue gases resulting from the combustion of carbonaceous material by contacting the flue gas with an aqueous scrubber solution containing an aqueous sulfur dioxide sorbent and an active metal chelating agent which promotes a reaction between dissolved SO/sub 2/ and dissolved NO to form hydroxylamine N-sulfonates. The hydroxylamine sulfonates are then separated from the scrubber solution which is recycled. 3 figs.

  4. [Spectroscopic studies on transition metal ions in colored diamonds].

    PubMed

    Meng, Yu-Fei; Peng, Ming-Sheng

    2004-07-01

    Transition metals like nickel, cobalt and iron have been often used as solvent catalysts in high pressure high temperature (HPHT) synthesis of diamond, and nickel and cobalt ions have been found in diamond lattice. Available studies indicated that nickel and cobalt ions could enter the lattice as interstitial or substitutional impurities and form complexes with nitrogen. Polarized microscopy, SEM-EDS, EPR, PL and FTIR have been used in this study to investigate six fancy color natural and synthetic diamonds in order to determine the spectroscopic characteristics and the existing forms of transition metal ions in colored diamond lattice. Cobalt-related optical centers were first found in natural chameleon diamonds, and some new nickel and cobalt-related optical and EPR centers have also been detected in these diamond samples. PMID:15766067

  5. Method for removing metal ions from solution with titanate sorbents

    DOEpatents

    Lundquist, Susan H.; White, Lloyd R.

    1999-01-01

    A method for removing metal ions from solution comprises the steps of providing titanate particles by spray-drying a solution or slurry comprising sorbent titanates having a particle size up to 20 micrometers, optionally in the presence of polymer free of cellulose functionality as binder, said sorbent being active towards heavy metals from Periodic Table (CAS version) Groups IA, IIA, IB, IIB, IIIB, and VIII, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size distribution in the range of 1 to 500 micrometers. The particles can be used free flowing in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove metal ions from aqueous or organic liquid.

  6. 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.

  7. Chitosan removes toxic heavy metal ions from cigarette mainstream smoke

    NASA Astrophysics Data System (ADS)

    Zhou, Wen; Xu, Ying; Wang, Dongfeng; Zhou, Shilu

    2013-09-01

    This study investigated the removal of heavy metal ions from cigarette mainstream smoke using chitosan. Chitosan of various deacetylation degrees and molecular weights were manually added to cigarette filters in different dosages. The mainstream smoke particulate matter was collected by a Cambridge filter pad, digested by a microwave digestor, and then analyzed for contents of heavy metal ions, including As(III/V), Pb(II), Cd(II), Cr(III/VI) and Ni(II), by graphite furnace atomic absorption spectrometry (GFAAS). The results showed that chitosan had a removal effect on Pb(II), Cd(II), Cr(III/VI) and Ni(II). Of these, the percent removal of Ni(II) was elevated with an increasing dosage of chitosan. Chitosan of a high deace tylation degree exhibited good binding performance toward Cd(II), Cr(III/VI) and Ni(II), though with poor efficiency for Pb(II). Except As(III/V), all the tested metal ions showed similar tendencies in the growing contents with an increasing chitosan molecular weight. Nonetheless, the percent removal of Cr(III/VI) peaked with a chitosan molecular weight of 200 kDa, followed by a dramatic decrease with an increasing chitosan molecular weight. Generally, chitosan had different removal effects on four out of five tested metal ions, and the percent removal of Cd(II), Pb(II), Cr(III/VI) and Ni(II) was approximately 55%, 45%, 50%, and 16%, respectively. In a word, chitosan used in cigarette filter can remove toxic heavy metal ions in the mainstream smoke, improve cigarette safety, and reduce the harm to smokers.

  8. Mechanism of Metal Ion Activation of the Diphtheria Toxin Repressor DtxR

    SciTech Connect

    D'Aquino,J.; Tetenbaum-Novatt, J.; White, A.; Berkovitch, F.; Ringe, D.

    2005-01-01

    The diphtheria toxin repressor (DtxR) is a metal ion-activated transcriptional regulator that has been linked to the virulence of Corynebacterium diphtheriae. Structure determination has shown that there are two metal ion binding sites per repressor monomer, and site-directed mutagenesis has demonstrated that binding site 2 (primary) is essential for recognition of the target DNA repressor, leaving the role of binding site 1 (ancillary) unclear. Calorimetric techniques have demonstrated that although binding site 1 (ancillary) has high affinity for metal ion with a binding constant of 2 x 10{sup -7}, binding site 2 (primary) is a low-affinity binding site with a binding constant of 6.3 x 10{sup -4}. These two binding sites act in an independent fashion, and their contribution can be easily dissected by traditional mutational analysis. Our results clearly demonstrate that binding site 1 (ancillary) is the first one to be occupied during metal ion activation, playing a critical role in stabilization of the repressor. In addition, structural data obtained for the mutants Ni-DtxR(H79A, C102D), reported here, and the previously reported DtxR(H79A) have allowed us to propose a mechanism of metal activation for DtxR.

  9. Nanopore analysis of the effect of metal ions on the folding of peptides and proteins.

    PubMed

    Lee, Jeremy S

    2014-03-01

    In this minireview, the nanopore analysis of peptides and proteins in the presence of divalent metal ions will be surveyed. In all cases the binding of the metal ions causes the peptide or protein to adopt a more compact conformation which can no longer enter the α-hemolysin pore. In the absence of Zn(II) the 30-amino acid Zn-finger peptide can readily translocate the pore; but upon addition of Zn(II) the peptide folds and only bumping events are observed. Similarly, the octapeptide repeat from the N-terminus of the prion protein binds Cu(II), which prevents it from translocating. The full-length prion protein also undergoes conformational changes upon binding Cu(II), which results in an increase in the proportion of bumping events. Myelin basic protein of 170 residues is intrinsically disordered and, perhaps surprisingly, for a basic protein of this size, can translocate against the electric field based on the observation that the event time increases with increasing voltage. It, too, folds into a more compact conformation upon binding Cu(II) and Zn(II), which prevents translocation. Finally even proteins such as maltose binding protein which does not contain a formal binding site for metal ions undergoes conformational changes in the presence of the metal chelator, EDTA. Thus, contamination of proteins with trace metal ions should be considered when studying proteins and peptides by nanopore analysis. PMID:24370255

  10. Efficient and selective adsorption of multi-metal ions using sulfonated cellulose as adsorbent.

    PubMed

    Dong, Cuihua; Zhang, Fulong; Pang, Zhiqiang; Yang, Guihua

    2016-10-20

    Contamination of heavy metal in wastewater has caused great concerns on human life and health. Developing an efficient material to eliminate the heavy metal ions has been a popular topic in recent years. In this work, sulfonated cellulose (SC) was explored as efficient adsorbent for metal ions in solution. Thermo gravimetric analyzer (TGA), X-ray diffraction (XRD) and Fourier-transform infrared spectrometer (FTIR) first analyzed the characterizations of SC. Subsequently, effects of solution pH, adsorbent loading, temperature and initial metal ion concentration on adsorption performance were investigated. The results showed that sulfonated modification of cellulose could decrease the crystallinity and thermostability of cellulose. Due to its excellent performance of adsorption to metal ions, SC could reach adsorption equilibrium status within as short as 2min. In multi-component solution, SC can orderly removes Fe(3+), Pb(2+) and Cu(2+) with excellent selectivity and high efficiency. In addition, SC is a kind of green and renewable adsorbent because it can be easily regenerated by treatment with acid or chelating liquors. The mechanism study shows that the sulfonic group play a major role in the adsorption process. PMID:27474562

  11. Potentiometric and spectroscopic study of the interaction of 3d transition metal ions with inositol hexakisphosphate

    NASA Astrophysics Data System (ADS)

    Veiga, Nicolás; Macho, Israel; Gómez, Kerman; González, Gabriel; Kremer, Carlos; Torres, Julia

    2015-10-01

    Among myo-inositol phosphates, the most abundant in nature is the myo-inositol hexakisphosphate, InsP6. Although it is known to be vital to cell functioning, the biochemical research into its metabolism needs chemical and structural analysis of all the protonation, complexation and precipitation processes that it undergoes in the biological media. In view of its high negative charge at physiological level, our group has been leading a thorough research into the InsP6 chemical and structural behavior in the presence of the alkali and alkaline earth metal ions essential for life. The aim of this article is to extend these studies, dealing with the chemical and structural features of the InsP6 interaction with biologically relevant 3d transition metal ions (Fe(II), Fe(III), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)), in a non-interacting medium and under simulated physiological conditions. The metal-complex stability constants were determined by potentiometry, showing under ligand-excess conditions the formation of mononuclear species in different protonation states. Under metal ion excess, polymetallic species were detected for Fe(II), Fe(III), Zn(II) and Cu(II). Additionally, the 31P NMR and UV-vis spectroscopic studies provided interesting structural aspects of the strong metal ion-InsP6 interaction.

  12. Modification of medical metals by ion implantation of copper

    NASA Astrophysics Data System (ADS)

    Wan, Y. Z.; Xiong, G. Y.; Liang, H.; Raman, S.; He, F.; Huang, Y.

    2007-10-01

    The effect of copper ion implantation on the antibacterial activity, wear performance and corrosion resistance of medical metals including 317 L of stainless steels, pure titanium, and Ti-Al-Nb alloy was studied in this work. The specimens were implanted with copper ions using a MEVVA source ion implanter with ion doses ranging from 0.5 × 10 17 to 4 × 10 17 ions/cm 2 at an energy of 80 keV. The antibacterial effect, wear rate, and inflexion potential were measured as a function of ion dose. The results obtained indicate that copper ion implantation improves the antibacterial effect and wear behaviour for all the three medical materials studied. However, corrosion resistance decreases after ion implantation of copper. Experimental results indicate that the antibacterial property and corrosion resistance should be balanced for medical titanium materials. The marked deteriorated corrosion resistance of 317 L suggests that copper implantation may not be an effective method of improving its antibacterial activity.

  13. 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.

  14. Metal negative ion beam extraction from a radio frequency ion source

    SciTech Connect

    Kanda, S.; Yamada, N.; Kasuya, T.; Romero, C. F. P.; Wada, M.

    2015-04-08

    A metal ion source of magnetron magnetic field geometry has been designed and operated with a Cu hollow target. Radio frequency power at 13.56 MHz is directly supplied to the hollow target to maintain plasma discharge and induce self-bias to the target for sputtering. The extraction of positive and negative Cu ion beams have been tested. The ion beam current ratio of Cu{sup +} to Ar{sup +} has reached up to 140% when Ar was used as the discharge support gas. Cu{sup −} ion beam was observed at 50 W RF discharge power and at a higher Ar gas pressure in the ion source. Improvement of poor RF power matching and suppression of electron current is indispensable for a stable Cu{sup −} ion beam production from the source.

  15. Microstructure-controllable Laser Additive Manufacturing Process for Metal Products

    NASA Astrophysics Data System (ADS)

    Huang, Wei-Chin; Chuang, Chuan-Sheng; Lin, Ching-Chih; Wu, Chih-Hsien; Lin, De-Yau; Liu, Sung-Ho; Tseng, Wen-Peng; Horng, Ji-Bin

    Controlling the cooling rate of alloy during solidification is the most commonly used method for varying the material microstructure. However, the cooling rate of selective laser melting (SLM) production is constrained by the optimal parameter settings for a dense product. This study proposes a method for forming metal products via the SLM process with electromagnetic vibrations. The electromagnetic vibrations change the solidification process for a given set of SLM parameters, allowing the microstructure to be varied via magnetic flux density. This proposed method can be used for creating microstructure-controllable bio-implant products with complex shapes.

  16. Additive-free thick graphene film as an anode material for flexible lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Rana, Kuldeep; Kim, Seong Dae; Ahn, Jong-Hyun

    2015-04-01

    This work demonstrates a simple route to develop mechanically flexible electrodes for Li-ion batteries (LIBs) that are usable as lightweight effective conducting networks for both cathodes and anodes. Removing electrochemically dead elements, such as binders, conducting agents and metallic current collectors, from the battery components will allow remarkable progress in this area. To investigate the feasibility of using thick, additive-free graphene films as anodes for flexible LIBs, we have synthesized and tested thick, additive-free, freestanding graphene films as anodes, first in a coin cell and further in a flexible full cell. As an anode material in a half cell, it showed a discharge capacity of about 350 mA h g-1 and maintained nearly this capacity over 50 cycles at various current rates. This film was also tested as an anode material in a full cell with a LiCoO2 cathode and showed good electrochemical performance. Because the graphene-based flexible film showed good performance in half- and full coin cells, we used this film as a flexible anode for flexible LIBs. No conducting agent or binder was used in the anode side, which helped in realizing the flexible LIBs. Using this, we demonstrate a thin, lightweight and flexible lithium ion battery with good electrochemical performance in both its flat and bent states.This work demonstrates a simple route to develop mechanically flexible electrodes for Li-ion batteries (LIBs) that are usable as lightweight effective conducting networks for both cathodes and anodes. Removing electrochemically dead elements, such as binders, conducting agents and metallic current collectors, from the battery components will allow remarkable progress in this area. To investigate the feasibility of using thick, additive-free graphene films as anodes for flexible LIBs, we have synthesized and tested thick, additive-free, freestanding graphene films as anodes, first in a coin cell and further in a flexible full cell. As an anode

  17. A novel Schiff base: Synthesis, structural characterisation and comparative sensor studies for metal ion detections.

    PubMed

    Köse, Muhammet; Purtas, Savas; Güngör, Seyit Ali; Ceyhan, Gökhan; Akgün, Eyup; McKee, Vickie

    2015-02-01

    A novel Schiff base ligand was synthesized by the condensation reaction of 2,6-diformylpyridine and 4-aminoantipyrine in MeOH and characterised by its melting point, elemental analysis, FT-IR, (1)H, (13)C NMR and mass spectroscopic studies. Molecular structure of the ligand was determined by single crystal X-ray diffraction technique. The electrochemical properties of the Schiff base ligand were studied in different solvents at various scan rates. Sensor ability of the Schiff base ligand was investigated by colorimetric and fluorometric methods. Visual colour change of the ligand was investigated in MeOH solvent in presence of various metal ions Na(+), Mg(2+), Al(3+), K(+), Cr(3+), Mn(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+). Upon addition of Al(3+) ion into a MeOH solution of the ligand, an orange colour developed which is detectable by naked eye. Fluorescence emission studies showed that the ligand showed single emission band at 630-665nm upon excitation at 560nm. Addition of metal ions Na(+), Mg(2+), K(+), Cr(3+), Mn(2+), Fe(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+) (1:1M ratio) cause fluorescence quenching, however addition of Al(+3) resulted in an increase in fluorescence intensity. No significant variation was observed in the fluorescence intensity caused by Al(3+) in presence of other metal ions. Therefore, the Schiff base ligand can be used for selective detection of Al(3+) ions in the presence of the other metal ions studied. PMID:25459697

  18. In vitro cytotoxicity of metallic ions released from dental alloys.

    PubMed

    Milheiro, Ana; Nozaki, Kosuke; Kleverlaan, Cornelis J; Muris, Joris; Miura, Hiroyuki; Feilzer, Albert J

    2016-05-01

    The cytotoxicity of a dental alloy depends on, but is not limited to, the extent of its corrosion behavior. Individual ions may have effects on cell viability that are different from metals interacting within the alloy structure. We aimed to investigate the cytotoxicity of individual metal ions in concentrations similar to those reported to be released from Pd-based dental alloys on mouse fibroblast cells. Metal salts were used to prepare seven solutions (concentration range 100 ppm-1 ppb) of the transition metals, such as Ni(II), Pd(II), Cu(II), and Ag(I), and the metals, such as Ga(III), In(III), and Sn(II). Cytotoxicity on mouse fibroblasts L929 was evaluated using the MTT assay. Ni, Cu, and Ag are cytotoxic at 10 ppm, Pd and Ga at 100 ppm. Sn and In were not able to induce cytotoxicity at the tested concentrations. Transition metals were able to induce cytotoxic effects in concentrations similar to those reported to be released from Pd-based dental alloys. Ni, Cu, and Ag were the most cytotoxic followed by Pd and Ga; Sn and In were not cytotoxic. Cytotoxic reactions might be considered in the etiopathogenesis of clinically observed local adverse reactions. PMID:25549610

  19. Antibacterial Behavior of Additively Manufactured Porous Titanium with Nanotubular Surfaces Releasing Silver Ions.

    PubMed

    Amin Yavari, S; Loozen, L; Paganelli, F L; Bakhshandeh, S; Lietaert, K; Groot, J A; Fluit, A C; Boel, C H E; Alblas, J; Vogely, H C; Weinans, H; Zadpoor, A A

    2016-07-13

    Additive manufacturing (3D printing) has enabled fabrication of geometrically complex and fully interconnected porous biomaterials with huge surface areas that could be used for biofunctionalization to achieve multifunctional biomaterials. Covering the huge surface area of such porous titanium with nanotubes has been already shown to result in improved bone regeneration performance and implant fixation. In this study, we loaded TiO2 nanotubes with silver antimicrobial agents to equip them with an additional biofunctionality, i.e., antimicrobial behavior. An optimized anodizing protocol was used to create nanotubes on the entire surface area of direct metal printed porous titanium scaffolds. The nanotubes were then loaded by soaking them in three different concentrations (i.e., 0.02, 0.1, and 0.5 M) of AgNO3 solution. The antimicrobial behavior and cell viability of the developed biomaterials were assessed. As far as the early time points (i.e., up to 1 day) are concerned, the biomaterials were found to be extremely effective in preventing biofilm formation and decreasing the number of planktonic bacteria particularly for the middle and high concentrations of silver ions. Interestingly, nanotubes not loaded with antimicrobial agents also showed significantly smaller numbers of adherent bacteria at day 1, which may be attributed to the bactericidal effect of high aspect ratio nanotopographies. The specimens with the highest concentrations of antimicrobial agents adversely affected cell viability at day 1, but this effect is expected to decrease or disappear in the following days as the rate of release of silver ions was observed to markedly decrease within the next few days. The antimicrobial effects of the biomaterials, particularly the ones with the middle and high concentrations of antimicrobial agents, continued until 2 weeks. The potency of the developed biomaterials in decreasing the number of planktonic bacteria and hindering the formation of biofilms make

  20. Humic colloid-borne natural polyvalent metal ions: dissociation experiment.

    PubMed

    Geckeis, H; Rabung, Th; Ngo Manh, T; Kim, J I; Beck, H P

    2002-07-01

    The natural association nature of the humic colloid-borne trace elements is investigated. Rare earth elements (REE) Th and U are chosen as naturally occurring representatives and chemical homologues for actinides of different oxidation states present in nuclear waste. Tri- and tetravalent elements in two investigated Gorleben groundwaters (Gohy-532 and -2227) almost exclusively occur as humic or fulvic colloid-borne species. Their desorption behavior from colloids is examined in the unperturbed groundwater (pH approximately 8) under anaerobic conditions (Ar/1% CO2) by addition of a chelating cation exchanger resin. Particularly, the dissociation process of naturally occurring Eu(III) in the groundwater is compared with the Eu(III) desorption from its humate complex prepared with purified Aldrich humic acid in a buffered aqueous solution at pH approximately 8. The Eu(III) dissociation from the groundwater colloids is found to be considerably slower than found for the humate complex synthesized in the laboratory. This suggests that under natural aquatic conditions the Eu(III) binding in colloids is chemically different from the simple humate complexation as observed in the laboratory experiment. The colloid characterization bythe size exclusion chromatography (SEC) and the flow field-flow fractionation (FFFF) indicates that natural colloid-borne trace elements are found predominantly in colloids of larger size (>15 nm in size), while Eu(III) in its humate complex is found mainly in colloids of hydrodynamic diameters <5 nm. The slower desorption kinetics and the larger colloid size suggest that the polyvalent metal ion binding in natural humic colloids is associated to polynucleation with other co-present trace metal ions. Radiotracer experiments reveal that isotopic equilibria with the naturally colloid-borne trace elements are not attained within a period of more than 100 days, indicating irreversible binding of at least a part of colloid-borne polyvalent trace

  1. Mechanical property measurements on ion-irradiated metals

    SciTech Connect

    Zinkle, S.J.; Oliver, W.C.

    1986-08-01

    A recently developed mechanical properties microprobe (MPM) has been used to investigate strength and elastic modulus changes in ion-irradiated metals. The indenter load and its displacement are simultaneously monitored while the indentation is being made and also during unloading. Microindentation hardness measurements have been performed on ion-irradiated copper and Cu-0.15% Zr (AMZIRC). The depth dependence of the ion damage has been investigated in selected specimens which were prepared using a cross-section technique. This procedure allows a direct comparison to be made of hardness data from different irradiation depths while the indent size is held constant. The displacement damage associated with ion irradiation caused either hardening or softening, depending on the irradiation conditions and the material.

  2. Metal Ion Binding to Polypeptides Characterized by Irmpd Spectroscopy. Metal-Amide Nitrogen Binding and the Iminol Tautomerization.

    NASA Astrophysics Data System (ADS)

    Dunbar, Robert C.; Polfer, Nicolas; Berden, Giel; Oomens, Jos

    2012-06-01

    We have recently uncovered a new binding mode for the complexation of metal ions with gas-phase peptides. Termed the iminol mode, this binding mode is adopted by strongly binding divalent metal ions including Mg2+ and Ni2+. The metal ion displaces the amide hydrogen, which moves to protonate the amide carbonyl oxygen. A spectroscopic signature of the tautomerization is the disappearance of the characteristic Amide II band normally seen in peptide ion infrared spectra. We find that in peptides up to pentapeptides, multiple iminol binding can take place, such that all amide linkages are tautomerized to the iminol form, and chelate the metal ion. However, the iminol tautomerization depends on the nature of the metal ion, as will be discussed. Spectra of the ions were acquired by irradiating the cell of the Fourier-transform ion cyclotron resonance mass spectrometer with infrared light from the FELIX laser at wavelengths in the approximate range 500 to 1900 cm-1.

  3. Optical studies of ion-beam synthesized metal alloy nanoparticles

    SciTech Connect

    Magudapathy, P. Srivatsava, S. K.; Gangopadhyay, P.; Amirthapandian, S.; Sairam, T. N.; Panigrahi, B. K.

    2015-06-24

    Au{sub x}Ag{sub 1-x} alloy nanoparticles with tunable surface plasmon resonance (SPR) have been synthesized on a silica glass substrate. A small Au foil on an Ag foil is irradiated as target substrates such that ion beam falls on both Ag foil and Au foils. Silica slides are kept at an angle ∼45° with respect to the metallic foils. While irradiating the metallic foils with 100 keV Ar{sup +} ions, sputtered Au and Ag atoms get deposited on the silica-glass. In this configuration the foils have been irradiated by Ar{sup +} ions to various fluences at room temperature and the sputtered species are collected on silica slides. Formation of Au{sub x}Ag{sub 1-x} nanoparticles has been confirmed from the optical absorption measurements. With respect to the exposure area of Au and Ag foils to the ion beam, the SPR peak position varies from 450 to 500 nm. Green photoluminescence has been observed from these alloy metal nanoparticles.

  4. Peptide immobilisation on porous silicon surface for metal ions detection

    NASA Astrophysics Data System (ADS)

    Sam, Sabrina S.; Chazalviel, Jean-Noël Jn; Gouget-Laemmel, Anne Chantal Ac; Ozanam, François F.; Etcheberry, Arnaud A.; Gabouze, Nour-Eddine N.

    2011-06-01

    In this work, a Glycyl-Histidyl-Glycyl-Histidine (GlyHisGlyHis) peptide is covalently anchored to the porous silicon PSi surface using a multi-step reaction scheme compatible with the mild conditions required for preserving the probe activity. In a first step, alkene precursors are grafted onto the hydrogenated PSi surface using the hydrosilylation route, allowing for the formation of a carboxyl-terminated monolayer which is activated by reaction with N-hydroxysuccinimide in the presence of a peptide-coupling carbodiimide N-ethyl- N'-(3-dimethylaminopropyl)-carbodiimide and subsequently reacted with the amino linker of the peptide to form a covalent amide bond. Infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy are used to investigate the different steps of functionalization. The property of peptides to form stable complexes with metal ions is exploited to achieve metal-ion recognition by the peptide-modified PSi-based biosensor. An electrochemical study of the GlyHisGlyHis-modified PSi electrode is achieved in the presence of copper ions. The recorded cyclic voltammograms show a quasi-irreversible process corresponding to the Cu(II)/Cu(I) couple. The kinetic factors (the heterogeneous rate constant and the transfer coefficient) and the stability constant of the complex formed on the porous silicon surface are determined. These results demonstrate the potential role of peptides grafted on porous silicon in developing strategies for simple and fast detection of metal ions in solution.

  5. Additive Manufacturing of Metal Cellular Structures: Design and Fabrication

    NASA Astrophysics Data System (ADS)

    Yang, Li; Harrysson, Ola; Cormier, Denis; West, Harvey; Gong, Haijun; Stucker, Brent

    2015-03-01

    With the rapid development of additive manufacturing (AM), high-quality fabrication of lightweight design-efficient structures no longer poses an insurmountable challenge. On the other hand, much of the current research and development with AM technologies still focuses on material and process development. With the design for additive manufacturing in mind, this article explores the design issue for lightweight cellular structures that could be efficiently realized via AM processes. A unit-cell-based modeling approach that combines experimentation and limited-scale simulation was demonstrated, and it was suggested that this approach could potentially lead to computationally efficient design optimizations with the lightweight structures in future applications.

  6. New Catalytic DNA Biosensors for Radionuclides and Metal ion

    SciTech Connect

    Yi Lu

    2008-03-01

    We aim to develop new DNA biosensors for simultaneous detection and quantification of bioavailable radionuclides, such as uranium, technetium, and plutonium, and metal contaminants, such as lead, chromium, and mercury. The sensors will be highly sensitive and selective. They will be applied to on-site, real-time assessment of concentration, speciation, and stability of the individual contaminants before and during bioremediation, and for long-term monitoring of DOE contaminated sites. To achieve this goal, we have employed a combinatorial method called “in vitro selection” to search from a large DNA library (~ 1015 different molecules) for catalytic DNA molecules that are highly specific for radionuclides or other metal ions through intricate 3-dimensional interactions as in metalloproteins. Comprehensive biochemical and biophysical studies have been performed on the selected DNA molecules. The findings from these studies have helped to elucidate fundamental principles for designing effective sensors for radionuclides and metal ions. Based on the study, the DNA have been converted to fluorescent or colorimetric sensors by attaching to it fluorescent donor/acceptor pairs or gold nanoparticles, with 11 part-per-trillion detection limit (for uranium) and over million fold selectivity (over other radionuclides and metal ions tested). Practical application of the biosensors for samples from the Environmental Remediation Sciences Program (ERSP) Field Research Center (FRC) at Oak Ridge has also been demonstrated.

  7. Polymer filtration systems for dilute metal ion recovery

    SciTech Connect

    Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

    1998-12-01

    Scientists at Los Alamos National Laboratory have developed a metal recovery system that meets the global treatment demands for all kinds of industrial and metal-processing streams. The Polymer Filtration (PF) System--a process that is easily operated and robust--offers metal-finishing businesses a convenient and inexpensive way to recover and recycle metal ions in-house, thus reducing materials costs, waste removal costs, and industrial liability. As a valuable economic and environmental asset, the PF System has been named a winner of a 1995 R and D 100 Award. These awards are presented annually by R and D Magazine to the one hundred most significant technical innovations of the year. The PF System is based on the use of water-soluble metal-binding polymers and on advanced ultrafiltration membranes. Customers for this technology will receive new soluble polymers, especially formulated for their waste stream, and the complete PF processing unit: a reaction reservoir, pumps, plumbing, controls, and the advanced ultrafiltration membranes, all in a skid mounted frame. Metal-bearing waste water is treated in the reaction reservoir, where the polymer binds with the metal ions under balanced acid/base conditions. The reservoir fluid is then pumped through the ultrafiltration system--a cartridge packed with ultrafiltration membranes shaped in hollow fibers. As the fluid travels inside the fiber, water and other small molecules--simple salts such as calcium and sodium, for example--pass through the porous membrane walls of the fibers and are discharged through the outlet as permeate. The polymer-bound metal, which is too large to pass through the pores, is both purified and concentrated inside the hollow fibers and is returned to the fluid reservoir for further waste water treatment.

  8. Recovery and Extraction of Heavy Metal Ions Using Ionic Liquid as Green Solvent

    NASA Astrophysics Data System (ADS)

    Kumano, Masami; Yabutani, Tomoki; Motonaka, Junko; Mishima, Yuji

    Ionic liquids are expected to replace conventional organic solvents in organic synthesis, solvent extraction and electrochemistry due to their unique characters such as low volatility, high stability and so on. In this work, N,N,-diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis(trifluoromethansulfonyl)imide was used as an alternative solvent to extract heavy metal ions. As the extracting conditions, the additional effect of 8-hydroxyquinoline (8-HQ) as metal chelating agent into ionic liquids, shaking time and volume ratio were investigated. As extraction efficiency depended on 8-HQ concentration significantly, in order to extract high concentrated metal ions the solubility of 8-HQ into ionic liquid was tested. N,N,-diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis(trifluoromethansulfonyl)imide had good solubility of 8-HQ. Consequently, 5 μmol of copper, zinc, cadmium and manganese could be completely recovered with 100 μl of ionic liquid.

  9. Infrared Spectroscopy of Metal Ion Complexes: Models for Metal Ligand Interactions and Solvation

    NASA Astrophysics Data System (ADS)

    Duncan, Michael

    2006-03-01

    Weakly bound complexes of the form M^+-Lx (M=Fe, Ni, Co, etc.; L=CO2, C2H2, H2O, benzene, N2) are prepared in supersonic molecular beams by laser vaporization in a pulsed-nozzle cluster source. These species are mass analyzed and size-selected in a reflectron time-of-flight mass spectrometer. Clusters are photodissociated at infrared wavelengths with a Nd:YAG pumped infrared optical parametric oscillator/amplifier (OPO/OPA) laser or with a tunable infrared free-electron laser. M^+-(CO2)x complexes absorb near the free CO2 asymmetric stretch near 2349 cm-1 but with an interesting size dependent variation in the resonances. Small clusters have blue-shifted resonances, while larger complexes have additional bands due to surface CO2 molecules not attached to the metal. M^+(C2H2)n complexes absorb near the C-H stretches in acetylene, but resonances in metal complexes are red-shifted with repect to the isolated molecule. Ni^+ and Co^+ complexes with acetylene undergo intracluster cyclization reactions to form cyclobutadiene. Transition metal water complexes are studied in the O-H stretch region, and partial rotational structure can be measured. M^+(benzene) and M^+(benzene)2 ions (M=V, Ti, Al) represent half-sandwich and sandwich species, whose spectra are measured near the free benzene modes. These new IR spectra and their assignments will be discussed as well as other new IR spectra for similar complexes.

  10. Part height control of laser metal additive manufacturing process

    NASA Astrophysics Data System (ADS)

    Pan, Yu-Herng

    Laser Metal Deposition (LMD) has been used to not only make but also repair damaged parts in a layer-by-layer fashion. Parts made in this manner may produce less waste than those made through conventional machining processes. However, a common issue of LMD involves controlling the deposition's layer thickness. Accuracy is important, and as it increases, both the time required to produce the part and the material wasted during the material removal process (e.g., milling, lathe) decrease. The deposition rate is affected by multiple parameters, such as the powder feed rate, laser input power, axis feed rate, material type, and part design, the values of each of which may change during the LMD process. Using a mathematical model to build a generic equation that predicts the deposition's layer thickness is difficult due to these complex parameters. In this thesis, we propose a simple method that utilizes a single device. This device uses a pyrometer to monitor the current build height, thereby allowing the layer thickness to be controlled during the LMD process. This method also helps the LMD system to build parts even with complex parameters and to increase material efficiency.

  11. Overview of Materials Qualification Needs for Metal Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Seifi, Mohsen; Salem, Ayman; Beuth, Jack; Harrysson, Ola; Lewandowski, John J.

    2016-03-01

    This overview highlights some of the key aspects regarding materials qualification needs across the additive manufacturing (AM) spectrum. AM technology has experienced considerable publicity and growth in the past few years with many successful insertions for non-mission-critical applications. However, to meet the full potential that AM has to offer, especially for flight-critical components (e.g., rotating parts, fracture-critical parts, etc.), qualification and certification efforts are necessary. While development of qualification standards will address some of these needs, this overview outlines some of the other key areas that will need to be considered in the qualification path, including various process-, microstructure-, and fracture-modeling activities in addition to integrating these with lifing activities targeting specific components. Ongoing work in the Advanced Manufacturing and Mechanical Reliability Center at Case Western Reserve University is focusing on fracture and fatigue testing to rapidly assess critical mechanical properties of some titanium alloys before and after post-processing, in addition to conducting nondestructive testing/evaluation using micro-computerized tomography at General Electric. Process mapping studies are being conducted at Carnegie Mellon University while large area microstructure characterization and informatics (EBSD and BSE) analyses are being conducted at Materials Resources LLC to enable future integration of these efforts via an Integrated Computational Materials Engineering approach to AM. Possible future pathways for materials qualification are provided.

  12. Ion beam mixing of metal/fluoropolymer interfaces

    SciTech Connect

    Dennis, D. L.; Giedd, R. E.; Wang, Y. Q.; Glass, G. A.

    1999-06-10

    Ion beam mixing of metals and polymers with very low dielectric constants such as Teflon can provide many applications in the area of electronic materials. This work is a study of the 'mixing' effect of 50 keV nitrogen implanted thin metal layers on Teflon PTFE (polytetrafluoroethylene) substrates. RBS analysis shows that the distribution of thin layers of copper and chromium (approximately 300-400 A thick) through the implant layer of the Teflon depends on the reactivity of the metal. As the implant fluence is increased, the distribution of metal atoms in the polymer matrix becomes concentrated over smaller ranges near the bottom of the implant layer. In situ RGA analysis during the implantation shows the liberation of an abundance of fluorine in many different forms. This is supported by results from a NRA experiment that shows the non-uniform concentration profile of fluorine throughout the implant layer. During the implantation process, the fluorine is released through the incident ion track leaving a carbon and metal rich region near the surface of the implant layer. The fluorine density increases with depth through the implant layer making a smooth transition to the undamaged bulk Teflon below. Low dielectric materials with highly conductive surfaces, such as this one, may provide an opportunity for a broad range of new microelectronic applications.

  13. Ion beam mixing of metal/fluoropolymer interfaces

    SciTech Connect

    Dennis, D.L.; Giedd, R.E.; Wang, Y.Q.; Glass, G.A.

    1999-06-01

    Ion beam mixing of metals and polymers with very low dielectric constants such as Teflon can provide many applications in the area of electronic materials. This work is a study of the {open_quotes}mixing{close_quotes} effect of 50 keV nitrogen implanted thin metal layers on Teflon PTFE (polytetrafluoroethylene) substrates. RBS analysis shows that the distribution of thin layers of copper and chromium (approximately 300-400 {Angstrom} thick) through the implant layer of the Teflon depends on the reactivity of the metal. As the implant fluence is increased, the distribution of metal atoms in the polymer matrix becomes concentrated over smaller ranges near the bottom of the implant layer. {ital In situ} RGA analysis during the implantation shows the liberation of an abundance of fluorine in many different forms. This is supported by results from a NRA experiment that shows the non-uniform concentration profile of fluorine throughout the implant layer. During the implantation process, the fluorine is released through the incident ion track leaving a carbon and metal rich region near the surface of the implant layer. The fluorine density increases with depth through the implant layer making a smooth transition to the undamaged bulk Teflon below. Low dielectric materials with highly conductive surfaces, such as this one, may provide an opportunity for a broad range of new microelectronic applications. {copyright} {ital 1999 American Institute of Physics.}

  14. Microbial metal-ion reduction and Mars: extraterrestrial expectations?

    PubMed

    Nealson, Kenneth H; Cox, B Lea

    2002-06-01

    Dissimilatory metal-ion-reducing bacteria (DMRB) can couple the reduction of a variety of different metal ions to cellular respiration and growth. The excitement of this metabolic group lies not only in the elucidation of a new type of metabolism, but also in the potential use of these abilities for the removal of toxic organics, and in their ability to reduce (and thus, detoxify) other toxic metals, such as U(VI) and Cr(VI). This review focuses on recent advances in the study of DMRB, including the use of external electron shuttles to enhance rates of metal reduction; genome sequencing and consequent genomic and proteomic analyses; new imaging approaches for high resolution analysis of both cells and chemical components; the demonstration of fractionation of stable isotopes of iron during iron reduction; and the elucidation of the types and patterns of secondary mineral formation during metal reduction. One of the secondary minerals is magnetite, the subject of intense controversy regarding the possibility of evidence for life from the Martian meteorite ALH84001. This review thus ends with a short consideration of the evidence for magnetic 'proof' of the existence of past life on Mars. PMID:12057684

  15. Metal fluoride coatings prepared by ion-assisted deposition

    NASA Astrophysics Data System (ADS)

    Bischoff, Martin; Sode, Maik; Gäbler, Dieter; Bernitzki, Helmut; Zaczek, Christoph; Kaiser, Norbert; Tünnermann, Andreas

    2008-09-01

    ArF lithography technology requires minimization of optical losses due to scattering and absorption. Consequently, it is necessary to optimize the coating process of metal fluorides. The properties of metal fluoride thin films are mainly affected by the deposition methods, their parameters (temperature and deposition rate) and the vacuum conditions. A substrate temperature of more than 300°C is a condition for high density and low water content of metal fluorides. Therefore, a substrate temperature of 150°C results in inhomogeneous films with high water content. Until now, the best results were achieved by boat evaporation. This paper will demonstrate that most of the common metal fluorides like MgF2, AlF3, and even LaF3 can be deposited by electron beam evaporation. In comparison to other deposition methods, the prepared thin films have the lowest absorption in the VUV spectral range. Furthermore, metal fluoride thin films were prepared by ion assistance. It will be demonstrated, that they have less water content, high packing density, and low absorption in the VUV spectral range. In this study, single layers of LaF3 and AlF3 and antireflection coatings were prepared by electron beam evaporation with and without ion-assistance. The mechanical, structural, and optical properties were examined and discussed.

  16. Metal Ion Toxins and Brain Aquaporin-4 Expression: An Overview.

    PubMed

    Ximenes-da-Silva, Adriana

    2016-01-01

    Metal ions such as iron, zinc, and manganese are essential to metabolic functions, protein synthesis, neurotransmission, and antioxidant neuroprotective mechanisms. Conversely, non-essential metals such as mercury and lead are sources of human intoxication due to occupational activities or environmental contamination. Essential or non-essential metal accumulation in the central nervous system (CNS) results in changes in blood-brain barrier (BBB) permeability, as well as triggering microglia activation and astrocyte reactivity and changing water transport through the cells, which could result in brain swelling. Aquaporin-4 is the main water channel in the CNS, is expressed in astrocyte foot processes in brain capillaries and along the circumventricular epithelium in the ventricles, and has important physiological functions in maintaining brain osmotic homeostasis and supporting brain excitability through regulation of the extracellular space. Some evidence has pointed to a role of AQP4 during metal intoxication in the brain, where it may act in a dual form as a neuroprotector or a mediator of the development of oxidative stress in neurons and astrocytes, resulting in brain swelling and neuronal damage. This mini-review presents the way some metal ions affect changes in AQP4 expression in the CNS and discuss the ways in which water transport in brain cells can be involved in brain damage. PMID:27313504

  17. Metal Ion Toxins and Brain Aquaporin-4 Expression: An Overview

    PubMed Central

    Ximenes-da-Silva, Adriana

    2016-01-01

    Metal ions such as iron, zinc, and manganese are essential to metabolic functions, protein synthesis, neurotransmission, and antioxidant neuroprotective mechanisms. Conversely, non-essential metals such as mercury and lead are sources of human intoxication due to occupational activities or environmental contamination. Essential or non-essential metal accumulation in the central nervous system (CNS) results in changes in blood-brain barrier (BBB) permeability, as well as triggering microglia activation and astrocyte reactivity and changing water transport through the cells, which could result in brain swelling. Aquaporin-4 is the main water channel in the CNS, is expressed in astrocyte foot processes in brain capillaries and along the circumventricular epithelium in the ventricles, and has important physiological functions in maintaining brain osmotic homeostasis and supporting brain excitability through regulation of the extracellular space. Some evidence has pointed to a role of AQP4 during metal intoxication in the brain, where it may act in a dual form as a neuroprotector or a mediator of the development of oxidative stress in neurons and astrocytes, resulting in brain swelling and neuronal damage. This mini-review presents the way some metal ions affect changes in AQP4 expression in the CNS and discuss the ways in which water transport in brain cells can be involved in brain damage. PMID:27313504

  18. Polydopamine-mediated surface-functionalization of graphene oxide for heavy metal ions removal

    SciTech Connect

    Dong, Zhihui; Zhang, Feng; Wang, Dong; Liu, Xia; Jin, Jian

    2015-04-15

    By utilizing polydopamine (PD) nano-thick interlayer as mediator, polyethylenimine (PEI) brushes with abundant amine groups were grafted onto the surface of PD coated graphene oxide (GO) uniformly via a Michael-Addition reaction and produced a PEI–PD/GO composite nanosheets. The PEI–PD/GO composite exhibited an improved performance for adsorption of heavy metal ions as compared to PEI-coated GO and pure GO. The adsorption capacities for Cu{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, Hg{sup 2+} are up to 87, 106, 197, and 110 mg/g, respectively. To further make the GO based composite operable, PEI–PD/RGO aerogel was prepared through hydrothermal and achieved a high surface area up to 373 m{sup 2}/g. Although the adsorption capacity of PEI–PD/RGO aerogel for heavy metal ions decreases a little as compared to PEI–PD/GO composite dispersion (38, 32, 95, 113 mg/g corresponding to Cu{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Hg{sup 2+}, respectively), it could be recycled several times in a simple way by releasing adsorbed metal ions, indicating its potential application for cleaning wastewater. - Graphical abstract: Polyethylenimine (PEI) brushes were grafted onto the surface of graphene oxide (GO) uniformly via a Michael-Addition reaction between the PEI and polydopamine interlayer coated on GO surface. The PEI–PD/GO composite exhibited an improved performance for adsorption of heavy metal ions compared to PEI-coated GO and pure GO. - Highlights: • We prepared polyethylenimine grafted polydopamine-mediated graphene oxide composites. • Introduction of PD layer increases metal ions adsorption capacity. • PEI–PD/RGO aerogel exhibited a superior adsorption performance. • PEI–PD/RGO aerogel can be recycled several times in a simple way.

  19. The Corrosion Protection of Metals by Ion Vapor Deposited Aluminum

    NASA Technical Reports Server (NTRS)

    Danford, M. D.

    1993-01-01

    A study of the corrosion protection of substrate metals by ion vapor deposited aluminum (IVD Al) coats has been carried out. Corrosion protection by both anodized and unanodized IVD Al coats has been investigated. Base metals included in the study were 2219-T87 Al, 7075-T6 Al, Titanium-6 Al-4 Vanadium (Ti-6Al-4V), 4130 steel, D6AC steel, and 4340 steel. Results reveal that the anodized IVD Al coats provide excellent corrosion protection, but good protection is also achieved by IVD Al coats that have not been anodized.

  20. The corrosion protection of metals by ion vapor deposited aluminum

    SciTech Connect

    Danford, M.D.

    1993-10-01

    A study of the corrosion protection of substrate metals by ion vapor deposited aluminum (IVD Al) coats has been carried out. Corrosion protection by both anodized and unanodized IVD Al coats has been investigated. Base metals included in the study were 2219-T87 Al, 7075-T6 Al, Titanium-6 Al-4 Vanadium (Ti-6Al-4V), 4130 steel, D6AC steel, and 4340 steel. Results reveal that the anodized IVD Al coats provide excellent corrosion protection, but good protection is also achieved by IVD Al coats that have not been anodized.

  1. Statistical evaluation of biogeochemical variables affecting spatiotemporal distributions of multiple free metal ion concentrationsin an urban estuary

    EPA Science Inventory

    Free metal ion concentrations have been recognized as a better indicator of metal bioavailability in aquatic environments than total dissolved metal concentrations. However, our understanding of the determinants of free ion concentrations, especially in a metal mixture, is limite...

  2. Density Functional Theory Study on the Interactions of Metal Ions with Long Chain Deprotonated Carboxylic Acids.

    PubMed

    Mehandzhiyski, Aleksandar Y; Riccardi, Enrico; van Erp, Titus S; Koch, Henrik; Åstrand, Per-Olof; Trinh, Thuat T; Grimes, Brian A

    2015-10-01

    In this work, interactions between carboxylate ions and calcium or sodium ions are investigated via density functional theory (DFT). Despite the ubiquitous presence of these interactions in natural and industrial chemical processes, few DFT studies on these systems exist in the literature. Special focus has been placed on determining the influence of the multibody interactions (with up to 4 carboxylates and one metal ion) on an effective pair-interaction potential, such as those used in molecular mechanics (MM). Specifically, DFT calculations are employed to quantify an effective pair-potential that implicitly includes multibody interactions to construct potential energy curves for carboxylate-metal ion pairs. The DFT calculated potential curves are compared to a widely used molecular mechanics force field (OPLS-AA). The calculations indicate that multibody effects do influence the energetic behavior of these ionic pairs and the extent of this influence is determined by a balance between (a) charge transfer from the carboxylate to the metal ions which stabilizes the complex and (b) repulsion between carboxylates, which destabilizes the complex. Additionally, the potential curves of the complexes with 1 and 2 carboxylates and one counterion have been examined to higher separation distance (20 Å) by the use of relaxed scan optimization and constrained density functional theory (CDFT). The results from the relaxed scan optimization indicate that near the equilibrium distance, the charge transfer between the metal ion and the deprotonated carboxylic acid group is significant and leads to non-negligible differences between the DFT and MM potential curves, especially for calcium. However, at longer separation distances the MM calculated interaction potential functions converge to those calculated with CDFT, effectively indicating the approximate domain of the separation distance coordinate where charge transfer between the ions is occurring. PMID:26331433

  3. Studying metal ion binding properties of a three-way junction RNA by heteronuclear NMR.

    PubMed

    Bartova, Simona; Pechlaner, Maria; Donghi, Daniela; Sigel, Roland K O

    2016-06-01

    Self-splicing group II introns are highly structured RNA molecules, containing a characteristic secondary and catalytically active tertiary structure, which is formed only in the presence of Mg(II). Mg(II) initiates the first folding step governed by the κζ element within domain 1 (D1κζ). We recently solved the NMR structure of D1κζ derived from the mitochondrial group II intron ribozyme Sc.ai5γ and demonstrated that Mg(II) is essential for its stabilization. Here, we performed a detailed multinuclear NMR study of metal ion interactions with D1κζ, using Cd(II) and cobalt(III)hexammine to probe inner- and outer-sphere coordination of Mg(II) and thus to better characterize its binding sites. Accordingly, we mapped (1)H, (15)N, (13)C, and (31)P spectral changes upon addition of different amounts of the metal ions. Our NMR data reveal a Cd(II)-assisted macrochelate formation at the 5'-end triphosphate, a preferential Cd(II) binding to guanines in a helical context, an electrostatic interaction in the ζ tetraloop receptor and various metal ion interactions in the GAAA tetraloop and κ element. These results together with our recently published data on Mg(II) interaction provide a much better understanding of Mg(II) binding to D1κζ, and reveal how intricate and complex metal ion interactions can be. PMID:26880094

  4. Quantify the loss of major ions induced by CO2 enrichment and nitrogen addition in subtropical model forest ecosystems

    NASA Astrophysics Data System (ADS)

    Liu, Juxiu; Zhang, Deqiang; Huang, Wenjuan; Zhou, Guoyi; Li, Yuelin; Liu, Shizhong

    2014-04-01

    Previous studies have reported that atmospheric CO2 enrichment would increase the ion concentrations in the soil water. However, none of these studies could exactly quantify the amount of ion changes in the soil water induced by elevated CO2 and all of these experiments were carried out only in the temperate areas. Using an open-top chamber design, we studied the effects of CO2 enrichment alone and together with nitrogen (N) addition on soil water chemistry in the subtropics. Three years of exposure to an atmospheric CO2 concentration of 700 ppm resulted in accelerated base cation loss via leaching water below the 70 cm soil profile. The total of base cation (K+ + Na+ + Ca2+ + Mg2+) loss in the elevated CO2 treatment was higher than that of the control by 220%, 115%, and 106% in 2006, 2007, and 2008, respectively. The N treatment decreased the effect of high CO2 treatment on the base cation loss in the leachates. Compared to the control, N addition induced greater metal cation (Al3+ and Mn2+) leaching loss in 2008 and net Al3+ and Mn2+ loss in the high N treatment increased by 100% and 67%, respectively. However, the CO2 treatment decreased the effect of high N treatment on the metal cation loss. Changes of ion export followed by the exposure to the elevated CO2, and N treatments were related to both ion concentrations and leached water amount. We hypothesize that forests in subtropical China might suffer from nutrient limitation and some poisonous metal activation in plant biomass under future global change.

  5. Production of intense metal ion beams from ECR ion sources using the MIVOC method

    NASA Astrophysics Data System (ADS)

    Bogomolov, S. L.; Bondarchenko, A. E.; Efremov, A. A.; Kuzmenkov, K. I.; Lebedev, A. N.; Lebedev, K. V.; Lebedev, V. Ya.; Loginov, V. N.; Mironov, V. E.; Yazvitsky, N. Yu.

    2015-12-01

    The production of metal ion beams by electron cyclotron resonance (ECR) ion sources using the MIVOC (Metal Ions from Volatile Compounds) method is described. The method is based on the use of metal compounds which have high vapor pressure at room temperature, e.g., C2B10H12, Fe(C5H5)2, etc. Intense ion beams of B and Fe were produced using this method at the FLNR JINR cyclotrons. Experiments on the production of cobalt, chromium, vanadium, germanium, and hafnium ion beams were performed at the test bench of ECR ion sources. Main efforts were put into production and acceleration of 50Ti ion beams at the U-400 cyclotron. The experiments on the production of 50Ti ion beams were performed at the test bench using natural and enriched compounds of titanium (CH3)5C5Ti(CH3)3. In these experiments, 80 μA 48Ti5+ and 70 μA 48Ti11+ beam currents were obtained at different settings of the source. Following successful tests, two 3-week runs were performed with 50Ti beams at the U-400 cyclotron aimed to perform experiments on the spectroscopy of superheavy elements. The intensity of the injected 50Ti5+ beam was 50-60 μA. The source worked stably during experiments. The compound consumption rate was determined at about 2.4 mg/h, which corresponded to the 50Ti consumption of 0.6 mg/h.

  6. Photoelectric properties in metal ion modified DNA nanostructure.

    PubMed

    Kulkarni, Atul; Dugasani, Sreekantha Reddy; Jang Ah Kim; Kim; Sung Ha Park; Taesung Kim

    2015-08-01

    Due to specific or as designed self-assembly, DNA nanostructures gaining popularity in various nanoscale electronic applications. Herein, a novel divalent metal ion-DNA complex known as M-DNA have been investigated for its photoelectric characteristics. The increased conductivity of M-DNA thin films is attributed to the metal ion electrical and optical properties. The gate voltage effect along with illumination on the conductivity of M-DNA demonstrates that M-DNA can be used as an active element of a field-effect transistor. The Zn DNA shows maximum conductivity of 300μS/cm at 480 nm light illumination suggest that M-DNA can be utilized in nano-opto-electronics and bio-sensing applications. PMID:26737260

  7. Nanomagnetic chelators for removal of toxic metal ions

    NASA Astrophysics Data System (ADS)

    Singh, Sarika; Barick, K. C.; Bahadur, D.

    2013-02-01

    Ethylenediamine trtraaceteic acid (EDTA) functionalized Fe3O4 nanomagnetic chelators (NMCs) were synthesized by co-precipitation method followed by in-situ grafting of EDTA. XRD and TEM analyses reveal the formation of highly crystalline single-phase Fe3O4 nanoparticles of size about 10 nm. Surface functionalization of Fe3O4 with EDTA was evident from FTIR spectroscopy, TGA analysis and zeta-potential measurement. These NMCs exhibit superparamagnetic behavior at room temperature with strong field dependent magnetic responsivity. It has been observed that NMCs have strong tendency for adsorption of various toxic metal ions (Ni2+, Cr3+, Cu2+, Cd2+, Co2+ and Pb2+) from waste-water. Furthermore, these magnetic chelators can be used as highly efficient separable and reusable material for removal of toxic metal ions.

  8. Chelating Agents and the Regulation of Metal Ions

    PubMed Central

    Bulman, Robert A.

    1994-01-01

    Up to about the early 1980s it was perhaps still possible to summarize in a review of a moderate length the development of the medicinal applications of chelation chemistry and the exploitation of such chemistry in regulating the metal ion concentrations in the body. However, in the last few years there has a great surge in the development of chelation chemistry and its usage in medicine and related areas of life sciences research. It is no longer the case that such a review primarily concentrates upon the use of chelating agents in removing toxic metals from the body but it must now cover the use of chelating agents in the imaging procedures nuclear medicine and magnetic resonance imaging (MRI), the use of chelating agents in unravelling the biochemistry of reactive oxidative species (ROS) and the control and measurement of intracellular calcium ions. It is in the recent applications that there have been the greatest developments over the last ten years. PMID:18476223

  9. Preorganized and Immobilized Ligands for Metal Ion Separations

    SciTech Connect

    Paine, Robert T.

    2015-07-01

    The research project, in the period 2003-2015, was focused on the discovery of fundamental new principles in f-element ion coordination chemistry and the application of the new knowledge to the development of advanced detection/separations reagents and methods for these ions. The findings relate to the Nation's efforts to safely and efficiently process nuclear materials. In addition, the project provided training for young scientists needed to maintain the Nation's preeminence in nuclear science.

  10. 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.

  11. Further studies of ion mixing in binary metal systems

    NASA Astrophysics Data System (ADS)

    Liu, Bai-Xin

    1985-03-01

    Using free energy-composition diagram, a simple model is proposed for the formation of amorphous alloys by ion mixing of metal layers. The basis of the model is the limited atomic mobility in such samples after ion mixing at a suitably low temperature. The model explains the formation of amorphous alloys that have been reported previously and those obtained in this study in the Zr-Ru and Ti-Au systems by ion mixing. These include phases with compositions in both two-phase and single-phase regions of the equilibrium phase diagram. In the Ni-Mo system, an unusual phase transition was observed by X-ray diffraction photos, i.e. an amorphous phase was formed after room temperature aging of an ion induced metastable crystalline phase (h.c.p. structure). Post-irradiation annealing of some ion mixed Ni-Mo amorphous alloys were performed at various temperatures. A schematic free energy diagram is proposed according to the phase evolution in the annealed samples upon annealing, and is used to discuss the ion induced phenomena in this system.

  12. Paramagnetic metal ions in pulsed ESR distance distribution measurements.

    PubMed

    Ji, Ming; Ruthstein, Sharon; Saxena, Sunil

    2014-02-18

    The use of pulsed electron spin resonance (ESR) to measure interspin distance distributions has advanced biophysical research. The three major techniques that use pulsed ESR are relaxation rate based distance measurements, double quantum coherence (DQC), and double electron electron resonance (DEER). Among these methods, the DEER technique has become particularly popular largely because it is easy to implement on commercial instruments and because programs are available to analyze experimental data. Researchers have widely used DEER to measure the structure and conformational dynamics of molecules labeled with the methanethiosulfonate spin label (MTSSL). Recently, researchers have exploited endogenously bound paramagnetic metal ions as spin probes as a way to determine structural constraints in metalloproteins. In this context Cu(2+) has served as a useful paramagnetic metal probe at X-band for DEER based distance measurements. Sample preparation is simple, and a coordinated-Cu(2+) ion offers limited spatial flexibility, making it an attractive probe for DEER experiments. On the other hand, Cu(2+) has a broad absorption ESR spectrum at low temperature, which leads to two potential complications. First, the Cu(2+)-based DEER time domain data has lower signal to noise ratio compared with MTSSL. Second, accurate distance distribution analysis often requires high-quality experimental data at different external magnetic fields or with different frequency offsets. In this Account, we summarize characteristics of Cu(2+)-based DEER distance distribution measurements and data analysis methods. We highlight a novel application of such measurements in a protein-DNA complex to identify the metal ion binding site and to elucidate its chemical mechanism of function. We also survey the progress of research on other metal ions in high frequency DEER experiments. PMID:24289139

  13. Interaction of heavy metal ions with ammonium humates

    SciTech Connect

    Budaeva, A.D.; Zoltoev, E.V.; Tikhova, V.D.; Bodoev, N.V.

    2006-06-15

    Sorption properties of ammonium humates with respect to Fe(III), Cu(II), Al(III), Ni(II), Pb(II), and Zn(II) are studied. The effect of the metal ion concentration on the ammonium humate consumption is examined and the corresponding dependences are analyzed using regression equations. The IR spectra of brown coal humic acids, ammonium humates, as well as Fe, Cu, Ni, Zn, Pb, and Al humates are presented.

  14. Lithium metal doped electrodes for lithium-ion rechargeable chemistry

    DOEpatents

    Liu, Gao; Battaglia, Vince; Wang, Lei

    2016-09-13

    An embodiment of the invention combines the superior performance of a polyvinylidene difluoride (PVDF) or polyethyleneoxide (POE) binder, the strong binding force of a styrene-butadiene (SBR) binder, and a source of lithium ions in the form of solid lithium metal powder (SLMP) to form an electrode system that has improved performance as compared to PVDF/SBR binder based electrodes. This invention will provide a new way to achieve improved results at a much reduced cost.

  15. Precious metal catalysts with oxygen-ion conducting support

    SciTech Connect

    Ganguli, P.S.; Sundaresan, S.

    1993-08-03

    A three-way supported catalyst is described for treatment of combustion gas emissions from mobile or stationary sources, comprising: an oxygen-ion conducting support material having surface area at least about 20 m[sup 2]/gm, and two active metals selected from the group consisting of (1) platinum and rhodium and (2) palladium and rhodium dispersed on the support material in overall amount of about 0.01-2.2 wt. % of the catalyst.

  16. NOVEL APPROACH TO METAL-HUMIC COMPLEXATION STUDIES BY LANTHANID ION PROBE SPECTROSCOPY

    EPA Science Inventory

    Naturally occurring humic substances are known to be potentially strong binders of metals in the environment. ensitive spectroscopic technique, based on the unique luminescence properties of the tripositive lanthanide metal ions, has been developed to selectively probe metal bind...

  17. The effect of additives and substrates on nonferrous metal electrodeposition

    NASA Astrophysics Data System (ADS)

    Zhou, Zeyang

    Electrodeposits play an important role in science and industry today. Control of the quality of electrodeposits becomes more critical. One of the major factors which can lead to better products is the ability to control the electrocrystallization process to obtain smooth, dense and coherent deposits with good mechanical and physical properties, such as corrosion resistance, ductility and less internal stress. Many parameters may play a prominent role in electrodeposition. Two of the more important parameters is the control of impurities/additives present in the solution and cathode condition. In this study, the effects of small concentrations of tin additions on the composition, structure and surface morphology of Zn-Ni alloy deposits were studied. Electrochemical impedance spectroscopy (EIS) were conducted to study the role of tin in changing the charge transfer resistance of the reaction. The results obtained were promising in elucidating some basic factors which influence Zn-Ni alloy electrocrystallization mechanisms. The effects of thermal oxidation of stainless steel cathodes used in copper electrodeposition were studied. Particular emphasis was given to the initial stages of copper nucleation and growth. The copper electrocrystallization process was strongly influenced by the temperature applied in oxidizing the stainless steel. In this research, the effects of the impurities Alsp{3+} and Crsp{3+} using two stainless steels as cathodes during Ni electrowinning from a sulfate bath were studied. The current efficiency decreased in the presence of the impurities over the concentration range studied. Certain changes in the surface morphology, internal stress, crystallographic orientation and polarization behavior were observed. The changes were different for two stainless steel substrates.

  18. Combined cytotoxicity and genotoxicity of a marine toxin and seafood contaminant metal ions (chromium and cadmium).

    PubMed

    Souid-Mensi, Ghada; Moukha, Serge; Maaroufi, Khira; Creppy, Edmond E

    2008-02-01

    Algal bloom with consequent production of marine toxins contaminating bivalves is increasing in costal regions worldwide because of sea water quality worsening. Contamination of seafood by diarrheic shellfish poisoning toxins (DSP) together with metals is frequently reported, a phenomenon not fully explained yet. In this context, metal ions were assayed in clams collected from the banned area of Boughrara, Tunisia, contaminated by Gymnodinium and other algae such as Dinophysis sp, accumulated by these bivalves. The presence of toxic metals ions such as Chromium (Cr) and Cadmium (Cd) in meat, shells, and water released by the clams prompted us to experiment in Caco-2 intestinal cell line toxic effects of these heavy metals ions in combination with okadaic acid, one DSP present in clams to assess the potential global toxicity. Cr and Cd produce additive effects in (i) reactive oxygen species production, (ii) cytotoxicity as assessed by the mitochondrial activity testing method (MTT test), and (iii) DNA lesions evaluated by agarose gel electrophoresis and acridine orange staining. Exaggerated DNA fragmentation is observed, suggesting an overloading of repair capacity of Caco-2 cells. The apoptosis suggested by a DNA fragment sizing (180-200 bp) in agarose gel and mechanisms underlying these additive effects in Caco-2 cells still need to be more comprehensively explained. PMID:18214935

  19. The use of Electrolyte Additives to Improve the High Temperature Resilience of Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Lucht, B. L.; Ratnakumar, Bugga V.

    2007-01-01

    This viewgraph presentation reviews the use of electrolyte additves to improve the resillience of Lithium ion cells. The objective of this work is to identify lithium-ion electrolytes, which will lead to Li-ion cells with a wide operational temperature range (+60 to -60 C), and to develop Li-ion electrolytes which result in cells that display improved high temperature resilience. Significant improvement in the high temperature resilience of Li-ion cells containing these additives was observed, with the most dramatic benefit being displayed by addition of DMAc. When the electrochemical properties of the individual electrodes were analyzed, the degradation of the anode kinetics was slowed most dramatically by the incorporation of DMAc into the electrolytes. Whereas, the greatest retention in the cathode kinetics was observed in the cell containing the electrolyte with VC added.

  20. 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. PMID:24136830

  1. Nanostructure operations by means of the liquid metal ion sourcesa)

    NASA Astrophysics Data System (ADS)

    Gasanov, I. S.; Gurbanov, I. I.

    2012-02-01

    Characteristics of a disperse phase of liquid metal ion source on the basis of various working substances are investigated. It is revealed that generation of the charged particles occurs in the threshold image and is simultaneously accompanied by excitation of capillary instability on a surface of the emitter. The majority of particles has the size about 2 nm (Sn) and a specific charge of 5 × 104 C/kg. If the working liquid possesses high viscosity (Ni), generation of nanodroplets does not occur. Gold nanoparticles are used for deposition on a surface of quartz cantilevers with the purpose of increase in sensitivity of biosensors and on an external surface of carbon nanotubes for creation pressure sensors. By means of an ion source nanostructures can be etched on a flat surface of conductive materials without difficult ion optics.

  2. Adsorption of heavy metal ions by immobilized phytic acid

    SciTech Connect

    Tsao, G.T.; Zheng, Yizhou; Lu, J.; Gong, Cheng S.

    1997-12-31

    Phytic acid (myoinositol hexaphosphate) or its calcium salt, phytate, is an important plant constituents. It accounts for up to 85% of total phosphorus in cereals and legumes. Phytic acid has 12 replaceable protons in the phytic molecule rendering it the ability to complex with multivalent cations and positively charged proteins. Poly 4-vinyl pyridine (PVP) and other strong-based resins have the ability to adsorb phytic acid. PVP has the highest adsorption capacity of 0.51 phytic acid/resins. The PVP resin was used as the support material for the immobilization of phytic acid. The immobilized phytic acid can adsorb heavy metal ions, such as cadmium, copper, lead, nickel, and zinc ions, from aqueous solutions. Adsorption isotherms of the selected ions by immobilized phytic acid were conducted in packed-bed column at room temperature. Results from the adsorption tests showed 6.6 mg of Cd{sup 2+}, 7 mg of Cu{sup 2+}, 7.2 mg of Ni{sup 2+}, 7.4 mg of Pb{sup 2+}, and 7.7 mg of Zn{sup 2+} can be adsorbed by each gram of PVP-phytic acid complex. The use of immobilized phytic acid has the potential for removing metal ions from industrial or mining waste water. 15 refs., 7 figs., 2 tabs.

  3. Template-directed synthesis of oligoguanylic acids - Metal ion catalysis

    NASA Technical Reports Server (NTRS)

    Bridson, P. K.; Fakhrai, H.; Lohrmann, R.; Orgel, L. E.; Van Roode, M.

    1981-01-01

    The effects of Zn(2+), Pb(2+) and other metal ions on the efficiency and stereo-selectivity of the template-directed oligomerization of guanosine 5'-phosphorimidazolide are investigated. Reactions were run in the presence of a polyC template in a 2,6-lutidine buffer, and products analyzed by high-performance liquid chromatography on an RPC-5 column. The presence of the Pb(2+) ion is found to lead to the formation of 2'-5' linked oligomers up to the 40-mer, while Zn(2+) favors the formation of predominantly 3'-5' linked oligomers up to the 35-mer. When amounts of uracil, cytidine or adenosine 5'-phosphorimidazole equal to those of the guanosine derivative are included in the reaction mixture, the incorrect base is incorporated into the oligomer about 10% of the time with a Pb(2+) catalyst, but less than 0.5% of the time with Zn(2+). The Sn(2+), Sb(3+) and Bi(3+) ions are also found to promote the formation of 2'-5' oligomers, although not as effectively as Pb(2+), while no metal ions other than Zn(2+) promote the formation of the 3'-5' oligomers. The results may be important for the understanding of the evolution of nucleic acid replication in the absence of enzymes.

  4. Optimization of soil mixing technology through metallic iron addition.

    SciTech Connect

    Moos, L. P.

    1999-01-15

    Enhanced soil mixing is a process used to remove volatile organic compounds (VOCs) from soil. In this process, also known as soil mixing with thermally enhanced soil vapor extraction, or SM/TESVE, a soil mixing apparatus breaks up and mixes a column of soil up to 9 m (30 ft) deep; simultaneously, hot air is blown through the soil. The hot air carries the VOCs to the surface where they are collected and safely disposed of. This technology is cost effective at high VOC concentrations, but it becomes cost prohibitive at low concentrations. Argonne National Laboratory-East conducted a project to evaluate ways of improving the effectiveness of this system. The project investigated the feasibility of integrating the SM/TESVE process with three soil treatment processes--soil vapor extraction, augmented indigenous biodegradation, and zero-valent iron addition. Each of these technologies was considered a polishing treatment designed to remove the contaminants left behind by enhanced soil mixing. The experiment was designed to determine if the overall VOC removal effectiveness and cost-effectiveness of the SM/TESVE process could be improved by integrating this approach with one of the polishing treatment systems.

  5. Note: An ion source for alkali metal implantation beneath graphene and hexagonal boron nitride monolayers on transition metals

    NASA Astrophysics Data System (ADS)

    de Lima, L. H.; Cun, H. Y.; Hemmi, A.; Kälin, T.; Greber, T.

    2013-12-01

    The construction of an alkali-metal ion source is presented. It allows the acceleration of rubidium ions to an energy that enables the penetration through monolayers of graphene and hexagonal boron nitride. Rb atoms are sublimated from an alkali-metal dispenser. The ionization is obtained by surface ionization and desorption from a hot high work function surface. The ion current is easily controlled by the temperature of ionizer. Scanning Tunneling Microscopy measurements confirm ion implantation.

  6. Note: An ion source for alkali metal implantation beneath graphene and hexagonal boron nitride monolayers on transition metals

    SciTech Connect

    Lima, L. H. de; Cun, H. Y.; Hemmi, A.; Kälin, T.; Greber, T.

    2013-12-15

    The construction of an alkali-metal ion source is presented. It allows the acceleration of rubidium ions to an energy that enables the penetration through monolayers of graphene and hexagonal boron nitride. Rb atoms are sublimated from an alkali-metal dispenser. The ionization is obtained by surface ionization and desorption from a hot high work function surface. The ion current is easily controlled by the temperature of ionizer. Scanning Tunneling Microscopy measurements confirm ion implantation.

  7. Cobalt activation of Escherichia coli 5'-nucleotidase is due to zinc ion displacement at only one of two metal-ion-binding sites.

    PubMed Central

    McMillen, Lyle; Beacham, Ifor R; Burns, Dennis M

    2003-01-01

    Escherichia coli 5'-nucleotidase activity is stimulated 30- to 50-fold in vitro by the addition of Co(2+). Seven residues from conserved sequence motifs implicated in the catalytic and metal-ion-binding sites of E. coli 5'-nucleotidase (Asp(41), His(43), Asp(84), His(117), Glu(118), His(217) and His(252)) were selected for modification using site-directed mutagenesis of the cloned ushA gene. On the basis of comparative studies between the resultant mutant proteins and the wild-type enzyme, a model is proposed for E. coli 5'-nucleotidase in which a Co(2+) ion may displace the Zn(2+) ion at only one of two metal-ion-binding sites; the other metal-ion-binding site retains the Zn(2+) ion already present. The studies reported herein suggest that displacement occurs at the metal-ion-binding site consisting of residues Asp(84), Asn(116), His(217) and His(252), leading to the observed increase in 5'-nucleotidase activity. PMID:12603203

  8. Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology

    SciTech Connect

    Lentz, Nicholas B.

    2007-01-01

    This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln11]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will

  9. 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

  10. Effects of metal ions on disinfection byproduct formation during chlorination of natural organic matter and surrogates.

    PubMed

    Zhao, Yu; Yang, Hong-wei; Liu, Shi-ting; Tang, Shun; Wang, Xiao-mao; Xie, Yuefeng F

    2016-02-01

    The effects of calcium, cupric, ferrous and ferric ions on the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) were investigated using natural organic matter (NOM), small molecular weight NOM surrogates and natural water samples. The results showed that the effects were greatly dependent on the disinfection byproduct (DBP) precursor structure and molecular weight, and metal ions species. While using NOM as precursors, addition of 4.00 mM calcium ions increased the formation of THMs, dihaloacetic acids (DHAAs) and trihaloacetic acids (THAAs) by 24-47%, 51-61% and 15-25%, respectively. Addition of cupric ions at 0.02 mM increased the formation of THMs and DHAAs by 74-83% and 90-100%, respectively, but decreased the formation of THAAs by 26-27%. Similar effect was not observed when 0.04 mM ferrous or ferric ions were added. The effects of calcium and cupric ions on DBP formation were generally more evident for the NOM surrogates than that for NOM. The primary catalytic effect of calcium ions was due to complexation and less sensitive to molecular structure or weight, while that of cupric ions was attributed to redox reactions and greatly dependent on molecular structure. Both ferric and ferrous iron had substantial effects on the DBP formation of surrogates (citric acid and catechol in particular), which implied that the catalytic effects of ferric and ferrous iron mainly depended on molecular weight. The catalytic effect of cupric ions was also observed on natural water samples, while the effects of calcium, ferrous and ferric ions on natural water samples were not evident. PMID:26454116

  11. Transition-Metal Additives For Long-Life Na/NiCI(2) Cells

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; Surampudi, Subbarao; Halpert, Gerald

    1995-01-01

    Transition-metal additives in cathodes of Na/NiCI(2) high-temperature, rechargeable electrochemical cells found to slow premature fading of charge/discharge capacity. Decline in capacity of cell attributed to agglomeration of Ni particles at cathode: this agglomeration reduces electrochemical area of cathode. Depending on choice of transition-metal additive for particular cell, additive might even participate in desired electrochemical reactions in cell, contributing to specific energy of cell.

  12. Metal ion complexation by ionizable crown ethers. Final report, January 1, 1988--June 30, 1994

    SciTech Connect

    Bartsch, R.A.

    1994-12-31

    During the report period a variety of new lipophilic ionizable crown ethers with pendent proton-ionizable groups has been synthesized. The ligands possess one or more ionizable group (carboxylic acid, phosphonic acid monoethyl ester, para-nitrophenol, phosphonic acid) attached to crown ether, monoazacrown ether or diazacrown ether frameworks. These novel chelating agents have either pendent or inward-facing proton-ionizable groups. Such lipophilic proton-ionizable crown ethers are designed for use in multiphase metal ion separations (solvent extraction, liquid membrane transport). In addition a series of proton-ionizable crown ethers without lipophilic groups was prepared to study how structural variations within the ligand influence metal ion complexation in homogeneous media as assessed by NMR spectroscopy or titration calorimetry. A third class of new metal ion-complexing agents is a series of lipophilic acyclic polyether dicarboxylic acids. Competitive solvent extractions of alkali metal and alkaline earth cations and of the mixed species have been conducted to reveal the influence of ring size, nature and attachment site of the lipophilic group, sidearm length, and proton-ionizable group identity and location upon the selectivity and efficiency of metal ion complexation. In addition to such studies of structural variation within the lipophilic proton-ionizable crown ether, the effect of changing the organic solvent and variation of the stripping conditions have been assessed. The influence of structural variations within lipophilic acyclic polyether dicarboxylic acids upon competitive solvent extraction of alkaline earth cations has been probed. Also a new chromogenic, di-ionizable crown ether with extremely high selectivity for Hg{sup 2+} has been discovered.

  13. Luminescent zinc metal-organic framework (ZIF-90) for sensing metal ions, anions and small molecules.

    PubMed

    Liu, Chang; Yan, Bing

    2015-09-26

    We synthesize a zinc zeolite-type metal-organic framework, the zeolitic imidazolate framework (ZIF-90), which exhibits an intense blue luminescence excited under visible light. Luminescent studies indicate that ZIF-90 could be an efficient multifunctional fluorescence material for high sensitivity metal ions, anions and organic small molecules, especially for Cd(2+), Cu(2+), CrO4(2-) and acetone. The luminescence intensity of ZIF-90 increases with the concentration of Cd(2+) and decreases proportionally with the concentration of Cu(2+), while the same quenched experimental phenomena appear in the sensing of CrO4(2-). With the increase of the amount of acetone, the luminescence intensity decreases gradually in the emulsions of ZIF-90. The mechanism of the sensing properties is studied in detail as well. This study shows that ZIF-90 could be a useful luminescent sensor for metal ions, anions and organic small molecules. PMID:26123790

  14. Radiation damage from single heavy ion impacts on metal surfaces

    SciTech Connect

    Donnelly, S.E.; Birtcher, R.C.

    1998-06-01

    The effects of single ion impacts on the surfaces of films of Au, Ag, In and Pb have been studied using in-situ transmission electron microscopy. On all of these materials, individual ion impacts produce surface craters, in some cases, with associated expelled material. The cratering efficiency scales with the density of the irradiated metal. For very thin Au foils ({approx} 20--50 nm), in some cases individual ions are seen to punch small holes completely through the foil. Continued irradiation results in a thickening of the foil. The process giving rise to crater and hole formation and other changes observed in the thin foils has been found to be due to pulsed localized flow--i.e. melting and flow due to the thermal spikes arising from individual ion impacts. Experiments carried out on thin films of silver sandwiched between SiO{sub 2} layers have indicated that pulsed localized flow also occurs in this system and contributes to the formation of Ag nanoclusters in SiO{sub 2}--a system of interest for its non-linear optical properties. Calculation indicates that, when ion-induced, collision cascades occur near surfaces (within {approx} 5 nm) with energy densities sufficient to cause melting, craters are formed. Crater formation occurs as a result of the explosive outflow of material from the hot molten core of the cascade. Processes occurring in the sandwiched layer are less well understood.

  15. Recovery of toxic metal ions from washing effluent containing excess aminopolycarboxylate chelant in solution.

    PubMed

    Hasegawa, Hiroshi; Rahman, Ismail M M; Nakano, Masayoshi; Begum, Zinnat A; Egawa, Yuji; Maki, Teruya; Furusho, Yoshiaki; Mizutani, Satoshi

    2011-10-15

    Aminopolycarboxylate chelants (APCs) are extremely useful for a variety of industrial applications, including the treatment of toxic metal-contaminated solid waste materials. Because non-toxic matrix elements compete with toxic metals for the binding sites of APCs, an excess of chelant is commonly added to ensure the adequate sequestration of toxic metal contaminants during waste treatment operations. The major environmental impacts of APCs are related to their ability to solubilize toxic heavy metals. If APCs are not sufficiently eliminated from the effluent, the aqueous transport of metals can occur through the introduction of APCs into the natural environment, increasing the magnitude of associated toxicity. Although several techniques that focus primarily on the degradation of APCs at the pre-release step have been proposed, methods that recycle not only the processed water, but also provide the option to recover and reuse the metals, might be economically feasible, considering the high costs involved due to the chelants used in metal ion sequestration. In this paper, we propose a separation process for the recovery of metals from effluents that contain an excess of APCs. Additionally, the option of recycling the processed water using a solid phase extraction (SPE) system with an ion-selective immobilized macrocyclic material, commonly known as a molecular recognition technology (MRT) gel, is presented. Simulated effluents containing As(V), Cd(II), Cr(III), Pb(II) or Se(IV) in the presence of APCs at molar ratios of 1:50 in H2O were studied with a flow rate of 0.2 mL min(-1). The 'captured' ions in the SPE system were quantitatively eluted with HNO3. The effects of solution pH, metal-chelant stability constants and matrix elements were assessed. Better separation performance for the metals was achieved with the MRT-SPE compared to other SPE materials. Our proposed technique offers the advantage of a non-destructive separation of both metal ions and chelants

  16. Craters produced on metals by single ion impacts.

    SciTech Connect

    Birtcher, R. C.

    1998-12-23

    Single ion impacts have been observed using in-situ transmission electron microscopy during irradiation. In addition to internal defects, single-ion impacts create surface craters as large as 12 nm on In, Ag, Pb and Au. Crater formation rates have been determined from video recordings with a time-resolution of 33 milliseconds. The cratering rate for Xe ions increases linearly with increasing target mass density above a threshold density of approximately 7 gm/cm{sup 3}. The cratering rate increases as the ion mass is increased. These results suggest that cratering requires a high energy-density, near-surface displacement cascade. TRIM calculations have been made in an effort to establish a near-surface energy-density criterion for cratering.

  17. Metal-air cell comprising an electrolyte with a room temperature ionic liquid and hygroscopic additive

    DOEpatents

    Friesen, Cody A.; Krishnan, Ramkumar; Tang, Toni; Wolfe, Derek

    2014-08-19

    An electrochemical cell comprising an electrolyte comprising water and a hydrophobic ionic liquid comprising positive ions and negative ions. The electrochemical cell also includes an air electrode configured to absorb and reduce oxygen. A hydrophilic or hygroscopic additive modulates the hydrophobicity of the ionic liquid to maintain a concentration of the water in the electrolyte is between 0.001 mol % and 25 mol %.

  18. Ion flotation behaviour of thirty-one metal ions in mixed hydrochloric/nitric acid solutions.

    PubMed

    Hualing, D; Zhide, H

    1989-06-01

    The ion flotation of 31 metal ions in hydrochloric/nitric acid solution with the cationic surfactant cetylpyridinium chloride was investigated. A 25-ml portion of 0.27-2.87 x 10(-4)M metal ion and 1.8-6.0 x 10(-4)M cetylpyridinium chloride solution in 0.17-3.4M acid mixture ([HCl]:[HNO(3)] = 2.4:1) was subjected to flotation in a cell, 22.5 cm high and 4.0 cm in diameter, for 5 min, with nitrogen bubbles. Ir(IV), Pt(IV), Ge(IV), Sn(IV), Bi(III), Au(III), Tl(III), Pd(II) and Sn(II) were floated from solution in 95-100% yield; Ru(III), Rh(III), Ir(III), Hg(II), Ag(I) and Tl(I) were partly floated, while Cr(VI), Ti(IV), Zr(IV), Ga(III), In(III), Fe(III), Sb(III), Al(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), CD(II) and Pb(II) were floated with less than 20% yield. The flotation behaviour of these metal ions in the mixed acid system was compared with that in hydrochloric acid. The flotation is more efficient in the mixed acid system. PMID:18964771

  19. Characterization of LiFePO4 cathode by addition of graphene for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Honggowiranto, Wagiyo; Kartini, Evvy

    2016-02-01

    The improvement of LiFePO4 (LFP) cathode performance has been performed by addition of Graphene (LFP+Graphene). The cathode was prepared from the active material with 5 wt % graphene and 10 wt % polyvinylidene fluoride in an n-methyl pyrrolidone solvent. Another cathode material used only 5% artificial graphite for comparison (LFP+Graphite). The crystal structure, microstructure, electronic conductivity, electrochemical impedance spectroscopy (EIS) of the cathodes were characterized by X-ray diffraction, SEM, and Impedance spectroscopy, respectively. Two half cell coin batteries were assembled using a lithium metal as an anode and LiPf6 as an electrolyte, and two cathodes (LFP+Graphene) and (LFP+Graphite). Charge discharge performance of battery was characterized by Battery analyser (BTS 8). The electronic conductivity of cathode with grapheme increased of about one order magnitude compared with the only cathode with graphite, namely from 1.97E-7S/cm (LFP+Graphite) to 1.92E-6S/cm (LFP+Graphene). The charge-discharge capacity after 10th cycles of LiFePO4 with graphene decreased of about 0.68% from 114.3 mAh/g to113.1 mAh/g, while LFP with graphite decreased of about 2.84% from 110.2 mAh/g to 107.1 mAh, at 0.1C-rates. It could be concluded that the addition of graphene has increased the ionic conductivity, and improved performance of the LFP lithium ion battery, such as higher capacity and better efficiency.

  20. No association between serum metal ions and implant fixation in large-head metal-on-metal total hip arthroplasty

    PubMed Central

    Søballe, Kjeld; Jakobsen, Stig Storgaard; Lorenzen, Nina Dyrberg; Mechlenburg, Inger; Stilling, Maiken

    2014-01-01

    Background The mechanism of failure of metal-on-metal (MoM) total hip arthroplasty (THA) has been related to a high rate of metal wear debris, which is partly generated from the head-trunnion interface. However, it is not known whether implant fixation is affected by metal wear debris. Patients and methods 49 cases of MoM THA in 41 patients (10 women) with a mean age of 52 (28–68) years were followed with stereoradiographs after surgery and at 1, 2, and 5 years to analyze implant migration by radiostereometric analysis (RSA). Patients also participated in a 5- to 7-year follow-up with measurement of serum metal ions, questionnaires (Oxford hip score (OHS) and Harris hip score (HHS)), and measurement of cup and stem positions and systemic bone mineral density. Results At 1–2 years, mean total translation (TT) was 0.04 mm (95% CI: –0.07 to 0.14; p = 0.5) for the stems; at 2–5 years, mean TT was 0.13 mm (95% CI: –0.25 to –0.01; p = 0.03), but within the precision limit of the method. For the cups, there was no statistically significant TT or total rotation (TR) at 1–2 and 2–5 years. At 2–5 years, we found 4 cups and 5 stems with TT migrations exceeding the precision limit of the method. There was an association between cup migration and total OHS < 40 (4 patients, 4 hips; p = 0.04), but there were no statistically significant associations between cup or stem migration and T-scores < –1 (n = 10), cup and stem positions, or elevated serum metal ion levels (> 7µg/L (4 patients, 6 hips)). Interpretation Most cups and stems were well-fixed at 1–5 years. However, at 2–5 years, 4 cups and 5 stems had TT migrations above the precision limits, but these patients had serum metal ion levels similar to those of patients without measurable migrations, and they were pain-free. Patients with serum metal ion levels > 7 µg/L had migrations similar to those in patients with serum metal ion levels < 7 µg/L. Metal wear debris does not appear to influence the

  1. Selective recovery of gold and other metal ions from an algal biomass

    SciTech Connect

    Darnall, D.W.; Greene, B.; Henzl, M.T.; Hosea, J.M.; McPherson, R.A.; Sneddon, J.; Alexander, M.D.

    1986-02-01

    The authors observed that the pH dependence of the binding of Au/sup 3 +/, Ag/sup +/, and Hg/sup 2 +/ to the algae Chlorella vulgaris is different than the binding of other metal ions. Between pH 5 and 7, a variety of metal ions bind strongly to the cell surface. Most of these algal-bound metal ions can be selectively desorbed by lowering the pH to 2; however, Au/sup 3 +/, Hg/sup 2 +/, and Ag/sup +/ are all bound strongly at pH 2. Addition of a strong ligand at different pHs is required to elute these ions from the algal surface. Algal-bound gold and mercury can be selectively eluted by using mercaptoethanol. An elution scheme is demonstrated for the binding and selective recovery of Cu/sup 2 +/, Zn/sup 2 +/, Au/sup 3 +/, and Hg/sup 2 +/ from an equimolar mixture. 20 references, 2 figures.

  2. Metal ion binding to phospholipid bilayers evaluated by microaffinity chromatography.

    PubMed

    Ross, Eric E; Hoag, Christian; Pfeifer, Zach; Lundeen, Christopher; Owens, Sarah

    2016-06-17

    Group I and II ion binding to phospholipid membranes was evaluated by affinity chromatography utilizing a new stationary phase system based on lipid bilayers supported within large-pore particles composed of Stöber silica spheres. Using an inductively coupled plasma mass spectrometer for detection, robust determination of binding selectivity within group II ions is achieved with capillary columns containing nanomole quantities of lipid and using picomoles of metal analyte. Columns with a unique lipid formulation can be prepared within three hours using a solvent-casting assembly method. The observable thermotropic phase behavior of dipalmitoylphosphatidylcholine has a significant effect on alkaline metal binding and demonstrates the dynamic nature of the supported bilayers. Of the group I ions, only lithium exhibits retention with neutral phosphatidylcholine bilayer stationary phases. A comparison of Stöber-based supports with two commercially available large-pore silicas reveals the effect that particle structure has on analyte accessibility to the bilayer surface as evaluated by retention per supported lipid mass. PMID:27189434

  3. 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. PMID:26852345

  4. Investigation of metal ion extraction and aggregate formation combining acidic and neutral organophosphorous reagents

    SciTech Connect

    Braatz, A.D.; Nilsson, M.; Ellis, R.; Antonio, M.

    2013-07-01

    In the present study, we investigate how varying mixtures of tri-n-butyl phosphate (TBP) and dibutyl phosphate (HDBP) results in enhanced extraction of lanthanum(III), La{sup 3+}, and dysprosium(III), Dy{sup 3+}. Water and metal ion extraction were carefully monitored as a function of TBP:HDBP mole ratio.In addition to these techniques, EXAFS was used to determine the coordination environment of the metal ion in this system. To produce the necessary signal, a concentration of 1.25*10{sup -3} M La{sup 3+} and Dy{sup 3+} was used. Although previous studies of synergistic extraction of metal cations using combinations of neutral and acidic reagents explain the enhanced extraction by increased dehydration of the metal ion and the formation of mixed extractant complexes, our evidence for the increased water extraction coupled with the aggregate formation suggests a reverse micellar aspect to synergism in the system containing TBP and HDBP. It is quite possible that both of these phenomena contribute to our system behavior. The EXAFS data shows that, based on coordination numbers alone, several possible structures may exist. From this study, we cannot provide a definitive answer as to the nature of extraction in this system or the exact complex formed during extraction.

  5. New Catalytic DNA Biosensors for Radionuclides and Metal ions

    SciTech Connect

    Lu, Yi

    2002-06-01

    The goals of the project are to develop new catalytic DNA biosensors for simultaneous detection and quantification of bioavailable radionuclides and metal ions, and apply the sensors for on-site, real-time assessment of concentration, speciation and stability of the individual contaminants during and after bioremediation. A negative selection strategy was tested and validated. In vitro selection was shown to yield highly active and specific transition metal ion-dependent catalytic DNA/RNA. A fluorescence resonance energy transfer (FRET) study of in vitro selected DNA demonstrated that the trifluorophore labeled system is a simple and powerful tool in studying complex biomolecules structure and dynamics, and is capable of revealing new sophisticated structural changes. New fluorophore/quenchers in a single fluorosensor yielded improved signal to noise ratio in detection, identification and quantification of metal contaminants. Catalytic DNA fluorescent and colorimetric sensors were shown useful in sensing lead in lake water and in leaded paint. Project results were described in two papers and two patents, and won an international prize.

  6. New Catalytic DNA Biosensors for Radionuclides and Metal ions

    SciTech Connect

    Lu, Yi

    2003-06-01

    The goals of the project are to develop new catalytic DNA biosensors for simultaneous detection and quantification of bioavailable radionuclides and metal ions, and apply the sensors for on-site, real-time assessment of concentration, speciation and stability of the individual contaminants during and after bioremediation. A negative selection strategy was tested and validated. In vitro selection was shown to yield highly active and specific transition metal ion-dependent catalytic DNA/RNA. A fluorescence resonance energy transfer (FRET) study of in vitro selected DNA demonstrated that the trifluorophore labeled system is a simple and powerful tool in studying complex biomolecules structure and dynamics, and is capable of revealing new sophisticated structural changes. New fluorophore/quenchers in a single fluorosensor yielded improved signal to noise ratio in detection, identification and quantification of metal contaminants. Catalytic DNA fluorescent and colorimetric sensors were shown useful in sensing lead in lake water and in leaded paint. Project results were described in two papers and two patents, and won an international prize.

  7. Lanthanide metal-organic frameworks as selective microporous materials for adsorption of heavy metal ions.

    PubMed

    Jamali, Abbas; Tehrani, Alireza Azhdari; Shemirani, Farzaneh; Morsali, Ali

    2016-06-14

    Four microporous lanthanide metal-organic frameworks (MOFs), namely Ln(BTC)(H2O)(DMF)1.1 (Ln = Tb, Dy, Er and Yb, DMF = dimethylformamide, H3BTC = benzene-1,3,5-tricarboxylic acid), have been used for selective adsorption of Pb(ii) and Cu(ii). Among these MOFs, the Dy-based MOF shows better adsorption property and selectivity toward Pb(ii) and Cu(ii) ions. Adsorption isotherms indicate that sorption of Pb(ii) and Cu(ii) on MOFs is via monolayer coverage. Preconcentration is based on solid-phase extraction in which MOFs were rapidly injected into water samples and adsorption of metal ions was rapid because of good contact with analyte; then adsorbed Pb(ii) and Cu(ii) ions were analyzed by FAAS. The optimized methodology represents good linearity between 1 and 120 μg L(-1) and detection limit of 0.4 and 0.26 μg L(-1) for Pb(ii) and Cu(ii), respectively. Subsequently the method was evaluated for preconcentration of target metal ions in some environmental water samples. PMID:27171975

  8. Additives

    NASA Technical Reports Server (NTRS)

    Smalheer, C. V.

    1973-01-01

    The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.

  9. Supercharging with Trivalent Metal Ions in Native Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Flick, Tawnya G.; Williams, Evan R.

    2012-11-01

    Addition of 1.0 mM LaCl3 to aqueous ammonium acetate solutions containing proteins in their folded native forms can result in a significant increase in the molecular ion charging obtained with electrospray ionization as a result of cation adduction. In combination with m-nitrobenzyl alcohol, molecular ion charge states that are greater than the number of basic sites in the protein can be produced from these native solutions, even for lysozyme, which is conformationally constrained by four intramolecular disulfide bonds. Circular dichroism spectroscopy indicates that the conformation of ubiquitin is not measurably affected with up to 1.0 M LaCl3, but ion mobility data indicate that the high charge states that are formed when 1.0 mM LaCl3 is present are more unfolded than the low charge states formed without this reagent. These and other results indicate that the increased charging is a result of La3+ preferentially adducting onto compact or more native-like conformers during ESI and the gas-phase ions subsequently unfolding as a result of increased Coulomb repulsion. Electron capture dissociation of these high charge-state ions formed from these native solutions results in comparable sequence coverage to that obtained for ions formed from denaturing solutions without supercharging reagents, making this method a potentially powerful tool for obtaining structural information in native mass spectrometry.

  10. Correlation between the limiting pH of metal ion solubility and total metal concentration

    SciTech Connect

    Apak, R.; Hizal, J.; Ustaer, C.

    1999-03-15

    As an alternative to species distribution diagrams (pM vs pH curves in aqueous solution) drawn for a fixed total metal concentration, this work has developed simple linear models for correlating the limiting pH of metal ion solubility -- in equilibrium with the least soluble amorphous metal hydroxide solid phase -- to the total metal concentration. Thus adsorptive metal removal processes in complex systems can be better designed once the limiting pH of heavy metal solubility (i.e., pH{sup *}) in such a complex environment can be envisaged by simple linear equations. pH{sup *} vs pM{sub t} (M{sub t} = total metal concentration that can exist in aqueous solution in equilibrium with M(OH){sub 2(s)}) linear curves for uranyl-hydroxide, uranyl-carbonate-hydroxide, and mercuric-chloride-hydroxide simple and mixed-ligand systems and cupric-carbonate-hydroxide complexes in equilibrium with mixed hydroxide solid phases may enable the experimental chemist to distinguish true adsorption (e.g., onto hydrous oxide sorbents) from bulk precipitation removal of the metal and to interpret some anomalous metal fixation data -- usually attributed to pure adsorption in the literature -- with precipitation if the pM{sub t} at the studied pH is lower than that tolerated by pH{sup *} vs pM{sub t} curves. This easily predictable pH{sup *} corresponding to a given pM{sub t} may aid the design of desorptive mobilization experiments for certain metals as well as their adsorptive removal with the purpose of simulating metal adsorption and desorption cycles in real complex environments with changing groundwater pH.

  11. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    ERIC Educational Resources Information Center

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  12. Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C. (Inventor); Smith, Kiah A. (Inventor); Bugga, Ratnakumar V. (Inventor); Prakash, Surya G. (Inventor); Krause, Frederick Charles (Inventor)

    2014-01-01

    The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

  13. Metallic atoms and ions in comets: Comet Halley 1986 3

    NASA Technical Reports Server (NTRS)

    Ibadov, S.

    1992-01-01

    The origin of metallic atoms and ions in the cometary comae is investigated theoretically. Two effects are revealed in the comas of bright comets: (1) the Na anomalous type effect is possible within the gas-dust jets of comet P/Halley 1986 3 due to cooling cometary dust by cryogenic gas flow from the nucleus; and (2) the production of ions of refractory elements (Fe(+), Si(+), etc.) at large heliocentric distances is possible in the comas of the Halley type dusty comets due to high-velocity impacts between cometary and zodiacal dust particles. Spectral observations of comets with high sensitivity and spatial resolution are important for studying both comets and interplanetary dust.

  14. Metal-organic frameworks for lithium ion batteries and supercapacitors

    NASA Astrophysics Data System (ADS)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-03-01

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100-1000 m2 g-1) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m2 g-1), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs.

  15. Coupled polaronic and ion transport in nanocrystalline metal oxide electrodes

    NASA Astrophysics Data System (ADS)

    Rosso, Kevin

    2012-02-01

    We report new computational methods and fundamental understanding in the dynamics of coupled charge and ion transport in nanoscale metal oxides. The methods attack the multi-scale problem of simulating the collective diffusivities of ions and charge compensating e-/h+ carriers in single crystal particles, across particle-particle grain boundaries, and through networks of grains for select systems. Methods include embedded quantum mechanical clusters at the DFT and MP2 levels of theory for atomic-scale polaronic and ion transport kinetics, classical DFT-based free energy calculations for grain-scale conductivity in the framework of the Poisson-Nernst-Planck formalism, and phase field simulation of charged particle diffusivity for conductivity at the grain network scale. This combination of approaches is one of a kind in terms of its multi-scale range, scaling, and computational efficiency. We are presently focused on coupled electron and Li+ ion transport in polymorphs of TiO2, and also in mixed valence spinel oxides, for electrode conductivity optimization and improving energy storage materials performance for Li+ batteries.

  16. Metal-organic frameworks for lithium ion batteries and supercapacitors

    SciTech Connect

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  17. Nucleoside-5'-phosphorothioate analogues are biocompatible antioxidants dissolving efficiently amyloid beta-metal ion aggregates.

    PubMed

    Amir, Aviran; Shmuel, Eran; Zagalsky, Rostislav; Sayer, Alon H; Nadel, Yael; Fischer, Bilha

    2012-07-28

    Amyloid beta (Aβ) peptide is known to precipitate and form aggregates with zinc and copper ions in vitro and, in vivo in Alzheimer's disease (AD) patients. Metal-ion-chelation was suggested as therapy for the metal-ion-induced Aβ aggregation, metal-ion overload, and oxidative stress. In a quest for biocompatible metal-ion chelators potentially useful for AD therapy, we tested a series of nucleoside 5'-phosphorothioate derivatives as re-solubilization agents of Cu(+)/Cu(2+)/Zn(2+)-induced Aβ-aggregates, and inhibitors of Fenton reaction in Cu(+) or Fe(2+)/H(2)O(2) system. The most promising chelator in this series was found to be APCPP-γ-S. This nucleotide was found to be more efficient than EDTA in re-solubilization of Aβ(40)-Cu(2+) aggregates as observed by the lower diameter, d(H), (86 vs. 64 nm, respectively) obtained in dynamic light scattering measurements. Likewise, APCPP-γ-S dissolved Aβ(40)-Cu(+) and Aβ(42)-Cu(2+)/Zn(2+) aggregates, as monitored by (1)H-NMR and turbidity assays, respectively. Furthermore, addition of APCPP-γ-S to nine-day old Aβ(40)-Cu(2+)/Zn(2+) aggregates, resulted in size reduction as observed by transition electron microscopy (diameter reduction from 2.5 to 0.1 μm for Aβ(40)-Cu(2+) aggregates). APCPP-γ-S proved to be more efficient than ascorbic acid and GSH in reducing OH radical production in Fe(2+)/H(2)O(2) system (IC(50) values 85, 216 and, 92 μM, respectively). Therefore, we propose APCPP-γ-S as a potential AD therapy capable of both reducing OH radical production and re-solubilization of Aβ(40/42)-M(n+) aggregates. PMID:22652964

  18. Low jitter metal vapor vacuum arc ion source for electron beam ion trap injections

    SciTech Connect

    Holland, Glenn E.; Boyer, Craig N.; Seely, John F.; Tan, J.N.; Pomeroy, J.M.; Gillaspy, J.D.

    2005-07-15

    We describe a metal vapor vacuum arc (MeVVA) ion source containing eight different cathodes that are individually selectable via the control electronics which does not require moving components in vacuum. Inside the vacuum assembly, the arc plasma is produced by means of a 30 {mu}s pulse (26 kV,125 A) delivering 2.4 mC of charge to the cathode sample material. The trigger jitter is minimized (<200 ns) to improve the capture efficiency of the ions which are injected into an ion trap. During a single discharge, the over-damped pulse produces an ion flux of 8.4x10{sup 9} ions/cm{sup 2}, measured by an unbiased Faraday cup positioned 20 cm from the extractor grid, at discharge rates up to 5 Hz. The electronic triggering of the discharge is via a fiber optic interface. We present the design, fabrication details, and performance of this MeVVA, recently installed on the National Institute of Standards and Technology electron beam ion trap (EBIT)

  19. Application of G criterion in metal vapor ion laser

    NASA Astrophysics Data System (ADS)

    Gang, Chen; Bailiang, Pan; Yi, Jin; Kun, Chen; Zhixin, Yao

    2003-09-01

    Application of G criterion to efficient operation of pulsed discharge-excited R-M transition metal vapor laser was successfully extended to univalent ionic lasing medium from neutral atomic lasing medium on the basis of analyzing the simulation results of 1.09 μm Sr + lasing process. All of the known 17 R-M transition laser lines of univalent ions follow the G criterion except one, to which an interpretation is given. Furthermore, we suggest that only 69 lines among 212 possible R-M transition laser lines predicted by S.V. Markova, which satisfy the G criterion, should be explored first.

  20. Negative ion photoelectron spectroscopy of bare transition metal dimers

    NASA Astrophysics Data System (ADS)

    Barker, Beau J.

    This thesis contains gas phase negative ion photoelectron spectra of Mo2, MoV, CrCu, MoCu and Cu2. Spectra were taken with 488 nm and 514 nm light at a resolution of 4-5 meV. Information such as electron affinities, vibrational frequencies, anharmonicities and bond dissociation energies are reported for the ground and excited electronic states of both the anion and neutral species. Theoretical calculations at the density functional level are also reported for these species. Experiment and theory are used to analyze the bonding in these bare transition metal dimers.

  1. Electrolyte materials containing highly dissociated metal ion salts

    DOEpatents

    Lee, H.S.; Geng, L.; Skotheim, T.A.

    1996-07-23

    The present invention relates to metal ion salts which can be used in electrolytes for producing electrochemical devices, including both primary and secondary batteries, photoelectrochemical cells and electrochromic displays. The salts have a low energy of dissociation and may be dissolved in a suitable polymer to produce a polymer solid electrolyte or in a polar aprotic liquid solvent to produce a liquid electrolyte. The anion of the salts may be covalently attached to polymer backbones to produce polymer solid electrolytes with exclusive cation conductivity. 2 figs.

  2. Electrolyte materials containing highly dissociated metal ion salts

    DOEpatents

    Lee, Hung-Sui; Geng, Lin; Skotheim, Terje A.

    1996-07-23

    The present invention relates to metal ion salts which can be used in electrolytes for producing electrochemical devices, including both primary and secondary batteries, photoelectrochemical cells and electrochromic displays. The salts have a low energy of dissociation and may be dissolved in a suitable polymer to produce a polymer solid electrolyte or in a polar aprotic liquid solvent to produce a liquid electrolyte. The anion of the salts may be covalently attached to polymer backbones to produce polymer solid electrolytes with exclusive cation conductivity.

  3. Theoretical study of transition-metal ions bound to benzene

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    Theoretical binding energies are reported for all first-row and selected second-row transition metal ions (M+) bound to benzene. The calculations employ basis sets of at least double-zeta plus polarization quality and account for electron correlation using the modified coupled-pair functional method. While the bending is predominantly electrostatic, the binding energies are significantly increased by electron correlation, because the donation from the metal d orbitals to the benzene pi* orbitals is not well described at the self-consistent-field level. The uncertainties in the computed binding energies are estimated to be about 5 kcal/mol. Although the calculated and experimental binding energies generally agree to within their combined uncertainties, it is likely that the true binding energies lie in the lower portion of the experimental range. This is supported by the very good agreement between the theoretical and recent experimental binding energies for AgC6H6(+).

  4. Feasibility Study on 3-D Printing of Metallic Structural Materials with Robotized Laser-Based Metal Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Ding, Yaoyu; Kovacevic, Radovan

    2016-05-01

    Metallic structural materials continue to open new avenues in achieving exotic mechanical properties that are naturally unavailable. They hold great potential in developing novel products in diverse industries such as the automotive, aerospace, biomedical, oil and gas, and defense. Currently, the use of metallic structural materials in industry is still limited because of difficulties in their manufacturing. This article studied the feasibility of printing metallic structural materials with robotized laser-based metal additive manufacturing (RLMAM). In this study, two metallic structural materials characterized by an enlarged positive Poisson's ratio and a negative Poisson's ratio were designed and simulated, respectively. An RLMAM system developed at the Research Center for Advanced Manufacturing of Southern Methodist University was used to print them. The results of the tensile tests indicated that the printed samples successfully achieved the corresponding mechanical properties.

  5. Feasibility Study on 3-D Printing of Metallic Structural Materials with Robotized Laser-Based Metal Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    Ding, Yaoyu; Kovacevic, Radovan

    2016-07-01

    Metallic structural materials continue to open new avenues in achieving exotic mechanical properties that are naturally unavailable. They hold great potential in developing novel products in diverse industries such as the automotive, aerospace, biomedical, oil and gas, and defense. Currently, the use of metallic structural materials in industry is still limited because of difficulties in their manufacturing. This article studied the feasibility of printing metallic structural materials with robotized laser-based metal additive manufacturing (RLMAM). In this study, two metallic structural materials characterized by an enlarged positive Poisson's ratio and a negative Poisson's ratio were designed and simulated, respectively. An RLMAM system developed at the Research Center for Advanced Manufacturing of Southern Methodist University was used to print them. The results of the tensile tests indicated that the printed samples successfully achieved the corresponding mechanical properties.

  6. Effect of combinations of additives on the performance of lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Santee, Stuart; Xiao, Ang; Yang, Li; Gnanaraj, Joe; Lucht, Brett L.

    Commercial lithium-ion batteries have excellent performance at room temperature for a few years. However, the calendar life and thermal stability (>50 °C) need to be improved for many applications, including electric vehicles. We have conducted an investigation of the effect of thermal stabilizing additives, including dimethyl acetamide, vinylene carbonate, and lithium bis(oxalato) borate, on the performance of lithium ion batteries stored at 70 °C for one month. The reactions of the lithium hexafluorophosphate/carbonate electrolyte, with and without electrolyte additives, with the surface of the electrodes after initial formation cycling have been analyzed via a combination of IR-ATR and XPS.

  7. Effect of flame-retarding additives on surface chemistry in Li-ion batteries

    SciTech Connect

    Nam, N.D.; Park, I.J.; Kim, J.G.; Kim, H.S.

    2012-10-15

    This study examined the properties of 1 wt.% vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and diphenyl octyl phosphate (DPOF) additive electrolytes as a promising way of beneficially improving the surface and cell resistance of Li-ion batteries. Surface film formation on the negative and positive electrodes was analyzed by electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FT-IR) spectroscopy, and scanning electron microscopy (SEM). In conclusion, EIS, FT-IR spectroscopy and SEM results confirmed that DPOF is an excellent additive to the electrolyte in the Li-ion batteries due to the improved co-intercalation of the solvent molecules.

  8. Metal Ion Dependence of the Matrix Metalloproteinase-1 Mechanism.

    PubMed

    Yang, Hao; Makaroff, Katherine; Paz, Nicholas; Aitha, Mahesh; Crowder, Michael W; Tierney, David L

    2015-06-16

    Matrix metalloproteinase-1 (MMP-1) plays crucial roles in disease-related physiologies and pathological processes in the human body. We report here solution studies of MMP-1, including characterization of a series of mutants designed to bind metal in either the catalytic site or the structural site (but not both). Circular dichroism and fluorescence spectroscopy of the mutants demonstrate the importance of the structural Zn(II) in maintaining both secondary and tertiary structure, while UV-visible, nuclear magnetic resonance, electron paramagnetic resonance, and extended X-ray absorption fine structure show its presence influences the catalytic metal ion's coordination number. The mutants allow us to demonstrate convincingly the preparation of a mixed-metal analogue, Co(C)Zn(S)-MMP-1, with Zn(II) in the structural site and Co(II) in the catalytic site. Stopped-flow fluorescence of the native form, Zn(C)Zn(S)-MMP-1, and the mixed-metal Co(C)Zn(S)-MMP-1 analogue shows that the internal fluorescence of a nearby Trp residue is modulated with catalysis and can be used to monitor reactivity under a number of conditions, opening the door to substrate profiling. PMID:26018933

  9. A nanoporous metal recuperated MnO2 anode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Guo, Xianwei; Han, Jiuhui; Zhang, Ling; Liu, Pan; Hirata, Akihiko; Chen, Luyang; Fujita, Takeshi; Chen, Mingwei

    2015-09-01

    Lithium-ion batteries (LIBs) have been intensively studied to meet the increased demands for the high energy density of portable electronics and electric vehicles. The low specific capacity of the conventional graphite based anodes is one of the key factors that limit the capacity of LIBs. Transition metal oxides, such as NiO, MnO2 and Fe3O4, are known to be promising anode materials that are expected to improve the specific capacities of LIBs for several times. However, the poor electrical conductivity of these oxides significantly restricts the lithium ion storage and charge/discharge rate. Here we report that dealloyed nanoporous metals can realize the intrinsic lithium storage performance of the oxides by forming oxide/metal composites. Without any organic binder, conductive additive and additional current collector, the hybrid electrodes can be directly used as anodes and show highly reversible specific capacity with high-rate capability and long cyclic stability.Lithium-ion batteries (LIBs) have been intensively studied to meet the increased demands for the high energy density of portable electronics and electric vehicles. The low specific capacity of the conventional graphite based anodes is one of the key factors that limit the capacity of LIBs. Transition metal oxides, such as NiO, MnO2 and Fe3O4, are known to be promising anode materials that are expected to improve the specific capacities of LIBs for several times. However, the poor electrical conductivity of these oxides significantly restricts the lithium ion storage and charge/discharge rate. Here we report that dealloyed nanoporous metals can realize the intrinsic lithium storage performance of the oxides by forming oxide/metal composites. Without any organic binder, conductive additive and additional current collector, the hybrid electrodes can be directly used as anodes and show highly reversible specific capacity with high-rate capability and long cyclic stability. Electronic supplementary

  10. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, James A.

    1997-01-01

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

  11. Reduction of spalling in mixed metal oxide desulfurization sorbents by addition of a large promoter metal oxide

    DOEpatents

    Poston, J.A.

    1997-12-02

    Mixed metal oxide pellets for removing hydrogen sulfide from fuel gas mixes derived from coal are stabilized for operation over repeated cycles of desulfurization and regeneration reactions by addition of a large promoter metal oxide such as lanthanum trioxide. The pellets, which may be principally made up of a mixed metal oxide such as zinc titanate, exhibit physical stability and lack of spalling or decrepitation over repeated cycles without loss of reactivity. The lanthanum oxide is mixed with pellet-forming components in an amount of 1 to 10 weight percent.

  12. The two faces of metal ions: From implants rejection to tissue repair/regeneration.

    PubMed

    Vasconcelos, Daniel M; Santos, Susana G; Lamghari, Meriem; Barbosa, Mário A

    2016-04-01

    The paradigm of metallic ions as exclusive toxic agents is changing. During the last 60 years, knowledge about toxicological and immunological reactions to metal particles and ions has advanced considerably. Hip prostheses, namely metal-on-metal bearings, have prompted studies about excessive and prolonged exposure to prosthetic debris. In that context, the interactions of metal particles and ions with cells and tissues are mostly harmful, inducing immune responses that lead to osteolysis and implant failure. However, in the last decade, new strategies to promote immunomodulation and healing have emerged based on the unique properties of metallic ions. The atom-size and charge enable ions to interact with key macromolecules (e.g. proteins, nucleic acids) that affect cellular function. Moreover, these agents are inexpensive, stable and can be integrated in biomaterials, which may open new avenues for a novel generation of medical devices. Herein, orthopedic devices are discussed as models for adverse responses to metal ions, and debated together with the potential to use metal ions-based therapies, thus bridging the gap between unmet clinical needs and cutting-edge research. In summary, this review addresses the two "faces" of metallic ions, from pathological responses to innovative research strategies that use metal ions for regenerative medicine. PMID:26851391

  13. Removal and selective recovery of heavy-metal ions from industrial waste waters. Technical completion report

    SciTech Connect

    Darnall, D.W.; Gardea-Torresdey, J.

    1989-02-01

    Accumulation of toxic metal ions in water supplies is a matter of increasingly grave concern. Primarily the undesirable by-products of mining and industrial activity, these ions can cause acute and chronic illnesses in humans and other animals. In an effort to limit further contamination, development of efficient, widely applicable, low-cost methods for removal of heavy-metal ions from waters deserves high priority. One new method that has allowed both the removal and recovery of metal ions from water has been the utilization of microorganisms such as algae. This metal-ion sorption process is based upon the natural, very strong affinity of the cell walls of algae for heavy metal ions. There appear to be distinct advantages of the immobilized algal system over other technology currently used for heavy-metal-ion cleanup from waste waters. The goals of the project were (1) to examine the effects of calcium(II) and magnesium(II) on transition metal binding to the algae, (2) to test the immobilized silica-algal polymers for removal of metal ions from electroplating plant waste waters, (3) to evaluate the effects of culturing conditions on the metal binding capacity of the resulting biomass, and (4) to investigate the mechanism of metal-ion binding to different algae.

  14. Effect of vermicomposting on concentration and speciation of heavy metals in sewage sludge with additive materials.

    PubMed

    He, Xin; Zhang, Yaxin; Shen, Maocai; Zeng, Guangming; Zhou, Mucen; Li, Meirong

    2016-10-01

    The aim of this work was to evaluate the total content and speciation of heavy metals (As, Cr, Cd, Cu, Fe, Mn, Ni, Pb and Zn) during vermicomposting of sewage sludge by Eisenia fetida earthworm with different additive materials (soil, straw, fly ash and sawdust). Results showed that the pH, total organic carbon were reduced, while the electric conductivity and germination index increased after a combined composting - vermicomposting process. The addition of bulking agents accelerated the stabilization of sludge and eliminated its toxicity. The total heavy metals after vermicomposting in 10 scenarios were lowered as compared with the initial values and the control without amendment. BCR sequential extraction indicated that vermicomposting significantly decreased the mobility of all heavy metals by increasing the residual fractions. The activity of earthworms and appropriate addition of amendment materials played a positive role in sequestering heavy metals during the treatment of sewage sludge. PMID:27434304

  15. A novel fluorocyclophosphazene as bifunctional additive for safer lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Xia, Lan; Xia, Yonggao; Liu, Zhaoping

    2015-03-01

    A high-efficiency flame-retarding additive, (Ethoxy)pentafluorocyclotriphosphazene (N3P3F5OCH2CH3, PFPN), has been synthesized and explored as a safer protection additive for rechargeable lithium batteries. The flammability tests indicate that only the addition of 5 wt% PFPN can make the electrolyte be totally non-flammable. As far as we know, the PFPN additive is the most efficient one of any flame-retarding additive ever synthesized and reported in the literature. The charge-discharge results demonstrate that the PFPN additive shows a good electrochemical compatibility on the graphitic anode and LiCoO2 cathode. Meanwhile, the incorporated PFPN additive can greatly improve the cyclic performance of LiCoO2 electrode at a high cut-off voltage of 4.5 V, showing a prospective flame-retarding additive for the applications in high-voltage lithium ion batteries.

  16. Amperometric detection of heavy metal ions in ion pair chromatography at an array of water/nitrobenzene micro interfaces.

    PubMed

    Wilke, S; Wang, H; Muraczewska, M; Müller, H

    1996-09-01

    A novel amperometric detector for heavy metal ions has been developed and successfully applied for ion pair chromatography. The detector is based on the electrochemical transfer of the metal ions across an array of water/nitrobenzene micro interfaces. The ion transfer is facilitated by the neutral ionophores methylenebis(diphenylphosphineoxide) and methylenebis(di- phenylphosphinesulfide). More than eight metals are separated in less than 15 min on an RP18 column using octyl sulfonate as ion pair reagent. For the heavy metals, the limits of decision are 19(Pb(2+)), 9(Zn(2+)), 9l (Co(2+)), 8(Cd(2+)) and 1.6(Mn(2+)) microg/L. The applicability of the new method for water samples is demonstrated. PMID:15048359

  17. Complexation of metal ion with poly(1-vinylimidazole) resin prepared by radiation-induced polymerization with template metal ion. [Gamma radiation

    SciTech Connect

    Kato, M.; Nishide, H.; Tsuchida, E.; Sasaki, T.

    1981-07-01

    Poly(1-vinylimidazole) (PVI) resin was prepared with Ni/sup 2 +/, CO/sup 2 +/, or Zn/sup 2 +/ as a template to study the adsorption of metal ions. The metal-1-vinylimidazole complex was copolymerized and cross-linked with 1-vinyl-2-pyrrolidone by ..gamma..-ray irradiation and the template metal ion was removed by treating the polymer complex with an acid. These PVI resins adsorbed metal ions more effectively than the PVI resin prepared without the template. The number of adsorption sites (As) and the stability constant (K) of Ni/sup 2 +/ complex were larger for the PVI resin prepared with the Ni ion template caused by the smaller dissociation rate constant of Ni ion from the resin. The composition of the Ni/sup 2 +/ complex in the resin remained constant. This suggests that the complexation proceeded via a one-step mechanism.

  18. Blood metal ion testing is an effective screening tool to identify poorly performing metal-on-metal bearing surfaces

    PubMed Central

    Sidaginamale, R. P.; Joyce, T. J.; Lord, J. K.; Jefferson, R.; Blain, P. G.; Nargol, A. V. F.; Langton, D. J.

    2013-01-01

    Objectives The aims of this piece of work were to: 1) record the background concentrations of blood chromium (Cr) and cobalt (Co) concentrations in a large group of subjects; 2) to compare blood/serum Cr and Co concentrations with retrieved metal-on-metal (MoM) hip resurfacings; 3) to examine the distribution of Co and Cr in the serum and whole blood of patients with MoM hip arthroplasties; and 4) to further understand the partitioning of metal ions between the serum and whole blood fractions. Methods A total of 3042 blood samples donated to the local transfusion centre were analysed to record Co and Cr concentrations. Also, 91 hip resurfacing devices from patients who had given pre-revision blood/serum samples for metal ion analysis underwent volumetric wear assessment using a coordinate measuring machine. Linear regression analysis was carried out and receiver operating characteristic curves were constructed to assess the reliability of metal ions to identify abnormally wearing implants. The relationship between serum and whole blood concentrations of Cr and Co in 1048 patients was analysed using Bland-Altman charts. This relationship was further investigated in an in vitro study during which human blood was spiked with trivalent and hexavalent Cr, the serum then separated and the fractions analysed. Results Only one patient in the transfusion group was found to have a blood Co > 2 µg/l. Blood/Serum Cr and Co concentrations were reliable indicators of abnormal wear. Blood Co appeared to be the most useful clinical test, with a concentration of 4.5 µg/l showing sensitivity and specificity for the detection of abnormal wear of 94% and 95%, respectively. Generated metal ions tended to fill the serum compartment preferentially in vivo and this was replicated in the in vitro study when blood was spiked with trivalent Cr and bivalent Co. Conclusions Blood/serum metal ion concentrations are reliable indicators of abnormal wear processes. Important differences exist

  19. Selective exchange of divalent transition metal ions in cryptomelane-type manganic acid with tunnel structure

    SciTech Connect

    Tsuji, M. ); Komarneni, S. )

    1993-03-01

    The ion-exchange selectivity of divalent transition metal ions on cryptomelane-type manganic acid (CMA) with tunnel structure has been studied using the distribution coefficients ([ital K][sub [ital d

  20. Metal ion sorption by untreated and chemically treated biomass

    SciTech Connect

    Kilbane, J.J.; Xie, J.

    1992-12-31

    The metal-binding ability of biosorbents is well known; however, in comparison with commercial ion-exchange resins the capacity of biosorbents is low. The purpose of this research was to examine chemically modified biosorbents and biosorbents prepared from microorganisms isolated from extreme environments to determine if significant improvements in metal-binding capacity or biosorbents with unique capabilities could be produced. Chemical treatments examined included acid, alkali, carbon disulfide, phosphorus oxychloride, anhydrous formamide, sodium thiosulfate, sodium chloroacetic acid, and phenylsulfonate. Biosorbents were prepared from microorganisms isolated from pristine and acid mine drainage impacted sites and included heterotrophs, methanotrophs, algae, and sulfate reducers. Chemical modification with carbon disulfide, phosphorous oxychloride, and sodium thiosulfate yielded biosorbents with such as much as 74%, 133%, and 155% improvements, respectively, in metal-binding capacity, but the performance of these chemically modified biosorbents deteriorated upon repeated use. A culture isolated from an acid mine drainage impacted site, IGTM17, exhibits about 3-fold higher metal-binding capacity in comparison with other biosorbents examined in this study. IGTM17 also exhibits superior metal-binding ability at decreased pH or in the presence of interfering common cations in comparison with other biosorbents or some commercially available cation exchange resins. Some biosorbents, such as IGTM5, can bind anions. To our knowledge this is the first demonstration of the ability of biosorbents to bind anions. Moreover, preliminary data indicate that the chemical modification of biosorbents may be capable of imparting the ability to selectively bind certain anions. Further research is needed to optimize conditions for the chemical modification and stabilization of biosorbents.

  1. Most spin-1/2 transition-metal ions do have single ion anisotropy

    SciTech Connect

    Liu, Jia; Whangbo, Myung-Hwan E-mail: mike-whangbo@ncsu.edu; Koo, Hyun-Joo; Xiang, Hongjun E-mail: mike-whangbo@ncsu.edu; Kremer, Reinhard K.

    2014-09-28

    The cause for the preferred spin orientation in magnetic systems containing spin-1/2 transition-metal ions was explored by studying the origin of the easy-plane anisotropy of the spin-1/2 Cu{sup 2+} ions in CuCl{sub 2}·2H{sub 2}O, LiCuVO{sub 4}, CuCl{sub 2}, and CuBr{sub 2} on the basis of density functional theory and magnetic dipole-dipole energy calculations as well as a perturbation theory treatment of the spin-orbit coupling. We find that the spin orientation observed for these spin-1/2 ions is not caused by their anisotropic spin exchange interactions, nor by their magnetic dipole-dipole interactions, but by the spin-orbit coupling associated with their crystal-field split d-states. Our study also predicts in-plane anisotropy for the Cu{sup 2+} ions of Bi{sub 2}CuO{sub 4} and Li{sub 2}CuO{sub 2}. The results of our investigations dispel the mistaken belief that magnetic systems with spin-1/2 ions have no magnetic anisotropy induced by spin-orbit coupling.

  2. State promotion and neutralization оf ions near metal surface

    NASA Astrophysics Data System (ADS)

    Zinoviev, A. N.

    2011-05-01

    When a multiply charged ion with charge Z approaches the metal surface, a dipole is formed by the multiply charged ion and the charge induced in the metal. The states for such a dipole are promoted into continuum with decreasing ion-surface distance and cross the states formed from metal atom. The model proposed explains the dominant population of deep bound states in collisions considered.

  3. 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

    2016-04-01

    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. PMID:26913810

  4. Structure of the alkali-metal-atom + strontium molecular ions: Towards photoassociation and formation of cold molecular ions

    SciTech Connect

    Aymar, M.; Dulieu, O.; Guerout, R.

    2011-08-14

    The potential energy curves, permanent and transition dipole moments, and the static dipolar polarizability, of molecular ions composed of one alkali-metal atom and a strontium ion are determined with a quantum chemistry approach. The molecular ions are treated as effective two-electron systems and are treated using effective core potentials including core polarization, large gaussian basis sets, and full configuration interaction. In the perspective of upcoming experiments aiming at merging cold atom and cold ion traps, possible paths for radiative charge exchange, photoassociation of a cold lithium or rubidium atom and a strontium ion are discussed, as well as the formation of stable molecular ions.

  5. 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

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

    PubMed

    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

  7. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity

    NASA Astrophysics Data System (ADS)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL1 and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL2 derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML(1-2)2 have been synthesized, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate ? coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mn < Zn < Cu < Co < Ni. The ligands and their complexes were tested for in vitro antibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu > Mn > Ni > Co > Zn.

  8. Nanoparticles reduce nickel allergy by capturing metal ions

    NASA Astrophysics Data System (ADS)

    Vemula, Praveen Kumar; Anderson, R. Rox; Karp, Jeffrey M.

    2011-05-01

    Approximately 10% of the population in the USA suffer from nickel allergy, and many are unable to wear jewellery or handle coins and other objects that contain nickel. Many agents have been developed to reduce the penetration of nickel through skin, but few formulations are safe and effective. Here, we show that applying a thin layer of glycerine emollient containing nanoparticles of either calcium carbonate or calcium phosphate on an isolated piece of pig skin (in vitro) and on the skin of mice (in vivo) prevents the penetration of nickel ions into the skin. The nanoparticles capture nickel ions by cation exchange, and remain on the surface of the skin, allowing them to be removed by simple washing with water. Approximately 11-fold fewer nanoparticles by mass are required to achieve the same efficacy as the chelating agent ethylenediamine tetraacetic acid. Using nanoparticles with diameters smaller than 500 nm in topical creams may be an effective way to limit the exposure to metal ions that can cause skin irritation.

  9. Photonic nanosensor for colorimetric detection of metal ions.

    PubMed

    Yetisen, Ali K; Montelongo, Yunuen; Qasim, Malik M; Butt, Haider; Wilkinson, Timothy D; Monteiro, Michael J; Yun, Seok Hyun

    2015-01-01

    The real-time sensing of metal ions at point of care requires integrated sensors with low energy and sample consumption, reversibility, and rapid recovery. Here, we report a photonic nanosensor that reversibly and quantitatively reports on variation in the concentrations of Pb(2+) and Cu(2+) ions in aqueous solutions (<500 μL) in the visible region of the spectrum (λ(max) ≈ 400-700 nm). A single 6 ns laser pulse (λ = 532 nm) was used to pattern an ∼10 μm thick photosensitive recording medium. This formed periodic AgBr nanocrystal (ø ∼ 5-20 nm) concentrated regions, which produced Bragg diffraction upon illumination with a white light source. The sensor functionalized with 8-hydroxyquinoline allowed sensing through inducing Donnan osmotic pressure and tuning its lattice spacing. The sensor quantitatively measured Pb(2+) and Cu(2+) ion concentrations within the dynamic range of 0.1-10.0 mM with limits of detection of 11.4 and 18.6 μM in under 10 min. The sensor could be reset in 3 min and was reused at least 100 times without compromising its accuracy. The plasmonic nanosensor represents a simple and label-free analytical platform with potential scalability for applications in medical diagnostics and environmental monitoring. PMID:25710792

  10. Nanoparticles reduce nickel allergy by capturing metal ions.

    PubMed

    Vemula, Praveen Kumar; Anderson, R Rox; Karp, Jeffrey M

    2011-05-01

    Approximately 10% of the population in the USA suffer from nickel allergy, and many are unable to wear jewellery or handle coins and other objects that contain nickel. Many agents have been developed to reduce the penetration of nickel through skin, but few formulations are safe and effective. Here, we show that applying a thin layer of glycerine emollient containing nanoparticles of either calcium carbonate or calcium phosphate on an isolated piece of pig skin (in vitro) and on the skin of mice (in vivo) prevents the penetration of nickel ions into the skin. The nanoparticles capture nickel ions by cation exchange, and remain on the surface of the skin, allowing them to be removed by simple washing with water. Approximately 11-fold fewer nanoparticles by mass are required to achieve the same efficacy as the chelating agent ethylenediamine tetraacetic acid. Using nanoparticles with diameters smaller than 500 nm in topical creams may be an effective way to limit the exposure to metal ions that can cause skin irritation. PMID:21460828

  11. Colorimetric Fluorescent Nanosensor Based on Hexamethylene Diisocyanate for Fluorescent Responses and Adsorption of Heavy Metal Ions.

    PubMed

    Xu, Yaohui; Zhou, Yang; Li, Ruixing

    2016-03-01

    An inorganic-organic hybrid material based on magnetic Fe3O4@SiO2 nanoparticles was synthesized for fluorescent responses and removal of heavy metal ions, in which superparamagnetic Fe3O4@SiO2 nanoparticles were firstly prepared and modified with hexamethylene diisocyanate (HDI) instead of 3-isocyanatopropyltriethoxysilane (IPTES) as the organic coupling agent, and then a rhodamine derivative with spirolactam structure (Rho-en) was conjugated on the HDI functionalized Fe3O4@SiO2 nanoparticles through isocyanate groups. Both of functionalized Fe3O4@SiO2 nanoparticles based on IPTES and HDI were characterized by FT-IR and XPS, and the results indicated that HDI was a good alternative as chemical bridge for surface modification on the surface of Fe3O4@SiO2 nanoparticles. The inorganic-organic hybrid composites synthesized based HDI showed naked-eye color changes and fluorescent responses towards Zn2+, Cd2+, Mn2+, Pb2+, Hg2+ and Fe3+, which could serve as the available proofs for the qualitative analysis. Moreover, the as-obtained composites not only had excellent adsorption capability for Pb2+ and Hg2+, but also showed strong magnetic sensitivity, which could help to the removal and separation of functionalized magnetic nanocomposites after capturing the heavy metal ions. In addition, the plausible interaction mode of functionalized Fe3O4@SiO2 nanoparticles with heavy metal ions was discussed. PMID:27455720

  12. Polydopamine-mediated surface-functionalization of graphene oxide for heavy metal ions removal

    NASA Astrophysics Data System (ADS)

    Dong, Zhihui; Zhang, Feng; Wang, Dong; Liu, Xia; Jin, Jian

    2015-04-01

    By utilizing polydopamine (PD) nano-thick interlayer as mediator, polyethylenimine (PEI) brushes with abundant amine groups were grafted onto the surface of PD coated graphene oxide (GO) uniformly via a Michael-Addition reaction and produced a PEI-PD/GO composite nanosheets. The PEI-PD/GO composite exhibited an improved performance for adsorption of heavy metal ions as compared to PEI-coated GO and pure GO. The adsorption capacities for Cu2+, Cd2+, Pb2+, Hg2+ are up to 87, 106, 197, and 110 mg/g, respectively. To further make the GO based composite operable, PEI-PD/RGO aerogel was prepared through hydrothermal and achieved a high surface area up to 373 m2/g. Although the adsorption capacity of PEI-PD/RGO aerogel for heavy metal ions decreases a little as compared to PEI-PD/GO composite dispersion (38, 32, 95, 113 mg/g corresponding to Cu2+, Cd2+, Pb2+, and Hg2+, respectively), it could be recycled several times in a simple way by releasing adsorbed metal ions, indicating its potential application for cleaning wastewater.

  13. Prostate cancer outcome and tissue levels of metal ions

    USGS Publications Warehouse

    Sarafanov, A.G.; Todorov, T.I.; Centeno, J.A.; MacIas, V.; Gao, W.; Liang, W.-M.; Beam, C.; Gray, Michael A.; Kajdacsy-Balla, A.

    2011-01-01

    BACKGROUND There are several studies examining prostate cancer and exposure to cadmium, iron, selenium, and zinc. Less data are available on the possible influence of these metal ions on prostate cancer outcome. This study measured levels of these ions in prostatectomy samples in order to examine possible associations between metal concentrations and disease outcome. METHODS We obtained formalin fixed paraffin embedded tissue blocks of prostatectomy samples of 40 patients with PSA recurrence, matched 1:1 (for year of surgery, race, age, Gleason grading, and pathology TNM classification) with tissue blocks from 40 patients without recurrence (n = 80). Case-control pairs were compared for the levels of metals in areas adjacent to tumors. Inductively coupled plasma-mass spectrometry (ICP-MS) was used for quantification of Cd, Fe, Zn, and Se. RESULTS Patients with biochemical (PSA) recurrence of disease had 12% lower median iron (95 ??g/g vs. 111 ??g/g; P = 0.04) and 21% lower zinc (279 ??g/g vs. 346 ??g/g; P = 0.04) concentrations in the normal-appearing tissue immediately adjacent to cancer areas. Differences in cadmium (0.489 ??g/g vs. 0.439 ??g/g; 4% higher) and selenium (1.68 ??g/g vs. 1.58 ??g/g; 5% higher) levels were not statistically significant in recurrence cases, when compared to non-recurrences (P = 0.40 and 0.21, respectively). CONCLUSIONS There is an association between low zinc and low iron prostate tissue levels and biochemical recurrence in prostate cancer. Whether these novel findings are a cause or effect of more aggressive tumors, or whether low zinc and iron prostatic levels raise implications for therapy, remains to be investigated. Copyright ?? 2011 Wiley-Liss, Inc.

  14. Mobile loop mutations in an archaeal inositol monophosphatase: Modulating three-metal ion assisted catalysis and lithium inhibition

    PubMed Central

    Li, Zheng; Stieglitz, Kimberly A; Shrout, Anthony L; Wei, Yang; Weis, Robert M; Stec, Boguslaw; Roberts, Mary F

    2010-01-01

    The inositol monophosphatase (IMPase) enzyme from the hyperthermophilic archaeon Methanocaldococcus jannaschii requires Mg2+ for activity and binds three to four ions tightly in the absence of ligands: KD = 0.8 μM for one ion with a KD of 38 μM for the other Mg2+ ions. However, the enzyme requires 5–10 mM Mg2+ for optimum catalysis, suggesting substrate alters the metal ion affinity. In crystal structures of this archaeal IMPase with products, one of the three metal ions is coordinated by only one protein contact, Asp38. The importance of this and three other acidic residues in a mobile loop that approaches the active site was probed with mutational studies. Only D38A exhibited an increased kinetic KD for Mg2+; D26A, E39A, and E41A showed no significant change in the Mg2+ requirement for optimal activity. D38A also showed an increased Km, but little effect on kcat. This behavior is consistent with this side chain coordinating the third metal ion in the substrate complex, but with sufficient flexibility in the loop such that other acidic residues could position the Mg2+ in the active site in the absence of Asp38. While lithium ion inhibition of the archaeal IMPase is very poor (IC50∼250 mM), the D38A enzyme has a dramatically enhanced sensitivity to Li+ with an IC50 of 12 mM. These results constitute additional evidence for three metal ion assisted catalysis with substrate and product binding reducing affinity of the third necessary metal ion. They also suggest a specific mode of action for lithium inhibition in the IMPase superfamily. PMID:20027624

  15. New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

    SciTech Connect

    Bartsch, Richard A.

    2012-06-04

    The project objective was the discovery of new ligands for performing metal ion separations. The research effort entailed the preparation of new metal ion complexing agents and polymers and their evaluation in metal ion separation processes of solvent extraction, synthetic liquid membrane transport, and sorption. Structural variations in acyclic, cyclic, and bicyclic organic ligands were used to probe their influence upon the efficiency and selectivity with which metal ion separations can be performed. A unifying feature of the ligand structures is the presence of one (or more) side arm with a pendent acidic function. When a metal ion is complexed within the central cavity of the ligand, ionization of the side arm(s) produces the requisite anion(s) for formation of an overall electroneutral complex. This markedly enhances extraction/transport efficiency for separations in which movement of aqueous phase anions of chloride, nitrate, or sulfate into an organic medium would be required. Through systematic structural variations, new ligands have been developed for efficient and selective separations of monovalent metal ions (e.g., alkali metal, silver, and thallium cations) and of divalent metal ion species (e.g., alkaline earth metal, lead, and mercury cations). Research results obtained in these fundamental investigations provide important insight for the design and development of ligands suitable for practical metal ion separation applications.

  16. NEW INSTRUMENTS AND METHODS OF MEASUREMENTS: Liquid-metal ion emitters

    NASA Astrophysics Data System (ADS)

    Gabovich, M. D.

    1983-05-01

    This article describes and discusses the fundamental laws of ion emission from liquid-metal tips in a strong electric field. The widespread views of a liquid-metal emitter as being the smoothed tip of a Taylor cone are examined critically. The instability of a liquid metal in an electric field is discussed, and in line with this, an alternative concept is given of a sharp-tipped electrohydrodynamic emitter. The prospects for applying liquid-metal ion emitters are noted.

  17. Structure and mode of action of cyclic lipopeptide pseudofactin II with divalent metal ions.

    PubMed

    Janek, Tomasz; Rodrigues, Lígia R; Gudiña, Eduardo J; Czyżnikowska, Żaneta

    2016-10-01

    The interaction of natural lipopeptide pseudofactin II with a series of doubly charged metal cations was examined by matrix-assisted laser-desorption ionization-time of flight (MALDI-TOF) mass spectrometry and molecular modelling. The molecular modelling for metal-pseudofactin II provides information on the metal-peptide binding sites. Overall, Mg(2+), Ca(2+) and Zn(2+) favor the association with oxygen atoms spanning the peptide backbone, whereas Cu(2+) is coordinated by three nitrogens. Circular dichroism (CD) results confirmed that Zn(2+) and Cu(2+) can disrupt the secondary structure of pseudofactin II at high concentrations, while Ca(2+) and Mg(2+) did not essentially affect the structure of the lipopeptide. Interestingly, our results showed that the addition of Zn(2+) and Cu(2+) helped smaller micelles to form larger micellar aggregates. Since pseudofactin II binds metals, we tested whether this phenomena was somehow related to its antimicrobial activity against Staphylococcus epidermidis and Proteus mirabilis. We found that the antimicrobial effect of pseudofactin II was increased by supplementation of culture media with all tested divalent metal ions. Finally, by using Gram-positive and Gram-negative bacteria we showed that the higher antimicrobial activity of metal complexes of pseudofactin II is attributed to the disruption of the cytoplasmic membrane. PMID:27416562

  18. Metal Oxide Nanosensors Using Polymeric Membranes, Enzymes and Antibody Receptors as Ion and Molecular Recognition Elements

    PubMed Central

    Willander, Magnus; Khun, Kimleang; Ibupoto, Zafar Hussain

    2014-01-01

    The concept of recognition and biofunctionality has attracted increasing interest in the fields of chemistry and material sciences. Advances in the field of nanotechnology for the synthesis of desired metal oxide nanostructures have provided a solid platform for the integration of nanoelectronic devices. These nanoelectronics-based devices have the ability to recognize molecular species of living organisms, and they have created the possibility for advanced chemical sensing functionalities with low limits of detection in the nanomolar range. In this review, various metal oxides, such as ZnO-, CuO-, and NiO-based nanosensors, are described using different methods (receptors) of functionalization for molecular and ion recognition. These functionalized metal oxide surfaces with a specific receptor involve either a complex formation between the receptor and the analyte or an electrostatic interaction during the chemical sensing of analytes. Metal oxide nanostructures are considered revolutionary nanomaterials that have a specific surface for the immobilization of biomolecules with much needed orientation, good conformation and enhanced biological activity which further improve the sensing properties of nanosensors. Metal oxide nanostructures are associated with certain unique optical, electrical and molecular characteristics in addition to unique functionalities and surface charge features which shows attractive platforms for interfacing biorecognition elements with effective transducing properties for signal amplification. There is a great opportunity in the near future for metal oxide nanostructure-based miniaturization and the development of engineering sensor devices. PMID:24841244

  19. Metal Ion Induced Pairing of Cytosine Bases: Formation of I-Motif Structures Identified by IR Ion Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gao, Juehan; Berden, Giel; Oomens, J.

    2015-06-01

    While the Watson-Crick structure of DNA is among the most well-known molecular structures of our time, alternative base-pairing motifs are also known to occur, often depending on base sequence, pH, or presence of cations. Pairing of two cytosine (C) bases induced by the sharing of a single proton (C-H^+-C) gives rise to the so-called i-motif, occurring particularly in the telomeric region of DNA, and particularly at low pH. At physiological pH, silver cations were recently suggested to form cytosine dimers in a C-Ag^+-C structure analogous to the hemiprotonated cytosine dimer, which was later confirmed by IR spectroscopy.^1 Here we investigate whether Ag^+ is unique in this behavior. Using infrared action spectroscopy employing the free-electron laser FELIX and a tandem mass spectrometer in combination with quantum-chemical computations, we investigate a series of C-M^+-C complexes, where M is Cu, Li and Na. The complexes are formed by electrospray ionization (ESI) from a solution of cytosine and the metal chloride salt in acetonitrile/water. The complexes of interest are mass-isolated in the cell of a FT ion cyclotron resonance mass spectrometer, where they are irradiated with the tunable IR radiation from FELIX in the 600 - 1800 wn range. Spectra in the H-stretching range are obtained with a LaserVision OPO. Both experimental spectra as well as theoretical calculations indicate that while Cu behaves as Ag, the alkali metal ions induce a clearly different dimer structure, in which the two cytosine units are parallelly displaced. In addition to coordination to the ring nitrogen atom, the alkali metal ions coordinate to the carbonyl oxygen atoms of both cytosine bases, indicating that the alkali metal ion coordination favorably competes with hydrogen bonding between the two cytosine sub-units of the i-motif like structure. 1. Berdakin, Steinmetz, Maitre, Pino, J. Phys. Chem. A 2014, 118, 3804

  20. Ion acceleration enhanced by additional neutralizing electrons in a magnetically expanding double layer plasma

    SciTech Connect

    Takahashi, Kazunori; Fujiwara, Tamiya

    2010-10-15

    Electrons neutralizing an ion beam are additionally supplied to a magnetically expanding double layer (DL) plasma from the downstream side of the DL. The rf power and the argon gas pressure are maintained at 200 W and 55 mPa, respectively, and the source magnetic field is varied in the range of about 70-550 G. It is observed that the ion beam energy corresponding to the DL potential drop increases up to 30 eV with an increase in the magnetic field when supplying the additional electrons, while it saturates at 20 eV for the case of the absence of the additional electrons. The supplied electrons are believed to be an energy source for the DL such that increasing the magnetic field is able to increase the potential drop beyond the limit found in the absence of the supplied electrons.

  1. Phosphazene Based Additives for Improvement of Safety and Battery Lifetimes in Lithium-Ion Batteries

    SciTech Connect

    Mason K Harrup; Kevin L Gering; Harry W Rollins; Sergiy V Sazhin; Michael T Benson; David K Jamison; Christopher J Michelbacher

    2011-10-01

    There need to be significant improvements made in lithium-ion battery technology, principally in the areas of safety and useful lifetimes to truly enable widespread adoption of large format batteries for the electrification of the light transportation fleet. In order to effect the transition to lithium ion technology in a timely fashion, one promising next step is through improvements to the electrolyte in the form of novel additives that simultaneously improve safety and useful lifetimes without impairing performance characteristics over wide temperature and cycle duty ranges. Recent efforts in our laboratory have been focused on the development of such additives with all the requisite properties enumerated above. We present the results of the study of novel phosphazene based electrolytes additives.

  2. Metal cation/anion adsorption on calcium carbonate: Implications to metal ion concentrations in groundwater

    SciTech Connect

    Zachara, J.M.; Cowan, C.E.; Resch, C.T.

    1990-05-01

    This chapter evaluates the sorption behavior of metallic ions on specimen calcite as a basis for determining the importance of calcite relative to other subsurface sorbents, such as layer silicates and oxides, in controlling metal ion concentration in calcareous groundwaters. A review of the literature shows the sorption of both metallic cations and anions on calcite over ranges in pH and CO{sub 2} partial pressure to be consistent with a surface-exchange process where cations exchange with surface Ca and anions exchange with surface CO{sub 3}. A general surface-exchange model was developed to account for the effects of Ca and CO{sub 3} concentrations, pH, and calcite surface area on cation and anion sorption onto calcite. The model was applied to recently developed experimental sorption data of Zn and SeO{sub 3} on specimen calcite in equilibrium CaCO{sub 3}(aq) suspensions. The surface-exchange model was able to describe the effects of pH on both cation and anion sorption, and provided good predictions of the effects of variable CO{sub 2}(g) pressure on Zn sorption and of PO{sub 4} on SeO{sub 3} sorption. The surface-exchange model, combined with sorption constants for other phases, was used to calculate Cd sorption to a hypothetical aquifer material containing a mixture of sorbents. The sorbent concentrations were fixed to those expected in groundwater zones. The multi-sorbent calculation documented the importance of calcite as a sorbent for metallic ions in groundwater.93 refs., 18 figs., 5 tabs.

  3. Metal Ion Dependence of Cooperative Collapse Transitions in RNA

    SciTech Connect

    Moghaddam, Sarvin; Caliskan, Gokhan; Chauhan, Seema; Hyeon, Changbong; Briber, R.M.; Thirumalai, D.; Woodson, Sarah A.

    2010-10-12

    Positively charged counterions drive RNA molecules into compact configurations that lead to their biologically active structures. To understand how the valence and size of the cations influences the collapse transition in RNA, small-angle X-ray scattering was used to follow the decrease in the radius of gyration (R{sub g}) of the Azoarcus and Tetrahymena ribozymes in different cations. Small, multivalent cations induced the collapse of both ribozymes more efficiently than did monovalent ions. Thus, the cooperativity of the collapse transition depends on the counterion charge density. Singular value decomposition of the scattering curves showed that folding of the smaller and more thermostable Azoarcus ribozyme is well described by two components, whereas collapse of the larger Tetrahymena ribozyme involves at least one intermediate. The ion-dependent persistence length, extracted from the distance distribution of the scattering vectors, shows that the Azoarcus ribozyme is less flexible at the midpoint of transition in low-charge-density ions than in high-charge-density ions. We conclude that the formation of sequence-specific tertiary interactions in the Azoarcus ribozyme overlaps with neutralization of the phosphate charge, while tertiary folding of the Tetrahymena ribozyme requires additional counterions. Thus, the stability of the RNA structure determines its sensitivity to the valence and size of the counterions.

  4. Interactive effects of waterborne metals in binary mixtures on short-term gill-metal binding and ion uptake in rainbow trout (Oncorhynchus mykiss).

    PubMed

    Niyogi, Som; Nadella, Sunita R; Wood, Chris M

    2015-08-01

    Metal binding to fish gills forms the basis of the biotic ligand model (BLM) approach, which has emerged as a useful tool for conducting site-specific water quality assessments for metals. The current BLMs are designed to assess the toxicity of individual metals, and cannot account for the interactive effects of metal mixtures to aquatic organisms including fish. The present study was designed mainly to examine the interactive effects of waterborne metals (Cd, Zn, Cu, Ag, and Ni) in specific binary combinations on short-term (3h) gill-metal binding and essential ion (Ca(2+) and Na(+)) uptake (a physiological index of toxicity) in fish, using juvenile freshwater rainbow trout (Oncorhynchus mykiss) as the model species. We hypothesized that binary mixtures of metals that share a common mode of uptake and toxicity (e.g., Cd and Zn - Ca(2+) antagonists, Cu and Ag - Na(+) antagonists) would reduce the gill binding of each other via competitive interactions and induce less than additive effects on ion transport. In addition, the mixture of metals that have different modes of uptake and toxicity (e.g., Cd and Cu, or Cd and Ni) would not exhibit any interactive effects either on gill-metal binding or ion transport. We found that both Zn and Cu reduced gill-Cd binding and vice versa, however, Ni did not influence gill-Cd binding in fish. Surprisingly, Ag was found to stimulate gill-Cu binding especially at high exposure concentrations, whereas, Cu had no effect on gill-Ag binding. The inhibitory effect of Cd and Zn in mixture on branchial Ca(2+) uptake was significantly greater than that of Cd or Zn alone. Similarly, the inhibitory effect of Cu and Ag in mixture on branchial Na(+) uptake was significantly greater than that of Cu or Ag alone. The inhibitory effects of Cd and Zn mixture on Ca(2+) uptake as well as Cu and Ag mixture on Na(+) uptake were found to follow the principles of simple additivity. In contrast, no significant additive effect on either Ca(2+) or Na

  5. Recycling of red muds with the extraction of metals and special additions to cement

    NASA Astrophysics Data System (ADS)

    Zinoveev, D. V.; Diubanov, V. G.; Shutova, A. V.; Ziniaeva, M. V.

    2015-01-01

    The liquid-phase reduction of iron oxides from red mud is experimentally studied. It is shown that, in addition to a metal, a slag suitable for utilization in the construction industry can be produced as a result of pyrometallurgical processing of red mud. Portland cement is shown to be produced from this slag with mineral additions and a high-aluminate expansion addition to cement.

  6. Fluorescent metal ion chemosensors via cation exchange reactions of complexes, quantum dots, and metal-organic frameworks.

    PubMed

    Cheng, Jinghui; Zhou, Xiangge; Xiang, Haifeng

    2015-11-01

    Due to their wide range of applications and biological significance, fluorescent sensors have been an active research area in the past few years. In the present review, recent research developments on fluorescent chemosensors that detect metal ions via cation exchange reactions (transmetalation, metal displacement, or metal exchange reactions) of complexes, quantum dots, and metal-organic frameworks are described. These complex-based chemosensors might have a much better selectivity than the corresponding free ligands/receptors because of the shielding function of the filled-in metal ions. Moreover, not only the chemical structure of the ligands/receptors but also the identity of the central metal ions have a tremendous impact on the sensing performances. Therefore, sensing via cation exchange reactions potentially provides a new, simple, and powerful way to design fluorescent chemosensors. PMID:26375420

  7. Effects of heavy metal and other elemental additives to activated sludge on growth of Eisenia foetida

    SciTech Connect

    Hartenstein, R.; Neuhauser, E.F.; Narahara, A.

    1981-09-01

    The approximate level at which added concentrations of certain elements would cause an activated sludge to induce a toxic effect upon the growth of Eisenia foetida was determined. During 43 trials on sludge samples obtained throughout 1 year of study, earthworms grew from 3 to 10 mg live wt at hatching to 792 mg +- 18% (mean +- C.V.) in 8 weeks, when sludge was 24/sup 0/C and contained no additives. None of several elements commonly used in microbial growth media enhanced the growth rate of the earthworm. At salt concentrations up to about 6.6% on a dry wt basis, none of six anions tested was in and of itself toxic, while five of 15 cations - Co, Hg, Cu, Ni, and Cd - appeared specifically to inhibit growth rate or cause death. Manganese, Cr, and Pb were innocuous even at the highest levels of application - 22,000, 46,000, and 52,000 mg/kg, respectively. Neither the anionic nor cationic component of certain salts, such as NaCl or NH/sub 4/Cl, could be said to inhibit growth, which occurred only at high concentrations of these salts (about 3.3 and/or 6.6%). Below 7 mmho/cm, toxicity could not be correlated with electrolytic conductance, though higher values may help to explain the nonspecific growth inhibitory effects of salts like NaCl and KCl. Nor could toxicity ever be ascribed to hydrogen ion activity, since sludge pH was not altered even at the highest salt dose. It is concluded that except under very extreme conditions, the levels of heavy metals and salts generally found in activated sludges will not have an adverse affect on the growth of E. foetida.

  8. Measurement of Two-Photon Absorption Cross Section of Metal Ions by a Mass Sedimentation Approach.

    PubMed

    Ma, Zhuo-Chen; Chen, Qi-Dai; Han, Bing; Liu, Xue-Qing; Song, Jun-Feng; Sun, Hong-Bo

    2015-01-01

    The photo-reduction of metal ions in solution induced by femtosecond laser is an important and novel method for fabricating three-dimensional metal microstructures. However, the nonlinear absorption cross section of metal ions remains unknown because its measurement is difficult. In the present study, a method based on Two-Photon Excited Sedimentation (TPES) is proposed to measure the two-photon absorption cross section (TPACS) of metal ions in solution. The power-squared dependence of the amount of sediment on the excitation intensity was confirmed, revealing that 800 nm femtosecond laser induced reduction of metal ions was a two photon absorption process. We believe that the proposed method may be applied to measure the TPACS of several metal ions, thereby opening a new avenue towards future analysis of two-photon absorption materials. PMID:26657990

  9. Transition metal ions at the crossroads of mucosal immunity and microbial pathogenesis

    PubMed Central

    Diaz-Ochoa, Vladimir E.; Jellbauer, Stefan; Klaus, Suzi; Raffatellu, Manuela

    2013-01-01

    Transition metal ions are essential micronutrients for all living organisms. In mammals, these ions are often protein-bound and sequestered within cells, limiting their availability to microbes. Moreover, in response to infection, mammalian hosts further reduce the availability of metal nutrients by activating epithelial cells and recruiting neutrophils, both of which release metal-binding proteins with antimicrobial function. Microorganisms, in turn, have evolved sophisticated systems to overcome these limitations and acquire the metal ions essential for their growth. Here we review some of the mechanisms employed by the host and by pathogenic microorganisms to compete for transition metal ions, with a discussion of how evading “nutritional immunity” benefits pathogens. Furthermore, we provide new insights on the mechanisms of host-microbe competition for metal ions in the mucosa, particularly in the inflamed gut. PMID:24478990

  10. Rational design of metal ion sequestering agents. 1998 annual progress report

    SciTech Connect

    Raymond, K.N.

    1998-06-01

    'This project addresses fundamental issues and requirements in developing hazardous metal ion separation technologies needed in the treatment and disposal of radioactive and chemical toxic waste. It encompasses the synthesis of new agents, followed by their characterization and evaluation, with the aim to optimize their metal ion sequestering properties for use in applied technologies. This research is focused on the following key areas: (1) basic design and synthesis of new metal ion specific sequestering ligands; (2) structural and thermodynamic investigations of these ligands and their complexes formed with the targeted metal ions; and (3) development of sequestering agents and their incorporation into systems designed to be prototypes of inexpensive and highly effective materials for hazardous metal ion decontamination. Basic studies of the sequestration of relevant toxic metals are required in order to develop processes that will treat effluents sufficiently well to allow direct release into the environment and minimize the production of secondary wastes.'

  11. Measurement of Two-Photon Absorption Cross Section of Metal Ions by a Mass Sedimentation Approach

    PubMed Central

    Ma, Zhuo-Chen; Chen, Qi-Dai; Han, Bing; Liu, Xue-Qing; Song, Jun-Feng; Sun, Hong-Bo

    2015-01-01

    The photo-reduction of metal ions in solution induced by femtosecond laser is an important and novel method for fabricating three-dimensional metal microstructures. However, the nonlinear absorption cross section of metal ions remains unknown because its measurement is difficult. In the present study, a method based on Two-Photon Excited Sedimentation (TPES) is proposed to measure the two-photon absorption cross section (TPACS) of metal ions in solution. The power-squared dependence of the amount of sediment on the excitation intensity was confirmed, revealing that 800 nm femtosecond laser induced reduction of metal ions was a two photon absorption process. We believe that the proposed method may be applied to measure the TPACS of several metal ions, thereby opening a new avenue towards future analysis of two-photon absorption materials. PMID:26657990

  12. Evaluation of the impact of multivalent metal ions on the permeation behavior of Dolutegravir sodium.

    PubMed

    Grießinger, Julia Anita; Hauptstein, Sabine; Laffleur, Flavia; Netsomboon, Kesinee; Bernkop-Schnürch, Andreas

    2016-07-01

    Interactions between active pharmaceutical ingredients (APIs) and polyvalent cations are an important factor within drug absorption in the gastrointestinal tract. Dolutegravir sodium, as a second-generation integrase stand transfer inhibitor for the treatment of HIV was investigated regarding chelation with Al(3+), Ca(2+), Fe(3+), Mg(2+ )and Zn(2+) ions at three different molar ratios. Furthermore, the influence of drug-ion chelates on the permeability of the drug across two intestinal membrane models was analyzed. For this purpose, Caco-2 monolayer model and Ussing chamber technique utilizing freshly excited rat intestinal mucosa were chosen and a buffer system without additional Mg(2+) and Ca(2+) ions was tested regarding cell detachment. The addition of polyvalent cations in an equal molar ratio to the drug solution decreased the dissolved drug by at least 11%. An increased multivalent cation concentration in a ratio of 1:10 afforded an API drop in the solution of at least 88% with the exception of Mg(2+). In particular, Dolutegravir sodium was chelated with iron ions to nearly 100%. Overall, the higher the amount of metal ions in the solution, the lower was the detected amount of the drug. The permeation experiments across the Caco-2 monolayer and the rat intestinal mucosa pointed out that the addition of AlCl3, CaCl2 and ZnCl2 in a molar ratio of 10:1 to the drug led to significantly decreased drug permeation. According to these results the co-administration of Al(3+), Ca(2+ )or Zn(2+ )as well as of supplementary medications containing these polyvalent ions is in case of oral Dolutegravir delivery not recommended. PMID:26552713

  13. 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.

  14. Surface modification by metal ion implantation forming metallic nanoparticles in an insulating matrix

    NASA Astrophysics Data System (ADS)

    Salvadori, M. C.; Teixeira, F. S.; Sgubin, L. G.; Cattani, M.; Brown, I. G.

    2014-08-01

    There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We have investigated nanocomposites produced by metal ion implantation into insulating substrates, where the implanted metal self-assembles into nanoparticles. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), which can be estimated by computer simulation using the TRIDYN code. TRIDYN is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study show that the nanoparticles form a bidimentional array buried a few nanometers below the substrate surface. We have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples show that metallic nanoparticles form in the insulating matrix. These nanocomposites have been characterized by measuring the resistivity of the composite layer as a function of the implantation dose. The experimental results are compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement is found between the experimental results and the predictions of the theory. We conclude in that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

  15. Evaluation of biosurfactants grown in corn oil by Rhodococcus rhodochrous on removing of heavy metal ion from aqueous solution

    NASA Astrophysics Data System (ADS)

    Suryanti, Venty; Hastuti, Sri; Pujiastuti, Dwi

    2016-02-01

    The potential application of biosurfactants to remove heavy metal ion from aqueous solution by batch technique was examined. The glycolipids type biosurfactants were grown in a media containing of 20% v/v corn oil with 7 days of fermentation by Rhodococcus rhodochrous. The biosurfactants reduced the surface tension of water of about 51% from 62 mN/m to 30 mN/m. The biosurfactant increased the E24 of water-palm oil emulsion of about 55% from 43% to 97% and could maintain this E24 value of above 50% for up to 9 days. Heavy metal ion removal, in this case cadmium ion, by crude and patially purified biosurfactants has been investigated from aqueous solution at pH 6. Adsorption capacity of Cd(II) ion by crude biosurfactant with 5 and 10 minutes of contact times were 1.74 and 1.82 mg/g, respectively. Additionally, the adsorption capacity of Cd(II) ion by partially purified biosurfactant with 5 and 10 minutes of contact times were 0.79 and 1.34 mg/g, respectively. The results demonstrated that the adsorption capacity of Cd(II) ion by crude biosurfactant was higher than that of by partially purified biosurfactant. The results suggested that the biosurfactant could be used in the removal of heavy metal ions from aqueous solution.

  16. 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.

  17. MeRNA: a Database of Metal Ion Binding Sites in RNAStructures

    SciTech Connect

    Stefan, Liliana R.; Zhang, Rui; Levitan, Aaron G.; Hendrix, DonnaF.; Brenner, Steven E.; Holbrook, Stephen R.

    2005-10-05

    Metal ions are essential for the folding of RNA into stable tertiary structures and for the catalytic activity of some RNA enzymes. To aid in the study of the roles of metal ions in RNA structural biology, we have created MeRNA (Metals in RNA), a comprehensive compilation of all metal binding sites identified in RNA three-dimensional structures available from the Protein Data Bank (PDB) and Nucleic Acid Database (NDB). Currently, our database contains information relating to binding of 9764 metal ions corresponding to 23 distinct elements; in 256 RNA structures. The metal ion locations were confirmed and ligands characterized using original literature references. MeRNA includes eight manually identified metal-ion binding motifs, which are described in the literature. MeRNA is searchable by PDB identifier, metal ion, method of structure determination, resolution and R-values for X-ray structure, and distance from metal to any RNA atom or to water. New structures with their respective binding motifs will be added to the database as they become available. The MeRNA database will further our understanding of the roles of metal ions in RNA folding and catalysis and have applications in structural and functional analysis, RNA design and engineering.

  18. 4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, Marshall; Bugga, Ratnakumar

    2006-01-01

    Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives

  19. High current liquid metal ion source using porous tungsten multiemitters.

    PubMed

    Tajmar, M; Vasiljevich, I; Grienauer, W

    2010-12-01

    We recently developed an indium Liquid-Metal-Ion-Source that can emit currents from sub-μA up to several mA. It is based on a porous tungsten crown structure with 28 individual emitters, which is manufactured using Micro-Powder Injection Molding (μPIM) and electrochemical etching. The emitter combines the advantages of internal capillary feeding with excellent emission properties due to micron-size tips. Significant progress was made on the homogeneity of the emission over its current-voltage characteristic as well as on investigating its long-term stability. This LMIS seems very suitable for space propulsion as well as for micro/nano manufacturing applications with greatly increased milling/drilling speeds. This paper summarizes the latest developments on our porous multiemitters with respect to manufacturing, emission properties and long-term testing. PMID:21111260

  20. Caging Metal Ions with Visible Light-Responsive Nanopolymersomes

    PubMed Central

    2015-01-01

    Polymersomes are bilayer vesicles that self-assemble from amphiphilic diblock copolymers, and provide an attractive system for the delivery of biological and nonbiological molecules due to their environmental compatibility, mechanical stability, synthetic tunability, large aqueous core, and hyperthick hydrophobic membrane. Herein, we report a nanoscale photoresponsive polymersome system featuring a meso-to-meso ethyne-bridged bis[(porphinato)zinc] (PZn2) fluorophore hydrophobic membrane solute and dextran in the aqueous core. Upon 488 nm irradiation in solution or in microinjected zebrafish embryos, the polymersomes underwent deformation, as monitored by a characteristic red-shifted PZn2 emission spectrum and confirmed by cryo-TEM. The versatility of this system was demonstrated through the encapsulation and photorelease of a fluorophore (FITC), as well as two different metal ions, Zn2+ and Ca2+. PMID:25518002

  1. Heterogeneous behavior of metalloproteins toward metal ion binding and selectivity: insights from molecular dynamics studies.

    PubMed

    Gogoi, Prerana; Chandravanshi, Monika; Mandal, Suraj Kumar; Srivastava, Ambuj; Kanaujia, Shankar Prasad

    2016-07-01

    About one-third of the existing proteins require metal ions as cofactors for their catalytic activities and structural complexities. While many of them bind only to a specific metal, others bind to multiple (different) metal ions. However, the exact mechanism of their metal preference has not been deduced to clarity. In this study, we used molecular dynamics (MD) simulations to investigate whether a cognate metal (bound to the structure) can be replaced with other similar metal ions. We have chosen seven different proteins (phospholipase A2, sucrose phosphatase, pyrazinamidase, cysteine dioxygenase (CDO), plastocyanin, monoclonal anti-CD4 antibody Q425, and synaptotagmin 1 C2B domain) bound to seven different divalent metal ions (Ca(2+), Mg(2+), Zn(2+), Fe(2+), Cu(2+), Ba(2+), and Sr(2+), respectively). In total, 49 MD simulations each of 50 ns were performed and each trajectory was analyzed independently. Results demonstrate that in some cases, cognate metal ions can be exchanged with similar metal ions. On the contrary, some proteins show binding affinity specifically to their cognate metal ions. Surprisingly, two proteins CDO and plastocyanin which are known to bind Fe(2+) and Cu(2+), respectively, do not exhibit binding affinity to any metal ion. Furthermore, the study reveals that in some cases, the active site topology remains rigid even without cognate metals, whereas, some require them for their active site stability. Thus, it will be interesting to experimentally verify the accuracy of these observations obtained computationally. Moreover, the study can help in designing novel active sites for proteins to sequester metal ions particularly of toxic nature. PMID:26248730

  2. New electrolytes and electrolyte additives to improve the low temperature performance of lithium-ion batteries

    SciTech Connect

    Yang, Xiao-Qing

    2008-08-31

    In this program, two different approaches were undertaken to improve the role of electrolyte at low temperature performance - through the improvement in (i) ionic conductivity and (ii) interfacial behavior. Several different types of electrolytes were prepared to examine the feasibil.ity of using these new electrolytes in rechargeable lithium-ion cells in the temperature range of +40°C to -40°C. The feasibility studies include (a) conductivity measurements of the electrolytes, (b) impedance measurements of lithium-ion cells using the screened electrolytes with di.fferent electrochemical history such as [(i) fresh cells prior to formation cycles, (ii) after first charge, and (iii) after first discharge], (c) electrical performance of the cells at room temperatures, and (d) charge discharge behavior at various low temperatures. Among the different types of electrolytes investigated in Phase I and Phase II of this SBIR project, carbonate-based LiPF6 electrolytes with the proposed additives and the low viscous ester as a third component to the carbonate-based LiPF6 electrolytes show promising results at low temperatures. The latter electrolytes deliver over 80% of room temperature capacity at -20{degrees}C when the lithium-ion cells containing these electrolytes were charged at -20 °C. Also, there was no lithium plating when the lithium­-ion cells using C-C composite anode and LiPF{sub 6} in EC/EMC/MP electrolyte were charged at -20{degrees}C at C/5 rate. The studies of ionic conductivity and AC impedance of these new electrolytes, as well as the charge discharge characteristics of lithium-ion cells using these new electrolytes at various low temperatures provide new findings: The reduced capacity and power capability, as well as the problem of lithium plating at low temperatures charging of lithium-ion cells are primarily due to slow the lithium-ion intercalation/de-intercalation kinetics in the carbon structure.

  3. Photoluminescence properties of Jahn-Teller transition-metal ions

    NASA Astrophysics Data System (ADS)

    Sanz-Ortiz, Marta N.; Rodríguez, Fernando

    2009-09-01

    This work investigates the influence of electron-phonon coupling associated with E ⊗e and T ⊗e Jahn-Teller (JT) effect in different transition-metal (TM) ions on de-excitation phenomena through nonradiative multiphonon relaxation, i.e., photoluminescence (PL) quenching. We developed a configurational curve model which is able to predict from the absorption spectrum whether a given JT-TM ion is PL or quenched. The prediction is made on the basis of an adapted Dexter-Klick-Russell parameter for JT systems, defined in terms of spectroscopic parameters through ΛJT=αΔeabs/Eabs, where Δeabs refers to the splitting of the parent octahedral Eg states by the JT distortion in E ⊗e (α =3/4) or T ⊗e (α =1/4), and Eabs is the energy of the first absorption band involving electronic transition between Eg and T2g. We show that PL in any JT-TM ion occurs whenever ΛJT<0.1 or is quenched if ΛJT>0.2. This result is noteworthy since it allows us to establish structural requirements for the JT-TM ion and the host crystal to be PL. Although PL properties of materials containing TM ions depend on a variety of structural factors such as the electronic configuration, the site symmetry, and the crystal field produced by neighboring atoms, the present model achieves this goal through a simple spectroscopic parameter: ΛJT. In this work we correlated the PL properties of different sixfold-coordinated JT systems such as Ti3+, Cu2+, Mn3+, Cr2+, Fe2+, Co3+, and Ni3+ in halides and oxides with ΛJT obtained from their respective absorption spectra. From this analysis we conclude that depending on the nature of the JT coupling and its strength, PL is either strongly favored or quenched in T ⊗e while it is mostly quenched in E ⊗e systems due to the larger JT distortion.

  4. Metal beta-diketonate chelates as emissions-reducing fuel additives and a lanthanide-containing polymeric selective sorbent

    SciTech Connect

    Williams, E.J.

    1985-01-01

    Metal chelates of the anion of H(tod), 2,2,7-trimethyl-3,5-octanedione, have been synthesized and studied for use as emissions-reducing fuel additives. The thermal stability and volatility of complexes containing Co(III), Ni(II), Mn(II) and Ce(IV) were examined. These metal complexes exhibit very high solubilities in solvents such as n-hexane and are unusually volatile and thermally stable compounds. The structure of Cu(tod)/sub 2/ was determined by x-ray crystallography. Tests using Mn(tod)/sub 3/, Cu(tod)/sub 2/ and Ce(tod)/sub 4/ as fuel additives for gasoline engines indicated that dissolution of Mn(tod)/sub 3/ in test fuels can lower carbon monoxide levels in exhaust gas. The total hydrocarbon concentration and the relative concentrations of twenty hydrocarbon compounds in the exhaust were unaffected by the addition of these fuel additives to test fuel. A new porous polymer sorbent material has been developed which exhibits large breakthrough volumes for nucleophilic compounds. A styrene-divinylbenzene copolymer was modified such that fluorinated beta-diketone moieties were bonded to the phenyl rings in the polymer. Europium(III) ions were then incorporated in the modified polmer by complexation with the bound ligands. This study showed that the Eu(III)-containing polymer can retain nucleophilic species, such as aldehydes and ketones, when used as a trapping sorbent in air analysis. Apparently the retention of these compounds occurs via complexation with immobilized Eu(III) ions. The retention is thermally reversible, which allows sorbed compounds to be desorbed for gas chromatographic analysis.

  5. Selective removal of alkali metal cations from multiply-charged ions via gas-phase ion/ion reactions using weakly coordinating anions.

    PubMed

    Luongo, Carl A; Bu, Jiexun; Burke, Nicole L; Gilbert, Joshua D; Prentice, Boone M; Cummings, Steven; Reed, Christopher A; McLuckey, Scott A

    2015-03-01

    Selective removal of alkali metal cations from mixed cation multiply-charged peptide ions is demonstrated here using gas-phase ion/ion reactions with a series of weakly coordinating anions (WCAs), including hexafluorophosphate (PF6 (-)), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BARF), tetrakis(pentafluorophenyl)borate (TPPB), and carborane (CHB11Cl11 (-)). In all cases, a long-lived complex is generated by dication/anion condensation followed by ion activation to compare proton transfer with alkali ion transfer from the peptide to the anion. The carborane anion was the only anion studied to undergo dissociation exclusively through loss of the metallated anion, regardless of the studied metal adduct. All other anions studied yield varying abundances of protonated and metallated peptide depending on the peptide sequence and the metal identity. Density functional theory calculations suggest that for the WCAs studied, metal ion transfer is most strongly favored thermodynamically, which is consistent with the experimental results. The carborane anion is demonstrated to be a robust reagent for the selective removal of alkali metal cations from peptide cations with mixtures of excess protons and metal cations. PMID:25560986

  6. Selective Removal of Alkali Metal Cations from Multiply-Charged Ions via Gas-Phase Ion/Ion Reactions Using Weakly Coordinating Anions

    NASA Astrophysics Data System (ADS)

    Luongo, Carl A.; Bu, Jiexun; Burke, Nicole L.; Gilbert, Joshua D.; Prentice, Boone M.; Cummings, Steven; Reed, Christopher A.; McLuckey, Scott A.

    2015-03-01

    Selective removal of alkali metal cations from mixed cation multiply-charged peptide ions is demonstrated here using gas-phase ion/ion reactions with a series of weakly coordinating anions (WCAs), including hexafluorophosphate (PF6 -), tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BARF), tetrakis(pentafluorophenyl)borate (TPPB), and carborane (CHB11Cl11 -). In all cases, a long-lived complex is generated by dication/anion condensation followed by ion activation to compare proton transfer with alkali ion transfer from the peptide to the anion. The carborane anion was the only anion studied to undergo dissociation exclusively through loss of the metallated anion, regardless of the studied metal adduct. All other anions studied yield varying abundances of protonated and metallated peptide depending on the peptide sequence and the metal identity. Density functional theory calculations suggest that for the WCAs studied, metal ion transfer is most strongly favored thermodynamically, which is consistent with the experimental results. The carborane anion is demonstrated to be a robust reagent for the selective removal of alkali metal cations from peptide cations with mixtures of excess protons and metal cations.

  7. Addition and subtraction of single phonons in a trapped ion system

    NASA Astrophysics Data System (ADS)

    Lv, Dingshun; An, Shuoming; Um, Mark; Lu, Yao; Zhang, Jingning; Kim, Kihwan

    2014-05-01

    We introduce an addition and subtraction of single phonons in a trapped ion system. The creation ↠and annihilation â operation have been realized with photons and used for the complete engineering of quantum states of light and the probe of fundamental quantum phenomena. The mathematical description of photon is identical to that of phonon. However, phonon is a particle of quantized matter wave, which should be interpreted differently from photon. We implement the addition and the subtraction of phonon by applying an anti-Jaynes-Cummings type of operation on our trapped ion and performing projective measurements. Our realization can be used for the accurate measurement of position and momentum as well as their relation. This work was supported by the National Basic Research Program of China Grant 2011CBA00300, 2011CBA00301, 2011CBA00302, the National Natural Science Foundation of China Grant 61073174, 61033001, 61061130540.

  8. Metal-clad optical waveguide fluorescence device for the detection of heavy metal ions

    NASA Astrophysics Data System (ADS)

    Margheri, Giancarlo; Giorgetti, Emilia; Marsili, Paolo; Zoppi, Angela; Lascialfari, Luisa; Cicchi, Stefano

    2014-07-01

    We developed Hg-sensing chips by decorating the external surface of metal-clad optical waveguides with a monolayer of Hg-sensitive fluorescent molecular probes. The emission properties of the original water-soluble form of the molecule were previously found to be selectively quenched in the presence of Hg ions. The fabricated samples were tested with optical waveguide fluorescence spectroscopy by putting them in contact with a 5-μM water solution of Hg ions and recording the emission spectra versus incubation time. The estimate of the limit of detection was 150 nM. A preliminary evaluation of the selectivity of the structure was also performed by using Cd as possible interfering analytes.

  9. Porous metal oxide microspheres from ion exchange resin

    NASA Astrophysics Data System (ADS)

    Picart, S.; Parant, P.; Caisso, M.; Remy, E.; Mokhtari, H.; Jobelin, I.; Bayle, J. P.; Martin, C. L.; Blanchart, P.; Ayral, A.; Delahaye, T.

    2015-07-01

    This study is devoted to the synthesis and the characterization of porous metal oxide microsphere from metal loaded ion exchange resin. Their application concerns the fabrication of uranium-americium oxide pellets using the powder-free process called Calcined Resin Microsphere Pelletization (CRMP). Those mixed oxide ceramics are one of the materials envisaged for americium transmutation in sodium fast neutron reactors. The advantage of such microsphere precursor compared to classical oxide powder is the diminution of the risk of fine dissemination which can be critical for the handling of highly radioactive powders such as americium based oxides and the improvement of flowability for the filling of compaction chamber. Those millimetric oxide microspheres incorporating uranium and americium were synthesized and characterizations showed a very porous microstructure very brittle in nature which occurred to be adapted to shaping by compaction. Studies allowed to determine an optimal heat treatment with calcination temperature comprised between 700-800 °C and temperature rate lower than 2 °C/min. Oxide Precursors were die-pressed into pellets and then sintered under air to form regular ceramic pellets of 95% of theoretical density (TD) and of homogeneous microstructure. This study validated thus the scientific feasibility of the CRMP process to prepare bearing americium target in a powder free manner.

  10. High energy metal ion implantation using `Magis`, a novel, broad-beam, Marx-generator-based ion source

    SciTech Connect

    Anders, A.; Brown, I.G.; Dickinson, M.R.; MacGill, R.A.

    1996-08-01

    Ion energy of the beam formed by an ion source is proportional to extractor voltage and ion charge state. Increasing the voltage is difficult and costly for extraction voltage over 100 kV. Here we explore the possibility of increasing the charge states of metal ions to facilitate high-energy, broad beam ion implantation at a moderate voltage level. Strategies to enhance the ion charge state include operating in the regimes of high-current vacuum sparks and short pulses. Using a time-of-flight technique we have measured charge states as high as 7+ (73 kA vacuum spark discharge) and 4+ (14 kA short pulse arc discharge), both for copper, with the mean ion charge states about 6.0 and 2.5, respectively. Pulsed discharges can conveniently be driven by a modified Marx generator, allowing operation of ``Magis`` with a single power supply (at ground potential) for both plasma production and ion extraction.

  11. New highly sensitive and selective catalytic DNA biosensors for metal ions.

    PubMed

    Lu, Yi; Liu, Juewen; Li, Jing; Bruesehoff, Peter J; Pavot, Caroline M-B; Brown, Andrea K

    2003-05-01

    While remarkable progress has been made in developing sensors for metal ions such as Ca(II) and Zn(II), designing and synthesizing sensitive and selective metal ion sensors remains a significant challenge. Perhaps the biggest challenge is the design and synthesis of a sensor capable of specific and strong metal binding. Since our knowledge about the construction of metal-binding sites in general is limited, searching for sensors in a combinatorial way is of significant value. Therefore, we have been able to use a combinatorial method called in vitro selection to obtain catalytic DNA that can bind a metal ion of choice strongly and specifically. The metal ion selectivity of the catalytic DNA was further improved using a 'negative selection' strategy where catalytic DNA that are selective for competing metal ions are discarded in the in vitro selection processes. By labeling the resulting catalytic DNA with a fluorophore/quencher pair, we have made a new class of metal ion fluorescent sensors that are the first examples of catalytic DNA biosensors for metal ions. The sensors combine the high selectivity of catalytic DNA with the high sensitivity of fluorescent detection, and can be applied to the quantitative detection of metal ions over a wide concentration range and with high selectivity. The use of DNA sensors in detection and quantification of lead ions in environmental samples such as water from Lake Michigan has been demonstrated. DNA is stable, cost-effective, environmentally benign, and easily adaptable to optical fiber and microarray technology for device manufacture. Thus, the DNA sensors explained here hold great promise for on-site and real-time monitoring of metal ions in the fields of environmental monitoring, developmental biology, clinical toxicology, wastewater treatment, and industrial process monitoring. PMID:12706559

  12. 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. PMID:26325483

  13. Topological design and additive manufacturing of porous metals for bone scaffolds and orthopaedic implants: A review.

    PubMed

    Wang, Xiaojian; Xu, Shanqing; Zhou, Shiwei; Xu, Wei; Leary, Martin; Choong, Peter; Qian, M; Brandt, Milan; Xie, Yi Min

    2016-03-01

    One of the critical issues in orthopaedic regenerative medicine is the design of bone scaffolds and implants that replicate the biomechanical properties of the host bones. Porous metals have found themselves to be suitable candidates for repairing or replacing the damaged bones since their stiffness and porosity can be adjusted on demands. Another advantage of porous metals lies in their open space for the in-growth of bone tissue, hence accelerating the osseointegration process. The fabrication of porous metals has been extensively explored over decades, however only limited controls over the internal architecture can be achieved by the conventional processes. Recent advances in additive manufacturing have provided unprecedented opportunities for producing complex structures to meet the increasing demands for implants with customized mechanical performance. At the same time, topology optimization techniques have been developed to enable the internal architecture of porous metals to be designed to achieve specified mechanical properties at will. Thus implants designed via the topology optimization approach and produced by additive manufacturing are of great interest. This paper reviews the state-of-the-art of topological design and manufacturing processes of various types of porous metals, in particular for titanium alloys, biodegradable metals and shape memory alloys. This review also identifies the limitations of current techniques and addresses the directions for future investigations. PMID:26773669

  14. Influence of metal ions on the interaction between gatifloxacin and calf thymus DNA

    NASA Astrophysics Data System (ADS)

    Yuan, Xiao-ying; Qin, Jun; Lu, Ling-ling

    2010-02-01

    To study the interaction between gatifloxacin (GT), metal ions (Cu 2+, Cd 2+, Co 2+, Mg 2+) and calf thymus DNA under condition of physiology pH, UV absorption and fluorescence methods were adopted. Result shows that metal ions and DNA are able to react with GT in ground state. In further research, by studying the influence of metal ions on binding of GT with DNA in metal ions-GT-DNA ternary system, we found that influential mechanism of Mg 2+ on the binding of GT with DNA may be different from the other three. Mg 2+ can act as a bridge in the binding of GT's carboxyl/carbonyl with DNA phosphate in certain concentration range; while Cu 2+, Cd 2+, Co 2+ can combine directly with GT by reaction between GT carboxyl/carbonyl and DNA base, and enhance the binding ability of GT with DNA. The influence extent and type depend not only on the binding site of DNA with metal ions (phosphate or base), but also the binding ability of which. The stronger the binding ability of metal ions with DNA base is, the larger their promotion to binding of GT with DNA is. The order of metal ions' influential ability on the binding of GT-DNA is identical to the binding ability order of metal ions with DNA base, that is: Cu 2+ > Cd 2+ > Co 2+ > Mg 2+.

  15. 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.

  16. Using diastereopeptides to control metal ion coordination in proteins.

    PubMed

    Peacock, Anna F A; Hemmingsen, Lars; Pecoraro, Vincent L

    2008-10-28

    Here, we report a previously undescribed approach for controlling metal ion coordination geometry in biomolecules by reorientating amino acid side chains through substitution of L- to D-amino acids. These diastereopeptides allow us to manipulate the spatial orientation of amino acid side chains to alter the sterics of metal binding pockets. We have used this approach to design the de novo metallopeptide, Cd(TRIL12L(D)L16C)(3)(-), which is an example of Cd(II) bound to 3 L-Cys as exclusively trigonal CdS(3), as characterized by a combination of (113)Cd NMR and (111m)Cd PAC spectroscopy. We subsequently show that the physical properties of such a site, such as the high pK(a2) for Cd(II) binding of 15.1, is due to the nature of the coordination number and not the ligating group. Further more this approach allowed for the design of a construct, GRANDL12L(D)L16CL26AL30C, capable of independently binding 2 equivalents of Cd(II) to 2 very similar Cys sites as exclusively 3- and 4-, CdS(3) and CdS(3)O, respectively. Demonstrating that we are capable of controlling the Cd(II) coordination number in these 2 sites solely by varying the nature of a noncoordinating second coordination sphere amino acid, with D-leucine and L-alanine resulting in exclusively 3- and 4-coordinate structures, respectively. Cd(II) was found to selectively bind to the 4-coordinate CdS(3)O site, demonstrating that a protein can be designed that displays metal-binding selectivity based solely on coordination number control and not on the chemical identity of coordinating ligands. PMID:18940928

  17. The interaction between oxytetracycline and divalent metal ions in aqueous and mixed solvent systems.

    PubMed

    Tongaree, S; Flanagan, D R; Poust, R I

    1999-01-01

    The effects of pH, mixed solvent systems, and divalent metal ions on oxytetracycline (OTC) solubility and the interactions between OTC and metal ions in aqueous and mixed solvent systems were investigated. OTC solubility profiles were obtained for pH 4-9. The cosolvents studied were glycerin, propylene glycol, PEG 400, and 2-pyrrolidone with the following metal ions: magnesium, calcium, and zinc. OTC and its interactions with these metal ions were evaluated by solubility, NMR, circular dichroism (CD), and electron diffraction (ED) methods. At pH 5.6, no complexation occurred with these metal ions, but OTC zwitterion formed aggregates in aqueous solutions as shown by NMR spectra. The hydration of the metal ions was observed to affect OTC aggregation, with Mg+2 causing the greatest OTC aggregation. At pH 7.5, OTC aggregation and metal-OTC complexation were observed in solutions with Ca+2 and Mg+2. Zinc ion was found to decrease OTC solubility because of zincate formation, which caused anionic OTC to precipitate. Electron diffraction revealed a relationship between OTC and metal-OTC complex crystallinity and solubility behavior. The zinc-OTC complex exhibited the highest crystallinity and lowest solubility at pH 8.0. Various cosolvents generally enhanced OTC solubility, with 2-pyrrolidone having the best solubility power. In OTC-metal-2-pyrrolidone and OTC-Zn(+2)-PEG 400 systems, circular dichroism provided evidence for the formation of soluble ternary complexes. PMID:10578513

  18. An exploratory program for using hydrous metal oxide ion exchangers as Fischer-Tropsch catalysts

    SciTech Connect

    Lynch, A.W.; Dosch, R.G.; Sault, A.G.

    1990-01-01

    The purpose of this program is to investigate the potential of hydrous metal oxide (HMO) ion exchangers, invented at Sandia National Laboratories, as Fischer-Tropsch (F-T) catalysts. Metals known to be active in F-T synthesis (e.g. Fe, Co) were ion exchanged on hydrous metal oxide supports. Although HMO catalysts based on Zr, Nb, and Ta have been investigated in direct coal liquefaction studies, this effect focused on formulations based on the hydrous titanium oxide (HTO) system. The program has the goals of developing a catalyst with (1) high activity, (2) selectively to fuel range or other useful products, and (3) better properties for use in slurry reactors. The program has three main tasks: (1) catalyst synthesis, to develop methods for preparing catalysts having desirable F-T properties, (2) characterization, to investigate catalysts proving to have desirable properties by a variety of analytical techniques to determine correlations between activity and material properties and (3) testing to determine activity and selectivity of catalysts. This paper discussed results of activity testing of Ruhrchemie catalyst and some catalyst formulations prepared using ion exchange on hydrous titanium oxide and precipitation. For example, at 250{degree}C the Ruhrchemie catalyst converts {approximately}50% of the syngas feed to reaction products. In comparison, iron catalysts prepared by ion exchange and precipitation had conversions ranging from 20 to 50% over a temperature range of 250 to 275{degree}C of the syngas feed. In addition, results are Auger surface analysis of Ruhrchemie catalyst are presented. 6 refs., 2 figs., 2 tabs.

  19. Effect and interactions of commercial additives and chloride ion in copper electrowinning

    NASA Astrophysics Data System (ADS)

    Cui, Wenyuan

    This thesis is to understand and compare the effects and interactions of modified polysaccharide (HydroStar), polyacrylamide (Cyquest N-900) and chloride ion on copper electrowinning. A study of the nucleation and growth was conducted in a synthetic electrolyte (40 g/L Cu, 160 g/L H2SO 4, 20 mg/L Cl-) with the addition of HydroStar or Cyquest N-900 using potential step measurements. The current responses generated were compared to theoretical models of nucleation and growth mechanisms. The nucleation and growth mechanism changed as function of potential and the presence of organic additives. The nucleation and growth mechanisms were confirmed using scanning electron microscopy (SEM). At low overpotentials, electrodeposition from the electrolyte without additives proceeded by progressive nucleation with three-dimensional (3-D) growth. The addition of HydroStar produced smaller nuclei and changed the mechanism to progressive nucleation and 2-D growth. Cyquest N-900 used there appeared to be progressive nucleation with 2-D growth and polarize the cathodes. In addition, instantaneous nucleation under diffusion control occurred at high overpotentials. Chloride ion and its interaction with HydroStar and Cyquest N-900 were further characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The trends observed from Nyquist plots and equivalent circuit models were consistent with the CV results. Chloride, on its own, depolarized copper electrodeposition, while chloride ion associated with Cyquest N-900 inhibited the reaction. It is proposed that Cl- acted as a bridging ligand between copper and Cyquest N-900. The addition of HydroStar depolarized copper deposition, but it did not interact with.

  20. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity.

    PubMed

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL(1) and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL(2) derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML((1-2)2) have been synthesized, where M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mnmetal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu>Mn>Ni>Co>Zn. PMID:22813991

  1. Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

    DOE R&D Accomplishments Database

    Cram, D. J.

    1980-01-15

    Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

  2. 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. PMID:23601876

  3. An artificial tongue fluorescent sensor array for identification and quantitation of various heavy metal ions.

    PubMed

    Xu, Wang; Ren, Changliang; Teoh, Chai Lean; Peng, Juanjuan; Gadre, Shubhankar Haribhau; Rhee, Hyun-Woo; Lee, Chi-Lik Ken; Chang, Young-Tae

    2014-09-01

    Herein, a small-molecule fluorescent sensor array for rapid identification of seven heavy metal ions was designed and synthesized, with its sensing mechanism mimicking that of a tongue. The photoinduced electron transfer and intramolecular charge transfer mechanism result in combinatorial interactions between sensor array and heavy metal ions, which lead to diversified fluorescence wavelength shifts and emission intensity changes. Upon principle component analysis (PCA), this result renders clear identification of each heavy metal ion on a 3D spatial dispersion graph. Further exploration provides a concentration-dependent pattern, allowing both qualitative and quantitative measurements of heavy metal ions. On the basis of this information, a "safe-zone" concept was proposed, which provides rapid exclusion of versatile hazardous species from clean water samples based on toxicity characteristic leaching procedure standards. This type of small-molecule fluorescent sensor array could open a new avenue for multiple heavy metal ion detection and simplified water quality analysis. PMID:25144824

  4. Graphene-DNAzyme Junctions: A Platform for Direct Metal Ion Detection with Ultrahigh Sensitivity

    PubMed Central

    Gao, Li; Li, Le-Le; Wang, Xiaolong; Wu, Peiwen; Cao, Yang; Liang, Bo; Li, Xin; Lin, Yuanwei

    2015-01-01

    Many metal ions are present in biology and in the human body in trace amounts. Despite numerous efforts, metal sensors with ultrahigh sensitivity (< a few picomolar) are rarely achieved. Here, we describe a platform method that integrates a Cu2+-dependent DNAzyme into graphene-molecule junctions and its application for direct detection of paramagnetic Cu2+ with femtomolar sensitivity and high selectivity. Since DNAzymes specific for other metal ions can be obtained through in vitro selection, the method demonstrated here can be applied to the detection of a broad range of other metal ions. PMID:26417425

  5. Method for forming metallic silicide films on silicon substrates by ion beam deposition

    DOEpatents

    Zuhr, Raymond A.; Holland, Orin W.

    1990-01-01

    Metallic silicide films are formed on silicon substrates by contacting the substrates with a low-energy ion beam of metal ions while moderately heating the substrate. The heating of the substrate provides for the diffusion of silicon atoms through the film as it is being formed to the surface of the film for interaction with the metal ions as they contact the diffused silicon. The metallic silicide films provided by the present invention are contaminant free, of uniform stoichiometry, large grain size, and exhibit low resistivity values which are of particular usefulness for integrated circuit production.

  6. 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

  7. Sunflower stalks as adsorbents for the removal of metal ions from wastewater

    SciTech Connect

    Sun, G.; Shi, W.

    1998-04-01

    Sunflower stalks as adsorbents for the removal of metal ions such as copper, cadmium, zinc, and chromium ions in aqueous solutions were studied with equilibrium isotherms and kinetic adsorptions. The maximum adsorptions of four heavy metals are 29.3 mg/g (Cu{sup 2+}), 30.73 mg/g (Zn{sup 2+}), 42.18 mg/g (Cd{sup 2+}), and 25.07 mg/g (Cr{sup 3+}), respectively. Particle sizes of sunflower stalks affected the adsorption of metal ions; the finer size of particles showed better adsorption to the ions. Temperature also plays an interesting role in the adsorption of different metal ions. Copper, zinc, and cadmium exhibited lower adsorption on sunflower stalks at higher temperature, while chromium showed the opposite phenomenon. The adsorption rates of copper, cadmium, and chromium are quite rapid. Within 60 min of operation about 60--80% of these ions were removed from the solutions.

  8. Slip casting and extruding shapes of rhenium with metal oxide additives. 1: Feasibility demonstration

    NASA Technical Reports Server (NTRS)

    Barr, F. A.; Page, R. J.

    1986-01-01

    The feasibility of fabricating small rhenium parts with metal oxide additives by means of slip casting and extrusion techniques is described. The metal oxides, ZrO2 and HfO2 were stabilized into the cubic phase with Y2O3. Additions of metal oxide to the rhenium of up to 15 weight percent were used. Tubes of 17 mm diameter with 0.5 mm walls were slip cast by adapting current ceramic oxide techniques. A complete cast double conical nozzle demonstrated the ability to meet shapes and tolerances. Extrusion of meter long tubing lengths of 3.9 mm o.d. x 2.3 mm i.d. final dimension is documented. Sintering schedules are presented to produce better than 95% of theoretical density parts. Finished machining was found possible were requried by electric discharge machining and diamond grinding.

  9. Enhanced electrokinetic extraction of heavy metals from soils assisted by ion exchange membranes.

    PubMed

    Kim, Won-Seok; Kim, Soon-Oh; Kim, Kyoung-Woong

    2005-02-14

    The potential of electrokinetic remediation technology has been successfully demonstrated for the remediation of heavy metal contaminated fine-grained soils through laboratory scale and field application studies. Various enhancement techniques have been proposed and used in order to further improve the remediation process. However, it has been reported that such enhancement schemes can create other obstacles, such as the introduction of non-target ions into the system and thereby decrease the efficiency of the remediation process. Electrokinetic soil remediation technology enhanced by an ion exchange membrane (IEM), IEM-enhanced EK processing, was experimentally evaluated for the purpose of overcoming these obstacles. In particular, this study focused on observations of a fouling problem and its settlement using an auxiliary solution cell (ASC). In addition, the efficacies of two different types of electrode configurations, rectangular and cylindrical, were investigated. The experimental results indicate that the effectiveness of the technology was increased by an enhancement scheme using an IEM. This may be explained by the prevention of metal precipitation in the region near the cathode originating from hydroxide ions generated by the electrolysis of water in the cathode. The experimental results also imply that placement of the ASC can nullify the fouling problem within the cation exchange membranes used in IEM-enhanced EK processing, and thus improve the overall effectiveness of the process. The experimental results indicate that the cylindrical electrode configuration can be implemented in practical situations to improve the treatability of cathode effluent containing a high level of contaminants after processing. PMID:15721533

  10. High current multicharged metal ion source using high power gyrotron heating of vacuum arc plasma.

    PubMed

    Vodopyanov, A V; Golubev, S V; Khizhnyak, V I; Mansfeld, D A; Nikolaev, A G; Oks, E M; Savkin, K P; Vizir, A V; Yushkov, G Yu

    2008-02-01

    A high current, multi charged, metal ion source using electron heating of vacuum arc plasma by high power gyrotron radiation has been developed. The plasma is confined in a simple mirror trap with peak magnetic field in the plug up to 2.5 T, mirror ratio of 3-5, and length variable from 15 to 20 cm. Plasma formed by a cathodic vacuum arc is injected into the trap either (i) axially using a compact vacuum arc plasma gun located on axis outside the mirror trap region or (ii) radially using four plasma guns surrounding the trap at midplane. Microwave heating of the mirror-confined, vacuum arc plasma is accomplished by gyrotron microwave radiation of frequency 75 GHz, power up to 200 kW, and pulse duration up to 150 micros, leading to additional stripping of metal ions by electron impact. Pulsed beams of platinum ions with charge state up to 10+, a mean charge state over 6+, and total (all charge states) beam current of a few hundred milliamperes have been formed. PMID:18315170

  11. High current multicharged metal ion source using high power gyrotron heating of vacuum arc plasma

    SciTech Connect

    Vodopyanov, A. V.; Golubev, S. V.; Khizhnyak, V. I.; Mansfeld, D. A.; Nikolaev, A. G.; Oks, E. M.; Savkin, K. P.; Vizir, A. V.; Yushkov, G. Yu.

    2008-02-15

    A high current, multi charged, metal ion source using electron heating of vacuum arc plasma by high power gyrotron radiation has been developed. The plasma is confined in a simple mirror trap with peak magnetic field in the plug up to 2.5 T, mirror ratio of 3-5, and length variable from 15 to 20 cm. Plasma formed by a cathodic vacuum arc is injected into the trap either (i) axially using a compact vacuum arc plasma gun located on axis outside the mirror trap region or (ii) radially using four plasma guns surrounding the trap at midplane. Microwave heating of the mirror-confined, vacuum arc plasma is accomplished by gyrotron microwave radiation of frequency 75 GHz, power up to 200 kW, and pulse duration up to 150 {mu}s, leading to additional stripping of metal ions by electron impact. Pulsed beams of platinum ions with charge state up to 10+, a mean charge state over 6+, and total (all charge states) beam current of a few hundred milliamperes have been formed.

  12. Thio Effects and an Unconventional Metal Ion Rescue in the Genomic HDV Ribozyme§

    PubMed Central

    Thaplyal, Pallavi; Ganguly, Abir; Golden, Barbara L.; Hammes-Schiffer, Sharon; Bevilacqua, Philip C.

    2013-01-01

    Metal ion and nucleobase catalysis are important for ribozyme mechanism, but the extent to which they cooperate is unclear. A crystal structure of the hepatitis delta virus (HDV) ribozyme suggested that the pro-RP oxygen at the scissile phosphate directly coordinates a catalytic Mg2+ ion and is within hydrogen bonding distance of the amine of the general acid C75. Prior studies on the genomic HDV ribozyme, however, showed neither a thio effect nor metal ion rescue using Mn2+. Here, we combine experiment and theory to explore phosphorothioate substitutions at the scissile phosphate. We report significant thio effects at the scissile phosphate and metal ion rescue with Cd2+. Reaction profiles with an SP-phosphorothioate substitution are indistinguishable from those of the unmodified substrate in the presence of Mg2+ or Cd2+, supporting that the pro-SP oxygen does not coordinate metal ions. The RP-phosphorothioate substitution, however, exhibits biphasic kinetics, with the fast-reacting phase displaying a thio effect of up to 5-fold effect and the slow-reacting phase displaying a thio effect of ~1,000-fold. Moreover, the fast- and slow-reacting phases give metal ion rescues in Cd2+ of up to 10- and 330-fold, respectively. The metal ion rescues are unconventional in that they arise from Cd2+ inhibiting the oxo substrate but not the RP substrate. This metal ion rescue suggests a direct interaction of the catalytic metal ion with the pro-RP oxygen, in line with experiments on the antigenomic HDV ribozyme. Experiments without divalent ions, with mutants that interfere with Mg2+ binding, or with C75 deleted suggest that the pro-RP oxygen plays at most a redundant role in positioning C75. Quantum mechanical/molecular mechanical (QM/MM) studies indicate that the metal ion contributes to catalysis by interacting with both the pro-RP oxygen and the nucleophilic 2’- hydroxyl, supporting the experimental findings. PMID:24001219

  13. 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

  14. METAL INTERACTIONS AT SULFIDE MINERAL SURFACES: PART 3, METAL AFFINITIES IN SINGLE AND MULTIPLE ION ADSORPTION REACTIONS

    EPA Science Inventory

    Adsorption reactions of both single ions and multiple ion mixtures with sulfide minerals (chalcocite, galena, pyrite, and sphalerite) were investigated in the metal concentration range of 0.0001 to 0.00001 M. Chromium (III), iron (III), barium (II), cadmium (II), copper (II), nic...

  15. Metal hydrides used as negative electrode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Sartori, Sabrina; Cuevas, Fermin; Latroche, Michel

    2016-02-01

    Energy is a key issue for future generation. Researches are conducted worldwide to develop new efficient means for energy conversion and storage. Electrochemical storage is foreseen as an efficient way to handle intermittent renewable energy production. The most advanced batteries are nowadays based on lithium-ion technology though their specific capacities should be significantly increased to bring solution to mass storage. Conversion reactions are one way to step forward larger capacities at the anode. We here review the possibility to use metallic or complex hydrides as negative electrode using conversion reaction of hydride with lithium. Moreover, promising alloying of lithium with the metallic species might provide additional reversible capacities. Both binary and ternary systems are reviewed and results are compared in the frame of the electrochemical application.

  16. Identifying alkali metal inhibitors of crystal growth: a selection criterion based on ion pair hydration energy.

    PubMed

    Farmanesh, Sahar; Alamani, Bryan G; Rimer, Jeffrey D

    2015-09-21

    We show that alkali metals function as effective modifiers of calcium oxalate monohydrate (COM) crystallization wherein alkali-oxalate ion parings reduce the rate of crystal growth by as much as 60%. Our findings reveal a distinct trend in alkali metal efficacy that cannot be explained by colloidal theories or simple descriptors, such as ion size, but is consistent with a theoretical model that accounts for the ion pair's affinity for water. PMID:26242310

  17. 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.

  18. Multidiagnostics analysis of ion dynamics in ultrafast laser ablation of metals over a large fluence range

    SciTech Connect

    Anoop, K. K.; Polek, M. P.; Bruzzese, R.; Amoruso, S.; Harilal, Sivanandan S.

    2015-02-28

    The ions dynamics in ultrafast laser ablation of metals is studied over a fluence range spanning from the ablation threshold up to ~75 J/cm2 by means of three established diagnostic techniques. Langmuir probe, Faraday cup and spectrally resolved ICCD imaging simultaneously monitor the laser-produced plasma ions produced during ultrafast laser ablation of a copper target. The fluence dependence of ion yield is analyzed observing the occurrence of three different regimes. Moreover, the specific ion yield shows a maximum at about 4-5 J/cm2, followed by a gradual reduction and a transition to a high-fluence regime above ~50 J/cm2. The fluence variation of the copper ions angular distribution is also analyzed, observing a gradual increase of forward peaking of Cu ions for fluences up to ~10 J/cm2. Then, a broader ion component is observed at larger angles for fluences larger than ~10 J/cm2. Finally, an experimental characterization of the ions angular distribution for several metallic targets (Mg, Al, Cr, Fe, Cu, and W) is carried out at a relatively high fluence of ~66 J/cm2. Interestingly, the ion emission from the volatile metals show a narrow forward peaked distribution and a high peak ion yield compared to the refractory metals. Moreover, the width of ion angular distributions presents a striking correlation with the peak ion yield.

  19. Formation of metallic nanostructures on the surface of ion- exchange glass by focused electron beam

    NASA Astrophysics Data System (ADS)

    Komissarenko, F. E.; Zhukov, M. V.; Mukhin, I. S.; Golubok, A. O.; Sidorov, A. I.

    2015-11-01

    This paper presents a new method for formation of metallic nanostructures on the surface of ion-exchange glass. The method is based on the interaction of a focused electron beam with ions in ion-exchange glass. In experiments nanostructures with different shapes were obtained, depending on the electrons irradiation conditions.

  20. 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. PMID:25904197

  1. Multicolour photochromism of colloidal solutions of niobate nanosheets intercalated with several kinds of metal ions.

    PubMed

    Kamada, Kai; Tanaka, Yosuke; Tokunaga, Motoko; Ueda, Taro; Hyodo, Takeo; Shimizu, Yasuhiro

    2016-02-25

    Colourless and transparent colloidal solutions of niobate nanosheets intercalated with some kinds of metal ions (M-NNS, M: metal) showed quasi-reversible photochromism. Ultraviolet light irradiation of the solutions induced a change in color while maintaining the transparency, and the color change was dependent on the metal ions. The coloured solutions were bleached by exposure to an oxidizing atmosphere. This cycle could be repeated several times. PMID:26821602

  2. The Interchangeability of Plasma and Whole Blood Metal Ion Measurement in the Monitoring of Metal on Metal Hips

    PubMed Central

    Malek, Ibrahim A.; Rogers, Joanne; King, Amanda Christina; Clutton, Juliet; Winson, Daniel; John, Alun

    2015-01-01

    One hundred and twenty six paired samples of plasma and whole blood were measured with inductively coupled plasma mass spectrometry technique for metal ions analysis to determine a relationship between them. There was a significant difference between the mean plasma and whole blood concentrations of both cobalt (Co) and chromium (Cr) (p < 0.0001 for both Co and Cr). The mean ratio between plasma and whole blood Cr and Co was 1.56 (range: 0.39–3.85) and 1.54 (range: 0.64–18.26), respectively, but Bland and Altman analysis illustrated that this relationship was not universal throughout the range of concentrations. There was higher variability at high concentrations for both ions. We conclude that both these concentrations should not be used interchangeably and conversion factors are unreliable due to concentration dependent variability. PMID:26798516

  3. Ion Mobility-Derived Collision Cross Section As an Additional Measure for Lipid Fingerprinting and Identification

    PubMed Central

    2014-01-01

    Despite recent advances in analytical and computational chemistry, lipid identification remains a significant challenge in lipidomics. Ion-mobility spectrometry provides an accurate measure of the molecules’ rotationally averaged collision cross-section (CCS) in the gas phase and is thus related to ionic shape. Here, we investigate the use of CCS as a highly specific molecular descriptor for identifying lipids in biological samples. Using traveling wave ion mobility mass spectrometry (MS), we measured the CCS values of over 200 lipids within multiple chemical classes. CCS values derived from ion mobility were not affected by instrument settings or chromatographic conditions, and they were highly reproducible on instruments located in independent laboratories (interlaboratory RSD < 3% for 98% of molecules). CCS values were used as additional molecular descriptors to identify brain lipids using a variety of traditional lipidomic approaches. The addition of CCS improved the reproducibility of analysis in a liquid chromatography-MS workflow and maximized the separation of isobaric species and the signal-to-noise ratio in direct-MS analyses (e.g., “shotgun” lipidomics and MS imaging). These results indicate that adding CCS to databases and lipidomics workflows increases the specificity and selectivity of analysis, thus improving the confidence in lipid identification compared to traditional analytical approaches. The CCS/accurate-mass database described here is made publicly available. PMID:25495617

  4. Biosorption of metal ions from aqueous solution and tannery effluent by Bacillus sp. FM1.

    PubMed

    Masood, Farhana; Malik, Abdul

    2011-01-01

    The metal binding capacity of Bacillus sp. FM1 isolated from soil irrigated with tannery effluent was assessed using synthetic metal solutions and tannery wastewater. Biosorption of Cr(VI) and Cu(II) ions from aqueous solutions using Bacillus was investigated as a function of pH, initial metal ion concentration and contact time. The optimum adsorption pH value observed for Cr(VI) and Cu(II) ions was 2 and 5, respectively. Metal ion uptake increased with increasing initial metal concentration but no significant difference was observed by increasing the time after 60 min. Maximum uptake capacity of chromium was estimated as 64.102 mg g(-1), and of copper to 78.125 mg g(-1). Equilibrium data were well described by the Langmuir and Freundlich adsorption relations. The presence of functional groups on the cell wall surface of the biomass that may interact with the metal ion was confirmed by Fourier Transform Infrared (FTIR) spectroscopy. The application of Bacillus to remove Cr(VI) and Cu(II) in tannery effluent revealed that the biomass was capable of removing both the metal ions. However, the biosorption performance was slightly lower compared to that of synthetic metal solutions. Several factors may be responsible for this difference. However, the most important factor appears to be the presence of other contaminants such as anions, organics, and other trace metals in the effluent. PMID:22126236

  5. 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. PMID:25044622

  6. Experimental study of combustion characteristics of nanoscale metal and metal oxide additives in biofuel (ethanol)

    PubMed Central

    2011-01-01

    An experimental investigation of the combustion behavior of nano-aluminum (n-Al) and nano-aluminum oxide (n-Al2O3) particles stably suspended in biofuel (ethanol) as a secondary energy carrier was conducted. The heat of combustion (HoC) was studied using a modified static bomb calorimeter system. Combustion element composition and surface morphology were evaluated using a SEM/EDS system. N-Al and n-Al2O3 particles of 50- and 36-nm diameters, respectively, were utilized in this investigation. Combustion experiments were performed with volume fractions of 1, 3, 5, 7, and 10% for n-Al, and 0.5, 1, 3, and 5% for n-Al2O3. The results indicate that the amount of heat released from ethanol combustion increases almost linearly with n-Al concentration. N-Al volume fractions of 1 and 3% did not show enhancement in the average volumetric HoC, but higher volume fractions of 5, 7, and 10% increased the volumetric HoC by 5.82, 8.65, and 15.31%, respectively. N-Al2O3 and heavily passivated n-Al additives did not participate in combustion reactively, and there was no contribution from Al2O3 to the HoC in the tests. A combustion model that utilized Chemical Equilibrium with Applications was conducted as well and was shown to be in good agreement with the experimental results. PMID:21711760

  7. π-Extended dipyrrins capable of highly fluorogenic complexation with metal ions

    PubMed Central

    Filatov, Mikhail A.; Lebedev, Artem Y.; Mukhin, Sergei N.; Vinogradov, Sergei A.; Cheprakov, Andrei V.

    2010-01-01

    Synthesis and properties of a new family of π-extended dipyrrins, capable of forming brightly fluorescent complexes with metal ions, are reported. The metal complexes posses tunable spectral bands and exhibit different emission properties depending on the mode of metal coordination. PMID:20583759

  8. Dual channel sensor for detection and discrimination of heavy metal ions based on colorimetric and fluorescence response of the AuNPs-DNA conjugates.

    PubMed

    Tan, Lulu; Chen, Zhengbo; Zhao, Yan; Wei, Xiangcong; Li, Yonghui; Zhang, Chi; Wei, Xinling; Hu, Xiaochen

    2016-11-15

    We have presented an extensible, facile and sensitive multidimensional sensor based on DNA-gold nanoparticle (DNA-AuNP) conjugates for heavy metal ions (Ag(+), Hg(2+), Cr(3+), Sn(4+), Cd(2+), Cu(2+), Pb(2+), Zn(2+), and Mn(2+)) discrimination. In the presence of metal ions, the excluded effect of DNA and AuNPs with the same negative charges is disrupted, and the amount of FAM-labeled DNA adsorbed on AuNP surfaces increases, resulting in a more obvious fluorescence quenching effect. With the addition of NH2OH and HAuCl4, AuNPs grow into morphologically varied nanostructures (spherical to branched) depending on the resulting aptamer coverage, which gives rise to different colored solutions (reddish blush, purple and blue) observed by naked eyes. By simply changing the DNA sequences, three sensing elements can be easily obtained and added into this dual-channel multidimensional sensor. 9 heavy metal ions are distinguished by linear discriminant analysis (LDA) and primary component analysis (PCA). A highly sensitive discrimination of metal ion targets with the detection limit as low as 50nM with 100% identification accuracy is obtained. Remarkably, Cu(2+) and Hg(2+) ions with similar catalytic performance at various concentrations (300nM, 400nM, 500nM, respectively) and the mixture of the two metal ions with different volume ratios (total metal ion concentration: 500nM) can be successfully discriminated. In addition, nine heavy metal ions are also well-distinguished in river samples, and the accuracy of discrimination of these metal ions samples reaches 100%. Therefore, it will broaden the application field of DNA-AuNP conjugates-based multidimensional sensors. PMID:27208473

  9. Recent Developments in Metal-Catalyzed Additions of Oxygen Nucleophiles to Alkenes and Alkynes

    NASA Astrophysics Data System (ADS)

    Hintermann, Lukas

    Progress in the field of metal-catalyzed redox-neutral additions of oxygen nucleophiles (water, alcohols, carboxylic acids, and others) to alkenes, alkynes, and allenes between 2001 and 2009 is critically reviewed. Major advances in reaction chemistry include development of chiral Lewis acid catalyzed asymmetric oxa-Michael additions and Lewis-acid catalyzed hydro-alkoxylations of nonactivated olefins, as well as further development of Markovnikov-selective cationic gold complex-catalyzed additions of alcohols or water to alkynes and allenes.

  10. Fluid mechanics of additive manufacturing of metal objects by accretion of droplets - a survey

    NASA Astrophysics Data System (ADS)

    Tesař, Václav

    2016-03-01

    Paper presents a survey of principles of additive manufacturing of metal objects by accretion of molten metal droplets, focusing on fluid-mechanical problems that deserve being investigated. The main problem is slowness of manufacturing due to necessarily small size of added droplets. Increase of droplet repetition rate calls for basic research of the phenomena that take place inside and around the droplets: ballistics of their flight, internal flowfield with heat and mass transfer, oscillation of surfaces, and the ways to elimination of satellite droplets.

  11. TiO2 anode materials for lithium-ion batteries with different morphology and additives

    NASA Astrophysics Data System (ADS)

    Liu, Xiang; Ng, Yip Hang; Leung, Yu Hang; Liu, Fangzhou; Djurišic, Aleksandra B.; Xie, Mao Hai; Chan, Wai Kin

    2014-03-01

    Electrochemical performances of different TiO2 nanostructures, TiO2/CNT composite and TiO2 with titanium isopropoxide (TTIP) treatment anode were investigated. For different TiO2 nanostructures, we investigated vertically aligned TiO2 nanotubes on Ti foil and TiO2 nanotube-powders fabricated by rapid breakdown anodization technique. The morphology of the prepared samples was characterized by scanning probe microscopy (SEM). The electrochemical lithium storage abilities were studied by galvanostatic method. In addition, carbon nanotubes (CNT) additives and solution treatment process of TiO2 anode were investigated, and the results show that the additives and treatment could enhance the cycling performance of the TiO2 anode on lithium ion batteries.

  12. Localization of alkali metal ions in sodium-promoted palladium catalysts as studied by low energy ion scattering and transmission electron microscopy

    SciTech Connect

    Liotta, L.F.; Deganello, G.; Delichere, P.

    1996-12-01

    Three series of palladium-based catalysts have been studied by Low Energy Ion Scattering (LEIS) and Transmission Electron Microscopy (TEM). The first series is comprised of Na-Pd/SiO{sub 2} catalysts, obtained by addition of palladium to a silica support and by further addition of sodium ions with a Na/Pd atomic ratio (R) equal to 0,6.4 and 25.6. The second series consists of palladium catalysts supported on natural pumice, in which, due to a different loading of supported palladium, R{prime}, the (Na+K)/Pd atomic ratio, is equal to 17.0 and 39.4. The third series is represented by two palladium-based catalysts supported on {open_quotes}model pumices,{close_quotes} synthetic silico-aluminates, obtained by sol-gel techniques, with a different amount of sodium, and R equal to 2.1 and 6.1 respectively. LEIS experiments and electron microscopy demonstrate a different location of alkali metal ions in the first two series: in the Na-Pd/SiO{sub 2} catalysts sodium is distributed in a way which is not uniform on the support and on the palladium metal, which is partly decorated with Na ions, whereas in the Pd/natural-pumice series the palladium surface is sodium-free. The results on the third series of catalysts, Pd/model pumice, are not definitive on the basis of the LEIS and TEM analyses, but by FTIR study of CO and CO{sub 2} adsorption, the decoration of palladium by sodium ions could be excluded. The results confirm the importance of the alkali metal ion location in alkali-promoted palladium catalysts and open new possibilities in the design of palladium-supported catalysts by a better control of promoter location. 18 refs., 5 figs., 2 tabs.

  13. Crystal phase competition by addition of a second metal cation in solid solution metal-organic frameworks.

    PubMed

    Castillo-Blas, C; Snejko, N; de la Peña-O'Shea, V A; Gallardo, J; Gutiérrez-Puebla, E; Monge, M A; Gándara, F

    2016-03-14

    Herein we report a synthetic study focused on the preparation of solid-solution metal-organic frameworks, MOFs, with the use of two kinds of linkers. In particular, we have explored the system composed by zinc, cobalt, 1,2,4-triazole and 4,4′-hexafluoroisopropylidenebisbenzoic acid (H2hfipbb). During this study, four new MOFs have been isolated, denoted TMPF-88 [M3(hfipbb)2(triazole)2(H2O)], TMPF-90 [M2(triazole)3(OCH2CH3)], TMPF-91 [M2(hfipbb)(triazole)2(H2O)] and TMPF-95 [M5(hfipbb)4(triazole)2(H2O)] (TMPF = transition metal polymeric framework, M = Zn, Co, or mixture of them). The study demonstrates that the addition of a second metal element during the MOF synthesis has a major effect in the formation of new phases, even at very high Zn/Co metal ratios. Furthermore, we show that during the MOF formation reaction, there is a competition among different crystal phases, where kinetically favoured phases of various compositions crystallize in short reaction times, precluding the formation of the pure solid-solution phases of other energetically more stable MOFs. PMID:26674593

  14. Alkali Metal Halide Salts as Interface Additives to Fabricate Hysteresis-Free Hybrid Perovskite-Based Photovoltaic Devices.

    PubMed

    Wang, Lili; Moghe, Dhanashree; Hafezian, Soroush; Chen, Pei; Young, Margaret; Elinski, Mark; Martinu, Ludvik; Kéna-Cohen, Stéphane; Lunt, Richard R

    2016-09-01

    A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells. PMID:27532662

  15. Metal-Ion Metathesis and Properties of Triarylboron-Functionalized Metal-Organic Frameworks.

    PubMed

    Wang, Xiaoqing; Zhang, Liangliang; Yang, Jie; Dai, Fangna; Wang, Rongming; Sun, Daofeng

    2015-07-01

    An anionic metal-organic framework, H3[(Mn4Cl)3L8]⋅30H2O⋅2.5 DMF⋅5 Diox (UPC-15), was successfully prepared by the reaction of MnCl2 with tris(p-carboxylic acid)tridurylborane (H3 L) under solvothermal conditions. UPC-15 with wide-open pores (∼18.8 Å) is constructed by packing of octahedral and cuboctahedral cages, and exhibits high gas-sorption capabilities. Notably, UPC-15 shows selective adsorption of cationic dyes due to the anion framework. Moreover, the catalytic and magnetic properties were investigated, and UPC-15 can highly catalyze the cyanosilylation of aromatic aldehydes. UPC-15 exhibits the exchange of metal ions from Mn to Cu in a single-crystal-to-single-crystal manner to generate UPC-16, which could not be obtained by the direct solvothermal reaction of CuCl2 and H3L. UPC-16 exhibits similar properties for gas sorption, dye separation, and catalytic activity. However, the magnetic behaviors for UPC-15 and UPC-16 are distinct due to the metal-specific properties. Below 47 K, UPC-15 exhibits a ferromagnetic coupling but UPC-16 shows a dominant antiferromagnetic behavior. PMID:25929722

  16. Influence of Surface Coating on Metal Ion Release: Evaluation in Patients With Metal Allergy.

    PubMed

    Thomas, Peter; Weik, Thomas; Roider, Gabriele; Summer, Burkhard; Thomsen, Marc

    2016-05-01

    Nickel, chromium, and cobalt in stainless steel and Cobalt-chrome-molybdenum (CoCrMo) alloys may induce allergy. The objectives of this study were to evaluate surface coating regarding ion release, patch test reactivity, and arthroplasty performance. Materials and methods included patch test in 31 patients with metal allergy and 30 patients with no allergy to stainless steel and CoCrMo disks that are uncoated or coated by titanium nitride/zirconium nitride (TiN/ZrN). Assessment include atomic absorption spectrometry of released nickel, cobalt, and chromium from the disks after exposure to distilled water, artificial sweat and culture medium. Results showed that both coatings reduced the nickel and chromium release from stainless steel and CoCrMo disks and mostly the cobalt release from the disks (maximally 11.755 µg/cm(2)/5 d to 1.624 by Ti-N and to 0.442 by ZrN). Six of the 31 patients with metal allergy reacted to uncoated disks, but none reacted to the coated disks. The current authors report on exemplary patients with metal allergy who had symptom relief by revision with surface-coated arthroplasty. The authors concluded that the surface coating may prevent cutaneous and peri-implant allergic reactions. [Orthopedics. 2016; 39(3):S24-S30.]. PMID:27219723

  17. A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Grady, Joseph E.; Halbig, Michael C.; Singh, Mrityunjay

    2015-01-01

    In a NASA Aeronautics Research Institute (NARI) sponsored program entitled "A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing," evaluation of emerging materials and additive manufacturing technologies was carried out. These technologies may enable fully non-metallic gas turbine engines in the future. This paper highlights the results of engine system trade studies which were carried out to estimate reduction in engine emissions and fuel burn enabled due to advanced materials and manufacturing processes. A number of key engine components were identified in which advanced materials and additive manufacturing processes would provide the most significant benefits to engine operation. In addition, feasibility of using additive manufacturing technologies to fabricate gas turbine engine components from polymer and ceramic matrix composite were demonstrated. A wide variety of prototype components (inlet guide vanes (IGV), acoustic liners, engine access door, were additively manufactured using high temperature polymer materials. Ceramic matrix composite components included first stage nozzle segments and high pressure turbine nozzle segments for a cooled doublet vane. In addition, IGVs and acoustic liners were tested in simulated engine conditions in test rigs. The test results are reported and discussed in detail.

  18. A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing

    NASA Technical Reports Server (NTRS)

    Grady, Joseph E.; Halbig, Michael C.; Singh, Mrityunjay

    2015-01-01

    In a NASA Aeronautics Research Institute (NARI) sponsored program entitled "A Fully Non-Metallic Gas Turbine Engine Enabled by Additive Manufacturing", evaluation of emerging materials and additive manufacturing technologies was carried out. These technologies may enable fully non-metallic gas turbine engines in the future. This paper highlights the results of engine system trade studies which were carried out to estimate reduction in engine emissions and fuel burn enabled due to advanced materials and manufacturing processes. A number of key engine components were identified in which advanced materials and additive manufacturing processes would provide the most significant benefits to engine operation. In addition, feasibility of using additive manufacturing technologies to fabricate gas turbine engine components from polymer and ceramic matrix composite were demonstrated. A wide variety of prototype components (inlet guide vanes (IGV), acoustic liners, engine access door) were additively manufactured using high temperature polymer materials. Ceramic matrix composite components included first stage nozzle segments and high pressure turbine nozzle segments for a cooled doublet vane. In addition, IGVs and acoustic liners were tested in simulated engine conditions in test rigs. The test results are reported and discussed in detail.

  19. Heavy-ion induced electronic desorption of gas from metals

    SciTech Connect

    Molvik, A W; Kollmus, H; Mahner, E; Covo, M K; Bellachioma, M C; Bender, M; Bieniosek, F M; Hedlund, E; Kramer, A; Kwan, J; Malyshev, O B; Prost, L; Seidl, P A; Westenskow, G; Westerberg, L

    2006-12-19

    During heavy ion operation in several particle accelerators world-wide, dynamic pressure rises of orders of magnitude were triggered by lost beam ions that bombarded the vacuum chamber walls. This ion-induced molecular desorption, observed at CERN, GSI, and BNL, can seriously limit the ion beam lifetime and intensity of the accelerator. From dedicated test stand experiments we have discovered that heavy-ion induced gas desorption scales with the electronic energy loss (dE{sub e}/d/dx) of the ions slowing down in matter; but it varies only little with the ion impact angle, unlike electronic sputtering.

  20. Triethylborate as an electrolyte additive for high voltage layered lithium nickel cobalt manganese oxide cathode of lithium ion battery

    NASA Astrophysics Data System (ADS)

    Wang, Zaisheng; Xing, Lidan; Li, JianHui; Xu, Mengqing; Li, Weishan

    2016-03-01

    Triethylborate (TEB) is used as an electrolyte additive to improve the electrochemical performances of LiNi1/3Co1/3Mn1/3O2 (LNCM) upon cycling at 4.5 V vs. Li/Li+. Charge/discharge tests demonstrate that the cyclic stability of LNCM at room and elevated temperature can be improved effectively by TEB. With addition of 10 wt. % TEB into STD electrolyte (1.0 M LiPF6/EC:EMC:DEC), LNCM achieves a capacity retention of 99.8% after 150 cycles and 94.7% after 120 cycles at room and elevated temperature, respectively, comparing to that of 68.9% and 68.8% of STD electrolyte. In addition, 10 wt. % TEB also improves the rate capability of LNCM at room temperature. Physical and electrochemical characterizations from XRD, SEM, TEM, XPS, ICP-MS, LSV, CA, and EIS reveal that the preferential oxidative reaction of TEB generates a thin, uniform and low interfacial resistance film on the LNCM surface. This film not only suppresses the subsequent decomposition of STD electrolyte, but also prevents the dissolution of transition metal ions from LNCM, resulting in improved cyclic stability and rate capability of LNCM.

  1. Impact of Protein-Metal Ion Interactions on the Crystallization of Silk Fibroin Protein

    NASA Astrophysics Data System (ADS)

    Hu, Xiao; Lu, Qiang; Kaplan, David; Cebe, Peggy

    2009-03-01

    Proteins can easily form bonds with a variety of metal ions, which provides many unique biological functions for the protein structures, and therefore controls the overall structural transformation of proteins. We use advanced thermal analysis methods such as temperature modulated differential scanning calorimetry and quasi-isothermal TMDSC, combined with Fourier transform infrared spectroscopy, and scanning electron microscopy, to investigate the protein-metallic ion interactions in Bombyx mori silk fibroin proteins. Silk samples were mixed with different metal ions (Ca^2+, K^+, Ma^2+, Na^+, Cu^2+, Mn^2+) with different mass ratios, and compared with the physical conditions in the silkworm gland. Results show that all metallic ions can directly affect the crystallization behavior and glass transition of silk fibroin. However, different ions tend to have different structural impact, including their role as plasticizer or anti-plasticizer. Detailed studies reveal important information allowing us better to understand the natural silk spinning and crystallization process.

  2. Sol-gel derived hybrid materials doped with rare earth metal ions

    NASA Astrophysics Data System (ADS)

    Zelazowska, E.; Rysiakiewicz-Pasek, E.; Borczuch-Laczka, M.; Cholewa-Kowalska, K.

    2011-10-01

    Sol-gel derived organic-inorganic hybrid materials doped with rare earth metal ions (Pr 3+) and small amounts of lithium ions (˜0.1-0.2 wt.%) were produced from the tetraethyl orthosilicate (TEOS), AlCl 3·6H 2O (about 10 mol%), ethyl methacrylate, butyl methacrylate and some other organic additions (ca. 35-40 wt.% of organics in the fresh gels) to obtain hybrid organic-inorganic hosts. The gel and hybrid materials obtained were aged at room temperature for three weeks, then heated in an electric drier for 3 h at temperature of 125 °C and investigated for morphology, structure and luminescence properties by X-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR), 29Si and 27Al MAS nuclear magnetic resonance and fluorescence spectroscopy. An influence of the organic additions and inorganic dopants on microstructure of the materials obtained and their luminescence properties has been examined. Under excitation with UV radiation in a range of ˜210-350 nm, the sharp and relatively intense luminescence emission lines due to 3P 0 → 3H 4 (blue) and 3P 0 → 3F 3 (red) transitions of Pr 3+ ions were observed in the luminescence spectra of gel and hybrid materials of SA-series.

  3. Improving sulfolane-based electrolyte for high voltage Li-ion cells with electrolyte additives

    NASA Astrophysics Data System (ADS)

    Xia, Jian; Dahn, J. R.

    2016-08-01

    An electrolyte mixture containing 1 M LiPF6 in sulfolane:ethylmethyl carbonate 3:7 with vinylene carbonate and other electrolyte additives exhibited promising cycling and storage performance in high voltage Li(Ni0·4Mn0·4Co0.2)O2/graphite pouch type Li-ion cells tested to 4.5 V. Voltage drop during storage, coulombic efficiency, charge endpoint capacity slippage during ultra high precision cycling, charge-transfer resistance after storage or cycling, gas evolution during storage and cycling as well as capacity retention during long-term cycling were examined. The results for cells with sulfolane-based electrolytes were compared with those for cells with ethylene carbonate-based electrolytes containing state-of-the-art electrolyte additives. This survey showed that the combination of vinylene carbonate and triallyl phosphate as electrolyte additives in sulfolane:ethylmethyl carbonate electrolyte yielded cells capable of better performance during tests to 4.5 V than cells with ethylene carbonate-based electrolytes. These results suggest that sulfolane-based electrolytes may be promising for high voltage Li-ion cells.

  4. Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

    DOEpatents

    Hartwig, John F.; Kawatsura, Motoi; Loeber, Oliver

    2002-01-01

    The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

  5. Metal ion specificities for folding and cleavage activity in the Schistosoma hammerhead ribozyme

    PubMed Central

    Boots, Jennifer L.; Canny, Marella D.; Azimi, Ehsan; Pardi, Arthur

    2008-01-01

    The effects of various metal ions on cleavage activity and global folding have been studied in the extended Schistosoma hammerhead ribozyme. Fluorescence resonance energy transfer was used to probe global folding as a function of various monovalent and divalent metal ions in this ribozyme. The divalent metals ions Ca2+, Mg2+, Mn2+, and Sr2+ have a relatively small variation (less than sixfold) in their ability to globally fold the hammerhead ribozyme, which contrasts with the very large difference (>10,000-fold) in apparent rate constants for cleavage for these divalent metal ions in single-turnover kinetic experiments. There is still a very large range (>4600-fold) in the apparent rate constants for cleavage for these divalent metal ions measured in high salt (2 M NaCl) conditions where the ribozyme is globally folded. These results demonstrate that the identity of the divalent metal ion has little effect on global folding of the Schistosoma hammerhead ribozyme, whereas it has a very large effect on the cleavage kinetics. Mechanisms by which the identity of the divalent metal ion can have such a large effect on cleavage activity in the Schistosoma hammerhead ribozyme are discussed. PMID:18755844

  6. Electric Double-Layer Effects Induce Separation of Aqueous Metal Ions.

    PubMed

    Ji, Qinghua; An, Xiaoqiang; Liu, Huijuan; Guo, Lin; Qu, Jiuhui

    2015-11-24

    Metal ion separation is crucial to environmental decontamination, chromatography, and metal recovery and recycling. Theoretical studies have suggested that the ion distributions in the electric double-layer (EDL) region depend on the nature of the ions and the characteristics of the charged electrode surface. We believe that rational design of the electrode material and device structure will enable EDL-based devices to be utilized in the separation of aqueous metal ions. On the basis of this concept, we fabricate an EDL separation (EDLS) device based on sandwich-structured N-functionalized graphene sheets (CN-GS) for selective separation of aqueous toxic heavy metal ions. We demonstrate that the EDLS enables randomly distributed soluble ions to form a coordination-driven layer and electrostatic-driven layer in the interfacial region of the CN-GS/solution. Through tuning the surface potential of the CN-GS, the effective separation of heavy metal ions (coordination-driven layer) from alkali or alkaline earth metal ions (electrostatic-driven layer) can be achieved. PMID:26481603

  7. Metal ion complexation by ionizable crown ethers. Progress report, January 1, 1991--December 31, 1993

    SciTech Connect

    Bartsch, R.A.

    1993-07-01

    Cyclic and acyclic polyether compounds with pendent carboxylic acid, phosphonic acid monoethyl ester, sulfonic acid, phosphinic acid and hydroxamic acid groups have been synthesized. The proton-ionizable polyethers can come with and without lipophilic groups. Two types of lipophilic di-ionizable lariat ethers have been prepared. Conformations of proton-ionizable lariat ethers have been probed. Competitive alkali metal cation transport by syn-(decyl)dibenzo-16-crown-5-oxyacetic acid and lipophilic proton-ionizable dibenzo lariat ethers in polymer-supported liquid membranes was studied. Complexation of alkali metal cations with ionized lariat ethers was studied. Condensation polymerization of cyclic and acyclic dibenzo polyethers containing pendent mono-ionizable groups with formaldehyde produces novel ion exchange resins with both ion exchange sites for metal ion complexation and polyether binding sites for metal ion recognition. Resins prepared from lariat ether dibenzo phosphonic acid monoethyl esters show strong sorption of divalent heavy metal cations with selectivity for Pb{sup 2+}.

  8. Determination of metal ion concentrations by SERS using 2,2'-bipyridyl complexes.

    PubMed

    Docherty, Julie; Mabbott, Samuel; Smith, W Ewen; Reglinski, John; Faulds, Karen; Davidson, Christine; Graham, Duncan

    2015-10-01

    Surface enhanced Raman scattering (SERS) can generate characteristic spectral "fingerprints" from metal complexes, thus providing the potential for the development of methods of analysis for the identification and quantitation of a range of metal ions in solution. The advantages include sensitivity and the use of one ligand for several metals without the need for a specific chromophore. Aqueous solutions of Fe(II), Ni(II), Zn(II), Cu(II), Cr(III) and Cd(II) in the presence of excess 2,2'-bipyridyl (bipy) were analysed using SERS. Specific marker bands enabled the identification of each metal ion and the limit of detection for each metal ion was estimated. Two of the ions, Zn(II) and Cu(II), could be detected below the World Health Organisation's (WHO) recommended limits for drinking water at levels of 0.22 and 0.6 mg L(-1), respectively. PMID:26312259

  9. Carboxylate Ion Pairing with Alkali-Metal Ions for β-Lactoglobulin and Its Role on Aggregation and Interfacial Adsorption.

    PubMed

    Beierlein, Frank R; Clark, Timothy; Braunschweig, Björn; Engelhardt, Kathrin; Glas, Lena; Peukert, Wolfgang

    2015-04-30

    We report a combined experimental and computational study of the whey protein β-lactoglobulin (BLG) in different electrolyte solutions. Vibrational sum-frequency generation (SFG) and ellipsometry were used to investigate the molecular structure of BLG modified air-water interfaces as a function of LiCl, NaCl, and KCl concentrations. Molecular dynamics (MD) simulations and thermodynamic integration provided details of the ion pairing of protein surface residues with alkali-metal cations. Our results at pH 6.2 indicate that BLG at the air-water interface forms mono- and bilayers preferably at low and high ionic strength, respectively. Results from SFG spectroscopy and ellipsometry are consistent with intimate ion pairing of alkali-metal cations with aspartate and glutamate carboxylates, which is shown to be more effective for smaller cations (Li(+) and Na(+)). MD simulations show not only carboxylate-alkali-metal ion pairs but also ion multiplets with the alkali-metal ion in a bridging position between two or more carboxylates. Consequently, alkali-metal cations can bridge carboxylates not only within a monomer but also between monomers, thus providing an important dimerization mechanism between hydrophilic surface patches. PMID:25825918

  10. Comparative Enzymology in the Alkaline Phosphatase Superfamily to Determine the Catalytic Role of an Active Site Metal Ion

    PubMed Central

    Zalatan, Jesse G.; Fenn, Timothy D.; Herschlag, Daniel

    2009-01-01

    Mechanistic models for biochemical systems are frequently proposed from structural data. Site-directed mutagenesis can be used to test the importance of proposed functional sites, but these data do not necessarily indicate how these sites contribute to function. Herein we apply an alternative approach to the catalytic mechanism of alkaline phosphatase (AP), a widely-studied, prototypical bimetallo enzyme. A third metal ion site in AP has been suggested to provide general base catalysis, but comparison with an evolutionarily-related enzyme casts doubt on this model. Removal of this metal site from AP has large differential effects on reactions of cognate and promiscuous substrates, and the results are inconsistent with general base catalysis. Instead, these and additional results suggest that the third metal ion stabilizes the transferred phosphoryl group in the transition state. These results establish a new mechanistic model for this prototypical bimetallo enzyme and demonstrate the power of a comparative approach for probing biochemical function. PMID:18851975

  11. Novel Metal Ion Based Estrogen Mimics for Molecular Imaging

    SciTech Connect

    Rajagopalan, Raghavan

    2006-01-30

    The overall objective of the SBIR Phase I proposal is to prepare and evaluate a new class of {sup 99m}Tc or {sup 94m}Tc containing estrogen-like small molecules ('estrogen mimics') for SPECT or PET molecular imaging of estrogen receptor positive (ER+) tumors. In this approach, the metal ion is integrated into the estrone skeleton by isosteric substitution of a carbon atom in the steroidal structure to give new class of mimics that are topologically similar to the native estrogen (Fig. 1). Although both N{sub 2}S{sub 2} and N{sub 3}S mimics 1 and 2 were considered as target structures, molecular modeling study revealed that the presence of the acetyl group at position-15 in the N{sub 3}S mimic 2 causes steric hinderance toward binding of 2 to SHBG. Therefore, initial efforts were directed at the synthesis and evaluation of the N{sub 2}S{sub 2} mimic 1.

  12. Regulation of the divalent metal ion transporter via membrane budding

    PubMed Central

    Mackenzie, KimberlyD; Foot, Natalie J; Anand, Sushma; Dalton, Hazel E; Chaudhary, Natasha; Collins, Brett M; Mathivanan, Suresh; Kumar, Sharad

    2016-01-01

    The release of extracellular vesicles (EVs) is important for both normal physiology and disease. However, a basic understanding of the targeting of EV cargoes, composition and mechanism of release is lacking. Here we present evidence that the divalent metal ion transporter (DMT1) is unexpectedly regulated through release in EVs. This process involves the Nedd4-2 ubiquitin ligase, and the adaptor proteins Arrdc1 and Arrdc4 via different budding mechanisms. We show that mouse gut explants release endogenous DMT1 in EVs. Although we observed no change in the relative amount of DMT1 released in EVs from gut explants in Arrdc1 or Arrdc4 deficient mice, the extent of EVs released was significantly reduced indicating an adaptor role in biogenesis. Furthermore, using Arrdc1 or Arrdc4 knockout mouse embryonic fibroblasts, we show that both Arrdc1 and Arrdc4 are non-redundant positive regulators of EV release. Our results suggest that DMT1 release from the plasma membrane into EVs may represent a novel mechanism for the maintenance of iron homeostasis, which may also be important for the regulation of other membrane proteins. PMID:27462458

  13. Interaction between ATP, metal ions, glycine, and several minerals

    NASA Technical Reports Server (NTRS)

    Rishpon, J.; Ohara, P. J.; Lawless, J. G.; Lahav, N.

    1982-01-01

    Interactions between ATP, glycine and montmorillonite and kaolinite clay minerals in the presence of various metal cations are investigated. The adsorption of adenine nucleotides on clays and Al(OH)3 was measured as a function of pH, and glycine condensation was followed in the presence of ATP, ZnCl2, MgCl2 and either kaolinite or montmorillonite. The amounts of ATP and ADP adsorbed are found to decrease with increasing Ph, and to be considerably enhanced in experiments with Mg(2+)- and Zn(2+)-montmorillonite with respect to Na(+)-montmorillonite. The effects of divalent cations are less marked in kaolinite. Results for Al(OH)3 show the importance of adsorption at clay platelet edges at high pH. The decomposition of ATP during drying at high temperature is observed to be inhibited by small amounts of clay, vacuum, or Mg(2+) or Zn(2+) ions, and to be accompanied by peptide formation in the presence of glycine. Results suggest the importance of Zn(2+) and Mg(2+) in chemical evolution.

  14. Phytochelatin Modified Electrode Surface as a Sensitive Heavy-Metal Ion Biosensor

    PubMed Central

    Adam, Vojtech; Zehnalek, Josef; Petrlova, Jitka; Potesil, David; Sures, Bernd; Trnkova, Libuse; Jelen, Frantisek; Vitecek, Jan; Kizek, Rene

    2005-01-01

    Electrochemical biosensors have superior properties over other existing measurement systems because they can provide rapid, simple and low-cost on-field determination of many biological active species and a number of dangerous pollutants. In our work, we suggested a new heavy metal biosensor based on interaction of heavy metal ions (Cd2+ and Zn2+) with phytochelatin, which was adsorbed on the surface of the hanging mercury drop electrode, using adsorptive transfer stripping differential pulse voltammetry. In addition, we applied the suggested technique for the determination of heavy metals in a biological sample – human urine and platinum in a pharmaceutical drug. The detection limits (3 S/N) of Cd(II), Zn(II) and cis-platin were about 1.0, 13.3 and 1.9 pmole in 5 μl, respectively. On the basis of the obtained results, we propose that the suggested technique offers simple, rapid, and low-cost detection of heavy metals in environmental, biological and medical samples.

  15. Ethylene sulfite as electrolyte additive for lithium-ion cells with graphitic anodes

    SciTech Connect

    Wrodnigg, G.H.; Besenhard, J.O.; Winter, M.

    1999-02-01

    A liquid organic electrolyte system for lithium-ion cells with graphitic anodes containing the solvents ethylene sulfite (ES) and propylene carbonate (PC) has been studied. Even in additive amounts (5 vol %) ES is suppressing cointercalation of PC into graphite. The PC-ES electrolytes are characterized by a high oxidation stability allowing the cycling of a LiMn{sub 2}O{sub 4} cathode with good reversibility. Moreover, the good low temperature performance compared to ethylene carbonate-dimethyl carbonate electrolytes may favor PC-ES electrolytes for special applications.

  16. Structures and energetics of complexation of metal ions with ammonia, water, and benzene: A computational study.

    PubMed

    Sharma, Bhaskar; Neela, Y Indra; Narahari Sastry, G

    2016-04-30

    Quantum chemical calculations have been performed at CCSD(T)/def2-TZVP level to investigate the strength and nature of interactions of ammonia (NH3 ), water (H2 O), and benzene (C6 H6 ) with various metal ions and validated with the available experimental results. For all the considered metal ions, a preference for C6 H6 is observed for dicationic ions whereas the monocationic ions prefer to bind with NH3 . Density Functional Theory-Symmetry Adapted Perturbation Theory (DFT-SAPT) analysis has been employed at PBE0AC/def2-TZVP level on these complexes (closed shell), to understand the various energy terms contributing to binding energy (BE). The DFT-SAPT result shows that for the metal ion complexes with H2 O electrostatic component is the major contributor to the BE whereas, for C6 H6 complexes polarization component is dominant, except in the case of alkali metal ion complexes. However, in case of NH3 complexes, electrostatic component is dominant for s-block metal ions, whereas, for the d and p-block metal ion complexes both electrostatic and polarization components are important. The geometry (M(+) -N and M(+) -O distance for NH3 and H2 O complexes respectively, and cation-π distance for C6 H6 complexes) for the alkali and alkaline earth metal ion complexes increases down the group. Natural population analysis performed on NH3 , H2 O, and C6 H6 complexes shows that the charge transfer to metal ions is higher in case of C6 H6 complexes. PMID:26833683

  17. Effects of soil water content and organic matter addition on the speciation and bioavailability of heavy metals.

    PubMed

    Hernandez-Soriano, Maria C; Jimenez-Lopez, Jose C

    2012-04-15

    The mobility and bioavailability of cadmium, copper, lead and zinc were evaluated in three soils amended with different organic materials for two moisture regimes. Agricultural and reclamation activities impose fresh inputs of organic matter on soil while intensive irrigation and rainstorm increase soil waterlogging incidence. Moreover, scarcity of irrigation water has prompted the use of greywater, which contain variable concentrations of organic compounds such as anionic surfactants. Soils added with hay, maize straw or peat at 1% w/w were irrigated, at field capacity (FC) or saturated (S), with an aqueous solution of the anionic surfactant Aerosol 22 (A22), corresponding to an addition of 200 mgC/kgsoil/day. Soil solution was extracted after one month and analysed for total soluble metals, dissolved soil organic matter and UV absorbance at 254 nm. Speciation analyses were performed with WHAM VI for Cd, Cu, Pb, and Zn. For selected scenarios, metal uptake by barley was determined. Metal mobility increased for all treatments and soils (Pb>Cu>Cd≥Zn) compared to control assays. The increase was significantly correlated (p<0.05) with soil organic matter solubilisation for Cd (R=0.68), Cu (R=0.73) and Zn (R=0.86). Otherwise, Pb release was related to aluminium solubilisation (R=0.75), which suggests that Pb was originally co-precipitated with Al-DOC complexes in the solid phase. The effect of A22 in metal bioavailability, determined as free ion activities (FIA), was mainly controlled by soil moisture regime. For soil 3, metal bioavailability was up to 20 times lower for soil amended with hay, peat or maize compared to soil treated only with A22. When soil was treated with A22 at FC barley yield significantly decreased (p<0.05) for the increase of Pb (R=0.71) and Zn (R=0.79) concentrations in shoot, while for saturated conditions such uptake was up to 3 times lower. Overall, metal bioavailability was controlled by solubilisation of soil organic matter and formation

  18. Injection of metallic elements into an electron-beam ion trap using a Knudsen cell

    SciTech Connect

    Yamada, C.; Nagata, K.; Nakamura, N.; Ohtani, S.; Takahashi, S.; Tobiyama, T.; Tona, M.; Watanabe, H.; Yoshiyasu, N.; Sakurai, M.; Kavanagh, A. P.; Currell, F. J.

    2006-06-15

    A method of injecting metallic elements into an electron-beam ion trap (EBIT) is described. The method is advantageous over the conventional coaxial and pulsed injection methods in two ways: (a) complicated switching of injection and extraction beams can be avoided when extracting beams of highly charged ions from the EBIT and (b) a beam of stable intensity can be achieved. This method may be applicable to any metallic elements or metallic compounds that have vapor pressures of {approx}0.1 Pa at a temperature lower than 1900 deg. C. We have employed this method for the extraction of highly charged ions of Bi, Er, Fe, and Ho.

  19. Determination of metal ions by fluorescence anisotropy exhibits a broad dynamic range

    NASA Astrophysics Data System (ADS)

    Thompson, Richard B.; Maliwal, Badri P.; Fierke, Carol A.

    1998-05-01

    Recently, we have shown that metal ions free in solution may be determined at low levels by fluorescence anisotropy (polarization) measurements. Anisotropy measurements enjoy the advantages of wavelength ratiometric techniques for determining metal ions such as calcium, because anisotropy measurements are ratiometric as well. Furthermore, fluorescence anisotropy may be imaged in the microscope. An advantage of anisotropy not demonstrated for wavelength ratiometric approaches using indicators such as Fura-2 and Indo-1 is that under favorable circumstances anisotropy-based determinations exhibit a much broader dynamic range in metal ion concentration. Determinations of free Zn(II) in the picomolar range are demonstrated.

  20. Sono-electrochemical recovery of metal ions from their aqueous solutions.

    PubMed

    Dong, Bingfeng; Fishgold, Asher; Lee, Paul; Runge, Keith; Deymier, Pierre; Keswani, Manish

    2016-11-15

    Metal recovery from aqueous waste streams is an important goal for recycling, agriculture and mining industries. The development of more effective methods of recovery have been of increasing interest. The most common methods for metal recovery include precipitation, electrochemical, ion exchange, flocculation/coagulation and filtration. In the current work, a sono-electrochemical technique employing sound field at megasonic frequency (500kHz or 1MHz) in conjunction with electrochemistry is evaluated for enhanced recovery of selected metal ions (palladium, lead and gallium) with different redox potentials from their aqueous solutions. The surface morphology and elemental composition of the metal deposits were characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The percent recovery was found to depend on the type of metal ion and the megasonic frequency used. Palladium was recovered in its metal form, while lead and gallium were oxidized during or after the recovery process. PMID:27450329

  1. Metal-ceramic microstructures in the Fe-Mn-O system -- Morphology control by impurity addition

    SciTech Connect

    Subramanian, R.; Uestuendag, E.; Sass, S.L.; Dieckmann, R.

    1995-10-01

    The influence of the addition of impurities and changes in the oxygen partial pressure on the formation of metal-ceramic microstructures by partial reduction of ternary or higher ceramic oxides was experimentally investigated in the model system Fe-Mn-O at constant temperature and total pressure. Electron microscopy studies were performed for microstructural characterization, phase identification and chemical analysis. It was observed that the addition of dopants such as BaO, CaO, MgO, SrO, Al{sub 2}O{sub 3}, Cr{sub 2}O{sub 3} or ZrO{sub 2} to the initial, polycrystalline oxide solid solution (Fe{sub 1{minus}x}Mn{sub x}){sub 1{minus}{Delta}}O strongly influences the location and rate of metal precipitation during reduction. Experimental observations are discussed based on solubility limits and the segregation of dopants.

  2. Remediation of metal polluted soils by phytorremediation combined with biochar addition

    NASA Astrophysics Data System (ADS)

    Méndez, Ana; Paz-Ferreiro, Jorge; Gómez-Limón, Dulce; César Arranz, Julio; Saa, Antonio; Gascó, Gabriel

    2016-04-01

    The main objective of this work is to optimize and quantify the treatment of metal polluted soils through phytoremediation techniques combined with the addition of biochar. Biochar is a carbon rich material obtained by thermal treatment of biomass in inert atmosphere. In recent years, it has been attracted considerable interest due to their positive effect after soil addition. The use of biochar also seems appropriate for the treatment of metal-contaminated soils decreasing their mobility. Biochar properties highly depend on the raw material composition and manufacturing conditions. This paper is based on the use of manure wastes, rich in nutrients and therefore interesting raw materials for biochar production, especially when combined with phytoremediation techniques since the biochar act as conditioner and slow release fertilizer. We are very grateful to Ministerio de Economia y Competitividad (Spain) for financial support under Project CGL2014-58322-R.

  3. Donnan dialysis of bromocomplexes of some platinum group metal ions

    SciTech Connect

    Brajter, K.; Slonawska, K. ); Cox, J.A. )

    1989-03-01

    The separation of bromocomplexes of platinum group metals by Donnan dialysis is demonstrated with both anion and cation exchange membranes. The inclusion of ethylenediamine (en) in the sample improves the separation of Pd(II) from Pt(IV) with experiments performed with an anion exchange membrane and decreases the amount of metal retained on the membrane phase. With a cation exchange membrane, the addition of a ligand such as en is required for transport. With 5.6 mM en in the sample at pH 10, 74% of Pd(II) is transported across an anion exchange membrane into 0.5 M NH{sub 4} Br after 6 hours while only 8% of the Pt(IV) is dialyzed. Rhodium(III) and iridium(III) behave like Pt(IV). Using a cation exchange membrane under the same conditions except with a 1 hour dialysis results in a 30-fold preferential preconcentration of Pd(II) relative to Pt(IV), and, based on the amount retained in the membrane, a preconcentration of Ir(III) which exceeds that of Pd(II) and Pt(IV) by factors of 40 and 20, respectively.

  4. Metal-Catalyzed β-Functionalization of Michael Acceptors through Reductive Radical Addition Reactions.

    PubMed

    Streuff, Jan; Gansäuer, Andreas

    2015-11-23

    Transition-metal-catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β-unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today's developments. PMID:26471460

  5. Review: Formation of Peptide Radical Ions Through Dissociative Electron Transfer in Ternary Metal-Ligand-Peptide Complexes

    SciTech Connect

    Chu, Ivan K.; Laskin, Julia

    2011-12-31

    The formation and fragmentation of odd-electron ions of peptides and proteins is of interest to applications in biological mass spectrometry. Gas-phase redox chemistry occurring during collision-induced dissociation of ternary metal-ligand-peptide complexes enables the formation of a variety of peptide radicals including the canonical radical cations, M{sup +{sm_bullet}}, radical dications, [M{sup +}H]{sup 2+{sm_bullet}}, radical anions, [M-2H]{sup -{sm_bullet}}. In addition, odd-electron peptide ions with well-defined initial location of the radical site are produced through side chain losses from the radical ions. Subsequent fragmentation of these species provides information on the role of charge and the location of the radical site on the competition between radical-induced and proton-driven fragmentation of odd-electron peptide ions. This account summarizes current understanding of the factors that control the efficiency of the intramolecular electron transfer (ET) in ternary metal-ligand-peptide complexes resulting in formation of odd-electron peptide ions. Specifically, we discuss the effect of the metal center, the ligand and the peptide structure on the competition between the ET, proton transfer (PT), and loss of neutral peptide and neutral peptide fragments from the complex. Fundamental studies of the structures, stabilities, and the energetics and dynamics of fragmentation of such complexes are also important for detailed molecular-level understanding of photosynthesis and respiration in biological systems.

  6. Cytotoxicity of Metal Ions Released from Nitinol Alloys on Endothelial Cells

    NASA Astrophysics Data System (ADS)

    Haider, W.; Munroe, N.; Tek, V.; Gill, P. K. S.; Tang, Y.; McGoron, A. J.

    2011-07-01

    Most implantable medical devices are expected to function in the body over an extended period of time. Therefore, immersion tests under simulated conditions can be useful for assessing the amount of metal ions released in situ. In this investigation, dissolved ions from as-received binary and ternary Nitinol alloys in cell culture media were periodically measured under static and dynamic conditions. Endothelial cells were grown in aliquots of culture media obtained and the effect of dissolved ions on cell proliferation and viability of endothelial cells (HUVEC) was studied by cytotoxicity assays. The concentration of metal ions in the media was measured by inductively coupled plasma mass spectrometry.

  7. Plastic flow produced by single ion impacts on metals.

    SciTech Connect

    Birtcher, R. C.

    1998-10-30

    Single ion impacts have been observed using in situ transmission electron microscopy and video recording with a time resolution of 33 milliseconds. Gold was irradiated at 50 K and room temperature. Single ion impacts produce holes, modify existing holes, and extrude material into the initial specimen hole and holes formed by other ion impacts. The same behavior is observed at both temperatures. At both temperatures, ion impacts result in craters and ejected material. Ion impacts produce more small craters than large ones for all ion masses, while heavier mass ions produce more and larger craters than lighter mass ions. This comparison is affected by the ion energy. As the energy of an ion is increased, the probability for deposition near the surface decreases and fewer craters are formed. For a given ion mass, crater production depends on the probability for displacement cascade production in the near surface region. Crater and holes are stable at room temperature, however, ion impacts near an existing crater may cause flow of material into the crater either reshaping or annihilating it. Holes and craters result from the explosive outflow of material from the molten zone of near-surface cascades. The outflow may take the form of molten material, a solid lid or an ejected particle. The surface is a major perturbation on displacement cascades resulting from ion impacts.

  8. Metal ion-dependent, reversible, protein filament formation by designed beta-roll polypeptides

    PubMed Central

    Scotter, Andrew J; Guo, Meng; Tomczak, Melanie M; Daley, Margaret E; Campbell, Robert L; Oko, Richard J; Bateman, David A; Chakrabartty, Avijit; Sykes, Brian D; Davies, Peter L

    2007-01-01

    Background A right-handed, calcium-dependent β-roll structure found in secreted proteases and repeat-in-toxin proteins was used as a template for the design of minimal, soluble, monomeric polypeptides that would fold in the presence of Ca2+. Two polypeptides were synthesised to contain two and four metal-binding sites, respectively, and exploit stacked tryptophan pairs to stabilise the fold and report on the conformational state of the polypeptide. Results Initial analysis of the two polypeptides in the presence of calcium suggested the polypeptides were disordered. The addition of lanthanum to these peptides caused aggregation. Upon further study by right angle light scattering and electron microscopy, the aggregates were identified as ordered protein filaments that required lanthanum to polymerize. These filaments could be disassembled by the addition of a chelating agent. A simple head-to-tail model is proposed for filament formation that explains the metal ion-dependency. The model is supported by the capping of one of the polypeptides with biotin, which disrupts filament formation and provides the ability to control the average length of the filaments. Conclusion Metal ion-dependent, reversible protein filament formation is demonstrated for two designed polypeptides. The polypeptides form filaments that are approximately 3 nm in diameter and several hundred nm in length. They are not amyloid-like in nature as demonstrated by their behaviour in the presence of congo red and thioflavin T. A capping strategy allows for the control of filament length and for potential applications including the "decoration" of a protein filament with various functional moieties. PMID:17908326

  9. Metal ion levels and functional results after either resurfacing hip arthroplasty or conventional metal-on-metal hip arthroplasty

    PubMed Central

    2011-01-01

    Background Modern metal-on-metal hip resurfacing was introduced as a bone-preserving method of joint reconstruction for young and active patients; however, the large diameter of the bearing surfaces is of concern for potentially increased metal ion release. Patients and methods 71 patients (< 65 years old) were randomly assigned to receive either a resurfacing (R) hip arthroplasty (n = 38) or a conventional metal-on-metal (C) hip arthroplasty (n = 33). Functional outcomes were assessed preoperatively and at 6, 12, and 24 months. Cobalt and chromium blood levels were analyzed preoperatively and at 3, 6, 12, and 24 months. Results All functional outcome scores improved for both groups. At 12 and 24 months, the median UCLA activity score was 8 in the R patients and 7 in the C patients (p < 0.05). At 24 months, OHS was median 16 in C patients and 13 in R patients (p < 0.05). However, in spite of randomization, UCLA scores also appeared to be higher in R patients at baseline. Satisfaction was similar in both groups at 24 months. Cobalt concentrations were statistically significantly higher for R patients only at 3 and 6 months. Chromium levels remained significantly higher for R patients until 24 months. No pseudotumors were encountered in either group. One R patient was revised for early aseptic loosening and in 2 C patients a cup insert was exchanged for recurrent dislocation. Interpretation R patients scored higher on UCLA, OHS, and satisfaction at some time points; however, as for the UCLA, preoperative levels were already in favor of R. The differences, although statistically significant, were of minor clinical importance. Chromium blood levels were statistically significantly higher for R patients at all follow-up measurements, whereas for cobalt this was only observed up to 6 months. The true value of resurfacing hip arthroplasty over conventional metal-on-metal hip arthroplasty will be determined by longer follow-up and a possible shift of balance between their

  10. Statistical evaluation of biogeochemical variables affecting spatiotemporal distributions of multiple free metal ion concentrations in an urban estuary.

    PubMed

    Dong, Zhao; Lewis, Christopher G; Burgess, Robert M; Coull, Brent; Shine, James P

    2016-05-01

    Free metal ion concentrations have been recognized as a better indicator of metal bioavailability in aquatic environments than total dissolved metal concentrations. However, our understanding of the determinants of free ion concentrations, especially in a metal mixture, is limited, due to underexplored techniques for measuring multiple free metal ions simultaneously. In this work, we performed statistical analyses on a large dataset containing repeated measurements of free ion concentrations of Cu, Zn, Pb, Ni, and Cd, the most commonly measured metals in seawater, at five inshore locations in Boston Harbor, previously collected using an in-situ equilibrium-based multi-metal free ion sampler, the 'Gellyfish'. We examined correlations among these five metals by season, and evaluated effects of 10 biogeochemical variables on free ion concentrations over time and location through multivariate regressions. We also explored potential clustering among the five metals through a principal component analysis. We found significant correlations among metals, with varying patterns over season. Our regression results suggest that instead of dissolved metals, pH, salinity, temperature and rainfall were the most significant determinants of free metal ion concentrations. For example, a one-unit decrease in pH was associated with a 2.2 (Cd) to 99 (Cu) times increase in free ion concentrations. This work is among the first to reveal key contributors to spatiotemporal variations in free ion concentrations, and demonstrated the usefulness of the Gellyfish sampler in routine sampling of free ions within metal mixtures and in generating data for statistical analyses. PMID:26901477

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

    SciTech Connect

    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.

  12. Visualizing metal ions in cells: an overview of analytical techniques, approaches, and probes

    PubMed Central

    Dean, Kevin M.; Qin, Yan; Palmer, Amy E.

    2012-01-01

    Quantifying the amount and defining the location of metal ions in cells and organisms are critical steps in understanding metal homeostasis and how dyshomeostasis causes or is a consequence of disease. A number of recent advances have been made in the development and application of analytical methods to visualize metal ions in biological specimens. Here, we briefly summarize these advances before focusing in more depth on probes for examining transition metals in living cells with high spatial and temporal resolution using fluorescence microscopy. PMID:22521452

  13. Method and apparatus for providing negative ions of actinide-metal hexafluorides

    DOEpatents

    Compton, Robert N.; Reinhardt, Paul W.; Garrett, William R.

    1978-01-01

    This invention relates to a novel method and a novel generator, or source, for providing gaseous negative ions of selected metal hexafluorides. The method is summarized as follows: in an evacuated zone, reacting gaseous fluorine with an actinide-metal body selected from the group consisting of uranium, plutonium, neptunium, and americium to convert at least part of the metal to the hexafluoride state, thus producing gaseous negatively charged metal-hexafluoride ions in the evacuated zone, and applying an electric field to the zone to remove the ions therefrom. The ion source comprises a chamber defining a reaction zone; means for evacuating the zone; an actinide-metal body in the zone, the metal being uranium, plutonium, neptunium, or americium; means for contacting the body with gaseous fluorine to convert at least a part thereof to the hexafluoride state; and means for applying an electric field to the evacuated zone to extract gaseous, negatively charged metal-hexafluoride ions therefrom. The invention provides unique advantages over conventional surface-ionization techniques for producing such ions.

  14. Hybrid gas-metal co-implantation with a modified vacuum arc ion source

    SciTech Connect

    Oks, E.M.; Yushkov, G.Y.; Evans, P.J.; Oztarhan, A.; Brown, I.G.; Dickinson, M.R.; Liu, F.; MacGill, R.A.; Monteiro, O.R.; Wang, Z.

    1996-08-01

    Energetic beams of mixed metal and gaseous ion species can be generated with a vacuum arc ion source by adding gas to the arc discharge region. This could be an important tool for ion implantation research by providing a method for forming buried layers of mixed composition such as e.g. metal oxides and nitrides. In work to date, we have formed a number of mixed metal-gas ion beams including Ti+N, Pt+N, Al+O, and Zr+O. The particle current fractions of the metal-gas ion components in the beam ranged from 100% metallic to about 80% gaseous, depending on operational parameters. We have used this new variant of the vacuum arc ion source to carry out some exploratory studies of the effect of Al+O and Zr+O co-implantation on tribology of stainless steel. Here we describe the ion source modifications, species and charge state of the hybrid beams produced, and results of preliminary studies of surface modification of stainless steel by co-implantation of mixed Al/O or Zr/O ion beams. 5 figs, 21 refs.

  15. Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue

    DOEpatents

    Sharp, David W.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about 249.degree. F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  16. Metal ions bound to the human milk immunoglobulin A: metalloproteomic approach.

    PubMed

    Pozzi, Carla Mariane Costa; Braga, Camila Pereira; Vieira, José Cavalcante Souza; Cavecci, Bruna; Vitor de Queiroz, João; de Souza Barbosa, Herbert; Arruda, Marco Aurelio Zezzi; Gozzo, Fabio Cesar; Padilha, Pedro de Magalhães

    2015-01-01

    The presence of calcium, iron, and zinc bound to human milk secretory IgA (sIgA) was investigated. The sIgA components were first separated by two-dimensional polyacrylamide gel electrophoresis and then identified by electrospray ionization-tandem mass spectrometry (ESI MS MS). The metal ions were detected by flame atomic absorption spectrometry after acid mineralization of the spots. The results showed eight protein spots corresponding to the IgA heavy chain constant region. Another spot was identified as the transmembrane secretory component. Calcium was bound to both the transmembrane component and the heavy chain constant region, while zinc was bound to the heavy chain constant region and iron was not bound with the identified proteins. The association of a metal ion with a protein is important for a number of reasons, and therefore, the findings of the present study may lead to a better understanding of the mechanisms of action and of additional roles that sIgA and its components play in human milk. PMID:25053085

  17. Negative ion production by backscattering from alkali-metal surfaces bombarded by ions of hydrogen and deuterium

    SciTech Connect

    Schneider, P.J.

    1980-03-01

    Measurements have been made of the total backscattered D/sup -/ and H/sup -/ yields from thick, clean targets of Cs, Rb, K, Na, and Li, bombarded with H/sub 2//sup +/, H/sub 3//sup +/, D/sub 2//sup +/, and D/sub 3//sup +/ with incident energies from 0.15 to 4.0 keV/nucleus. All of the measurements were made at background pressures less than 10/sup -9/ Torr and the alkali-metal targets were evaporated onto a cold substrate (T = 77K) in situ to assure thick, uncontaminated targets. Measurements of the H/sup -/ yield from various transition metal targets with thin coverages of alkali-metals have also been made as a function of the surface work function. The negative ion yields are discussed in terms of the probabilities of reflection of the incident particles, of formation of the negative ion at the surface and of the survival of the negative ion leaving the surface. For each thick alkali-metal target, the negative ion yield measurements have been used in a least squares fit to determine two parameters in a theoretically derived expression for the negative ion yield. The parameters obtained from a thick Na target have been used to calculate the yield from a Cu target with thin coverage of Na (such that the surface work function is equal to thick Na).

  18. Adsorptions of some heavy metal ions in aqueous solutions by acrylamide/maleic acid hydrogels

    SciTech Connect

    Saraydin, D.; Karadag, E.; Gueven, O.

    1995-10-01

    In this study, acrylamide-maleic acid (AAm/MA) hydrogels in the form of rod have been prepared by {gamma}-radiation. They have been used for adsorption of some heavy metal ions such as uranium, iron, and copper. For the hydrogel containing 40 mg of maleic acid and irradiated at 3.73 kGy, maximum and minimum swellings in the aqueous solutions of the heavy metal ions have been observed with water (1480%) and the aqueous solution of iron(III) nitrate (410%), respectively. Diffusions of water and heavy metal ions onto hydrogels have been found to be of the non-Fickian type of diffusion. In experiments of uranyl ions adsorption, Type II adsorption has been found. One gram of AAa/MA hydrogels sorbed 14-86 mg uranyl ions from solutions of uranyl acetate, 14-90 mg uranyl ions from solutions of uranyl nitrate, 16-39 mg iron ions from solutions of iron(IV) nitrate, and 28-81 mg copper ions from solutions of copper acetate, while acrylamide hydrogel did not sorb any heavy metals ions.

  19. Structure Determination of Noble Metal Clusters by Trapped Ion Electron Diffraction

    NASA Astrophysics Data System (ADS)

    Schooss, Detlef

    2006-03-01

    The structures of noble metal cluster ions have been studied by the recently developed technique of trapped ion electron diffraction (TIED)^1. In brief, cluster ions are generated by a magnetron sputter source and injected into a cooled (95 K) quadrupole ion trap. After mass selection and thermalization, the trapped ions are irradiated with a 40 keV electron beam. The resulting diffraction pattern is integrated with a CCD detector. The assignment of the structural motif is done via a comparison of the experimental and simulated scattering function, calculated from density functional theory structure calculations. The structures of mass selected silver cluster cations Ag19^+, Ag38^+, Ag55^+, Ag59^+, Ag75^+ and Ag79^+ have been investigated^2. The resulting experimental data are best described by structures based on the icosahedral motif, while closed packed structures could be ruled out. Additionally, we present a comparison of the structures of Cu20^+/-, Ag20^+/- and Au20^+/-. Our findings show unambiguously that the structure of Au20^- is predominantly given by a tetrahedron in agreement with the results of L.S. Wang et al.^3 In contrast, structures of Ag20^- and Cu20^- based on the icosahedral motif agree best with the experimental data. Small structural differences between the charge states are observed. The possibilities and limitations of the TIED method are discussed. (1) M. Maier-Borst, D. B. Cameron, M. Rokni, and J. H. Parks, Physical Review A 59 (5), R3162 (1999); S. Krückeberg, D. Schooss, M. Maier-Borst, and J. H. Parks, Physical Review Letters 85 (21), 4494 (2000). (2) D. Schooss, M.N. Blom, B. v. Issendorff, J. H. Parks, and M.M. Kappes, Nano Letters 5 (10), 1972 (2005). (3) J. Li, X. Li, H. J. Zhai, and L. S. Wang, Science 299, 864 (2003)

  20. Removing adsorbed heavy metal ions from sand surfaces via applying interfacial properties of rhamnolipid.

    PubMed

    Haryanto, Bode; Chang, Chien-Hsiang

    2015-01-01

    In this study, the interfacial properties of biosurfactant rhamnolipid were investigated and were applied to remove adsorbed heavy metal ions from sand surfaces with flushing operations. The surface tension-lowering activity, micelle charge characteristic, and foaming ability of rhamnolipid were identified first. For rhamnolipid in water, the negatively charged characteristic of micelles or aggregates was confirmed and the foaming ability at concentrations higher than 40 mg/L was evaluated. By using the rhamnolipid solutions in a batch washing approach, the potential of applying the interfacial properties of rhamnolipid to remove adsorbed copper ions from sand surfaces was then demonstrated. In rhamnolipid solution flushing operations for sand-packed medium, higher efficiency was found for the removal of adsorbed copper ions with residual type than with inner-sphere interaction type, implying the important role of interaction type between the copper ion and the sand surface in the removal efficiency. In addition, the channeling effect of rhamnolipid solution flow in the sand-packed medium was clearly observed in the solution flushing operations and was responsible for the low removal efficiency with low contact areas between solution and sand. By using rhamnolipid solution with foam to flush the sand-packed medium, one could find that the channeling effect of the solution flow was reduced and became less pronounced with the increase in the rhamnolipid concentration, or with the enhanced foaming ability. With the reduced channeling effect in the flushing operations, the removal efficiency for adsorbed copper ions was significantly improved. The results suggested that the foam-enhanced rhamnolipid solution flushing operation was efficient in terms of surfactant usage and operation time. PMID:25748376