Control of cerium oxidation state through metal complex secondary structures

DOE PAGES

Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; ...

2015-08-11

A series of alkali metal cerium diphenylhydrazido complexes, M x(py) y[Ce(PhNNPh) 4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li + or Na +, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reductionmore » of 1,2-diphenylhydrazine was not observed when M = K +, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce( IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.« less

Radiopharmaceuticals for imaging the heart

DOEpatents

Green, M.A.; Tsang, B.W.

1994-06-28

Radiopharmaceuticals for imaging myocardial tissues are prepared by forming lipophilic, cationic complexes of radioactive metal ions with metal chelating ligands comprising the Schiff base adducts of triamines and tetraamines with optionally substituted salicylaldehydes. The lipophilic, cationic, radioactive complexes of the invention exhibit high uptake and retention in myocardial tissues. Preferred gallium-68(III) complexes in accordance with this invention can be used to image the heart using positron emission tomography. 6 figures.

Electronic structure of the [MNH2]+ (M = Sc-Cu) complexes.

PubMed

Hendrickx, Marc F A; Clima, Sergiu

2006-11-23

B3LYP geometry optimizations for the [MNH2]+ complexes of the first-row transition metal cations (Sc+-Cu+) were performed. Without any exception the ground states of these unsaturated amide complexes were calculated to possess planar geometries. CASPT2 binding energies that were corrected for zero-point energies and including relativistic effects show a qualitative trend across the series that closely resembles the experimental observations. The electronic structures for the complexes of the early and middle transition metal cations (Sc+-Co+) differ from the electronic structures derived for the complexes of the late transition metal cations (Ni+ and Cu+). For the former complexes the relative higher position of the 3d orbitals above the singly occupied 2p(pi) HOMO of the uncoordinated NH2 induces an electron transfer from the 3d shell to 2p(pi). The stabilization of the 3d orbitals from the left to the right along the first-row transition metal series causes these orbitals to become situated below the HOMO of the NH2 ligand for Ni+ and Cu+, preventing a transfer from occurring in the [MNH2]+ complexes of these metal cations. Analysis of the low-lying states of the amide complexes revealed a rather unique characteristic of their electronic structures that was found across the entire series. Rather exceptionally for the whole of chemistry, pi-type interactions were calculated to be stronger than the corresponding sigma-type interactions. The origin of this extraordinary behavior can be ascribed to the low-lying sp2 lone pair orbital of the NH2 ligand with respect to the 3d level.

Metal Cationization Extractive Electrospray Ionization Mass Spectrometry of Compounds Containing Multiple Oxygens

NASA Astrophysics Data System (ADS)

Swanson, Kenneth D.; Spencer, Sandra E.; Glish, Gary L.

2017-06-01

Extractive electrospray ionization is an ambient ionization technique that allows real-time sampling of liquid samples, including organic aerosols. Similar to electrospray ionization, the composition of the electrospray solvent used in extractive electrospray ionization can easily be altered to form metal cationized molecules during ionization simply by adding a metal salt to the electrospray solvent. An increase in sensitivity is observed for some molecules that are lithium, sodium, or silver cationized compared with the protonated molecule formed in extractive electrospray ionization with an acid additive. Tandem mass spectrometry of metal cationized molecules can also significantly improve the ability to identify a compound. Tandem mass spectrometry of lithium and silver cationized molecules can result in an increase in the number and uniqueness of dissociation pathways relative to [M + H]+. These results highlight the potential for extractive electrospray ionization with metal cationization in analyzing complex aerosol mixtures. [Figure not available: see fulltext.

Pentavalent neptunyl ([OΞNpΞO] +) cation–cation interactions in aqueous/polar organic mixed-solvent media

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

Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.

Bonding interactions between polyvalent cations and oxo-anions are well known and characterized by predictably favorable Gibbs energies in solution-phase coordination chemistry. In contrast, interactions between ions of like charge are generally expected to be repulsive and strongly influenced by cation solvation. An exception to this instinctive rule is found in the existence of complexes resulting from interactions of pentavalent actinyl cations ([O≡An≡O] +) with selected polyvalent cations. Such cation–cation complexes have been known to exist since the 1960s, when they were first reported by Sullivan and co-workers. The weak actinyl cation–cation complex, resulting from a bonding interaction between a pentavalentmore » linear dioxo actinyl cation donor and hexavalent actinyl or trivalent/tetravalent metal cation acceptor, has been most commonly seen in media in which water activities are reduced, principally highly-salted aqueous media. Such interactions of pentavalent actinides are of relevance in ongoing research that focuses on advanced nuclear fuel processing systems based on the upper oxidation states of americium. This investigation focuses on exploring the thermodynamic stability of complexes between selected highly-charged metal cations (Al 3+, Sc 3+, Cr 3+, Fe 3+, In 3+ and UO 2+ 2) and the pentavalent neptunyl cation (NpO + 2, whose coordination chemistry is similar to that of AmO + 2 while exhibiting significantly greater oxidation state stability) in aqueous–polar organic mixed-solvents. As a result, the Gibbs energies for the cation–cation complexation reactions are correlated with general features of electrostatic bonding models; the NpO + 2 • Cr 3+ complex exhibits unexpectedly strong interactions that may indicate significant covalency in the cation–cation bonding interaction.« less

Pentavalent neptunyl ([OΞNpΞO] +) cation–cation interactions in aqueous/polar organic mixed-solvent media

DOE PAGES

Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.

2017-06-17

Bonding interactions between polyvalent cations and oxo-anions are well known and characterized by predictably favorable Gibbs energies in solution-phase coordination chemistry. In contrast, interactions between ions of like charge are generally expected to be repulsive and strongly influenced by cation solvation. An exception to this instinctive rule is found in the existence of complexes resulting from interactions of pentavalent actinyl cations ([O≡An≡O] +) with selected polyvalent cations. Such cation–cation complexes have been known to exist since the 1960s, when they were first reported by Sullivan and co-workers. The weak actinyl cation–cation complex, resulting from a bonding interaction between a pentavalentmore » linear dioxo actinyl cation donor and hexavalent actinyl or trivalent/tetravalent metal cation acceptor, has been most commonly seen in media in which water activities are reduced, principally highly-salted aqueous media. Such interactions of pentavalent actinides are of relevance in ongoing research that focuses on advanced nuclear fuel processing systems based on the upper oxidation states of americium. This investigation focuses on exploring the thermodynamic stability of complexes between selected highly-charged metal cations (Al 3+, Sc 3+, Cr 3+, Fe 3+, In 3+ and UO 2+ 2) and the pentavalent neptunyl cation (NpO + 2, whose coordination chemistry is similar to that of AmO + 2 while exhibiting significantly greater oxidation state stability) in aqueous–polar organic mixed-solvents. As a result, the Gibbs energies for the cation–cation complexation reactions are correlated with general features of electrostatic bonding models; the NpO + 2 • Cr 3+ complex exhibits unexpectedly strong interactions that may indicate significant covalency in the cation–cation bonding interaction.« less

Thermodynamics of binding interactions between extracellular polymeric substances and heavy metals by isothermal titration microcalorimetry.

PubMed

Yan, Peng; Xia, Jia-Shuai; Chen, You-Peng; Liu, Zhi-Ping; Guo, Jin-Song; Shen, Yu; Zhang, Cheng-Cheng; Wang, Jing

2017-05-01

Extracellular polymeric substances (EPS) play a crucial role in heavy metal bio-adsorption using activated sludge, but the interaction mechanism between heavy metals and EPS remains unclear. Isothermal titration calorimetry was employed to illuminate the mechanism in this study. The results indicate that binding between heavy metals and EPS is spontaneous and driven mainly by enthalpy change. Extracellular proteins in EPS are major participants in the binding process. Environmental conditions have significant impact on the adsorption performance. Divalent and trivalent cations severely impeded the binding of heavy metal ions to EPS. Electrostatic interaction mainly attributed to competition between divalent cations and heavy metal ions; trivalent cations directly competed with heavy metal ions for EPS binding sites. Trivalent cations were more competitive than divalent cations for heavy metal ion binding because they formed complexing bonds. This study facilitates a better understanding about the interaction between heavy metals and EPS in wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms for organometallic complexes

NASA Astrophysics Data System (ADS)

Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO(exp 2+) transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possibly through a ring-slippage mechanism.

Energy-resolved collision-induced dissociation studies of 1,10-phenanthroline complexes of the late first-row divalent transition metal cations: determination of the third sequential binding energies.

PubMed

Nose, Holliness; Chen, Yu; Rodgers, M T

2013-05-23

The third sequential binding energies of the late first-row divalent transition metal cations to 1,10-phenanthroline (Phen) are determined by energy-resolved collision-induced dissociation (CID) techniques using a guided ion beam tandem mass spectrometer. Five late first-row transition metal cations in their +2 oxidation states are examined including: Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+). The kinetic energy dependent CID cross sections for loss of an intact Phen ligand from the M(2+)(Phen)3 complexes are modeled to obtain 0 and 298 K bond dissociation energies (BDEs) after accounting for the effects of the internal energy of the complexes, multiple ion-neutral collisions, and unimolecular decay rates. Electronic structure theory calculations at the B3LYP, BHandHLYP, and M06 levels of theory are employed to determine the structures and theoretical estimates for the first, second, and third sequential BDEs of the M(2+)(Phen)x complexes. B3LYP was found to deliver results that are most consistent with the measured values. Periodic trends in the binding of these complexes are examined and compared to the analogous complexes to the late first-row monovalent transition metal cations, Co(+), Ni(+), Cu(+), and Zn(+), previously investigated.

Cation-Inhibited Transport of Graphene Oxide Nanomaterials in Saturated Porous Media: The Hofmeister Effects.

PubMed

Xia, Tianjiao; Qi, Yu; Liu, Jing; Qi, Zhichong; Chen, Wei; Wiesner, Mark R

2017-01-17

Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + < K + < Cs + , and those of alkaline earth metal ions followed the order of Mg 2+ < Ca 2+ < Ba 2+ . With batch adsorption experiments and microscopic data, we verified that cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

Bonding and Mobility of Alkali Metals in Helicenes.

PubMed

Barroso, Jorge; Murillo, Fernando; Martínez-Guajardo, Gerardo; Ortíz-Chi, Filiberto; Pan, Sudip; Fernández-Herrera, María A; Merino, Gabriel

2018-06-04

In this work, we analyze the interaction of alkali metal cations with [6]- and [14]helicene and the cation mobility of therein. We found that the distortion of the carbon skeleton is the cause that some of the structures that are local minima for the smallest cations are not energetically stable for K+, Rb+, and Cs+. Also, the most favorable complexes are those where the cation is interacting with two rings forming a metallocene-like structure, except for the largest cation Cs+, where the distortion provoked by the size of the cation desestabilizes the complex. As far as mobility is concerned, the smallest cations, particularly Na+, are the ones that can move most efficiently. In [6]helicene, the mobility is limited by the capture of the cation forming the metallocene-like structure. In larger helicenes, the energy barriers for the cation to move are similar both inside and outside the helix. However, complexes with the cation between two layers are more energetically favored so that the movement will be preferred in that region. The bonding analysis reveals that interactions with no less than 50% of orbitalic contribution are taking place for the series of E+-[6]helicene. Particularly, the complexes of Li+ stand out showing a remarkably orbitalic character bonding (72.5 - 81.6%). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption Equilibrium and Kinetics at Goethite-Water and Related Interfaces

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

Katz, Lynn Ellen

This research study is an important component of a broader comprehensive project, “Geochemistry of Interfaces: From Surfaces to Interlayers to Clusters,” which sought to identify and evaluate the critical molecular phenomena at metal-oxide interfaces that control many geochemical and environmental processes. The primary goal of this research study was to better understand and predict adsorption of metal ions at mineral/water surfaces. Macroscopic data in traditional batch experiments was used to develop predictive models that characterize sorption in complex systems containing a wide range of background solution compositions. Our studies focused on systems involving alkaline earth metal (Mg 2+, Ca 2+,more » Sr 2+, Ba 2+) and heavy metal (Hg 2+, Co 2+, Cd 2+, Cu 2+, Zn 2+, Pb 2+) cations. The anions we selected for study included Cl -, NO 3 -, ClO 4 -, SO 4 2-, CO 3 2- and SeO 3 2- and the background electrolyte cations we examined included (Na +, K +, Rb + and Cs +) because these represent a range of ion sizes and have varying potentials for forming ion-pairs or ternary complexes with the metal ions studied. The research led to the development of a modified titration congruency approach for estimating site densities for mineral oxides such as goethite. The CD-MUSIC version of the surface complexation modeling approach was applied to potentiometric titration data and macroscopic adsorption data for single-solute heavy metals, oxyanions, alkaline earth metals and background electrolytes over a range of pH and ionic strength. The model was capable of predicting sorption in bi-solute systems containing multiple cations, cations and oxyanions, and transition metal cations and alkaline earth metal ions. Incorporation of ternary complexes was required for modeling Pb(II)-Se(IV) and Cd(II)-Se(IV) systems. -Both crystal face contributions and capacitance values were shown to be sensitive to varying specific surface area but were successfully accounted for in the modeling strategy. The insights gained from the macroscopic, spectroscopic and CD-MUSIC modeling developed in this study can be used to guide the implementation of less complex models which may be more applicable to field conditions. The findings of this research suggest that surface complexation models can be used as a predictive tool for fate and transport modeling of metal ions and oxyanions in fresh and saline systems typical of energy production waters and wastewaters.« less

Metal cation controls phosphate release in the myosin ATPase.

PubMed

Ge, Jinghua; Huang, Furong; Nesmelov, Yuri E

2017-11-01

Myosin is an enzyme that utilizes ATP to produce a conformational change generating a force. The kinetics of the myosin reverse recovery stroke depends on the metal cation complexed with ATP. The reverse recovery stroke is slow for MgATP and fast for MnATP. The metal ion coordinates the γ phosphate of ATP in the myosin active site. It is accepted that the reverse recovery stroke is correlated with the phosphate release; therefore, magnesium "holds" phosphate tighter than manganese. Magnesium and manganese are similar ions in terms of their chemical properties and the shell complexation; hence, we propose to use these ions to study the mechanism of the phosphate release. Analysis of octahedral complexes of magnesium and manganese show that the partial charge of magnesium is higher than that of manganese and the slightly larger size of manganese ion makes its ionic potential smaller. We hypothesize that electrostatics play a role in keeping and releasing the abstracted γ phosphate in the active site, and the stronger electric charge of magnesium ion holds γ phosphate tighter. We used stable myosin-nucleotide analog complex and Raman spectroscopy to examine the effect of the metal cation on the relative position of γ phosphate analog in the active site. We found that in the manganese complex, the γ phosphate analog is 0.01 nm further away from ADP than in the magnesium complex. We conclude that the ionic potential of the metal cation plays a role in the retention of the abstracted phosphate. © 2017 The Protein Society.

Metal cation exchange reactions of ore minerals in Fe-Mn crusts of the Marcus Wake Rise (Pacific Ocean) in aqueous-salt solutions

NASA Astrophysics Data System (ADS)

Novikov, G. V.; Bogdanova, O. Yu.; Melnikov, M. E.; Drozdova, A. N.; Lobus, N. V.; Shulga, N. A.

2017-12-01

It is shown that the reaction ability of metal cations of ore minerals in Fe-Mn crusts of the Marcus Wake Rise increases in the following manner: (Co2+ < Cu2+ < Ni2+) < (Mg2+ < Mn2+ < K+ ≈ Ca2+ ≈ Na+). The composition of the exchange complex of the ore minerals is constant and includes these metal cations. Ca2+ and Na+ are major contributors to the exchange capacity of the ore minerals. The capacity of the ore minerals by cations of alkali and base metals is 0.43-0.60 and 2.08-2.70 mg-equiv/g, respectively. The exchange capacity of the ore minerals by cations of base metals increases linearly with the increase in the MnO2 content of the crust and does not depend on the geographical locations of the Marcus Wake guyots.

Notable effects of metal salts on UV-vis absorption spectra of α-, β-, γ-, and δ-tocopheroxyl radicals in acetonitrile solution. The complex formation between tocopheroxyls and metal cations.

PubMed

Mukai, Kazuo; Kohno, Yutaro; Ouchi, Aya; Nagaoka, Shin-ichi

2012-08-02

The measurements of the UV-vis absorption spectra of α-, β-, γ-, and δ-tocopheroxyl (α-, β-, γ-, and δ-Toc(•)) radicals were performed by reacting aroxyl (ArO(•)) radical with α-, β-, γ-, and δ-tocopherol (α-, β-, γ-, and δ-TocH), respectively, in acetonitrile solution including three kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), and Mg(ClO(4))(2)) (MX or MX(2)), using stopped-flow spectrophotometry. The maximum wavelengths (λ(max)) of the absorption spectra of the α-, β-, γ-, and δ-Toc(•) located at 425-428 nm without metal salts increased with increasing concentrations of metal salts (0-0.500 M) in acetonitrile and approached some constant values, suggesting (Toc(•)···M(+) (or M(2+))) complex formations. Similarly, the values of the apparent molar extinction coefficient (ε(max)) increased drastically with increasing concentrations of metal salts in acetonitrile and approached some constant values. The result suggests that the formations of Toc(•) dimers were suppressed by the metal ion complex formations of Toc(•) radicals. The stability constants (K) were determined for Li(+), Na(+), and Mg(2+) complexes of α-, β-, γ-, and δ-Toc(•). The K values increased in the order of NaClO(4) < LiClO(4) < Mg(ClO(4))(2), being independent of the kinds of Toc(•) radicals. Furthermore, the K values increased in the order of δ- < γ- < β- < α-Toc(•) radicals for each metal salt. The alkali and alkaline earth metal salts having a smaller ionic radius of the cation and a larger charge of the cation gave a larger shift of the λ(max) value, a larger ε(max) value, and a larger K value. The result of the DFT molecular orbital calculations indicated that the α-, β-, γ-, and δ-Toc(•) radicals were stabilized by the (1:1) complex formation with metal cations (Li(+), Na(+), and Mg(2+)). Stabilization energy (E(S)) due to the complex formation increased in the order of Na(+) < Li(+) < Mg(2+) complexes, being independent of the kinds of Toc(•) radicals. The calculated result also indicated that the metal cations coordinate to the O atom at the sixth position of α-, β-, γ-, and δ-Toc(•) radicals.

All-metal aromatic cationic palladium triangles can mimic aromatic donor ligands with Lewis acidic cations† †Electronic supplementary information (ESI) available: Reaction procedures, characterization of complexes, copies of all spectra and cif files, modelling details and XYZ coordinates. CCDC 1410440–1410442. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03475j Click here for additional data file. Click here for additional data file.

PubMed Central

Wang, Yanlan; Monfredini, Anna; Deyris, Pierre-Alexandre; Blanchard, Florent; Derat, Etienne; Malacria, Max

2017-01-01

We present that cationic rings can act as donor ligands thanks to suitably delocalized metal–metal bonds. This could grant parent complexes with the peculiar properties of aromatic rings that are crafted with main group elements. We assembled Pd nuclei into equilateral mono-cationic triangles with unhindered faces. Like their main group element counterparts and despite their positive charge, these noble-metal rings form stable bonding interactions with other cations, such as positively charged silver atoms, to deliver the corresponding tetranuclear dicationic complexes. Through a mix of modeling and experimental techniques we propose that this bonding mode is an original coordination-like one rather than a 4-centre–2-electron bond, which have already been observed in three dimensional aromatics. The present results thus pave the way for the use of suitable metal rings as ligands. PMID:29163890

Interactions of trace metals with hydrogels and filter membranes used in DET and DGT techniques.

PubMed

Garmo, Oyvind A; Davison, William; Zhang, Hao

2008-08-01

Equilibrium partitioning of trace metals between bulk solution and hydrogels/filter was studied. Under some conditions, trace metal concentrations were higher in the hydrogels or filter membranes compared to bulk solution (enrichment). In synthetic soft water, enrichment of cationic trace metals in polyacrylamide hydrogels decreased with increasing trace metal concentration. Enrichment was little affected by Ca and Mg in the concentration range typically encountered in natural freshwaters, indicating high affinity but low capacity binding of trace metals to solid structure in polyacrylamide gels. The apparent binding strength decreased in the sequence: Cu > Pb > Ni approximately to Cd approximately to Co and a low concentration of cationic Cu eliminated enrichment of weakly binding trace metal cations. The polyacrylamide gels also had an affinity for fulvic acid and/or its trace metal complexes. Enrichment of cationic Cd in agarose gel and hydrophilic polyethersulfone filter was independent of concentration (10 nM to 5 microM) but decreased with increasing Ca/ Mg concentration and ionic strength, suggesting that it is mainly due to electrostatic interactions. However, Cu and Pb were enriched even after equilibration in seawater, indicating that these metals additionally bind to sites within the agarose gel and filter. Compared to the polyacrylamide gels, agarose gel had a lower affinity for metal-fulvic complexes. Potential biases in measurements made with the diffusive equilibration in thin-films (DET) technique, identified by this work, are discussed.

The role of multivalent metal cations and organic complexing agents in bitumen-mineral interactions in aqueous solutions

NASA Astrophysics Data System (ADS)

Gan, Weibing

A systematic investigation was carried out to study the interactions between bitumen (or hexadecane) and minerals (quartz, kaolinite and illite) in aqueous solutions containing multivalent metal cations Ca2+, Mg2+ and Fe2+/Fe3+, in the absence and presence of organic complexing agents (oxalic acid, EDTA and citric acid). A range of experimental techniques, including coagulation measurement, visualization of bitumen-mineral attachment, metal ion adsorption measurement, zeta potential measurement, Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopic analyses, were employed in the investigation. Free energy changes of adsorption of metal cations on the minerals and bitumen were evaluated using the James & Healy thermodynamic model. Total interaction energies between the minerals and bitumen were calculated using classical DLVO theory. It was observed that while the tested minerals showed varying degrees of mutual-coagulation with bitumen (or hexadecane), the presence of the multivalent metal cations could prominently increase the mutual coagulation. It was also found that such enhancement of the mutual coagulation was only significant when the metal cations formed first-order hydroxyl complexes (such as CaOH +, MgOH+, etc.) or metal hydroxides (such as Fe(OH) 3, Mg(OH)2, etc.). Therefore, the increase of the bitumen-mineral mutual coagulation by the metal cations was strongly pH dependent. Organic complexing agents (oxalic acid, citric acid and EDTA) used in this study, citric acid in particular, significantly reduced or virtually eliminated the mutual coagulation between bitumen (or hexadecane) and minerals caused by metal cations Ca2+, Mg2+, Fe 2+ and Fe3+. Due to its ability to substantially lower the mutual coagulation between bitumen and mineral particles, citric acid was found the most effective in improving bitumen-mineral liberation in solutions containing the multivalent metal cations at pH 8--10. In small scale flotation experiments to recover the residual bitumen from Syncrude Froth Treatment Tailings, the addition of up to 2x10-3 mol/L citric acid improved the separation efficiency by 24 percentage points. The sequential additions of 1.5x10-3 mol/L citric acid and 30 mg/L polyacrylamide further increased the flotation separation efficiency, which was attributed to the improved liberation of bitumen from the minerals by the citric acid, and the flocculation of the liberated minerals fines by the polyacrylamide. The latter was expected to reduce the mechanical entrainment of the liberated mineral fines. Pretreatment of the Froth Treatment Tailings in an ultrasonic bath was also effective for bitumen liberation and recovery from the Froth Treatment Tailings. Through measurements of zeta potentials of the minerals and adsorption densities of the metal cations on mineral surfaces, coupled with speciation diagrams, it was shown that the multivalent metal cations functioned in the studied systems through three distinctly different mechanisms. These included electrical double layer compression by the metal cations; adsorption of the first-order metal hydroxyl species; and adsorption of the metal hydroxides on the mineral particles. Reversibility of adsorption and analyses by X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) indicated that the adsorption of the first-order metal hydroxyl species on quartz and kaolinite was through electrostatic attraction, while that of metal hydroxides was possibly through chemisorption. It was also shown that classical DLVO theory could be used to describe and predict bitumen-mineral interactions with and without the presence of citric acid. The energy barriers for the interaction between bitumen and the minerals were greatly raised in the presence of citric acid, as a contribution to the repulsive electrical double layers interaction between bitumen droplets and mineral particles.

Trivalent Lewis Acidic Cations Govern the Electronic Properties and Stability of Heterobimetallic Complexes of Nickel.

PubMed

Kumar, Amit; Lionetti, Davide; Day, Victor W; Blakemore, James D

2018-01-02

Assembly of heterobimetallic complexes is synthetically challenging due to the propensity of ditopic ligands to bind metals unselectively. Here, we employ a novel divergent approach for selective preparation of a variety of bimetallic complexes within a ditopic macrocyclic ligand platform. In our approach, nickel is readily coordinated to a Schiff base cavity, and then a range of redox-inactive cations (M=Na + , Ca 2+ , Nd 3+ , and Y 3+ ) are installed in a pendant crown-ether-like site. This modular strategy allows access to complexes with the highly Lewis acidic trivalent cations Nd 3+ and Y 3+ , a class of compounds that were previously inaccessible. Spectroscopic and electrochemical studies reveal wide variations in properties that are governed most strongly by the trivalent cations. Exposure to dimethylformamide drives loss of Nd 3+ and Y 3+ from the pendant crown-ether site, suggesting solvent effects must be carefully considered in future applications involving use of highly Lewis acidic metals. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

PubMed

Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

2016-09-27

Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

Simultaneous separation of inorganic anions and metal-citrate complexes on a zwitterionic stationary phase with on-column complexation.

PubMed

Nesterenko, Ekaterina P; Nesterenko, Pavel N; Paull, Brett

2008-12-05

The retention and separation selectivity of inorganic anions and on-column derivatised negatively charged citrate or oxalate metal complexes on reversed-phase stationary phases dynamically coated with N-(dodecyl-N,N-dimethylammonio)undecanoate (DDMAU) has been investigated. The retention mechanism for the metal-citrate complexes was predominantly anion exchange, although the amphoteric/zwitterionic nature of the stationary phase coating undoubtedly also contributed to the unusual separation selectivity shown. A mixture of 10 inorganic anions and metal cations was achieved using a 20 cm monolithic DDMAU modified column and a 1 mM citrate eluent, pH 4.0, flow rate equal to 0.8 mL/min. Selectivity was found to be strongly pH dependent, allowing additional scope for manipulation of solute retention, and thus application to complex samples. This is illustrated with the analysis of an acidic mine drainage sample with a range of inorganic anions and transition metal cations, varying significantly in their concentrations levels.

Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

NASA Astrophysics Data System (ADS)

Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

2017-10-01

The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water

DOEpatents

Moore, Robert C; Holt-Larese, Kathleen C; Bontchev, Ranko

2013-08-13

Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesium oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.

Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water

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

Moore, Robert C.; Larese, Kathleen Caroline; Bontchev, Ranko Panayotov

Systems and methods for use of magnesium hydroxide, either directly or through one or more precursors, doped with a divalent or trivalent metal cation, for removing arsenic from drinking water, including water distribution systems. In one embodiment, magnesium hydroxide, Mg(OH).sub.2 (a strong adsorbent for arsenic) doped with a divalent or trivalent metal cation is used to adsorb arsenic. The complex consisting of arsenic adsorbed on Mg(OH).sub.2 doped with a divalent or trivalent metal cation is subsequently removed from the water by conventional means, including filtration, settling, skimming, vortexing, centrifugation, magnetic separation, or other well-known separation systems. In another embodiment, magnesiummore » oxide, MgO, is employed, which reacts with water to form Mg(OH).sub.2. The resulting Mg(OH).sub.2 doped with a divalent or trivalent metal cation, then adsorbs arsenic, as set forth above. The method can also be used to treat human or animal poisoning with arsenic.« less

Spiropyran-Isoquinoline Dyad as a Dual Chemosensor for Co(II) and In(III) Detection.

PubMed

Kho, Yong-Min; Shin, Eun Ju

2017-09-19

Spiropyran derivatives have been studied as light-regulated chemosensors for a variety of metal cations and anions, but there is little research on chemosensors that simultaneously detect multiple metal cations. In this study, a spiropyran derivative with isoquinoline, SP-IQ , was prepared and it functions investigated as a light-regulated sensor for both Co 2+ and In 3+ cations. A colorless nonfluorescent SP-IQ converts to a pink-colored fluorescent MC-IQ by UV irradiation or standing in the dark, and MC-IQ returns to SP-IQ with visible light. Upon UV irradiation with the Co 2+ cation for 7 min, the stronger absorption at 540 nm and the similar fluorescence intensity at 640 nm are observed, compared to when no metal cation is added, due to the formation of a Co 2+ complex with pink color and pink fluorescence. When placed in the dark with the In 3+ cation for 7 h, the colorless solution of SP-IQ changes to the In 3+ complex with yellow color and pink fluorescence, which shows strong absorption at 410 nm and strong fluorescence at 640 nm. Selective detection of the Co 2+ cation with UV irradiation and the In 3+ cation in the dark could be possible with SP-IQ by both absorption and fluorescence spectroscopy or by the naked eye.

Redox potential tuning by redox-inactive cations in nature's water oxidizing catalyst and synthetic analogues.

PubMed

Krewald, Vera; Neese, Frank; Pantazis, Dimitrios A

2016-04-28

The redox potential of synthetic oligonuclear transition metal complexes has been shown to correlate with the Lewis acidity of a redox-inactive cation connected to the redox-active transition metals of the cluster via oxo or hydroxo bridges. Such heterometallic clusters are important cofactors in many metalloenzymes, where it is speculated that the redox-inactive constituent ion of the cluster serves to optimize its redox potential for electron transfer or catalysis. A principal example is the oxygen-evolving complex in photosystem II of natural photosynthesis, a Mn4CaO5 cofactor that oxidizes water into dioxygen, protons and electrons. Calcium is critical for catalytic function, but its precise role is not yet established. In analogy to synthetic complexes it has been suggested that Ca(2+) fine-tunes the redox potential of the manganese cluster. Here we evaluate this hypothesis by computing the relative redox potentials of substituted derivatives of the oxygen-evolving complex with the cations Sr(2+), Gd(3+), Cd(2+), Zn(2+), Mg(2+), Sc(3+), Na(+) and Y(3+) for two sequential transitions of its catalytic cycle. The theoretical approach is validated with a series of experimentally well-characterized Mn3AO4 cubane complexes that are structural mimics of the enzymatic cluster. Our results reproduce perfectly the experimentally observed correlation between the redox potential and the Lewis acidities of redox-inactive cations for the synthetic complexes. However, it is conclusively demonstrated that this correlation does not hold for the oxygen evolving complex. In the enzyme the redox potential of the cluster only responds to the charge of the redox-inactive cations and remains otherwise insensitive to their precise identity, precluding redox-tuning of the metal cluster as a primary role for Ca(2+) in biological water oxidation.

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

PubMed

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

2014-04-24

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

Crystal and electronic structures of magnesium(II), copper(II), and mixed magnesium(II)-copper(II) complexes of the quinoline half of styrylquinoline-type HIV-1 integrase inhibitors.

PubMed

Courcot, B; Firley, D; Fraisse, B; Becker, P; Gillet, J-M; Pattison, P; Chernyshov, D; Sghaier, M; Zouhiri, F; Desmaële, D; d'Angelo, J; Bonhomme, F; Geiger, S; Ghermani, N E

2007-05-31

A new target in AIDS therapy development is HIV-1 integrase (IN). It was proven that HIV-1 IN required divalent metal cations to achieve phosphodiester bond cleavage of DNA. Accordingly, all newly investigated potent IN inhibitors contain chemical fragments possessing a high ability to chelate metal cations. One of the promising leads in the polyhydroxylated styrylquinolines (SQLs) series is (E)-8-hydroxy-2-[2-(4,5-dihydroxy-3-methoxyphenyl)-ethenyl]-7-quinoline carboxylic acid (1). The present study focuses on the quinoline-based progenitor (2), which is actually the most probable chelating part of SQLs. Conventional and synchrotron low-temperature X-ray crystallographic studies were used to investigate the chelating power of progenitor 2. Mg2+ and Cu2+ cations were selected for this purpose, and three types of metal complexes of 2 were obtained: Mg(II) complex (4), Cu(II) complex (5) and mixed Mg(II)-Cu(II) complexes (6 and 7). The analysis of the crystal structure of complex 4 indicates that two tridentate ligands coordinate two Mg2+ cations, both in octahedral geometry. The Mg-Mg distance was found equal to 3.221(1) A, in agreement with the metal-metal distance of 3.9 A encountered in the crystal structure of Escherichia coli DNA polymerase I. In 5, the complex is formed by two bidentate ligands coordinating one copper ion in tetrahedral geometry. Both mixed Mg(II)-Cu(II) complexes, 6 and 7 exhibit an original arrangement of four ligands linked to a central heterometallic cluster consisting of three octahedrally coordinated magnesium ions and one tetrahedrally coordinated copper ion. Quantum mechanics calculations were also carried out in order to display the electrostatic potential generated by the dianionic ligand 2 and complex 4 and to quantify the binding energy (BE) during the formation of the magnesium complex of progenitor 2. A comparison of the binding energies of two hypothetical monometallic Mg(II) complexes with that found in the bimetallic magnesium complex 4 was made.

Ag[Fe(CO)5]2(+) : a bare silver complex with Fe(CO)5 as a ligand.

PubMed

Malinowski, Przemysław J; Krossing, Ingo

2014-12-01

Attempts to prepare Fe(CO)5 (+) from Ag[Al(OR(F) )4 ] (R(F) =C(CF3 )3 ) and Fe(CO)5 in CH2 Cl2 yielded the first complex of a neutral metal carbonyl bound to a simple metal cation. The Ag[Fe(CO)5 ]2 (+) cation consists of two Fe(CO)5 molecules coordinating Ag(+) in an almost linear fashion. The ν(CO) modes are blue-shifted compared to Fe(CO)5 , with one band above 2143 cm(-1) indicating that back-bonding is heavily decreased in the Ag[Fe(CO)5 ]2 (+) cation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coordination Chemistry of Alkali and Alkaline-Earth Cations with Macrocyclic Ligands.

ERIC Educational Resources Information Center

Dietrich, Bernard

1985-01-01

Discusses: (l) alkali and alkaline-earth cations in biology (considering naturally occurring lonophores, their X-ray structures, and physiochemical studies); (2) synthetic complexing agents for groups IA and IIA; and (3) ion transport across membranes (examining neutral macrobicyclic ligands as metal cation carriers, transport by anionic carriers,…

An Experiment on Isomerism in Metal-Amino Acid Complexes.

ERIC Educational Resources Information Center

Harrison, R. Graeme; Nolan, Kevin B.

1982-01-01

Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

A comprehensive study of the complexation of alkali metal cations by lower rim calix[4]arene amide derivatives.

PubMed

Horvat, Gordan; Frkanec, Leo; Cindro, Nikola; Tomišić, Vladislav

2017-09-13

The complexation of alkali metal cations by lower rim N,N-dihexylacetamide (L1) and newly synthesized N-hexyl-N-methylacetamide (L2) calix[4]arene tertiary-amide derivatives was thoroughly studied at 25 °C in acetonitrile (MeCN), benzonitrile (PhCN), and methanol (MeOH) by means of direct and competitive microcalorimetric titrations, and UV and 1 H NMR spectroscopies. In addition, by measuring the ligands' solubilities, the solution (transfer) Gibbs energies of the ligands and their alkali metal complexes were obtained. The inclusion of solvent molecules in the free and complexed calixarene hydrophobic cavities was also investigated. Computational (classical molecular dynamics) investigations of the studied systems were also carried out. The obtained results were compared with those previously obtained by studying the complexation ability of an N-hexylacetamidecalix[4]arene secondary-amide derivative (L3). The stability constants of 1 : 1 complexes were determined in all solvents used (the values obtained by different methods being in excellent agreement), as were the corresponding complexation enthalpies and entropies. Almost all of the examined reactions were enthalpically controlled. The most striking exceptions were reactions of Li + with both ligands in methanol, for which the entropic contribution to the reaction Gibbs energy was substantial due the entropically favourable desolvation of the smallest lithium cation. The thermodynamic stabilities of the complexes were quite solvent dependent (the stability decreased in the solvent order: MeCN > PhCN ≫ MeOH), which could be accounted for by considering the differences in the solvation of the ligand and free and complexed alkali metal cations in the solvents used. Comparison of the stability constants of the ligand L1 and L2 complexes clearly revealed that the higher electron-donating ability of the hexyl with respect to the methyl group is of considerable importance in determining the equilibria of the complexation reactions. Additionally, the quite strong influence of intramolecular hydrogen bond formation in compound L3 (not present in ligands L1 and L2) and that of the inclusion of solvent molecules in the calixarene hydrophobic cone were shown to be of great importance in determining the thermodynamic stability of the calixarene-cation complexes. The experimental results were fully supported by those obtained by MD simulations.

Size charge fractionation of metals in municipal solid waste landfill leachate.

PubMed

Oygard, Joar Karsten; Gjengedal, Elin; Røyset, Oddvar

2007-01-01

Municipal solid waste landfill leachates from 9 Norwegian sites were size charge fractionated in the field, to obtain three fractions: particulate and colloidal matter >0.45microm, free anions/non-labile complexes <0.45microm and free cations/labile complexes <0.45microm. The fractionation showed that Cd and Zn, and especially Cu and Pb, were present to a large degree (63-98%) as particulate and colloidal matter >0.45microm. Cr, Co and Ni were on the contrary present mostly as non-labile complexes (69-79%) <0.45microm. The major cations Ca, Mg, K, and Mn were present mainly as free cations/labile complexes <0.45microm, while As and Mo were present to a large degree (70-90%) as free anions/non-labile complexes <0.45microm. Aluminium was present mainly as particulate and colloidal matter >0.45microm. The particulate and colloidal matter >0.45microm was mainly inorganic; indicating that the metals present in this fraction were bound as inorganic compounds. The fractionation gives important information on the mobility and potential bioavailability of the metals investigated, in contrast to the total metal concentrations usually reported. To study possible changes in respective metal species in leachate in aerated sedimentation tanks, freshly sampled leachate was stored for 48h, and subsequently fractionated. This showed that the free heavy metals are partly immobilized during storage of leachate with oxygen available. The largest effects were found for Cd and Zn. The proportion of As and Cr present as particulate matter or colloids >0.45microm also increased.

Infrared multiple-photon dissociation spectroscopy of group II metal complexes with salicylate.

PubMed

Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; van Stipdonk, Michael J

2011-07-15

Ion trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations, were used to characterize singly charged, 1:1 complexes of Ca(2+), Sr(2+) and Ba(2+) with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO(2) and (b) formation of [MOH](+) where M = Ca(2+), Sr(2+) or Ba(2+). DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cation is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 and 1650 cm(-1), and the best correlation between theoretical and experimental spectra is found for the structure that features coordination of the metal ion by phenoxide and the carbonyl O of the carboxylic acid group, consistent with the calculated energies for the respective species. Copyright © 2011 John Wiley & Sons, Ltd.

[Noncovalent cation-π interactions--their role in nature].

PubMed

Fink, Krzysztof; Boratyński, Janusz

2014-11-07

Non-covalent interactions play an extremely important role in organisms. The main non-covalent interactions in nature are: ion-ion interactions, dipole-dipole interactions, hydrogen bonds, and van der Waals interactions. A new kind of intermolecular interactions--cation-π interactions--is gaining increasing attention. These interactions occur between a cation and a π system. The main contributors to cation-π interactions are electrostatic, polarization and, to a lesser extent, dispersion interactions. At first, cation-π interactions were studied in a gas phase, with metal cation-aromatic system complexes. The characteristics of these complexes are as follows: an increase of cation atomic number leads to a decrease of interaction energy, and an increase of cation charge leads to an increase of interaction energy. Aromatic amino acids bind with metal cations mainly through interactions with their main chain. Nevertheless, cation-π interaction with a hydrophobic side chain significantly enhances binding energy. In water solutions most cations preferentially interact with water molecules rather than aromatic systems. Cation-π interactions occur in environments with lower accessibility to a polar solvent. Cation-π interactions can have a stabilizing role on the secondary, tertiary and quaternary structure of proteins. These interactions play an important role in substrate or ligand binding sites in many proteins, which should be taken into consideration when the screening of effective inhibitors for these proteins is carried out. Cation-π interactions are abundant and play an important role in many biological processes.

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI) 2 in Diglyme: Implications for Multivalent Electrolytes

DOE PAGES

Baskin, Artem; Prendergast, David

2016-02-05

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitalsmore » are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2)/diglyme) and its singly charged ion pair, MgTFSI +. In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

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

Baskin, Artem; Prendergast, David

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitalsmore » are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2)/diglyme) and its singly charged ion pair, MgTFSI +. In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

Locating the Binding Sites of Pb(II) Ion with Human and Bovine Serum Albumins

PubMed Central

Belatik, Ahmed; Hotchandani, Surat; Carpentier, Robert; Tajmir-Riahi, Heidar-Ali

2012-01-01

Lead is a potent environmental toxin that has accumulated above its natural level as a result of human activity. Pb cation shows major affinity towards protein complexation and it has been used as modulator of protein-membrane interactions. We located the binding sites of Pb(II) with human serum (HSA) and bovine serum albumins (BSA) at physiological conditions, using constant protein concentration and various Pb contents. FTIR, UV-visible, CD, fluorescence and X-ray photoelectron spectroscopic (XPS) methods were used to analyse Pb binding sites, the binding constant and the effect of metal ion complexation on HSA and BSA stability and conformations. Structural analysis showed that Pb binds strongly to HSA and BSA via hydrophilic contacts with overall binding constants of KPb-HSA = 8.2 (±0.8)×104 M−1 and KPb-BSA = 7.5 (±0.7)×104 M−1. The number of bound Pb cation per protein is 0.7 per HSA and BSA complexes. XPS located the binding sites of Pb cation with protein N and O atoms. Pb complexation alters protein conformation by a major reduction of α-helix from 57% (free HSA) to 48% (metal-complex) and 63% (free BSA) to 52% (metal-complex) inducing a partial protein destabilization. PMID:22574219

Monitoring of photoluminescence decay by alkali and alkaline earth metal cations using a photoluminescent bolaamphiphile self-assembly as an optical probe.

PubMed

Kim, Sunhyung; Kwak, Jinyoung; Lee, Sang-Yup

2014-05-01

Photoluminescence (PL) decay induced by the displacement of an ionic fluorescence component, Tb(3+), with alkali and alkaline earth metal cations was investigated using photoluminescent spherical self-assemblies as optical probes. The photoluminescent spherical self-assembly was prepared by the self-organization of a tyrosine-containing bolaamphiphile molecule with a photosensitizer and Tb(3+) ion. The lanthanide ion, Tb(3+), electrically bound to the carboxyl group of the bolaamphiphile molecule, was displaced by alkali and alkaline earth metal cations that had stronger electrophilicity. The PL of the self-assembly decayed remarkably due to the substitution of lanthanide ions with alkali and alkaline earth metal cations. The PL decay showed a positive correlation with cation concentration and was sensitive to the cation valency. Generally, the PL decay was enhanced by the electrophilicity of the cations. However, Ca(2+) showed greater PL decay than Mg(2+) because Ca(2+) could create various complexes with the carboxyl groups of the bolaamphiphile molecule. Microscopic and spectroscopic investigations were conducted to study the photon energy transfer and displacement of Tb(3+) by the cation exchange. This study demonstrated that the PL decay by the displacement of the ionic fluorescent compound was applied to the detection of various cations in aqueous media and is applicable to the development of future optical sensors. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of ionic strength, anions, cations, and natural organic matter on the adsorption of pharmaceuticals to silica.

PubMed

Bui, Tung Xuan; Choi, Heechul

2010-08-01

The adsorption of four wide-use pharmaceuticals (carbamazepine, diclofenac, ibuprofen, and ketoprofen) onto a porous silica was investigated under varied ionic strengths, different anions, divalent cations (Ca(2+) and Mg(2+)), trivalent cations (Al(3+) and Fe(3+)), and natural organic matter (NOM). The experiments demonstrated that at a given pH the adsorption was most affected by ionic strength, trivalent cations, and properties of pharmaceuticals. The increase of ionic strength resulted in an increase in the adsorption of ketoprofen, but a decrease in the adsorption of carbamazepine. Trivalent metal cations made intense increases in the adsorption of three acidic pharmaceuticals, which could be due to the formation of inner-sphere complex of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the adsorption of carbamazepine was not affected by divalent and trivalent cations, whereas the adsorption of diclofenac was solely impacted by the presence of Al(3+). Moreover, divalent cations at low concentration could slightly enhance the adsorption of ibuprofen and ketoprofen, whereas NOM caused a reduction in the adsorption of the tested pharmaceuticals except for diclofenac. These results suggest that ionic strength, divalent cations, trivalent cations, and NOM are notable factors affecting the adsorption of pharmaceuticals and thus the ultimate fate of pharmaceuticals in the aqueous environment. Copyright 2010 Elsevier Ltd. All rights reserved.

Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

NASA Astrophysics Data System (ADS)

Ke, Haochen; van der Linde, Christian; Lisy, James M.

2014-06-01

Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

Tetracycline adsorption on kaolinite: pH, metal cations and humic acid effects.

PubMed

Zhao, Yanping; Geng, Jinju; Wang, Xiaorong; Gu, Xueyuan; Gao, Shixiang

2011-07-01

Contamination of environmental matrixes by human and animal wastes containing antibiotics is a growing health concern. Because tetracycline is one of the most widely-used antibiotics in the world, it is important to understand the factors that influence its mobility in soils. This study investigated the effects of pH, background electrolyte cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), heavy metal Cu(2+) and humic acid (HA) on tetracycline adsorption onto kaolinite. Results showed that tetracycline was greatly adsorbed by kaolinite over pH 3-6, then decreased with the increase of pH, indicating that tetracycline adsorption mainly through ion exchange of cations species and complexation of zwitterions species. In the presence of five types of cations (Li(+), Na(+), K(+), Ca(2+) and Mg(2+)), tetracycline adsorption decreased in accordance with the increasing of atomic radius and valence of metal cations, which suggested that outer-sphere complexes formed between tetracycline and kaolinite, and the existence of competitor ions lead to the decreasing adsorption. The presence of Cu(2+) greatly enhanced the adsorption probably by acting as a bridge ion between tetracycline species and the edge sites of kaolinite. HA also showed a major effect on the adsorption: at pH < 6, the presence of HA increased the adsorption, while the addition of HA showed little effect on tetracycline adsorption at higher pH. The soil environmental conditions, like pH, metal cations and soil organic matter, strongly influence the adsorption behavior of tetracycline onto kaolinite and need to be considered when assessing the environmental toxicity of tetracycline.

Binding selectivity of dibenzo-18-crown-6 for alkali metal cations in aqueous solution: A density functional theory study using a continuum solvation model.

PubMed

Choi, Chang Min; Heo, Jiyoung; Kim, Nam Joon

2012-08-08

Dibenzo-18-crown-6 (DB18C6) exhibits the binding selectivity for alkali metal cations in solution phase. In this study, we investigate the main forces that determine the binding selectivity of DB18C6 for the metal cations in aqueous solution using the density functional theory (DFT) and the conductor-like polarizable continuum model (CPCM). The bond dissociation free energies (BDFE) of DB18C6 complexes with alkali metal cations (M+-DB18C6, M = Li, Na, K, Rb, and Cs) in aqueous solution are calculated at the B3LYP/6-311++G(d,p)//B3LYP/6-31 + G(d) level using the CPCM. It is found that the theoretical BDFE is the largest for K+-DB18C6 and decreases as the size of the metal cation gets larger or smaller than that of K+, which agrees well with previous experimental results. The solvation energy of M+-DB18C6 in aqueous solution plays a key role in determining the binding selectivity of DB18C6. In particular, the non-electrostatic dispersion interaction between the solute and solvent, which depends strongly on the complex structure, is largely responsible for the different solvation energies of M+-DB18C6. This study shows that the implicit solvation model like the CPCM works reasonably well in predicting the binding selectivity of DB18C6 in aqueous solution.

Nitrogen-Rich Multinuclear Ferrocenophanes as Multichannel Chemosensor Molecules for Transition and Heavy-Metal Cations

PubMed Central

Sola, Antonia; Espinosa, Arturo; Tárraga, Alberto; Molina, Pedro

2014-01-01

[m.n] Multinuclear ferrocenophanes prepared by aza-Wittig reaction of bisiminophosphoranes derived from 1,1′-diazidoferrocene and isophthaladelhyde or 2,5-diformylthiophene, behave as efficient electrochemical and chromogenic chemosensor molecules for Zn2+, Pb2+, and Hg2+ metal cations. Whereas the OSWV of receptor 3, bearing two m-phenylene units in the bridges, display one oxidation peak, receptor 4 incorporating two thiophene rings in the bridges, exhibits two well-separated oxidation peaks. In both receptors only the addition of Zn2+, Pb2+, and Hg2+ metal cations induced a remarkable anodic shift of ferrocene/ferrocenium redox couple. Likewise, in the absorption spectra of these receptors the low energy band is red-shifted by Δλ = 165 − 209 nm, and these changes promoted a significant color changes which could be used for the naked eye detection of these metal cations. The coordination modes for two representative cases were unveiled by DFT calculations that show an unsual coordination in the [42Pb]2+ complex with the Pb2+ cation in a distorted cubic N4S4 donor cage. PMID:25106019

MODIFICATION OF METAL PARTITIONING BY SUPPLEMENTING ACID VOLATILE SULFIDE IN FRESHWATER SEDIMENTS

EPA Science Inventory

Acid volatile sulfide is a component of sediments which complexes some cationic metals and thereby influences the toxicity of these metals to benthic organisms. EPA has proposed AVS as a key normalization phase for the development of sediment quality criteria for metals. Experime...

Resorcarene-based receptor: versatile behavior in its interaction with heavy and soft metal cations.

PubMed

Danil de Namor, Angela F; Chaaban, Jinane K; Piro, Oscar E; Castellano, Eduardo E

2006-02-09

Standard solution Gibbs energies, DeltasG degrees, of the resorcarene-based receptor 5,11,17,23-ethylthiomethylated calix[4]resorcarene, (characterized by 1H NMR and X-ray diffraction studies) in its monomeric state (established through partition experiments) in various solvents are for the first time reported in the area of resorcarene chemistry. Transfer Gibbs energies of from hexane (reference solvent) to other medium are calculated. Agreement between DeltatG degrees (referred to the pure solvents) and standard partition Gibbs energies, DeltapG degrees (solvent mutually saturated) is found. Cation-ligand interactions were investigated through 1H NMR (CD3CN and CD3OD) and conductometric titrations in acetonitrile and methanol. 1H NMR data revealed the sites of interaction of with the metal cation. The composition of the metal-ion complexes (Ag+ and Pb2+ in acetonitrile and Ag+ and Cu2+ in methanol) was established through conductometric titrations. Thus, complexes of 1:1 stoichiometry were formed between and Ag+ and Pb2+ in acetonitrile and Cu2+ in methanol. However, in moving from acetonitrile to methanol, the composition of the silver complex was altered. Thus, two metal cations are hosted by a unit of the ligand. As far as Cu2+ and in acetonitrile is concerned, conductance data suggest that metalates are formed in which up to four units of Cu2+ are taken up per unit of resorcarene. The contrasting behavior of with Cu2+ in acetonitrile relative to methanol is discussed. As far as mercury (II) is concerned, the unusual jump in conductance observed in the titration of Hg2+ with in acetonitrile and methanol after the formation of a multicharged complex (undefined composition) is attributed to the presence of highly charged smaller units (higher mobility) resulting from the departure of pendant arms from the resorcarene backbone. Isolation of these species followed by X-ray diffraction studies corroborated this statement. The thermodynamic characterization of metal-ion complexes of Ag+ and Pb2+ in acetonitrile and Cu2+ and Ag+ in methanol is reported. Final conclusions are given.

Competitive/co-operative interactions in acid base sandwich: role of cation vs. substituents.

PubMed

Kalpana, Ayyavoo; Akilandeswari, Lakshminarayanan

2017-11-15

The cation-π interaction can be envisaged as a lewis acid base interaction, and it is in line with Pearson's acid base concept. The critical examination of interactions between the π-acids (alkali metal cations - Li + , Na + and alkaline earth metal cations Mg 2+ , Ca 2+ ) on one face and tripodal Cr(CO) 3 moiety on the other π face of substituted arenes demonstrates the role of cation and substitutents in manipulating the interactions between them. The interaction of the two π acids on both faces of arene is not expectedly additive, rather it shows either depreciation of interaction energy revealing the competition of acids toward the base or enhancement of interaction energy denoting a cooperative effect. Among the metal cations under study, Mg 2+ shows a cooperative gesture. Although the substituents play a meek role, they unfailingly exert their electronic effects and are amply documented by excellent correlation of various parameters with the Hammett constant σ m . The elusive switching of λ max from the UV to IR region on binding Mg 2+ with substituted arene-Cr(CO) 3 complex is a characteristic clue that TDDFT can help design the ionic sensors for Mg 2+ cations.

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

PubMed

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

2016-01-01

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

Methods for preparing metal ion photocages: application to the synthesis of crowncast.

PubMed

Kennedy, Daniel P; Gwizdala, Celina; Burdette, Shawn C

2009-06-18

Three different synthetic strategies were utilized in the construction of a novel class of macrocyclic containing o-nitrobenzhydrol group II cation cages. The synthetic methodology presented herein is unparalleled in scope toward the preparation of caged complexes for various main group and transition block cations.

How Do Structure and Charge Affect Metal-Complex Binding to DNA? An Upper-Division Integrated Laboratory Project Using Cyclic Voltammetry

ERIC Educational Resources Information Center

Kulczynska, Agnieszka; Johnson, Reed; Frost, Tony; Margerum, Lawrence D.

2011-01-01

An advanced undergraduate laboratory project is described that integrates inorganic, analytical, physical, and biochemical techniques to reveal differences in binding between cationic metal complexes and anionic DNA (herring testes). Students were guided to formulate testable hypotheses based on the title question and a list of different metal…

Studies on the interactions between purified bovine caseins and alkaline-earth-metalions

PubMed Central

Dickson, I. R.; Perkins, D. J.

1971-01-01

1. Alkaline-earth-metal cations at low concentrations form soluble complexes with bovine caseins. The relative order of binding capacities is: Mg2+>Ca2+>Ba2+>Sr2+. 2. The cations interact with both free ionized carboxyl groups of aspartic acid and glutamic acid and with monoester phosphate groups covalently bound to serine and threonine; at low concentrations of the cations interactions are predominantly with the phosphate groups. 3. The order of binding capacities for purified components of the casein complex is: αs1-casein>β-casein>κ-casein. PMID:5166590

Quantum-chemistry based calibration of the alkali metal cation series (Li(+)-Cs(+)) for large-scale polarizable molecular mechanics/dynamics simulations.

PubMed

Dudev, Todor; Devereux, Mike; Meuwly, Markus; Lim, Carmay; Piquemal, Jean-Philip; Gresh, Nohad

2015-02-15

The alkali metal cations in the series Li(+)-Cs(+) act as major partners in a diversity of biological processes and in bioinorganic chemistry. In this article, we present the results of their calibration in the context of the SIBFA polarizable molecular mechanics/dynamics procedure. It relies on quantum-chemistry (QC) energy-decomposition analyses of their monoligated complexes with representative O-, N-, S-, and Se- ligands, performed with the aug-cc-pVTZ(-f) basis set at the Hartree-Fock level. Close agreement with QC is obtained for each individual contribution, even though the calibration involves only a limited set of cation-specific parameters. This agreement is preserved in tests on polyligated complexes with four and six O- ligands, water and formamide, indicating the transferability of the procedure. Preliminary extensions to density functional theory calculations are reported. © 2014 Wiley Periodicals, Inc.

Solvent extraction: the coordination chemistry behind extractive metallurgy.

PubMed

Wilson, A Matthew; Bailey, Phillip J; Tasker, Peter A; Turkington, Jennifer R; Grant, Richard A; Love, Jason B

2014-01-07

The modes of action of the commercial solvent extractants used in extractive hydrometallurgy are classified according to whether the recovery process involves the transport of metal cations, M(n+), metalate anions, MXx(n-), or metal salts, MXx into a water-immiscible solvent. Well-established principles of coordination chemistry provide an explanation for the remarkable strengths and selectivities shown by most of these extractants. Reagents which achieve high selectivity when transporting metal cations or metal salts into a water-immiscible solvent usually operate in the inner coordination sphere of the metal and provide donor atom types or dispositions which favour the formation of particularly stable neutral complexes that have high solubility in the hydrocarbons commonly used in recovery processes. In the extraction of metalates, the structures of the neutral assemblies formed in the water-immiscible phase are usually not well defined and the cationic reagents can be assumed to operate in the outer coordination spheres. The formation of secondary bonds in the outer sphere using, for example, electrostatic or H-bonding interactions are favoured by the low polarity of the water-immiscible solvents.

Infrared multiple photon dissociation spectroscopy of group I and group II metal complexes with Boc-hydroxylamine.

PubMed

Dain, Ryan P; Gresham, Gary; Groenewold, Gary S; Steill, Jeffrey D; Oomens, Jos; Van Stipdonk, Michael J

2013-08-30

Hydroxamates are essential growth factors for some microbes, acting primarily as siderophores that solubilize iron for transport into a cell. Here we determined the intrinsic structure of 1:1 complexes between Boc-protected hydroxylamine and group I ([M(L)](+)) and group II ([M(L-H)](+)) cations, where M and L are the cation and ligand, respectively, which are convenient models for the functional unit of hydroxamate siderphores. The relevant complex ions were generated by electrospray ionization (ESI) and isolated and stored in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Infrared spectra of the isolated complexes were collected by monitoring (infrared) photodissociation yield as a function of photon energy. Experimental spectra were then compared to those predicted by density functional theory (DFT) calculations. The infrared multiple photon dissociation (IRMPD) spectra collected are in good agreement with those predicted to be lowest-energy by DFT. The spectra for the group I complexes contain six resolved absorptions that can be attributed to amide I and II type and hydroxylamine N-OH vibrations. Similar absorptions are observed for the group II cation complexes, with shifts of the amide I and amide II vibrations due to the change in structure with deprotonation of the hydroxylamine group. IRMPD spectroscopy unequivocally shows that the intrinsic binding mode for the group I cations involves the O atoms of the amide carbonyl and hydroxylamine groups of Boc-hydroxylamine. A similar binding mode is preferred for the group II cations, except that in this case the metal ion is coordinated by the O atom of the deprotonated hydroxylamine group. Copyright © 2013 John Wiley & Sons, Ltd.

Method of removing arsenic and other anionic contaminants from contaminated water using enhanced coagulation

DOEpatents

Teter, David M.; Brady, Patrick V.; Krumhansl, James L.; Khandaker, Nadim R.

2006-11-21

An improved water decontamination process comprising contacting water containing anionic contaminants with an enhanced coagulant to form an enhanced floc, which more efficiently binds anionic species (e.g., arsenate, arsenite, chromate, fluoride, selenate, and borate, and combinations thereof) predominantly through the formation of surface complexes. The enhanced coagulant comprises a trivalent metal cation coagulant (e.g., ferric chloride or aluminum sulfate) mixed with a divalent metal cation modifier (e.g., copper sulfate or zinc sulfate).

The effect of specific solvent-solute interactions on complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative.

PubMed

Horvat, Gordan; Stilinović, Vladimir; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

2013-11-04

Complexation of alkali-metal cations with calix[4]arene secondary-amide derivative, 5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetra(N-hexylcarbamoylmethoxy)calix[4]arene (L), in benzonitrile (PhCN) and methanol (MeOH) was studied by means of microcalorimetry, UV and NMR spectroscopies, and in the solid state by X-ray crystallography. The inclusion of solvent molecules (including acetonitrile, MeCN) in the calixarene hydrophobic cavity was also investigated. The classical molecular dynamics (MD) simulations of the systems studied were carried out. By combining the results obtained using the mentioned experimental and computational techniques, an attempt was made to get an as detailed insight into the complexation reactions as possible. The thermodynamic parameters, that is, equilibrium constants, reaction Gibbs energies, enthalpies, and entropies, of the investigated processes were determined and discussed. The stability constants of the 1:1 (metal:ligand) complexes measured by different methods were in very good agreement. Solution Gibbs energies of the ligand and its complexes with Na(+) and K(+) in methanol and acetonitrile were determined. It was established that from the thermodynamic point of view, apart from cation solvation, the most important reason for the huge difference in the stability of these complexes in the two solvents lay in the fact that the transfer of complex species from MeOH to MeCN was quite favorable. That could be at least partly explained by a more exergonic inclusion of the solvent molecule in the complexed calixarene cone in MeCN as compared to MeOH, which was supported by MD simulations. Molecular and crystal structures of the lithium cation complex of L with the benzonitrile molecule bound in the hydrophobic calixarene cavity were determined by single-crystal X-ray diffraction. As far as we are aware, for the first time the alkali-metal cation was found to be coordinated by the solvent nitrile group in a calixarene adduct. According to the results of MD simulations, the probability of such orientation of the benzonitrile molecule included in the ligand cone was by far the largest in the case of LiL(+) complex. Because of the favorable PhCN-Li(+) interaction, L was proven to have the highest affinity toward the lithium ion in benzonitrile, which was not the case in the other solvents examined (in acetonitrile, sodium complex was the most stable, whereas in methanol, complexation of lithium was not even observed). That could serve as a remarkable example showing the importance of specific solvent-solute interactions in determining the equilibrium in solution.

Intercalated layered clay composites and their applications

NASA Astrophysics Data System (ADS)

Phukan, Anjali

Supported inorganic reagents are rapidly emerging as new and environmentally acceptable reagents and catalysts. The smectite group of layered clay minerals, such as, Montmorillonite, provides promising character for adsorption, catalytic activity, supports etc. for their large surface area, swelling behavior and ion exchange properties. Aromatic compounds intercalated in layered clays are useful in optical molecular devices. Clay is a unique material for adsorption of heavy metals and various toxic substances. Clay surfaces are known to be catalytically active due to their surface acidity. Acid activated clays possess much improved surface areas and acidities and have higher pore volumes so that can absorb large molecules in the pores. The exchangeable cations in clay minerals play a key role in controlling surface acidity and catalytic activity. Recently, optically active metal-complex-Montmorillonite composites are reported to be active in antiracemization purposes. In view of the above, a research work, relating to the preparation of different modified clay composites and their catalytic applications were carried out. The different aspects and results of the present work have been reported in four major chapters. Chapter I: This is an introductory chapter, which contains a review of the literature regarding clay-based materials. Clay minerals are phyllosilicates with layer structure. Montmorillonite, a member of smectite group of clay, is 2:1 phyllosilicate, where a layer is composed of an octahedral sheet sandwiched by two tetrahedral sheets. Such clay shows cation exchange capacity (CEC) and is expressed in milli-equivalents per 100 gm of dry clay. Clays can be modified by interaction with metal ion, metal complexes, metal cluster and organic cations for various applications. Clays are also modified by treating with acid followed by impregnation with metal salts or ions. Montmorillonite can intercalate suitable metal complexes in excess of CEC to form double or pseudo-trilayer composites. Metal ion and metal ion metal salts intercalated on Montmorillonite are efficient catalysts for Friedel-Crafts (FC) reactions, such as benzylation of benzene, synthesis of Raspberry ketone [4-(4'-hydroxyphenyl)butan-2-one] etc. Montmorillonite clay can be used as a good support for controlled release of pesticides and medicinal drugs, adsorbent for cationic dyes, toxic substances and heavy metals effective adsorbent for radioactive and toxic industrial wastes,...

Group transfer and electron transfer reactions of organometallic complexes

NASA Astrophysics Data System (ADS)

Atwood, Jim D.

During 1994, despite the disruptions, the authors have made progress in several aspects of their research on electron transfer reactions between organometallic complexes. This summary covers three areas that are relatively complete: (1) reactions between metal carbonyl anions and metal carbonyl halides, (2) reactions of hydrido- and alkyl-containing anions (RFe(CO)4(-) and RW(CO)5(-) with metal carbonyl cations; and (3) reactions of a seventeen-electron complex (Cp* Cr(CO)3*) with metal carbonyl derivatives. Two areas of examination that have just begun (possible carbene transfer and the possible role of metal carbonyl anions in carbon-hydrogen bond activation) will also be described.

An Integrated approach (thermodynamic, structural, and computational) to the study of complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative in acetonitrile.

PubMed

Horvat, Gordan; Stilinović, Vladimir; Hrenar, Tomica; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

2012-06-04

The calix[4]arene secondary-amide derivative L was synthesized, and its complexation with alkali-metal cations in acetonitrile (MeCN) was studied by means of spectrophotometric, NMR, conductometric, and microcalorimetric titrations at 25 °C. The stability constants of the 1:1 (metal/ligand) complexes determined by different methods were in excellent agreement. For the complexation of M(+) (M = Li, Na, K) with L, both enthalpic and entropic contributions were favorable, with their values and mutual relations being quite strongly dependent on the cation. The enthalpic and overall stability was the largest in the case of the sodium complex. Molecular and crystal structures of free L, its methanol and MeCN solvates, the sodium complex, and its MeCN solvate were determined by single-crystal X-ray diffraction. The inclusion of a MeCN molecule in the calixarene hydrophobic cavity was observed both in solution and in the solid state. This specific interaction was found to be stronger in the case of metal complexes compared to the free ligand because of the better preorganization of the hydrophobic cone to accept the solvent molecule. Density functional theory calculations showed that the flattened cone conformation (C(2) point group) of L was generally more favorable than the square cone conformation (C(4) point group). In the complex with Na(+), L was in square cone conformation, whereas in its adduct with MeCN, the conformation was slightly distorted from the full symmetry. These conformations were in agreement with those observed in the solid state. The classical molecular dynamics simulations indicated that the MeCN molecule enters the L hydrophobic cavity of both the free ligand and its alkali-metal complexes. The inclusion of MeCN in the cone of free L was accompanied by the conformational change from C(2) to C(4) symmetry. As in solution studies, in the case of ML(+) complexes, an allosteric effect was observed: the ligand was already in the appropriate square cone conformation to bind the solvent molecule, allowing it to more easily and faster enter the calixarene cavity.

Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

DOE PAGES

Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; ...

2014-04-23

Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

Coagulation of bitumen with kaolinite in aqueous solutions containing Ca2+, Mg2+ and Fe3+: effect of citric acid.

PubMed

Gan, Weibing; Liu, Qi

2008-08-01

Heterocoagulation experiments of kaolinite with solvent-diluted-bitumen were carried out to investigate the effect of hydrolyzable metal cations and citric acid on the liberation of bitumen from kaolinite. The adsorption of Ca(2+) and Mg(2+) on kaolinite, and zeta potentials of kaolinite and bitumen droplets in solutions containing 10(-3)mol/L of Ca(2+), Mg(2+) and Fe(3+) with or without citric acid were also measured. It was found that the heterocoagulation of bitumen with kaolinite was enhanced in the presence of the metal cations from pH 7 to pH 10.5, accompanied by a decrease in the magnitude of the zeta potentials and an increase in the adsorption of the metal cations on kaolinite and possibly on bitumen droplets. The addition of 5 x 10(-4)mol/L citric acid reduced the degree of coagulation from 90% to less than 40% in the presence of 10(-3)mol/L Ca(2+) and Mg(2+) cations at pH approximately 10, and at pH approximately 8 for Fe(3+). It was found that hydrolyzable metal cations enhanced bitumen-kaolinite interactions through electrical double layer compression and specific adsorption of the metal hydrolysis species on the surface of kaolinite. The effect of metal cations was removed by citric acid through formation of metal-citrate complexes and/or the adsorption of citrate anions, which restored the zeta potentials of both kaolinite and bitumen. Therefore, electrostatic attraction or repulsion was responsible for the coagulation or dispersion of kaolinite particles from bitumen droplets in the tested system.

Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

PubMed Central

Boughlala, Zakaria; Fonseca Guerra, Célia

2016-01-01

Abstract We have analyzed the structure and bonding of gas‐phase Cl−X and [HCl−X]+ complexes for X+= H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl− and HCl for the various cations. The Cl−X bond becomes longer and weaker along X+ = H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn–Sham molecular orbital (KS‐MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. PMID:27551660

Bimetallic complexes and polymerization catalysts therefrom

DOEpatents

Patton, Jasson T.; Marks, Tobin J.; Li, Liting

2000-11-28

Group 3-6 or Lanthanide metal complexes possessing two metal centers, catalysts derived therefrom by combining the same with strong Lewis acids, Bronsted acid salts, salts containing a cationic oxidizing agent or subjected to bulk electrolysis in the presence of compatible, inert non-coordinating anions and the use of such catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers are disclosed.

Binding of Alkali Metal Ions with 1,3,5-Tri(phenyl)benzene and 1,3,5-Tri(naphthyl)benzene: The Effect of Phenyl and Naphthyl Ring Substitution on Cation-π Interactions Revealed by DFT Study.

PubMed

Mirchi, Ali; Sizochenko, Natalia; Dinadayalane, Tandabany; Leszczynski, Jerzy

2017-11-22

The effect of substitution of phenyl and naphthyl rings to benzene was examined to elucidate the cation-π interactions involving alkali metal ions with 1,3,5-tri(phenyl)benzene (TPB) and 1,3,5-tri(naphthyl)benzene (TNB). Benzene, TPB, and four TNB isomers (with ααα, ααβ, αββ, and βββ types of fusion) and their complexes with Li + , Na + , K + , Rb + , and Cs + were optimized using DFT approach with B3LYP and M06-2X functionals in conjunction with the def2-QZVP basis set. Higher relative stability of β,β,β-TNB over α,α,α-TNB can be attributed to peri repulsion, which is defined as the nonbonding repulsive interaction between substituents in the 1- and the 8-positions on the naphthalene core. Binding energies, distances between ring centroid and the metal ions, and the distance to metal ions from the center of other six-membered rings were compared for all complexes. Our computational study reveals that the binding affinity of alkali metal cations increases significantly with the 1,3,5-trisubstitution of phenyl and naphthyl rings to benzene. The detailed computational analyses of geometries, partial charges, binding energies, and ligand organization energies reveal the possibility of favorable C-H···M + interactions when a α-naphthyl group exists in complexes of TNB structures. Like benzene-alkali metal ion complexes, the binding affinity of metal ions follows the order: Li + > Na + > K + > Rb + > Cs + for any considered 1,3,5-trisubstituted benzene systems. In case of TNB, we found that the strength of interactions increases as the fusion point changes from α to β position of naphthalene.

Cation hydrolysis and the regulation of trace metal composition in seawater

NASA Astrophysics Data System (ADS)

Kumar, M. Dileep

1987-08-01

Thermodynamic calculations have been performed for cation hydrolysis, including temperatures from 2°C to the high values of significance near Mid-Oceanic Ridge Systems (MORS). Eighteen elements with wide range of residence times ( t) in seawater (Mn, Th, Al, Bi, Ce, Co, Cr(III), Fe, Nd, Pb, Sc, Sm, Ag, Cd, Cu, Hg, Ni and Zn) have been considered. A model for the regulation of trace metal composition in seawater by cation hydrolytic processes, including those at MORS, is presented. Results show an increase in the abundance of neutral metal hydroxyl species with increase in temperature. During hydrothermal mixing, as the temperature increases, transformation from lower positive hydroxyl complexes to higher or neutral complexes would occur for Cd, Ce, Co, Cr(III), Cu, Mn, Nd, Ni, Pb, Sm and Zn. pH values for adsorption of the metal ion onto solid surfaces have direct relation with pH values of hydrolysis. Co, Mn and Pb could be oxidized to higher states (at Mn-oxide surfaces) that would occur even at MORS. Ce can also be oxidized at 25°C. Solubility calculations show that Al, Bi, Cr(III), Sc, Fe and Th are saturated while Ce, Nd and Sm are not with respect to their oxyhydroxide solids at their concentrations in seawater at 25°C. Cu, Hg, Ni and Zn reach saturation equilibrium at 250°C, whereas Co, Mn and Pb exhibit unsaturation. The results suggest an increase in scavenging capacity of a cation with rise in temperature.

Ylide Ligands as Building Blocks for Bioactive Group 11 Metal Complexes.

PubMed

Gimeno, M Concepción; Johnson, Alice; Marzo, Isabel

2018-05-22

The reactivity of the phosphonium salt, (cyanomethyl)triphenylphosphonium chloride, and the ylide, triphenylphosphoniumcyanomethylide, towards group eleven metal complexes is described. Mononuclear neutral gold(I) and gold(III) complexes of the type [AuX{CH(CN)PPh3}] or [AuX3{CH(CN)PPh3}], and cationic derivatives such as [AuL{CH(CN)PPh3}]X have been prepared. Surprisingly the cationic gold species could only be prepared with ligands with a large steric hindrance such as bulky NHCs or the JohnPhos phosphine, in contrast with silver and copper derivatives which have dimeric structures with coordination to the cyano group of the ylide. Bis(ylide)metal complexes have been synthesised in which a different structure is observed for gold compared to copper and silver. While gold shows mononuclear species, the silver complex presents a bidimensional polymeric structure as a result of further coordination of the silver centre to the nitrogen of the cyano group. These complexes possess two chiral centres and the gold compound is obtained as a mixture of diastereoisomers, whereas the copper and silver derivatives afford only one diastereroisomer. These compounds were screened for the in vitro cytotoxic activity against the human lung carcinoma cell line (A549). The IC50 values reveal an excellent cytotoxic activity for these metal complexes compared with cisplatin. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel thioarsenates {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2'-bipyridine.

PubMed

Liu, Guang-Ning; Guo, Guo-Cong; Wang, Ming-Sheng; Huang, Jin-Shun

2014-03-14

Two novel manganese thioarsenates, {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 (1, 2,2'-bipy = 2,2'-bipyridine) and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2'-bipy complex cations were synthesized. They feature two terminal [Mn(2,2'-bipy)2(SCN)](+) complex cations bridged by a polyanion {[Mn(2,2'-bipy)]2(As(V)S4)2}(2-) for 1 and a cyclic thioarsenate anion (As(III)2S6)(2-) for 2. In 2, the [As(III)2(S2)2S2](2-) anion can be described as two (As(III)S3)(3-) trigonal-pyramids interlinked through S-S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between Mn(II) centers in the two compounds.

Interaction of monovalent cations with acetonitrile

NASA Astrophysics Data System (ADS)

Černušák, Ivan; Aranyosiová, Monika; Vollárová, Ol'ga; Velič, Dušan; Kirdajová, Ol'ga; Benko, Ján

Solvation of monovalent cations (Me+) of alkali metals=Na+, K+, Rb+, and Cs+, coinage metals=Cu+, Ag+, Au+, and p-block elements Ga+, In+, and Tl+ with acetonitrile was studied by means of ab initio calculations and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The intermolecular interactions in the complexes Me+···CH3CN were investigated using the coupled clusters theory including single, double, and noniterative triple substitutions (CCSD(T)) in conjunction with the Pol and Pol-dk basis sets. The binding energies of these donor-acceptor complexes were estimated; taking into account the basis set superposition error, zero-point vibrations, correlation contribution, and scalar relativistic corrections. The theoretical ΔG0298 K values based on CCSD(T)/Pol and/or CCSD(T)/Pol-dk binding energies correlated well with experimental transfer Gibbs energies (from water to acetonitrile) for the series of cations. In the case of Au monocation, relativistic correction turned out to be extremely important. Composition of the complex of Ag+ and Na+ with acetonitrile was determined by using SIMS supporting both theoretical and experimental transfer Gibbs energies.

Cation-induced coagulation of aquatic plant-derived dissolved organic matter: Investigation by EEM-PARAFAC and FT-IR spectroscopy.

PubMed

Liu, Shasha; Zhu, Yuanrong; Liu, Leizhen; He, Zhongqi; Giesy, John P; Bai, Yingchen; Sun, Fuhong; Wu, Fengchang

2018-03-01

Complexation and coagulation of plant-derived dissolved organic matter (DOM) by metal cations are important biogeochemical processes of organic matter in aquatic systems. Thus, coagulation and fractionation of DOM derived from aquatic plants by Ca(II), Al(III), and Fe(III) ions were investigated. Metal ion-induced removal of DOM was determined by analyzing dissolved organic carbon in supernatants after addition of these metal cations individually. After additions of metal ions, both dissolved and coagulated organic fractions were characterized by use of fluorescence excitation emission matrix-parallel factor (EEM-PARAFAC) analysis and Fourier transform infrared (FT-IR) spectroscopy. Addition of Ca(II), Fe(III) or Al(III) resulted in net removal of aquatic plant-derived DOM. Efficiencies of removal of DOM by Fe(III) or Al(III) were greater than that by Ca(II). However, capacities to remove plant-derived DOM by the three metals were less than which had been previously reported for humic materials. Molecular and structural features of plant-derived DOM fractions in associations with metal cations were characterized by changes in fluorescent components and infrared absorption peaks. Both aromatic and carboxylic-like organic matters could be removed by Ca(II), Al(III) or Fe(III) ions. Whereas organic matters containing amides were preferentially removed by Ca(II), and phenolic materials were selectively removed by Fe(III) or Al(III). These observations indicated that plant-derived DOM might have a long-lasting effect on water quality and organisms due to its poor coagulation with metal cations in aquatic ecosystems. Plant-derived DOM is of different character than natural organic matter and it is not advisable to attempt removal through addition of metal salts during treatment of sewage. Copyright © 2017 Elsevier Ltd. All rights reserved.

Visual Observation of Dissolution of Copper Ions from a Copper Electrode

ERIC Educational Resources Information Center

Ikemoto, Isao; Saitou, Kouichi

2013-01-01

During electrolysis, to visually observe the conversion of a metal to its cation, either the cation or its complex ion should have a distinct color while the electrolyte solution must be colorless and transparent. A demonstration is described in which copper is used as the electrodes and sodium polyacrylate (a superabsorbent polymer) solution is…

[Ni(cod) 2][Al(OR F) 4], a Source for Naked Nickel(I) Chemistry

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

Schwab, Miriam M.; Himmel, Daniel; Kacprzak, Sylwia

The straightforward synthesis of the cationic, purely organometallic Ni I salt [Ni(cod) 2] +[Al(OR F) 4] - was realized through a reaction between [Ni(cod) 2] and Ag[Al(OR F) 4] (cod=1,5-cyclooctadiene). Crystal-structure analysis and EPR, XANES, and cyclic voltammetry studies confirmed the presence of a homoleptic NiI olefin complex. Weak interactions between the metal center, the ligands, and the anion provide a good starting material for further cationic NiI complexes.

Structural investigations of transition metal (II) tetracyanonickelate complexes of 3-chloropyridine using Fourier transform-infrared and laser Raman spectroscopy

NASA Astrophysics Data System (ADS)

Akyüz, Sevim; Akyüz, Tanil; Eric, J.; Davies, D.

1992-01-01

The FT-IR and laser-Raman spectra of five new complexes of the formula ML 2Ni(CN) 4 (where MMn, Fe, Ni, Zn or Cd; L3-chloropyridine) are reported. The complexes are shown to have a structure consisting of two dimensional polymeric layers formed with Ni(CN) 4 ions bridged by ML 2 cations. For a given series of isomorphous complexes, the effects of metal ligand bond formation on the ligand vibrational modes are examined and the metal-sensitivity sequence of the ligand frequencies is found to be Mn≈Cd

Structures and physical properties of gaseous metal cationized biological ions.

PubMed

Burt, Michael B; Fridgen, Travis D

2012-01-01

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

A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2·M] 4+ Cation–Cation Complexes

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

Freiderich, John W.; Burn, Adam G.; Martin, Leigh R.

The equilibrium constants for [NpO 2M∙] 4+ (M = Al 3+, In 3+, Sc 3+, Fe 3+) in μ = 10 M nitric acid and [NpO 2∙Ga] 4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe 3+ > Sc 3+ In 3+ > Ga 3+ Al 3+. These equilibrium constants are compared to those of previously reported values for NpO 2 + complexes with Cr 3+ and Rh 3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicatingmore » that the NpO 2 + dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.« less

Transition-Metal Hydride Radical Cations.

PubMed

Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R

2016-08-10

Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2·M] 4+ Cation–Cation Complexes

DOE PAGES

Freiderich, John W.; Burn, Adam G.; Martin, Leigh R.; ...

2017-04-14

The equilibrium constants for [NpO 2M∙] 4+ (M = Al 3+, In 3+, Sc 3+, Fe 3+) in μ = 10 M nitric acid and [NpO 2∙Ga] 4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe 3+ > Sc 3+ In 3+ > Ga 3+ Al 3+. These equilibrium constants are compared to those of previously reported values for NpO 2 + complexes with Cr 3+ and Rh 3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicatingmore » that the NpO 2 + dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.« less

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

Koepf, Matthieu; Bergkamp, Jesse J.; Teillout, Anne-Lucie

The association of different metals in stable, well-defined molecular assemblies remains a great challenge of supramolecular chemistry. In such constructs, the emergence of synergism, or cooperative effects between the different metal centers is particularly intriguing. These effects can lead to uncommon reactivity or remarkable physico-chemical properties that are not otherwise achievable. For example, the association of alkaline or alkaline-earth cations and transition metals is pivotal for the activity of several biomolecules and human-made catalysts that carry out fundamental redox transformations (water oxidation, nitrogen reduction, water–gas shift reaction, etc.). In many cases the precise nature of the interactions between the alkaline-earthmore » cations and the redox-active transition metals remains elusive due to the difficulty of building stable molecular heterometallic assemblies that associate transition metals and alkaline or alkaline-earth cations in a controlled way. In this work we present the rational design of porphyrin-based ligands possessing a second binding site for alkaline-earth cations above the porphyrin macrocycle primary complexation site. We demonstrate that by using a combination of crown ether and carboxylic acid substituents suitably positioned on the periphery of the porphyrin, bitopic ligands can be obtained. The binding of calcium, a typical alkaline-earth cation, by the newly prepared ligands has been studied in detail and we show that a moderately large binding constant can be achieved in protic media using ligands that possess some degree of structural flexibility. The formation of Zn–Ca assemblies discussed in this work is viewed as a stepping stone towards the assembly of well defined molecular transition metal-alkaline earth bimetallic centers using a versatile organic scaffold.« less

Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions.

PubMed

Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry

2013-05-20

A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.

Atomistic Modeling of Cation Diffusion in Transition Metal Perovskites La1-xSrxMnO3+/-δfor Solid Oxide Fuel Cell Cathodes Applications

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan; Abernathy, Harry

Cation diffusion in La1-xSrxMnO3+/-δ (LSM) and in related perovskite materials play an important role in controlling long term performance and stability of solid oxide fuel cell (SOFCs) cathodes. Due to sluggish rates of cation diffusion and complex coupling between defect chemistry and cation diffusion pathways, currently there is still lack of quantitative theoretical model predictions on cation diffusivity vs. T and P(O2) to describe experimental cation tracer diffusivities. In this work, based on ab initio modeling of LSM defect chemistry and migration barriers of the possible cation diffusion pathways, we assess the rates of A-site and B-site cation diffusion in a wide range of T and P(O2) at x =0.0 and 0.2 for SOFC applications. We demonstrate the active cation diffusion pathways in LSM involve cation defect clusters as cation transport carriers, where reduction in the cation migration barriers, which are governed by the steric effect associated with the metal-oxygen cage in the perovskite lattice, is much greater than the penalty of repulsive interaction in the A-site and B-site cation vacancy clusters, leading to higher cation diffusion rates as compared to those of single cation vacancy hopping mechanisms. The predicted Mn and La/Sr cation self-diffusion coefficients of LSM at at x =0.0 and 0.2 along with their 1/T and P(O2) dependences, are in good agreement with the experimental tracer diffusion coefficients.

Structure of zirconocene complexes relevant for olefin catalysis: infrared fingerprint of the Zr(C(5)H(5))(2)(OH)(CH(3)CN)(+) cation in the gas phase.

PubMed

Lagutschenkov, Anita; Springer, Andreas; Lorenz, Ulrich Joseph; Maitre, Philippe; Dopfer, Otto

2010-02-11

Cationic zirconocene complexes are active species in Ziegler-Natta catalysis for olefin polymerization. Their structure and metal-ligand bond strength strongly influence their activity. In the present work, the infrared multiphoton dissociation (IRMPD) spectrum of mass selected Zr(C(5)H(5))(2)(OH)(CH(3)CN)(+) cations was obtained in the 300-1500 cm(-1) fingerprint range by coupling a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer equipped with an electrospray ionization (ESI) source and the infrared free electron laser (IR-FEL) at the Centre Laser Infrarouge d'Orsay (CLIO). The experimental efforts are complemented by quantum chemical calculations at the MP2 and B3LYP levels using the 6-311G* basis set. Vibrational assignments of transitions observed in the IRMPD spectra to modes of the Zr-O-H, C(5)H(5), and CH(3)CN moieties are based on comparison to calculated linear absorption spectra. Both the experimental data and the calculations provide unprecedented information about structure, metal-ligand bonding, charge distribution, and binding energy of the complex.

Bimetallic d10 -Metal Complexes of a Bipyridine Substituted N-Heterocyclic Carbene.

PubMed

Kaub, Christoph; Lebedkin, Sergei; Li, Alina; Kruppa, Sebastian V; Strebert, Patrick H; Kappes, Manfred M; Riehn, Christoph; Roesky, Peter W

2018-04-20

The hybrid ligand 3-(2,2'-bipyridine-6-ylmethyl)-1-mesityl-1H-imidazolylidene (NHC Bipy ) featuring both carbene and N-donor sites, was selectively complexed with various d 10 metal cations in order to examine its coordination behavior with regard to homo and heterometallic structures. Respective silver complexes can be obtained by the silver oxide route and are suitable transmetallation reagents for the synthesis of gold(I) compounds. Starting from the mononuclear complexes [(NHC Bipy )AuCl], [(NHC Bipy )Au(C 6 F 5 )] and [(NHC Bipy ) 2 Au][ClO 4 ], open-chain as well as cyclic heterobimetallic complexes containing Cu + , Ag + , Zn 2+ , Cd 2+ , and Hg 2+ were synthesized. Furthermore, the homobimetallic species [(NHC Bipy ) 2 M 2 ][ClO 4 ] 2 (M=Cu, Ag) were obtained. All bimetallic compounds were fully characterized including single-crystal X-ray analysis. Their photoluminescence (PL) properties were investigated in the solid state at temperatures between 15 and 295 K and compared with those of the mononuclear species. There is a clear difference in PL properties between the open chain and the cyclic heterobimetallic complexes. The latter species show different PL properties, depending on the metals involved. In addition, collision-induced dissociation (CID) experiments were performed on electrosprayed cations of the cyclic heterobimetallic compounds, to compare the metal binding at the carbene and N-donor sites. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal complexes of quinolone antibiotics and their applications: an update.

PubMed

Uivarosi, Valentina

2013-09-11

Quinolones are synthetic broad-spectrum antibiotics with good oral absorption and excellent bioavailability. Due to the chemical functions found on their nucleus (a carboxylic acid function at the 3-position, and in most cases a basic piperazinyl ring (or another N-heterocycle) at the 7-position, and a carbonyl oxygen atom at the 4-position) quinolones bind metal ions forming complexes in which they can act as bidentate, as unidentate and as bridging ligand, respectively. In the polymeric complexes in solid state, multiple modes of coordination are simultaneously possible. In strongly acidic conditions, quinolone molecules possessing a basic side nucleus are protonated and appear as cations in the ionic complexes. Interaction with metal ions has some important consequences for the solubility, pharmacokinetics and bioavailability of quinolones, and is also involved in the mechanism of action of these bactericidal agents. Many metal complexes with equal or enhanced antimicrobial activity compared to the parent quinolones were obtained. New strategies in the design of metal complexes of quinolones have led to compounds with anticancer activity. Analytical applications of complexation with metal ions were oriented toward two main directions: determination of quinolones based on complexation with metal ions or, reversely, determination of metal ions based on complexation with quinolones.

Novel alanines bearing a heteroaromatic side chain: synthesis and studies on fluorescent chemosensing of metal cations with biological relevance.

PubMed

Ferreira, Rosa Cristina M; Raposo, Maria Manuela M; Costa, Susana P G

2018-06-01

A family of novel thienylbenzoxazol-5-yl-L-alanines, consisting of an alanine core bearing a benzoxazole at the side chain with a thiophene ring at position 2, substituted with different (hetero)aryl substituents, was synthesised to study the tuning of the photophysical and chemosensory properties of the resulting compounds. These novel heterocyclic alanines 3a-f and a series of structurally related bis-thienylbenzoxazolyl-alanines 3g-j were evaluated for the first time in the recognition of selected metal cations with environmental, medicinal and analytical interest such as Co 2+ , Cu 2+ , Zn 2+ and Ni 2+ , in acetonitrile solution, with the heterocycles at the side chain acting simultaneously as the coordinating and reporting units, via fluorescence changes. This behaviour can be explained by the involvement of the electron donor heteroatoms in the recognition event, through complexation of the metal cations. The spectrofluorimetric titrations showed that thienylbenzoxazolyl-alanines 3a-j and 4a,b were non-selective fluorimetric chemosensors for the above-mentioned cations, with the best results being obtained for the interaction of Cu 2+ with bis-alanine 3j and deprotected alanines 4a,b. The encouraging photophysical and metal ion sensing properties of these thienylbenzoxazolyl-alanines suggest that they can be used to obtain bioinspired fluorescent reporters for metal ion such as peptides/proteins with chemosensory/probing ability.

Double C-H activation of ethane by metal-free SO2*+ radical cations.

PubMed

de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

2010-06-01

The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

Single metal catalysis: DFT and CAS modelling of species involved in the Fe cation assisted transformation of acetylene to benzene

NASA Astrophysics Data System (ADS)

Altun, Zikri; Bleda, Erdi; Trindle, Carl

2017-09-01

Gas phase conversion of acetylene to benzene, assisted by a single metal cation such as Fe(+), Ru(+) and Rh(+), offers an attractive prospect for application of computational modelling techniques to catalytic processes. Gas phase processes are not complicated by environmental effects and the participation of a single metal atom is a significant simplification. Still the process is complex, owing to the possibility of several low-energy spin states and the abundance of alternative structures. By density functional theory modelling using recently developed models with range and dispersion corrections, we locate and characterise a number of extreme points on the FeC6H6(+) surface, some of which have not been described previously. These include eta-1, eta-2 and eta-3 complexes of Fe(+) with the C4H4 ring. We identify new FeC6H6(+) structures as well, which may be landmarks for the Fe(+)-catalysed production of benzene from acetylene. The Fe(+) benzene complex is the most stable species on the FeC6H6 cation surface. With the abundant energy of complexation available in the isolated gas phase species, detachment of the Fe(+) and production of benzene can be efficient. We address the issue raised by other investigators whether multi-configurational self-consistent field methods are essential to the proper description of these systems. We find that the relative energy of intrinsically multi-determinant doublets is strongly affected, but judge that the density functional theory (DFT) description provides more accurate estimates of energetics and a more plausible reaction path.

Analysis of the bonding in XH3Cu+ (XB, Al, Ga) complexes

NASA Astrophysics Data System (ADS)

Corral, Inés; Mó, Otilia; Yáñez, Manuel

High-level density functional theory (DFT) calculations on XH3Cu+ (XB, Al, Ga) complexes show that the attachment of the metal cation to the base takes place through agostic-type interactions. These interactions that can be viewed as dative bonds from the σXH bonding orbitals of the base toward low-lying empty 4s orbitals of the metal cation, and back-donations from the lone pairs of the metal into the σ *XH antibonding orbitals of the neutral, are particularly favored when the XH bonds have a high X+δH-δ polarity. Accordingly, the AlH3 and GaH3 Cu+ binding energies are very similar, but much larger than that of BH3. Depopulation of the σXH bonding orbital and the concomitant population of the σ *XH antibonding orbital involved in the agostic interaction result in a significant weakening of the corresponding XH linkages, whose bond length increases and whose stretching frequency appears red-shifted.

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

Alí-Torres, Jorge; Mirats, Andrea; Maréchal, Jean-Didier

Amyloid plaques formation and oxidative stress are two key events in the pathology of the Alzheimer disease (AD), in which metal cations have been shown to play an important role. In particular, the interaction of the redox active Cu{sup 2+} metal cation with Aβ has been found to interfere in amyloid aggregation and to lead to reactive oxygen species (ROS). A detailed knowledge of the electronic and molecular structure of Cu{sup 2+}-Aβ complexes is thus important to get a better understanding of the role of these complexes in the development and progression of the AD disease. The computational treatment ofmore » these systems requires a combination of several available computational methodologies, because two fundamental aspects have to be addressed: the metal coordination sphere and the conformation adopted by the peptide upon copper binding. In this paper we review the main computational strategies used to deal with the Cu{sup 2+}-Aβ coordination and build plausible Cu{sup 2+}-Aβ models that will afterwards allow determining physicochemical properties of interest, such as their redox potential.« less

Examination of molecular mechanism for the enhanced thermal stability of anthocyanins by metal cations and polysaccharides.

PubMed

Tachibana, Noriko; Kimura, Yukihiro; Ohno, Takashi

2014-01-15

Anthocyanins exhibit colour variation over wide pH range but the colour stability is relatively low at the physiological pH. To improve the stability of anthocyanins in neutral to weakly acidic pH region, effects of metal cations and polysaccharides on the colour stability of cyanidin-3-glucoside (C3G) were examined by ultraviolet-visible and resonance Raman spectroscopies. C3G was thermally stabilized by the addition of Fe(3+) but formed aggregation. However, further addition of anionic polysaccharides enhanced the thermal stability of C3G without aggregation. Similar stabilisation was confirmed for delphinidin-3-glucoside (D3G) but not for pelargonidin-3-glucoside. The stability of anthocyanins considerably varied depending on pHs and kinds of metal cations, polysaccharides and buffer molecules. The characteristic resonance Raman bands of C3G-Fe(3+) and D3G-Fe(3+) complexes were significantly affected by the addition of alginate, (18)O/(16)O-isotope substitution, and Fe(2+)/Fe(3+)-replacement. These results suggest that alginate associates with C3G through Fe(3+) to form a stable complex, which enhances the thermal stability of C3G. Copyright © 2013 Elsevier Ltd. All rights reserved.

Properties and applications of zeolites.

PubMed

Rhodes, Christopher J

2010-01-01

Zeolites are aluminosilicate solids bearing a negatively charged honeycomb framework of micropores into which molecules may be adsorbed for environmental decontamination, and to catalyse chemical reactions. They are central to green-chemistry since the necessity for organic solvents is minimised. Proton-exchanged (H) zeolites are extensively employed in the petrochemical industry for cracking crude oil fractions into fuels and chemical feedstocks for other industrial processes. Due to their ability to perform cation-exchange, in which the cations that are originally present to counterbalance the framework negative charge may be exchanged out of the zeolite by cations present in aqueous solution, zeolites are useful as industrial water-softeners, in the removal of radioactive Cs+ and Sr2+ cations from liquid nuclear waste and in the removal of toxic heavy metal cations from groundwaters and run-off waters. Surfactant-modified zeolites (SMZ) find particular application in the co-removal of both toxic anions and organic pollutants. Toxic anions such as arsenite, arsenate, chromate, cyanide and radioactive iodide can also be removed by adsorption into zeolites that have been previously loaded with co-precipitating metal cations such as Ag+ and Pb2+ which form practically insoluble complexes that are contained within the zeolite matrix.

Nuclear quantum effects on adsorption of H2 and isotopologues on metal ions

NASA Astrophysics Data System (ADS)

Savchenko, Ievgeniia; Gu, Bing; Heine, Thomas; Jakowski, Jacek; Garashchuk, Sophya

2017-02-01

The nuclear quantum effects on the zero-point energy (ZPE), influencing adsorption of H2 and isotopologues on metal ions, are examined using normal mode analysis of ab initio electronic structure results for complexes with 17 metal cations. The lightest metallic nuclei, Li and Be, are found to be the most 'quantum'. The largest selectivity in adsorption is predicted for Cu, Ni and Co ions. Analysis of the nuclear wavepacket dynamics on the ground state electronic potential energy surfaces (PES) performed for complexes of Li+ and Cu+2 with H2/D2/HD shows that the PES anharmonicity changes the ZPE by up to 9%.

Manganese(II), iron(II), cobalt(II), and copper(II) complexes of an extended inherently chiral tris-bipyridyl cage.

PubMed

Perkins, David F; Lindoy, Leonard F; McAuley, Alexander; Meehan, George V; Turner, Peter

2006-01-17

Manganese(II), iron(II), cobalt(II), and copper(II) derivatives of two inherently chiral, Tris(bipyridyl) cages (L and L') of type [ML]-(PF(6))(2)(solvent)(n) and [FeL'](ClO(4))(2) are reported, where L is the hexa-tertiary butyl-substituted derivative of L'. These products were obtained by using the free cage and metal template procedures; the latter involved the reductive amination of the respective Tris-dialdehyde precursor complexes of iron(II), cobalt(II), or nickel(II). Electrochemical, EPR, and NMR studies have been used to probe the nature of the individual complexes. X-ray structures of the manganese(II), iron(II), and copper(II) complexes of L and the iron(II) complex of L' are presented; these are compared with the previously reported structures of the corresponding nickel(II) complex and metal-free cage (L). In each complex the metal cation occupies the cage's central cavity and is coordinated to six nitrogens from the three bipyridyl groups. The cations [MnL](2+) and [FeL](2+) are isostructural but both exhibit a different arrangement of the bound cage to that observed in the corresponding nickel(II) and copper(II) complexes. The latter have an exo-exo arrangement of the bridgehead nitrogen lone pairs, with the metal inducing a triple helical twist that extends approximately 22 A along the axial length of each complex. In contrast, [MnL](2+) and [FeL](2+) have their terminal nitrogen lone pairs directed endo, causing a significant change in the configuration of the bound ligand. In [FeL'](2+), the cage has both bridgehead nitrogen lone pairs orientated exo. Semiempirical calculations indicate that the observed endo-endo and exo-exo arrangements are of comparable energy.

The fundamental flaw of the HSAB principle is revealed by a complete speciation analysis of the [PtCl(6-n)Br(n)](2-) (n = 0-6) system.

PubMed

Gerber, W J; van Wyk, P-H; van Niekerk, D M E; Koch, K R

2015-02-28

Bjerrum's model of step-wise ligand exchange is extended to compute a complete speciation diagram for the [PtCl6-nBrn](2-) (n = 0-6) system including all 17 equilibrium constants concerning the Pt(IV) chlorido-bromido exchange reaction network (HERN). In contrast to what the hard soft acid base (HSAB) principle "predicts", the thermodynamic driving force for the replacement of chloride by bromide in an aqueous matrix, for each individual ligand exchange reaction present in the Pt(IV) HERN, is due to the difference in halide hydration energy and not bonding interactions present in the acid-base complex. A generalized thermodynamic test calculation was developed to illustrate that the HSAB classified class (b) metal cations Ag(+), Au(+), Au(3+), Rh(3+), Cd(2+), Pt(2+), Pt(4+), Fe(3+), Cd(2+), Sn(2+) and Zn(2+) all form thermodynamically stable halido complexes in the order F(-) ≫ Cl(-) > Br(-) > I(-) irrespective of the sample matrix. The bonding interactions in the acid-base complex, e.g. ionic-covalent σ-bonding, Π-bonding and electron correlation effects, play no actual role in the classification of these metal cations using the HSAB principle. Instead, it turns out that the hydration/solvation energy of halides is the reason why metal cations are categorized into two classes using the HSAB principle which highlights the fundamental flaw of the HSAB principle.

Magnetic behavior control in niccolite structural metal formate frameworks [NH2(CH3)2][Fe(III)M(II)(HCOO)6] (M = Fe, Mn, and Co) by varying the divalent metal ions.

PubMed

Zhao, Jiong-Peng; Hu, Bo-Wen; Lloret, Francesc; Tao, Jun; Yang, Qian; Zhang, Xiao-Feng; Bu, Xian-He

2010-11-15

By changing template cation but introducing trivalent iron ions in the known niccolite structural metal formate frameworks, three complexes formulated [NH(2)(CH(3))(2)][Fe(III)M(II)(HCOO)(6)] (M = Fe for 1, Mn for 2, and Co for 3) were synthesized and magnetically characterized. The variation in the compositions of the complexes leads to three different complexes: mixed-valent complex 1, heterometallic but with the same spin state complex 2, and heterometallic heterospin complex 3. The magnetic behaviors are closely related to the divalent metal ions used. Complex 1 exhibits negative magnetization assigned as Néel N-Type ferrimagnet, with an asymmetric magnetization reversal in the hysteresis loop, and complex 2 is an antiferromagnet with small spin canting (α(canting) ≈ 0.06° and T(canting) = 35 K), while complex 3 is a ferrimagnet with T(N) = 32 K.

Interaction of Cu(+) with cytosine and formation of i-motif-like C-M(+)-C complexes: alkali versus coinage metals.

PubMed

Gao, Juehan; Berden, Giel; Rodgers, M T; Oomens, Jos

2016-03-14

The Watson-Crick structure of DNA is among the most well-known molecular structures of our time. However, alternative base-pairing motifs are also known to occur, often depending on base sequence, pH, or the presence of cations. Pairing of cytosine (C) bases induced by the sharing of a single proton (C-H(+)-C) may give rise to the so-called i-motif, which occurs primarily in expanded trinucleotide repeats and the telomeric region of DNA, particularly at low pH. At physiological pH, silver cations were recently found to stabilize C dimers in a C-Ag(+)-C structure analogous to the hemiprotonated C-dimer. Here we use infrared ion spectroscopy in combination with density functional theory calculations at the B3LYP/6-311G+(2df,2p) level to show that copper in the 1+ oxidation state induces an analogous formation of C-Cu(+)-C structures. In contrast to protons and these transition metal ions, alkali metal ions induce a different dimer structure, where each ligand coordinates the alkali metal ion in a bidentate fashion in which the N3 and O2 atoms of both cytosine ligands coordinate to the metal ion, sacrificing hydrogen-bonding interactions between the ligands for improved chelation of the metal cation.

Involvement of the exomer complex in the polarized transport of Ena1 required for Saccharomyces cerevisiae survival against toxic cations

PubMed Central

Anton, Carlos; Zanolari, Bettina; Arcones, Irene; Wang, Congwei; Mulet, Jose Miguel; Spang, Anne; Roncero, Cesar

2017-01-01

Exomer is an adaptor complex required for the direct transport of a selected number of cargoes from the trans-Golgi network (TGN) to the plasma membrane in Saccharomyces cerevisiae. However, exomer mutants are highly sensitive to increased concentrations of alkali metal cations, a situation that remains unexplained by the lack of transport of any known cargoes. Here we identify several HAL genes that act as multicopy suppressors of this sensitivity and are connected to the reduced function of the sodium ATPase Ena1. Furthermore, we find that Ena1 is dependent on exomer function. Even though Ena1 can reach the plasma membrane independently of exomer, polarized delivery of Ena1 to the bud requires functional exomer. Moreover, exomer is required for full induction of Ena1 expression after cationic stress by facilitating the plasma membrane recruitment of the molecular machinery involved in Rim101 processing and activation of the RIM101 pathway in response to stress. Both the defective localization and the reduced levels of Ena1 contribute to the sensitivity of exomer mutants to alkali metal cations. Our work thus expands the spectrum of exomer-dependent proteins and provides a link to a more general role of exomer in TGN organization. PMID:29021337

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

USGS Publications Warehouse

Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W.

2004-01-01

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the pKa2 and ?? values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER. ?? 2003 Elsevier Ltd. All rights reserved.

Evidence of an inverted hexagonal phase in self-assembled phospholipid-DNA-metal complexes

NASA Astrophysics Data System (ADS)

Francescangeli, O.; Pisani, M.; Stanic, V.; Bruni, P.; Weiss, T. M.

2004-08-01

We report the first observation of an inverted hexagonal phase of phospholipid-DNA-metal complexes. These ternary complexes are formed in a self-assembled manner when water solutions of neutral lipid dioleoylphosphatidylethanolamine (DOPE), DNA and divalent metal cations (Me2+; Me=Fe, Co, Mg, Mn) are mixed, which represents a striking example of supramolecular chemistry. The structure, derived from synchrotron X-ray diffraction, consists of cylindrical DNA strands coated by neutral lipid monolayers and arranged on a two-dimensional hexagonal lattice (HIIc). Besides the fundamental aspects, DOPE-DNA-Me2+ complexes may be of great interest as efficient nonviral delivery systems in gene therapy applications because of the low inherent cytotoxicity and the potential high transfection efficiency.

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Copper toxicity and organic matter: Resiliency of watersheds in the Duluth Complex, Minnesota, USA

USGS Publications Warehouse

Piatak, Nadine; Seal, Robert; Jones, Perry M.; Woodruff, Laurel G.

2015-01-01

We estimated copper (Cu) toxicity in surface water with high dissolved organic matter (DOM) for unmined mineralized watersheds of the Duluth Complex using the Biotic Ligand Model (BLM), which evaluates the effect of DOM, cation competition for biologic binding sites, and metal speciation. A sediment-based BLM was used to estimate stream-sediment toxicity; this approach factors in the cumulative effects of multiple metals, incorporation of metals into less bioavailable sulfides, and complexation of metals with organic carbon. For surface water, the formation of Cu-DOM complexes significantly reduces the amount of Cu available to aquatic organisms. The protective effects of cations, such as calcium (Ca) and magnesium (Mg), competing with Cu to complex with the biotic ligand is likely not as important as DOM in water with high DOM and low hardness. Standard hardness-based water quality criteria (WQC) are probably inadequate for describing Cu toxicity in such waters and a BLM approach may yield more accurate results. Nevertheless, assumptions about relative proportions of humic acid (HA) and fulvic acid (FA) in DOM significantly influence BLM results; the higher the HA fraction, the higher calculated resiliency of the water to Cu toxicity. Another important factor is seasonal variation in water chemistry, with greater resiliency to Cu toxicity during low flow compared to high flow.Based on generally low total organic carbon and sulfur content, and equivalent metal ratios from total and weak partial extractions, much of the total metal concentration in clastic streambedsediments may be in bioavailable forms, sorbed on clays or hydroxide phases. However, organicrich fine-grained sediment in the numerous wetlands may sequester significant amount of metals, limiting their bioavailability. A high proportion of organic matter in waters and some sediments will play a key role in the resiliency of these watersheds to potential additional metal loads associated with future mining operations.

Superconductor precursor mixtures made by precipitation method

DOEpatents

Bunker, Bruce C.; Lamppa, Diana L.; Voigt, James A.

1989-01-01

Method and apparatus for preparing highly pure homogeneous precursor powder mixtures for metal oxide superconductive ceramics. The mixes are prepared by instantaneous precipitation from stoichiometric solutions of metal salts such as nitrates at controlled pH's within the 9 to 12 range, by addition of solutions of non-complexing pyrolyzable cations, such as alkyammonium and carbonate ions.

Fluorophore Metal-Organic Complexes: High-Throughput Optical Screening for Aprotic Electrochemical Systems.

PubMed

Park, Sung Hyeon; Choi, Chang Hyuck; Lee, Seung Yong; Woo, Seong Ihl

2017-02-13

Combinatorial optical screening of aprotic electrocatalysts has not yet been achieved primarily due to H + -associated mechanisms of fluorophore modulation. We have overcome this problem by using fluorophore metal-organic complexes. In particular, eosin Y and quinine can be coordinated with various metallic cations (e.g., Li + , Na + , Mg 2+ , Zn 2+ , and Al 3+ ) in aprotic solvents, triggering changes in their fluorescent properties. These interactions have been used in a reliable screening method to determine oxygen reduction/evolution reaction activities of 100 Mn-based binary catalysts for the aprotic Li-air battery.

New electrolyte systems for capillary zone electrophoresis of metal cations and non-ionic organic compounds

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

Shi, Youchun

Excellent separations of metal ions can be obtained very quickly by capillary electrophoresis provided a weak complexing reagent is incorporated into the electrolyte to alter the effective mobilities of the sample ions. Indirect photometric detection is possible by also adding a UV-sensitive ion to the electrolyte. Separations are described using phthalate, tartrate, lactate or hydroxyisobutyrate as the complexing reagent. A separation of twenty-seven metal ions was achieved in only 6 min using a lactate system. A mechanism for the separation of lanthanides is proposed for the hydroxyisobutyrate system.

Self-assembly of Terbium(III)-based metal-organic complexes with two-photon absorbing active

NASA Astrophysics Data System (ADS)

Li, Dandan; Shao, Nanqi; Sun, Xianshun; Zhang, Guocui; Li, Shengli; Zhou, Hongping; Wu, Jieying; Tian, Yupeng

2014-12-01

Hybrid complexes based on D-π-A type dyes p-aminostyryl-pyridinum and Terbium(III) complex anion (1, 2) have been synthesized by ionic exchange reaction. Meanwhile two different alkyl-substituted amino groups were used as electron donors in organic dyes cations. The synthesized complexes were characterized by element analysis. In addition, the structural features of them were systematic studied by single crystal X-ray diffraction analysis. Their linear properties have been systematically investigated by absorption spectra and fluorescence, the results show that the energy transfer takes place from the trans-4-[4‧-(N,N-diethylamino)styryl]-N-methyl pyridinium (2‧) cation to Tb(III). In addition, complex 2 exhibit a large two-photon absorption coefficient β: 0.044 cm/GW at 710 nm.

Effect of solvent, electronic, and steric factors on the reactivity of 1,1'-diethylferrocene, 1,1'-diacetylferrocene, and 1,1'-bis(diphenylphosphino)ferrocene towards hydrogen peroxide

NASA Astrophysics Data System (ADS)

Fomin, V. M.; Kochetkova, K. S.; Galkina, M. S.

2017-07-01

The oxidation of Fc(C2H5)2, Fc(COCH3)2, and Fc(PPh2)2, where Fc is a ferrocene, with hydrogen peroxide in aprotic (dioxane and acetonitrile) and hydroxyl-containing (ethanol, acetonitrile-water, and water) solvents is studied via electron spectroscopy. The reactivity of these metal complexes relative to an oxidant is due to the electron-donor or electron-acceptor properties of substituents, their sizes, and their capability for the specific solvation by a particular solvent. Possible mechanisms of the oxidation of metal complexes are discussed. When Fc(PPh2)2 is oxidized, the formation of ferrocenyl cation Fc+(PPh2)2 is due to the redox isomerism of ferrocenylphosphonium cation Fc(PPh2)P+Ph2, which can form during the reaction between protonated complex Fc(PPh2)P(H+)Ph2 and H2O2.

Antimicrobial, spectral, magnetic and thermal studies of Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes of the Schiff base derived from oxalylhydrazide.

PubMed

Melha, Khlood Abou

2008-04-01

The Schiff base ligand, oxalyl [( 2 - hydroxybenzylidene) hydrazone] [corrected].H(2)L, and its Cu(II), Ni(II), Co(II), UO(2)(VI) and Fe(III) complexes were prepared and tested as antibacterial agents. The Schiff base acts as a dibasic tetra- or hexadentate ligand with metal cations in molar ratio 1:1 or 2:1 (M:L) to yield either mono- or binuclear complexes, respectively. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, Mass, and UV-Visible spectra and the magnetic moments and electrical conductance of the complexes were also determined. For binuclear complexes, the magnetic moments are quite low compared to the calculated value for two metal ions complexes and this shows antiferromagnetic interactions between the two adjacent metal ions. The ligand and its metal complexes were tested against a Gram + ve bacteria (Staphylococcus aureus), a Gram -ve bacteria (Escherichia coli), and a fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.

Environmentally-relevant concentrations of Al(III) and Fe(III) cations induce aggregation of free DNA by complexation with phosphate group.

PubMed

Qin, Chao; Kang, Fuxing; Zhang, Wei; Shou, Weijun; Hu, Xiaojie; Gao, Yanzheng

2017-10-15

Environmental persistence of free DNA is influenced by its complexation with other chemical species and its aggregation mechanisms. However, it is not well-known how naturally-abundant metal ions, e.g., Al(III) and Fe(III), influence DNA aggregation. This study investigated aggregation behaviors of model DNA from salmon testes as influenced by metal cations, and elucidated the predominant mechanism responsible for DNA aggregation. Compared to monovalent (K + and Na + ) and divalent (Ca 2+ and Mg 2+ ) cations, Al(III) and Fe(III) species in aqueous solution caused rapid DNA aggregations. The maximal DNA aggregation occurred at 0.05 mmol/L Al(III) or 0.075 mmol/L Fe(III), respectively. A combination of atomic force microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy revealed that Al(III) and Fe(III) complexed with negatively charged phosphate groups to neutralize DNA charges, resulting in decreased electrostatic repulsion and subsequent DNA aggregation. Zeta potential measurements and molecular computation further support this mechanism. Furthermore, DNA aggregation was enhanced at higher temperature and near neutral pH. Therefore, DNA aggregation is collectively determined by many environmental factors such as ion species, temperature, and solution pH. Copyright © 2017 Elsevier Ltd. All rights reserved.

Crystal structure of bis-(1,3-di-meth-oxy-imidazolin-2-yl-idene)silver(I) hexa-fluorido-phosphate, N-heterocyclic carbene (NHC) complex.

PubMed

Rietzler, Barbara; Laus, Gerhard; Kahlenberg, Volker; Schottenberger, Herwig

2015-12-01

The title salt, [Ag(C5H8N2O2)2]PF6, was obtained by deprotonation and metalation of 1,3-di-meth-oxy-imidazolium hexa-fluorido-phosphate using silver(I) oxide in methanol. The C-Ag-C angle in the cation is 178.1 (2)°, and the N-C-N angles are 101.1 (4) and 100.5 (4)°. The meth-oxy groups adopt an anti conformation. In the crystal, anions (A) are sandwiched between cations (C) in a layered arrangement {C…A…C} n stacked along [001]. Within a C…A…C layer, the hexafluoridophosphate anions accept several C-H⋯F hydrogen bonds from the cationic complex.

Potassium Binding Adjacent to Cationic Transition-Metal Fragments: Unusual Heterobimetallic Adducts of a Calix[4]arene-Based Thione Ligand.

PubMed

Patchett, Ruth; Knighton, Richard C; Mattock, James D; Vargas, Alfredo; Chaplin, Adrian B

2017-11-20

The synthesis of cationic rhodium and iridium complexes of a bis(imidazole-2-thione)-functionalized calix[4]arene ligand and their surprising capacity for potassium binding are described. In both cases, uptake of the alkali metal into the calix[4]arene cavity occurs despite adverse electrostatic interactions associated with close proximity to the transition-metal fragment [Rh + ···K + = 3.715(1) Å; Ir + ···K + = 3.690(1) Å]. The formation and constituent bonding of these unusual heterobimetallic adducts have been interrogated through extensive solution and solid-state characterization, examination of the host-guest chemistry of the ligand and its upper-rim unfunctionalized calix[4]arene analogue, and use of density functional theory based energy decomposition analysis.

Ligand reprogramming in dinuclear helicate complexes: a consequence of allosteric or electrostatic effects?

PubMed

Jeffery, John C; Rice, Craig R; Harding, Lindsay P; Baylies, Christian J; Riis-Johannessen, Thomas

2007-01-01

The ditopic ligand 6,6'-bis(4-methylthiazol-2-yl)-3,3'-([18]crown-6)-2,2'-bipyridine (L(1)) contains both a potentially tetradentate pyridyl-thiazole (py-tz) N-donor chain and an additional "external" crown ether binding site which spans the central 2,2'-bipyridine unit. In polar solvents (MeCN, MeNO(2)) this ligand forms complexes with Zn(II), Cd(II), Hg(II) and Cu(I) ions via coordination of the N donors to the metal ion. Reaction with both Hg(II) and Cu(I) ions results in the self-assembly of dinuclear double-stranded helicate complexes. The ligands are partitioned by rotation about the central py--py bond, such that each can coordinate to both metals as a bis-bidentate donor ligand. With Zn(II) ions a single-stranded mononuclear species is formed in which one ligand coordinates the metal ion in a planar tetradentate fashion. Reaction with Cd(II) ions gives rise to an equilibrium between both the dinuclear double-stranded helicate and the mononuclear species. These complexes can further coordinate s-block metal cations via the remote crown ether O-donor domains; a consequence of which are some remarkable changes in the binding modes of the N-donor domains. Reaction of the Hg(II)- or Cd(II)-containing helicate with either Ba(2+) or Sr(2+) ions effectively reprogrammes the ligand to form only the single-stranded heterobinuclear complexes [MM'(L(1))](4+) (M=Hg(II), Cd(II); M'=Ba(2+), Sr(2+)), where the transition and s-block cations reside in the N- and O-donor sites, respectively. In contrast, the same ions have only a minor structural impact on the Zn(II) species, which already exists as a single-stranded mononuclear complex. Similar reactions with the Cd(II) system result in a shift in equilibrium towards the single-stranded species, the extent of which depends on the size and charge of the s-block cation in question. Reaction of the dicopper(I) double-stranded helicate with Ba(2+) shows that the dinuclear structure still remains intact but the pitch length is significantly increased.

Calix[3]carbazole: A C3-symmetrical receptor for barium ion

NASA Astrophysics Data System (ADS)

Yang, Zhaozheng; Tian, Zhangmin; Yang, Peng; Deng, Tuo; Li, Gang; Zhou, Xue; Chen, Yan; Zhao, Liang; Shen, Hongyan

2017-03-01

The binding ability of calix[3]carbazole (1) to metal ions has been investigated. It is found that 1 could serve as a non crown ether based, C3-symmetrical receptor for Ba2 + via the marriage of cation-π and cation-dipole interactions. FID assay further illustrates that 1 could selectively interact with Ba2 + over Pd2 +. A possible binding mechanism for [1-Ba2 +] complex is proposed.

Compartmentation of metals in foliage of Populus tremula grown on soils with mixed contamination. II. Zinc binding inside leaf cell organelles.

PubMed

Vollenweider, Pierre; Bernasconi, Petra; Gautschi, Hans-Peter; Menard, Terry; Frey, Beat; Günthardt-Goerg, Madeleine S

2011-01-01

The phytoextraction potential of plants for removing heavy metals from polluted soils is determined by their capacity to store contaminants in aboveground organs and complex them safely. In this study, the metal compartmentation, elemental composition of zinc deposits and zinc complexation within leaves from poplars grown on soil with mixed metal contamination was analysed combining several histochemical and microanalytical approaches. Zinc was the only heavy metal detected and was stored in several organelles in the form of globoid deposits showing β-metachromasy. It was associated to oxygen anions and different cations, noteworthy phosphorous. The deposit structure, elemental composition and element ratios indicated that zinc was chelated by phytic acid ligands. Maturation processes in vacuolar vs. cytoplasmic deposits were suggested by differences in size and amounts of complexed zinc. Hence, zinc complexation by phytate contributed to metal detoxification and accumulation in foliage but could not prevent toxicity reactions therein. Copyright © 2010 Elsevier Ltd. All rights reserved.

Structural characterization of 1,8-naphthalimides and in vitro microbiological activity of their Cu(II) and Zn(II) complexes

NASA Astrophysics Data System (ADS)

Grabchev, Ivo; Yordanova, Stanislava; Bosch, Paula; Vasileva-Tonkova, Evgenia; Kukeva, Rositsa; Stoyanov, Stanimir; Stoyanova, Radostina

2017-02-01

Two new 1,8-naphthalimide derivatives (NI1 and NI2) have been synthesized and characterized. The photophysical properties of the new compounds have been investigated in organic solvents of different polarity. It has been shown that both compounds are solvent depended. Cu(II) and Zn(II) complexes of NI2 were obtained and characterized by IR-NMR, fluorescence and EPR spectroscopy. The influence of different metal cations on the fluorescence intensity has been investigated in acetonitrile solution. Antimicrobial composite PLA-metal complexes materials have been obtained for the first time. Microbiological activity of both metal complexes has been investigated in vitro against different Gram-positive and Gram-negative bacteria and two yeasts. The various antimicrobial activities and the minimum inhibitory concentrations (MICs) of both complexes have been determined. The microbiological activity of composite materials PLA-metal complexes in thin polymeric film has also been investigated. The results suggest that the new metal complexes could find application in designing new antimicrobial preparations to control the spread of infections.

Nuclear magnetic resonance studies of formyltetrahydrofolate synthetase interactions with formate and methylammonium ion.

PubMed

Wendland, M F; Stevens, T H; Buttlaire, D H; Everett, G W; Himes, R H

1983-02-15

Using nuclear magnetic resonance techniques, we have measured the internuclear distances separating the nucleotide-bound metal from the carbon and hydrogen nuclei of formate as well as the carbon of methylammonium cation when bound to formyltetrahydrofolate synthetase. Measurements were made of the paramagnetic effect on the spin-lattice relaxation rates (1/T1) of 13C and 1H nuclei arising from the replacement of Mg2+ with Mn2+, which binds to the enzyme in the form of a metal-nucleotide complex. Distances from Mn2+ to the formate carbon and proton were found to be 6.3 and 7.4 A, respectively, in the E . ATP . Mn2+ . formate complex and 6.0 and 7.1 A, respectively, in the E . ADP . Mn2+ . formate complex. When tetrahydrofolate was added to the latter complex, the exchange of formate was greatly reduced and became rate limiting for relaxation. These results are consistent with substantial conformational effects produced by the binding of the cofactor. The distance from Mn2+ to the methylammonium carbon in the E . ADP . Mn2+ . CH3NH+3, E . ADP . Mn2+ . formate . CH3NH3+, and E . ADP . Mn2+ . tetrahydrofolate . CH3NH3+ complexes was estimated to be in the range of 7.4-12 A. However, in the E . ADP . Mn2+ formate . tetrahydrofolate . CH3NH3+ complex, the data suggest that exchange of cation contributes significantly to relaxation. These results, combined with other known features of the enzyme, suggest that there may be a monovalent cation site within the active site of the enzyme.

Solid-state chelation of metal ions by ethylenediaminetetraacetate intercalated in a layered double hydroxide.

PubMed

Tarasov, Konstantin A; O'Hare, Dermot; Isupov, Vitaly P

2003-03-24

The solid-state chelation of transition metal ions (Co(2+), Ni(2+), and Cu(2+)) from aqueous solutions into the lithium aluminum layered double hydroxide ([LiAl(2)(OH)(6)]Cl x 0.5H(2)O or LDH) which has been pre-intercalated with EDTA (ethylenediaminetetraacetate) ligand has been investigated. The intercalated metal cations form [M(edta)](2)(-) complexes between the LDH layers as indicated by elemental analysis, powder X-ray diffraction, and IR and UV-vis spectroscopies. If metal chloride or nitrate salts are used in the reaction with the LDH then co-intercalation of either the Cl(-) or NO(3)(-) anions is observed. In the case of metal acetate salts the cations intercalate without the accompanying anion. This can be explained by the different intercalation selectivity of the anions in relation to the LDH. In the latter case the introduction of the positive charge into LDH structure was compensated for by the release from the solid of the equivalent quantity of lithium and hydrogen cations. Time-resolved in-situ X-ray diffraction measurements have revealed that the chelation/intercalation reactions proceed very quickly. The rate of the reaction found for nickel acetate depends on concentration as approximately k[Ni(Ac)(2)](3).

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

Thornton, Michelle

Capillary electrophoresis (CE) is an effective method for separating ionic species according to differences in their electrophoretic mobilities. CE separations of amino acids by direct detection are difficult due to their similar electrophoretic mobilities and low absorbances. However, native amino acids can be separated by CE as cations at a low pH by adding an alkanesulfonic acid to the electrolyte carrier which imparts selectivity to the system. Derivatization is unnecessary when direct UV detection is used at 185 nm. Simultaneous speciation of metal cations such as vanadium (IV) and vanadium (V) can easily be performed without complexation prior to analysis.more » An indirect UV detection scheme for acidic conditions was also developed using guanidine as the background carrier electrolyte (BCE) for the indirect detection of metal cations. Three chapters have been removed for separate processing. This report contains introductory material, references, and general conclusions. 80 refs.« less

Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.

PubMed

Klimovica, Kristine; Kirschbaum, Kristin; Daugulis, Olafs

2016-09-12

Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a . The upper limit of Δ G ‡ , assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with Δ G 298 ‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9 , with Δ G 298 ‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

Behavior of cesium and thallium cations inside a calixarene cavity as probed by nuclear spin relaxation. Evidence of cation-pi interactions in water.

PubMed

Cuc, Diana; Bouguet-Bonnet, Sabine; Morel-Desrosiers, Nicole; Morel, Jean-Pierre; Mutzenhardt, Pierre; Canet, Daniel

2009-08-06

We have studied the complexes formed between the p-sulfonatocalix[4]arene and cesium or thallium metal cation, first by carbon-13 longitudinal relaxation of the calixarene molecule at two values of the magnetic field B(0). From the longitudinal relaxation times of an aromatic carbon directly bonded to a proton, thus subjected essentially to the dipolar interaction with that proton, we could obtain the correlation time describing the reorientation of the CH bond. The rest of this study has demonstrated that it is also the correlation time describing the tumbling of the whole calixarene assembly. From three non-proton-bearing carbons of the aromatic cycles (thus subjected to the chemical shift anisotropy and dipolar mechanisms), we have been able to determine the variation of the chemical shift anisotropy when going from the free to the complex form of the calixarene. These variations not only provide the location of the cation inside the calixarene cavity but also constitute a direct experimental proof of the cation-pi interactions. These results are complemented by cesium and thallium relaxation measurements performed again at two values of the magnetic field B(0). An estimation of the mean distance between the cation and the calixarene protons could be obtained. These measurements have also revealed an important chemical shift anisotropy of thallium upon complexation.

Self-assembly of Terbium(III)-based metal-organic complexes with two-photon absorbing active.

PubMed

Li, Dandan; Shao, Nanqi; Sun, Xianshun; Zhang, Guocui; Li, Shengli; Zhou, Hongping; Wu, Jieying; Tian, Yupeng

2014-12-10

Hybrid complexes based on D-π-A type dyes p-aminostyryl-pyridinum and Terbium(III) complex anion (1, 2) have been synthesized by ionic exchange reaction. Meanwhile two different alkyl-substituted amino groups were used as electron donors in organic dyes cations. The synthesized complexes were characterized by element analysis. In addition, the structural features of them were systematic studied by single crystal X-ray diffraction analysis. Their linear properties have been systematically investigated by absorption spectra and fluorescence, the results show that the energy transfer takes place from the trans-4-[4'-(N,N-diethylamino)styryl]-N-methyl pyridinium (2') cation to Tb(III). In addition, complex 2 exhibit a large two-photon absorption coefficient β: 0.044cm/GW at 710nm. Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrated Cations in the General Chemistry Course.

ERIC Educational Resources Information Center

Kauffman, George B.; Baxter, John F., Jr.

1981-01-01

Presents selected information regarding the descriptive chemistry of the common metal ions and their compounds, including the concepts of process of solution, polar molecules, ionic size and charge, complex ions, coordination number, and the Bronsted-Lowry acid-base theory. (CS)

Physical and Chemical Properties of Anthropogenic Aerosols: An Overview

EPA Science Inventory

Aerosol chemical composition is complex. Combustion aerosols can comprise tens of thousands of organic compounds, refractory brown and black carbon, heavy metals, cations, anions, salts, and other inorganic phases. Aerosol organic matter normally contains semivolatile material th...

Modeling the IR spectra of aqueous metal carboxylate complexes: correlation between bonding geometry and stretching mode wavenumber shifts.

PubMed

Sutton, Catherine C R; da Silva, Gabriel; Franks, George V

2015-04-27

A widely used principle is that shifts in the wavenumber of carboxylate stretching modes upon bonding with a metal center can be used to infer if the geometry of the bonding is monodentate or bidentate. We have tested this principle with ab initio modeling for aqueous metal carboxylate complexes and have shown that it does indeed hold. Modeling of the bonding of acetate and formate in aqueous solution to a range of cations was used to predict the infrared spectra of the metal-carboxylate complexes, and the wavenumbers of the symmetric and antisymmetric vibrational modes are reported. Furthermore, we have shown that these shifts in wavenumber occur primarily due to how bonding with the metal changes the carboxylate C-O bond lengths and O-C-O angle. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Design and synthesis of imine compound for metal cation logical gates recognition and setup of double-control fluorescent molecule switch].

PubMed

Huang, Tao; Zhu, Yu-lian; Dai, Xue-qin; Zhang, Qi; Huang, Yan

2011-07-01

The Schiff base's reduced product N,N-bis(4-methoxybenzyl) ethane-1,2-diamine, which was used as a receptor L, was designed and synthesized for the first time in the present article. It was found that Cu2+ and Fe3+ could quench L in fluorescence observably and Zn2+ and Cd2+ could enhance L remarkably. So the two pair metal cation could set up "OR" logical gate relation with the receptor molecule L, then a logical recognition system be formed. The data of resolved ZnL's single crystal indicated that ZnL belonged to monoclinic (CCDC No. 747994). Integrated spectrum instrument was used to characterize the structure of its alike series of complex compound. According to ZnL's excellent fluorescence character and the ability to exchange with contiguous metal cation, ZnZ+/ZnL/Co2+, Zn2+/ZnL/Nit+ fluorescent molecule switch was designed. It is hoped that the work above could be positive for the development of molecule computer, bio-intellectualized inspection technology (therapy) and instrument.

Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model.

PubMed

Tian, Lei; Shi, Zhenqing; Lu, Yang; Dohnalkova, Alice C; Lin, Zhang; Dang, Zhi

2017-09-19

Quantitative understanding the kinetics of toxic ion reactions with various heterogeneous ferrihydrite binding sites is crucial for accurately predicting the dynamic behavior of contaminants in environment. In this study, kinetics of As(V), Cr(VI), Cu(II), and Pb(II) adsorption and desorption on ferrihydrite was studied using a stirred-flow method, which showed that metal adsorption/desorption kinetics was highly dependent on the reaction conditions and varied significantly among four metals. High resolution scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy showed that all four metals were distributed within the ferrihydrite aggregates homogeneously after adsorption reactions. Based on the equilibrium model CD-MUSIC, we developed a novel unified kinetics model applicable for both cation and oxyanion adsorption and desorption on ferrihydrite, which is able to account for the heterogeneity of ferrihydrite binding sites, different binding properties of cations and oxyanions, and variations of solution chemistry. The model described the kinetic results well. We quantitatively elucidated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites and the formation of various surface complexes controlled the adsorption and desorption kinetics at different reaction conditions and time scales. Our study provided a unified modeling method for the kinetics of ion adsorption/desorption on ferrihydrite.

The Correlation of Adsorption Behavior between Ciprofloxacin Hydrochloride and the Active Sites of Fe-doped MCM-41.

PubMed

Wu, Ying; Tang, Yiming; Li, Laisheng; Liu, Peihong; Li, Xukai; Chen, Weirui; Xue, Ying

2018-01-01

HIGHLIGHTS Fe incorporation significantly accelerated the adsorption of CPX on MCM-41.Fe leaching can be ignored when pH was higher than 4.0.pH played an important role in CPX adsorption on Fe-MCM-41.Co-effect of CPX and metal cations on Fe-MCM-41 was investigated. Fe-MCM-41s with various molar ratios of silicon to iron (20, 40, 80, and 160) were prepared to investigate adsorption properties of ciprofloxacin hydrochloride (CPX) in aqueous solutions. Fe-MCM-41s were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption isotherms, and infrared spectroscopy (FT-IR). Effects of silicon-iron ratio, adsorbent dosage, pH, and temperature were conducted to explore the adsorption mechanism of CPX on Fe-MCM-41. The results showed that the introduction of iron facilitated the absorption quantity for CPX from 20.04 to 83.33 mg g -1 at 120 min of reaction time, which was mainly attributed to surface complexation. The promotion of hydrophobic effect, electrostatic interactions, and π-π electron donor-acceptor interaction also played coordinate roles in the adsorption process. The experimental kinetic data followed both the pseudo-second-order and intra-particle diffusion models, while the adsorption isotherm data fit well to Freundlich model at high temperature. Thermodynamic study showed that the adsorption was spontaneous. Under the effect of electrostatic interaction, pH of the solution strongly affected CPX adsorption. Five representative metal cations (Ca, Cu, Ni, Pb, and Cd) were chosen to study the effects on CPX adsorption and their complexation. The inhibiting effect of metal cations on CPX adsorption was sequenced in the order of Cu > Ni > Pb > Cd > Ca, which followed the same order as the complexation stability constants between CPX and cations. The Fe-MCM-41 adsorbent possessed excellent reusability for 4 cycles use, suggesting a potential applicability of Fe-MCM-41 to remove CPX in water.

The Correlation of Adsorption Behavior between Ciprofloxacin Hydrochloride and the Active Sites of Fe-doped MCM-41

PubMed Central

Wu, Ying; Tang, Yiming; Li, Laisheng; Liu, Peihong; Li, Xukai; Chen, Weirui; Xue, Ying

2018-01-01

HIGHLIGHTS Fe incorporation significantly accelerated the adsorption of CPX on MCM-41.Fe leaching can be ignored when pH was higher than 4.0.pH played an important role in CPX adsorption on Fe-MCM-41.Co-effect of CPX and metal cations on Fe-MCM-41 was investigated. Fe-MCM-41s with various molar ratios of silicon to iron (20, 40, 80, and 160) were prepared to investigate adsorption properties of ciprofloxacin hydrochloride (CPX) in aqueous solutions. Fe-MCM-41s were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption isotherms, and infrared spectroscopy (FT-IR). Effects of silicon-iron ratio, adsorbent dosage, pH, and temperature were conducted to explore the adsorption mechanism of CPX on Fe-MCM-41. The results showed that the introduction of iron facilitated the absorption quantity for CPX from 20.04 to 83.33 mg g−1 at 120 min of reaction time, which was mainly attributed to surface complexation. The promotion of hydrophobic effect, electrostatic interactions, and π-π electron donor-acceptor interaction also played coordinate roles in the adsorption process. The experimental kinetic data followed both the pseudo-second-order and intra-particle diffusion models, while the adsorption isotherm data fit well to Freundlich model at high temperature. Thermodynamic study showed that the adsorption was spontaneous. Under the effect of electrostatic interaction, pH of the solution strongly affected CPX adsorption. Five representative metal cations (Ca, Cu, Ni, Pb, and Cd) were chosen to study the effects on CPX adsorption and their complexation. The inhibiting effect of metal cations on CPX adsorption was sequenced in the order of Cu > Ni > Pb > Cd > Ca, which followed the same order as the complexation stability constants between CPX and cations. The Fe-MCM-41 adsorbent possessed excellent reusability for 4 cycles use, suggesting a potential applicability of Fe-MCM-41 to remove CPX in water. PMID:29468153

Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins.

PubMed

Pesavento, Maria; Sturini, Michela; D'Agostino, Girolamo; Biesuz, Raffaela

2010-02-19

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs-Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition. Copyright 2009. Published by Elsevier B.V.

A Bis-Triazacyclononane Tris-Pyridyl N9 -Azacryptand "Beer Can" Receptor for Complexation of Alkali Metal and Lead(II) Cations.

PubMed

Brown, Asha; Bunchuay, Thanthapatra; Crane, Christopher G; White, Nicholas G; Thompson, Amber L; Beer, Paul D

2018-04-18

A new bis-triazacyclononane tris-pyridyl N 9 -azacryptand ligand is prepared via a convenient one-pot [2+3] condensation reaction between triazacyclononane and 2,6-bis(bromomethyl) pyridine in the presence of M 2 CO 3 (M=Li, Na, K). The proton, lithium, sodium, potassium and lead(II) complexes of the ligand are characterised in the solid state. Preliminary solution-phase competition experiments indicate that the cryptand ligand preferentially binds lead(II) in the presence of sodium, calcium, potassium and zinc cations in methanol solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogenation of coal liquid utilizing a metal carbonyl catalyst

DOEpatents

Feder, Harold M.; Rathke, Jerome W.

1979-01-01

Coal liquid having a dissolved transition metal, catalyst as a carbonyl complex such as Co.sub.2 (CO.sub.8) is hydrogenated with hydrogen gas or a hydrogen donor. A dissociating solvent contacts the coal liquid during hydrogenation to form an immiscible liquid mixture at a high carbon monoxide pressure. The dissociating solvent, e.g. ethylene glycol, is of moderate coordinating ability, while sufficiently polar to solvate the transition metal as a complex cation along with a transition metal, carbonyl anion in solution at a decreased carbon monoxide pressure. The carbon monoxide pressure is reduced and the liquids are separated to recover the hydrogenated coal liquid as product. The dissociating solvent with the catalyst in ionized form is recycled to the hydrogenation step at the elevated carbon monoxide pressure for reforming the catalyst complex within fresh coal liquid.

Relaxation of the structure of simple metal ion complexes in aqueous solutions at up to supercritical conditions

USGS Publications Warehouse

Mayanovic, Robert A.; Jayanetti, Sumedha; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

2003-01-01

Recently x-ray absorption fine structure (XAFS) studies of various ions in aqueous solutions showed a variation of cation-ligand bond lengths, often coupled with other structure changes, with increasing temperatures. Thus, the variations of the structure of several metal ion complexes with temperature based on observations from the X-ray absorption fine structure (XAFS) studies in the hope that it will stimulate the development of either first- principles theory or molecular dynamics simulations that might adequately describes these results are discussed.

Testing of WW-85

DTIC Science & Technology

2005-11-21

secondary ROS, superoxide (O2 -) and hydrogen peroxide (H2O2), the latter can react via Fenton chemistry with cellular metal ions to produce additional ·OH...nitrogen dioxide (NO2), and nitrosonium cation. Oxidations of thiols, sulfides, transition metal complexes, deoxyribose, phenols and other...respiratory chain and disruption of the zinc-thiolate center at the active site of enzymes. Peroxynitrite has been shown to inhibit a variety of ion

Salinomycin Hydroxamic Acids: Synthesis, Structure, and Biological Activity of Polyether Ionophore Hybrids.

PubMed

Borgström, Björn; Huang, Xiaoli; Chygorin, Eduard; Oredsson, Stina; Strand, Daniel

2016-06-09

The polyether ionophore salinomycin has recently gained attention due to its exceptional ability to selectively reduce the proportion of cancer stem cells within a number of cancer cell lines. Efficient single step strategies for the preparation of hydroxamic acid hybrids of this compound varying in N- and O-alkylation are presented. The parent hydroxamic acid, salinomycin-NHOH, forms both inclusion complexes and well-defined electroneutral complexes with potassium and sodium cations via 1,3-coordination by the hydroxamic acid moiety to the metal ion. A crystal structure of an cationic sodium complex with a noncoordinating anion corroborates this finding and, moreover, reveals a novel type of hydrogen bond network that stabilizes the head-to-tail conformation that encapsulates the cation analogously to the native structure. The hydroxamic acid derivatives display down to single digit micromolar activity against cancer cells but unlike salinomycin selective reduction of ALDH(+) cells, a phenotype associated with cancer stem cells was not observed. Mechanistic implications are discussed.

Salinomycin Hydroxamic Acids: Synthesis, Structure, and Biological Activity of Polyether Ionophore Hybrids

PubMed Central

2016-01-01

The polyether ionophore salinomycin has recently gained attention due to its exceptional ability to selectively reduce the proportion of cancer stem cells within a number of cancer cell lines. Efficient single step strategies for the preparation of hydroxamic acid hybrids of this compound varying in N- and O-alkylation are presented. The parent hydroxamic acid, salinomycin-NHOH, forms both inclusion complexes and well-defined electroneutral complexes with potassium and sodium cations via 1,3-coordination by the hydroxamic acid moiety to the metal ion. A crystal structure of an cationic sodium complex with a noncoordinating anion corroborates this finding and, moreover, reveals a novel type of hydrogen bond network that stabilizes the head-to-tail conformation that encapsulates the cation analogously to the native structure. The hydroxamic acid derivatives display down to single digit micromolar activity against cancer cells but unlike salinomycin selective reduction of ALDH+ cells, a phenotype associated with cancer stem cells was not observed. Mechanistic implications are discussed. PMID:27326340

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

Ho, I-Ting; Sessler, Jonathan L.; Gambhir, Sanjiv Sam

Chemical tools that can report radioactive isotopes would be of interest to the defense community. Here in this paper we report –250 nm polymeric nanoparticles containing porphyrinoid macrocycles with and without pre-complexed depleted uranium and demonstrate that the latter species may be detected easily and with high sensitivity via photoacoustic imaging. The porphyrinoid macrocycles used in the present study are non-aromatic in the absence of the uranyl cation, but aromatic after cation complexation. We solubilized both the freebase and metalated forms of the macrocycles in poly(lactic-co-glycolic acid) and found a peak in the photoacoustic spectrum at 910 nm excitation inmore » the case of the uranyl complex. The signal was stable for at least 15 minutes and allowed detection of uranium concentrations down to 6.2 ppb (5.7 nM) in vitro and 0.57 ppm (19 fCi; 0.52 μM) in vivo. Furthermore, to the best of our knowledge, this is the first report of a nanoparticle that detects an actinide cation via photoacoustic imaging.« less

The Discovery of Crown Ethers

NASA Astrophysics Data System (ADS)

Pedersen, Charles J.

1988-07-01

The discovery of the crown ethers stemmed from efforts to control the catalytic activity of vanadium and copper by complexation with multidentate ligands. The first crown ether, 2,3,11,12-dibenzo-1,4,7,10,13,16-hexaoxacyclo-octadeca-2,11-diene, was obtained in 0.4% yield during an attempt to prepare a phenolic ligand from catechol and bis(2-chloroethyl)ether. This compound, which complexed with the sodium cation, was the first compound known to display such activity and became known as dibenzo-18-crown-6, an 18-atom heterocycle containing 6 oxygen atoms. Some 60 related compounds were made involving heterocyclic rings containing 12 to 60 atoms including 4 and 10 oxygen atoms. There are optimum polyether ring sizes for the different alkali metal cations: 15 to 18 for sodium, 18 for potassium, and 18 to 21 for cesium. Complexes having polyether to cation ratios of 1:1, 3:2, and 2:1 were prepared. Solubilization of inorganic salts in aprotic solvents, especially by saturated crown ethers, was demonstrated.

Effects of protonation and metal coordination on intramolecular charge transfer of tetrathiafulvalene compound.

PubMed

Zhu, Qin-Yu; Liu, Yu; Lu, Wen; Zhang, Yong; Bian, Guo-Qing; Niu, Gai-Yan; Dai, Jie

2007-11-26

A protonated bifunctional pyridine-based tetrathiafulvalene (TTF) derivative (DMT-TTF-pyH)NO3 and a copper(II) complex Cu(acac)2(DMT-TTF-py)2 have been obtained and studied. Electronic spectra of the protonated compound show a large ICT (intramolecular charge transfer) band shift (Deltalambda=136 nm) compared with that of the neutral compound. Cyclic voltammetry also shows a large shift of the redox potentials (DeltaE1/2(1)=77 mV). Theoretical calculation suggests that the pyridium substituent is a strong pi-electron acceptor. Crystal structures of the protonated compound and the metal complex have been obtained. The dihedral angle between least-squares planes of the pyridyl group and the dithiole ring might reflect the intensity of the ICT effect between the TTF moiety and the pyridyl group. It is also noteworthy that the TTF moiety could be oxidized to TTF2+ dication by Fe(ClO4)(3).6H2O when forming a metal complex, while the protonated TTF derivative can only be oxidized to the TTF*+ radical cation by Fe(ClO4)(3).6H2O even with an excess amount of the Fe(III) salt, which can be used to control the oxidation process to obtain neutral TTF, TTF*+ radical cation, or TTF2+ dication.

Cation Distribution and Local Configuration of Fe 2+ Ions in Structurally Nonequivalent Lattice Sites of Heterometallic Fe(II)/ M(II) ( M = Mn, Co, Ni, Cu, Zn) Diaquadiformato Complexes

NASA Astrophysics Data System (ADS)

Devillers, M.; Ladrière, J.

1993-03-01

57Fe Mössbauer investigations are carried out on a wide series of heterometallic diaquadiformato Fe(II)/ M(II) complexes with M = Mn, Co, Ni, Cu, and Zn to provide a local picture of the coordination environment of the 57Fe 2+ ions as a function of (i) the nature of the host cation and (ii) the relative amounts of both metals in the matrix (between 50 and 0.25 at.% Fe). Information is obtained on the quantitative distribution of both metals between the two structurally nonequivalent lattice sites and on the local geometry around the dopant atom in each crystal site. In the mixed Fe-Cu complexes. Fe 2+ ions are preferentially incorporated in the tetrahydrated site; in Cu-rich Fe xCu 1- x(HCO 2) 2· 2H 2O, the 57Fe 2+ ions located in the hexaformato-coordinated site are surrounded by an axially compressed octahedron of formate ligands which contrasts with the elongated configuration observed in the pure iron compound and in the other mixed systems. Semiquantitative estimations of the tetragonal field splitting and of the extent of metal-ligand interactions are proposed from the temperature dependence of the quadrupole splitting values.

Metal ion attachment to the matrix meso-tetrakis(pentafluorophenyl)porphyrin, related matrices and analytes: an experimental and theoretical study.

PubMed

van Kampen, Jeroen J A; Luider, Theo M; Ruttink, Paul J A; Burgers, Peter C

2009-11-01

In a previous study [van Kampen et al. Analytical Chemistry 2006; 78: 5403], we found that meso-tetrakis (pentafluorophenyl)porphyrin (F20TPP), in combination with lithium salts, provides an efficient matrix to cationize small molecules by Li+ attachment and that this combination can be successfully applied to the quantitative analysis of drugs, such as antiretroviral compounds using matrix-assisted laser desorption ionization in conjunction with a time-of-flight analyzer (MALDI-TOF). In the present study, we further explore the mechanism of metal ion attachment to F20TPP and analytes by MALDI-FTMS(/MS). To this end, we have studied the interaction of F20TPP and analytes with various mono-, di- and trivalent metal ions (Li+, Na+, K+, Rb+, Cs+, Co2+, Cu2+, Zn2+, Fe2+, Fe3+ and Ga3+). For the alkali cations, we find that F20TPP forms complexes only with Li+ and Na+; in addition, model analyte molecules such as poly(ethyleneglycol)s, mixed with F20TPP and the alkali cations, also only form Li+ and Na+ adducts. This contrasts sharply with the commonly used matrix 2,5-dihydroxybenzoic acid, where analytes are most efficiently cationized by Na+ or K+. Reasons for this difference are delineated. Ab initio calculations on porphyrin itself reveal that even the smallest alkali cation, Li+, does not fit in the porphyrin cavity, but lies on top of it, pushing the 21H and 23 H hydrogen atoms out of and below the plane with concomitant bending of the porphyrin skeleton in the opposite direction, i.e. toward the cation. Thus, the Li+ ion is not effectively sequestered and is in fact exposed and thus accessible for donation to analyte molecules. Interaction of F20TPP with di- and trivalent metal ions leads to protoporphyrin-metal ions, where the metal ion is captured within the protoporphyrin dianion cavity. The most intense signal is obtained when F20TPP is reacted with CuCl2 and then subjected to laser ablation. This method presents an easy general route to study the metal containing protoporphyrin molecules, which could all act as potential MALDI matrices. Copyright 2009 John Wiley & Sons, Ltd.

The Effects of Trivalent Lanthanide Cationization on the Electron Transfer Dissociation of Acidic Fibrinopeptide B and its Analogs

NASA Astrophysics Data System (ADS)

Commodore, Juliette J.; Cassady, Carolyn J.

2016-09-01

Electrospray ionization (ESI) on mixtures of acidic fibrinopeptide B and two peptide analogs with trivalent lanthanide salts generates [M + Met + H]4+, [M + Met]3+, and [M + Met -H]2+, where M = peptide and Met = metal (except radioactive promethium). These ions undergo extensive and highly efficient electron transfer dissociation (ETD) to form metallated and non-metallated c- and z-ions. All metal adducted product ions contain at least two acidic sites, which suggest attachment of the lanthanide cation at the side chains of one or more acidic residues. The three peptides undergo similar fragmentation. ETD on [M + Met + H]4+ leads to cleavage at every residue; the presence of both a metal ion and an extra proton is very effective in promoting sequence-informative fragmentation. Backbone dissociation of [M + Met]3+ is also extensive, although cleavage does not always occur between adjacent glutamic acid residues. For [M + Met - H ]2+, a more limited range of product ions form. All lanthanide metal peptide complexes display similar fragmentation except for europium (Eu). ETD on [M + Eu - H]2+ and [M + Eu]3+ yields a limited amount of peptide backbone cleavage; however, [M + Eu + H]4+ dissociates extensively with cleavage at every residue. With the exception of the results for Eu(III), metallated peptide ion formation by ESI, ETD fragmentation efficiencies, and product ion formation are unaffected by the identity of the lanthanide cation. Adduction with trivalent lanthanide metal ions is a promising tool for sequence analysis of acidic peptides by ETD.

Analysis of the chemical and physical properties of combustion aerosols: Properties overview

EPA Science Inventory

Aerosol chemical composition is remarkably complex. Combustion aerosols can comprise tens of thousands of organic compounds and fragments, refractory carbon, metals, cations, anions, salts, and other inorganic phases and substituents [Hays et al., 2004]. Aerosol organic matter no...

The role of halide ions on the electrochemical behaviour of iron in alkali solutions

NASA Astrophysics Data System (ADS)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

Selective Metal Cation Capture by Soft Anionic Metal-Organic Frameworks via Drastic Single-Crystal-to-Single-Crystal Transformations

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

Tian, Jian; Saraf, Laxmikant V.; Schwenzer, Birgit

2012-05-25

Flexible anionic metal-organic frameworks transform to neutral heterobimetallic systems via single-crystal-to-single-crystal processes invoked by cation insertion. These transformations are directed by cooperative bond breakage and formation, resulting in expansion or contraction of the 3D framework by up to 33% due to the flexible nature of the organic linker. These MOFs displays highly selective uptake of divalent transition metal cations (Co2+ and Ni2+ for example) over alkali metal cations (Li+ and Na+).

Sonication-assisted synthesis of a new cationic zinc nitrate complex with a tetradentate Schiff base ligand: Crystal structure, Hirshfeld surface analysis and investigation of different parameters influence on morphological properties.

PubMed

Mousavi, S A; Montazerozohori, M; Masoudiasl, A; Mahmoudi, G; White, J M

2018-09-01

A nanostructured cationic zinc nitrate complex with a formula of [ZnLNO 3 ]NO 3 (where L = (N 2 E,N 2' E)-N 1 ,N 1' -(ethane-1,2-diyl)bis(N 2 -((E)-3-phenylallylidene)ethane-1,2-diamine)) was prepared by sonochemical process and characterized by single crystal X-ray crystallography, scanning electron microscopy (SEM), FT-IR and NMR spectroscopy and X-ray powder diffraction (XRPD). The X-ray analysis demonstrates the formation of a cationic complex that metal center is five-coordinated by four nitrogen atom from Schiff base ligand and one oxygen atom from nitrate group. The crystal packing analysis demonstrates the essential role of the nitrate groups in the organization of supramolecular structure. The morphology and size of ultrasound-assisted synthesized zinc nitrate complex have been investigated using scanning electron microscopy (SEM) by changing parameters such as the concentration of initial reactants, the sonication power and reaction temperature. In addition the calcination of zinc nitrate complex in air atmosphere led to production of zinc oxide nanoparticles. Copyright © 2018. Published by Elsevier B.V.

Fluconazole affects the alkali-metal-cation homeostasis and susceptibility to cationic toxic compounds of Candida glabrata.

PubMed

Elicharova, Hana; Sychrova, Hana

2014-08-01

Candida glabrata is a salt-tolerant and fluconazole (FLC)-resistant yeast species. Here, we analyse the contribution of plasma-membrane alkali-metal-cation exporters, a cation/proton antiporter and a cation ATPase to cation homeostasis and the maintenance of membrane potential (ΔΨ). Using a series of single and double mutants lacking CNH1 and/or ENA1 genes we show that the inability to export potassium and toxic alkali-metal cations leads to a slight hyperpolarization of the plasma membrane of C. glabrata cells; this hyperpolarization drives more cations into the cells and affects cation homeostasis. Surprisingly, a much higher hyperpolarization of C. glabrata plasma membrane was produced by incubating cells with subinhibitory concentrations of FLC. FLC treatment resulted in a substantially increased sensitivity of cells to various cationic drugs and toxic cations that are driven into the cell by negative-inside plasma-membrane potential. The effect of the combination of FLC plus cationic drug treatment was enhanced by the malfunction of alkali-metal-cation transporters that contribute to the regulation of membrane potential and cation homeostasis. In summary, we show that the combination of subinhibitory concentrations of FLC and cationic drugs strongly affects the growth of C. glabrata cells. © 2014 The Authors.

SEPARATION OF PLUTONIUM VALUES FROM OTHER METAL VALUES IN AQUEOUS SOLUTIONS BY SELECTIVE COMPLEXING AND ADSORPTION

DOEpatents

Beaton, R.H.

1960-06-28

A process is given for separating tri- or tetravalent plutonium from fission products in an aqueous solution by complexing the fission products with oxalate, tannate, citrate, or tartrate anions at a pH value of at least 2.4 (preferably between 2.4 and 4), and contacting a cation exchange resin with the solution whereby the plutonium is adsorbed while the complexed fission products remain in solution.

Infrared Multiple-Photon Dissociation spectroscopy of group II metal complexes with salicylate

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

Ryan P. Dain; Gary Gresham; Gary S. Groenewold

2011-07-01

Ion-trap tandem mass spectrometry with collision-induced dissociation, and the combination of infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) calculations were used to characterize singly-charged, 1:1 complexes of Ca2+, Sr2+ and Ba2+ with salicylate. For each metal-salicylate complex, the CID pathways are: (a) elimination of CO2 and (b) formation of [MOH]+ where M=Ca2+, Sr2+ or Ba2+. DFT calculations predict three minima for the cation-salicylate complexes which differ in the mode of metal binding. In the first, the metal ion is coordinated by O atoms of the (neutral) phenol and carboxylate groups of salicylate. In the second, the cationmore » is coordinated by phenoxide and (neutral) carboxylic acid groups. The third mode involves coordination by the carboxylate group alone. The infrared spectrum for the metal-salicylate complexes contains a number of absorptions between 1000 – 1650 cm-1, and the best correlation between theoretical and experimental spectra for the structure that features coordination of the metal ion by phenoxide and the carbonyl group of the carboxylic acid group, consistent with calculated energies for the respective species.« less

An influence of structural changes in ammonium cations on ecotoxicity of 2,2'-thiodiacetate mono and bis-salts.

PubMed

Biczak, R; Turek, M; Pawłowska, B; Różycka-Sokołowska, E; Marciniak, B; Deska, M; Krupa, P; Jatulewicz, I; Skalik, J; Bałczewski, P

2018-07-15

2,2'-Thiodiacetates with their excellent complexing properties may be used as metal extraction agents, fluorescent and superparamagnetic materials, antibacterial and anticancer medical agents, however there are no data concerning the environmental impact of 2,2'-thiodiacetates derivatives and data definying the potential hazard connected with their use. This study describes the ecotoxicity assessment of seven 2,2'-thiodiacetates with non-metallic, alkyl and aryl ammonium cations, which were obtained in an environmentally friendly, solvent-free syntheses. The ecotoxicity of these water soluble compounds was tested in aquatic and benthic environments using luminescent marine bacteria Vibrio fischeri (Microtox ® test) and the crustaceans Heterocypris incongruens (Ostracodtoxkit F™), respectively. The antimicrobial and antifungal activity against Trichoderma viridis, Aspergillus niger, Rhizoctonia solani and Escherichia coli was also investigated. The results showed how structural changes within ammonium cations themselves influence ecotoxicity: the QASs with alkylammonium cations exhibited a similar, rather low toxicity both to Vibrio fischeri and Heterocypris incongruens, and they would not pose a risk to these organisms in case of leakage. Higher toxicity was observed in case of two isoquinolinium salts, however it was rather associated with the heteroaromatic cation, than with the 2,2'-thiodiacetate anion. Copyright © 2018 Elsevier Inc. All rights reserved.

Peptide Fragmentation by Corona Discharge Induced Electrochemical Ionization

PubMed Central

Lloyd, John R.; Hess, Sonja

2010-01-01

Fundamental studies have greatly improved our understanding of electrospray, including the underlying electrochemical reactions. Generally regarded as disadvantageous, we have recently shown that corona discharge (CD) can be used as an effective method to create a radical cation species [M]+•, thus optimizing the electrochemical reactions that occur on the surface of the stainless steel (SS) electrospray capillary tip. This technique is known as CD initiated electrochemical ionization (CD-ECI). Here, we report on the fundamental studies using CD-ECI to induce analytically useful in-source fragmentation of a range of molecules that complex transition metals. Compounds that have been selectively fragmented using CD-ECI include enolate forming phenylglycine containing peptides, glycopeptides, nucleosides and phosphopeptides. Collision induced dissociation (CID) or other activation techniques were not necessary for CD-ECI fragmentation. A four step mechanism was proposed: 1. Complexation using either Fe in the SS capillary tip material or Cu(II) as an offline complexation reagent; 2. Electrochemical oxidation of the complexed metal and thus formation of a radical cation (e.g.; Fe - e− → Fe +•); 3. Radical fragmentation of the complexed compound. 4. Electrospray ionization of the fragmented neutrals. Fragmentation patterns resembling b- and y-type ions were observed and allowed the localization of the phosphorylation sites. PMID:20869880

Transition Metal Polypyridine Complexes: Studies of Mediation in Dye-Sensitized Solar Cells and Charge Separation

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

Elliott, C. Michael; Prieto, Amy L.

2017-02-08

The Elliott group has long been supported by DOE for studies of cobalt(II/III) trisbypiridine (DTB) mediator complexes in dye sensitized solar cells. Previous work demonstrated that Co(II/III) chemistry is sensitive to the environment, showing unprecedented electrode-surface and electrolyte dependant voltammetry. In electrolytes that have large lipophilic cations, voltammetry of the [Co(DTB) 3] 2+/3+ couple is nearly Nernstian in appearance on nominally oxide-free metal surfaces. In contrast, on semiconductor electrodes in electrolytes with small, hard cations such as Li +, the electron transfer rates are so slow that it is difficult to measure any Faradaic current even at overpotentials of ±1more » V. These studies are of direct relevance to the operation of cobalt-based mediators in solar cells. The research has also shown that these mediators are compatible with copper phenantroline based dyes, in contrast to I - due to the insolubility of CuI.« less

pH profile of the adsorption of nucleotides onto montmorillonite. I - Selected homoionic clays

NASA Technical Reports Server (NTRS)

Lawless, J. G.; Church, F. M.; Mazzurco, J.; Banin, A.; Huff, R.; Kao, J.; Cook, A.; Lowe, T.; Orenberg, J. B.; Edelson, E.

1985-01-01

The effect of pH and adsorbed ions on the adsorption of purine and pyrimidine nucleotides on montmorillonite clay was studied experimentally. The specific nucleotides examined were: 5 prime-AMP; 3-prime AMP; and 5 prime-CMP. The pH of the clay samples was adjusted to various levels in the 2-12 pH range using microliter volumes of concentrated acid (1N HCl) and base (1NHNaOH). It was found that preferential adsorption among nulceotides was dependent on the pH level and on the characteristics of the substituted metal cation and anion exchange mechanisms. Below pH 4, adsorption was attributed to cation and anion exchange mechanisms. Above pH 4, however, adsorption was attributed to the complexation mechanisms occurring between the metal cations in the clay exchange site and in the biomolecule. The possible role of homoionic clays in the concentration mechanisms of biomonomers in the prebiotic environment is discussed.

Electroregulated Metal-Binding with a Crown Ether Tetrathiafulvalene Derivative: Toward Electrochemically Addressed Metal Cation Sponges.

PubMed

Le Derf, Franck; Mazari, Miloud; Mercier, Nicolas; Levillain, Eric; Richomme, Pascal; Becher, Jan; Garín, Javier; Orduna, Jesus; Gorgues, Alain; Sallé, Marc

1999-12-27

A redox responsive ligand incorporating the tetrathiafulvalene unit has been synthesized. The crystal structure of the free ligand (Z)-1 (C(20)H(30)O(5)S(8), triclinic P&onemacr;, Z = 2, a = 9.087(6) Å, b = 11.637(7) Å, c = 14.370(8) Å, alpha = 65.54(3) degrees, beta = 82.32(5) degrees, gamma = 84.18(6) degrees, V = 1368 Å(3)) shows the redox-active tetrathiafulvalene core to be essentially planar, which allows observation of two reversible one-electron processes upon electrochemical oxidation. The efficiency of this system in the control of the reversible complexation/expulsion sequence of a metallic cation (i.e., Ba(2+)) has been made possible thanks to a combination of (a) an unprecedented high coordination ability among tetrathiafulvalene-based macrocycles as determined by LSI mass spectrometry (log K degrees = 3.5, NBA-matrix) as well as by solution investigations ((1)H NMR and cyclic voltammetry titration studies), which remarkably converge to similar binding constant values (i.e., log K degrees = 4.2-4.3), and (b) reversible metal cation expulsion upon electrochemical oxidation to the dicationic state. A channel-like solid-state structure is observed for the Ba(2+) complex (C(20)H(30)O(5)S(8), Ba(2+)(CF(3)SO(3))(2)(2-), (H(2)O)(2), CD(3)CN, monoclinic C2/c, Z = 8, a = 45.66(1) Å, b = 8.897(5) Å, c = 23.124(8) Å, beta = 105.54(4) degrees, V = 9050 Å(3)), which results from the segregated stacking mode of the crown ether and the redox-active tetrathiafulvalene subunits, respectively.

Mechanism of host-guest complexation by cucurbituril.

PubMed

Márquez, César; Hudgins, Robert R; Nau, Werner M

2004-05-12

The factors affecting host-guest complexation between the molecular container compound cucurbit[6]uril (CB6) and various guests in aqueous solution are studied, and a detailed complexation mechanism in the presence of cations is derived. The formation of the supramolecular complex is studied in detail for cyclohexylmethylammonium ion as guest. The kinetics and thermodynamics of complexation is monitored by NMR as a function of temperature, salt concentration, and cation size. The binding constants and the ingression rate constants decrease with increasing salt concentration and cation-binding constant, in agreement with a competitive binding of the ammonium site of the guest and the metal cation with the ureido carbonyl portals of CB6. Studies as a function of guest size indicate that the effective container volume of the CB6 cavity is approximately 105 A(3). It is suggested that larger guests are excluded for two reasons: a high activation barrier for ingression imposed by the tight CB6 portals and a destabilization of the complex due to steric repulsion inside. For example, in the case of the nearly spherical azoalkane homologues 2,3-diazabicyclo[2.2.1]hept-2-ene (DBH, volume ca. 96 A(3)) and 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO, volume ca. 110 A(3)), the former forms the CB6 complex promptly with a sizable binding constant (1300 M(-1)), while the latter does not form a complex even after several months at optimized complexation conditions. Molecular mechanics calculations are performed for several CB6/guest complexes. A qualitative agreement is found between experimental and calculated activation energies for ingression as a function of both guest size and state of protonation. The potential role of constrictive binding by CB6 is discussed.

Experimental and quantum chemical modeling studies of the interactions of L-phenylalanine with divalent transition metal cations.

PubMed

Mandal, Shilpi; Das, Gunajyoti; Askari, Hassan

2014-09-22

Encoded by the UUU and UUC codons of the genetic code, L-phenylalanine (LPA) serves as an important precursor for tyrosine and various other compounds that are necessary to support life on earth. Here, we report the synthesis (both in solid and solvent phases) and characterization of the Ni(2+), Cu(2+), and Zn(2+) complexes of LPA by several analytical, spectral, thermal, and electrochemical techniques. The results reveal that the products formed by following the two synthetic approaches are the same, and the metal ions bind to the LPA molecules in a 1:2 molar ratio (M(+2)/LPA). Complementary geometries of the metal complexes are modeled involving the most predominant LPA conformers predicted at the MP2/6-311++G(d,p) level. The gaseous and aqueous phase interaction enthalpies and free energies; theoretical IR and UV-vis spectra; HOMO-LUMO energy gaps; dipole moments; Wiberg bond indices as well as the partial atomic charges in LPA and its metallic complexes are calculated and evaluated using B3LYP/6-311++G(d,p) as the main computational method. This study also incorporates analyses on the efficacy of the DFT-D2 level in describing dispersion contributions, performance of the BHandHLYP functional for the open-shell Cu(2+)-LPA system, and relative metal binding affinities of the singlet versus triplet states of the Ni(2+)-LPA complex. Metal-π interactions established via the aromatic side chain of LPA add to the thermodynamic stability of the complexes, whereas metal coordination induces considerable intrinsic structural rearrangements in the molecular geometry of LPA. The LPA binding affinity order of the three Lewis acids investigated emerges as Cu(2+) > Ni(2+) > Zn(2+), paralleling the Irving-Williams series. The illustrative evidence offered by the present work suggests that the B3LYP/6-311++G(d,p) level in combination with an empirical dispersion-correction term performs well in describing the vibrational frequencies and cation-π interactions, which are undoubtedly of immense significance for natural sciences.

Metal-dependent inhibition of HIV-1 integrase by 5CITEP inhibitor: A theoretical QM/MM approach

NASA Astrophysics Data System (ADS)

do Nascimento, Josenaide P.; Araújo Silva, José Rogério; Lameira, Jerônimo; Alves, Cláudio N.

2013-09-01

HIV-1 integrase (IN) is a potential target for developing drugs against AIDS. In this letter, QM/MM approach was used to study the inhibition of IN by 5CITEP inhibitor in presence of divalent cations (Mg2+ or Mn2+). In addition, the main interactions occurring in 5CITEP-IN complex and the influence of divalent cations (Mg2+ or Mn2+) in enzymatic inhibition were investigated using B3LYP/6-31+G(d,p)/MM. The results suggest that the Asp64, Asp116 and four crystal water molecules plays a crucial role in cation (Mg2+ or Mn2+) coordination sphere.

Nuclear quantum effects on adsorption of H 2 and isotopologues on metal ions

DOE PAGES

Savchenko, Ievgeniia; Gu, Bing; Heine, Thomas; ...

2017-01-03

The nuclear quantum effects on the zero-point energy (ZPE), influencing adsorption of Hmore » $$_2$$ and isotopologues on metal ions, are examined in this study using normal mode analysis of ab initio electronic structure results for complexes with 17 metal cations. To estimate for the anharmonicity, a nuclear wavepacket dynamics on the ground state electronic potential energy surfaces (PES) have been employed for complexes of Li$^+$ and Cu$$^{+2}$$ with H$$_2$$, D$$_2$$, HD. The dynamics analysis shows that incorporation of the PES anharmonicity changes the ZPE by up to 9%. Finally, the lightest metallic nuclei, Li and Be, are found to be the most 'quantum'. The largest selectivity in adsorption is predicted for Cu, Ni and Co ions.« less

High-Permeability Magnetic Polymer Additives for Lightweight Electromagnetic Shielding

DTIC Science & Technology

2015-08-01

organometallic complexes containing Fe2+ cations. [Cp] = cyclopentadiene; [Py] = pyrrole ; [Imid] = imidazole. ΔEmag values calculated with DFT using the...27 Table A-6 Energy difference between high- and low-spin magnetic states in transition metal ion- pyrrole (Py) complexes...2-],52 pyrrole (C4NH5),53 and other heterocyclic ligands.36,54 The cyclopentadienyl ligand, in particular, is ubiquitous in organometallic chemistry

Ionic conductivity of β-cyclodextrin-polyethylene-oxide/alkali-metal-salt complex.

PubMed

Yang, Ling-Yun; Fu, Xiao-Bin; Chen, Tai-Qiang; Pan, Li-Kun; Ji, Peng; Yao, Ye-Feng; Chen, Qun

2015-04-20

Highly conductive, crystalline, polymer electrolytes, β-cyclodextrin (β-CD)-polyethylene oxide (PEO)/LiAsF6 and β-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, β-CD, and LiAsF6 /NaAsF6 . The assembled β-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective sorbents for purification of hydrocarbons

DOEpatents

Yang, Ralph T.; Hernandez-Maldonado, Arturo J.; Yang, Frances H.; Takahashi, Akira

2006-08-22

A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

Selective sorbents for purification of hydrocarbons

DOEpatents

Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hernandez-Maldonado, Arturo J.

2006-05-30

A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

Synergy between tobramycin and trivalent chromium ion in electrochemical control of Pseudomonas aeruginosa.

PubMed

Niepa, Tagbo H R; Wang, Hao; Dabrowiak, James C; Gilbert, Jeremy L; Ren, Dacheng

2016-05-01

We recently demonstrated that the effectiveness of tobramycin (Tob), an aminoglycoside, against antibiotic-tolerant persister cells of Pseudomonas aeruginosa can be enhanced by electrochemical factors generated from direct currents (DC). Supplementation of Ni(II), Cr(III) and Fe(II) during carbon-mediated DC treatment revealed that these metal cations promote killing of persister cells in the presence of tobramycin, which led to our hypothesis that specific interactions between Tob and some metal ions contribute to the synergistic killing of persister cells. In this study, the interactions between selected metal cations and Tob were investigated using (1)H-(13)C HSQC NMR. Increase in the concentration of Cr(III) (in the form of [CrCl2(H2O)4](+)) in solutions containing Tob was found to shift the HSQC NMR peaks of Tob to new positions, suggesting the formation of a Cr(III)-Tob complex. Crystal field effects and electrochemical properties of the complex were further studied using UV-visible spectroscopy and cyclic voltammetry, which led to the finding that the Cr(III)-Tob complex has increased affinity with negatively charged nucleic acids. These findings are helpful for understanding the mechanism of electrochemical control of bacterial cells and for developing more effective antimicrobial therapies based on aminoglycosides and electrochemical species released from various metallic biomaterials. Medical device associated infections present a major challenge to healthcare and the quality of life of affected individuals. This problem is further exacerbated by the emergence of multidrug resistant pathogens. Thus, alternative methods for microbial control are urgently needed. Recently, we reported synergy between tobramycin and low-level electrochemical currents generated using stainless steel electrodes in killing bacterial persister cells, a dormant population with high-level intrinsic tolerance to antibiotics. In this article, we describe how electrically-induced interaction between aminoglycosides and certain metal cations enhance the potency of tobramycin in bacterial killing. The findings will help design new methods for controlling infections through electrochemical disruption of cellular function and associated drug resistance. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Gas phase reactions of doubly charged alkaline earth and transition metal(II)-ligand complexes generated by electrospray ionization

NASA Astrophysics Data System (ADS)

Kohler, Martin; Leary, Julie A.

1997-03-01

Doubly charged metal(II)-complexes of [alpha] 1-3, [alpha] 1-6 mannotriose and the conserved trimannosyl core pentasaccharide as well as doubly charged complexes of Co(II), Mn(II), Ca(II) and Sr(II) with acetonitrile generated by electrospray ionization were studied by low energy collision induced dissociation (CID). Two main fragmentation pathways were observed for the metal(II)-oligosaccharide complexes. Regardless of the coordinating metal, loss of a neutral dehydrohexose residue (162 Da) from the doubly charged precursor ion is observed, forming a doubly charged product ion. However, if the oligosaccharide is coordinated to Co(II) or Mn(II), loss of a dehydroxyhexose cation is also observed. Investigation of the low mass region of the mass spectra of the metal coordinated oligosaccharides revealed intense signals corresponding to [metal(II) + (CH3CN)n2+ (where n = 1-6) species which were being formed by the metal(II) ions and the acetonitrile present in the sample. Analysis of these metal(II)-acetonitrile complexes provided further insight into the processes occurring upon low energy CID of doubly charged metal complexes. The metal(II)-acetonitrile system showed neutral loss and ligand cleavage as observed with the oligosaccharide complexes, as well as a series of six different dissociation mechanisms, most notable among them reduction from [metal(II) + (CH3CN)n2+ to the bare [metal(I)]+ species by electron transfer. Depending on the metal and collision gas chosen, one observes electron transfer from the ligand to the metal, electron transfer from the collision gas to the metal, proton transfer between ligands, heterolytic cleavage of the ligands, reactive collisions and loss of neutral ligands.

Metal-Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox-Active Ligands.

PubMed

Broere, Daniël L J; Modder, Dieuwertje K; Blokker, Eva; Siegler, Maxime A; van der Vlugt, Jarl Ivar

2016-02-12

The tuning of metal-metal interactions in multinuclear assemblies is a challenge. Selective P coordination of a redox-active PNO ligand to Au(I) followed by homoleptic metalation of the NO pocket with Ni(II) affords a unique trinuclear Au-Ni-Au complex. This species features two antiferromagnetically coupled ligand-centered radicals and a double intramolecular d(8)-d(10) interaction, as supported by spectroscopic, single-crystal X-ray diffraction, and computational data. A corresponding cationic dinuclear Au-Ni analogue with a stronger d(8)-d(10) interaction is also reported. Although both heterobimetallic structures display rich electrochemistry, only the trinuclear Au-Ni-Au complex facilitates electrocatalytic C-X bond activation of alkyl halides in its doubly reduced state. Hence, the presence of a redox-active ligand framework, an available coordination site at gold, and the nature of the nickel-gold interaction appear to be essential for this reactivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A series of energetic metal pentazolate hydrates.

PubMed

Xu, Yuangang; Wang, Qian; Shen, Cheng; Lin, Qiuhan; Wang, Pengcheng; Lu, Ming

2017-09-07

Singly or doubly bonded polynitrogen compounds can decompose to dinitrogen (N 2 ) with an extremely large energy release. This makes them attractive as potential explosives or propellants, but also challenging to produce in a stable form. Polynitrogen materials containing nitrogen as the only element exist in the form of high-pressure polymeric phases, but under ambient conditions even metastability is realized only in the presence of other elements that provide stabilization. An early example is the molecule phenylpentazole, with a five-membered all-nitrogen ring, which was first reported in the 1900s and characterized in the 1950s. Salts containing the azide anion (N 3 - ) or pentazenium cation (N 5 + ) are also known, with compounds containing the pentazole anion, cyclo-N 5 - , a more recent addition. Very recently, a bulk material containing this species was reported and then used to prepare the first example of a solid-state metal-N 5 complex. Here we report the synthesis and characterization of five metal pentazolate hydrate complexes [Na(H 2 O)(N 5 )]·2H 2 O, [M(H 2 O) 4 (N 5 ) 2 ]·4H 2 O (M = Mn, Fe and Co) and [Mg(H 2 O) 6 (N 5 ) 2 ]·4H 2 O that, with the exception of the Co complex, exhibit good thermal stability with onset decomposition temperatures greater than 100 °C. For this series we find that the N 5 - ion can coordinate to the metal cation through either ionic or covalent interactions, and is stabilized through hydrogen-bonding interactions with water. Given their energetic properties and stability, pentazole-metal complexes might potentially serve as a new class of high-energy density materials or enable the development of such materials containing only nitrogen. We also anticipate that the adaptability of the N 5 - ion in terms of its bonding interactions will enable the exploration of inorganic nitrogen analogues of metallocenes and other unusual polynitrogen complexes.

A series of energetic metal pentazolate hydrates

NASA Astrophysics Data System (ADS)

Xu, Yuangang; Wang, Qian; Shen, Cheng; Lin, Qiuhan; Wang, Pengcheng; Lu, Ming

2017-09-01

Singly or doubly bonded polynitrogen compounds can decompose to dinitrogen (N2) with an extremely large energy release. This makes them attractive as potential explosives or propellants, but also challenging to produce in a stable form. Polynitrogen materials containing nitrogen as the only element exist in the form of high-pressure polymeric phases, but under ambient conditions even metastability is realized only in the presence of other elements that provide stabilization. An early example is the molecule phenylpentazole, with a five-membered all-nitrogen ring, which was first reported in the 1900s and characterized in the 1950s. Salts containing the azide anion (N3-) or pentazenium cation (N5+) are also known, with compounds containing the pentazole anion, cyclo-N5-, a more recent addition. Very recently, a bulk material containing this species was reported and then used to prepare the first example of a solid-state metal-N5 complex. Here we report the synthesis and characterization of five metal pentazolate hydrate complexes [Na(H2O)(N5)]·2H2O, [M(H2O)4(N5)2]·4H2O (M = Mn, Fe and Co) and [Mg(H2O)6(N5)2]·4H2O that, with the exception of the Co complex, exhibit good thermal stability with onset decomposition temperatures greater than 100 °C. For this series we find that the N5- ion can coordinate to the metal cation through either ionic or covalent interactions, and is stabilized through hydrogen-bonding interactions with water. Given their energetic properties and stability, pentazole-metal complexes might potentially serve as a new class of high-energy density materials or enable the development of such materials containing only nitrogen. We also anticipate that the adaptability of the N5- ion in terms of its bonding interactions will enable the exploration of inorganic nitrogen analogues of metallocenes and other unusual polynitrogen complexes.

Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd.

PubMed

Duguid, J; Bloomfield, V A; Benevides, J; Thomas, G J

1993-11-01

Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) induce the greatest structural changes in B-DNA. The Raman (vibrational) band differences are extensive and indicate partial disordering of the B-form backbone, reduction in base stacking, reduction in base pairing, and specific metal interaction with acceptor sites on the purine (N7) and pyrimidine (N3) rings. Many of the observed spectral changes parallel those accompanying thermal denaturation of B-DNA and suggest that the metals link the bases of denatured DNA. While exocyclic carbonyls of dT, dG, and dC may stabilize metal ligation, correlation plots show that perturbations of the carbonyls are mainly a consequence of metal-induced denaturation of the double helix. Transition metal interactions with the DNA phosphates are weak in comparison to interactions with the bases, except in the case of Cu2+, which strongly perturbs both base and phosphate group vibrations. On the other hand, the Raman signature of B-DNA is largely unperturbed by Mg2+, Ca2+, Sr2+, and Ba2+, suggesting much weaker interactions of the alkaline earth metals with both base and phosphate sites. A notable exception is a moderate perturbation by alkaline earths of purine N7 sites in 160-base pair DNA, with Ca2+ causing the greatest effect. Correlation plots demonstrate a strong interrelationship between perturbations of Raman bands assigned to ring vibrations of the bases and those of bands assigned to exocyclic carbonyls and backbone phosphodiester groups. However, strong correlations do not occur between the Raman phosphodioxy band (centered near 1092 cm-1) and other Raman bands, suggesting that the former is not highly sensitive to the structural changes induced by divalent metal cations. The structural perturbations induced by divalent cations are much greater for > 23-kilobase pair DNA than for 160-base pair DNA, as evidenced by both the Raman difference spectra and the tendency toward the formation of insoluble aggregates. In the presence of transition metals, aggregation of high-molecular-weight DNA is evident at temperatures as low as 11 degrees C. A relationship between DNA melting and aggregation is proposed in which initial metal binding at major groove sites locally destabilizes the B-DNA double helix, causing displacement of the bases away from one another and exposing additional metal binding sites. Metal cation linkage of two displaced bases would allow separate DNA strands to crosslink. Aggregation is proposed to result from the formation of an extended network of these crosslinks.

I. The synthesis and coordination chemistry of novel 6pi-electron ligands. II. Improvement of student writing skills in general chemistry lab reports through the use of Calibrated Peer Review

NASA Astrophysics Data System (ADS)

William, Wilson Ngambeki

Abstract I. The goal of this study was to synthesize and characterize a set of coordination complexes containing 6pi-cationic ligands. These compounds could be extremely useful as catalysts for the polymerization of olefins that are widely used in the synthetic polymer industry. The original strategy was to synthesize the 6pi-cationic ligands using (Ph2P) 3CH (1) and (Me2P)3CH (10) as precursors; however, both precursors 1 and 10 were found to be highly reactive leading to the fragmentation products (Ph 2P)2CH2 and (Me2P)2CH 2 respectively. In trying to control the reactivity, precursor 1 was coordinated to the group 6B metal carbonyl in two modes, Mo(CO)3(C 2H5CN)(Ph2P)2CHPPh2 and W(CO) 3(C2H5CN)(Ph2P)2CHPPh 2. In these novel compounds, two of the three phosphorus atoms are chelated to the metal. These complexes were isolated and characterized by X-ray analysis, elemental analysis, NMR and infrared spectroscopy. When these metal complexes were reacted with B(C6F5)3, the complexes were stabilized, and no molecular fragmentation was observed. Instead, a second mode of coordination was observed by 31P{1H} NMR spectroscopy, where all three phosphorus atoms are bonded to the metal in a tridentate fashion, yielding the novel product EtCNB(C6F 5)3, which was characterized by X-ray analysis. However, because there was no hydride abstraction from the tertiary carbon in either compound, further studies will be required to develop a strategy for hydride abstraction to produce a cationic ligand. Another strategy for the synthesis of 6pi-cationic ligands was to directly synthesize the halogenated version of the tertiary carbon atom of compound 10. Fractional recrystallization of the crude product yielded two compounds of 2,4,6-trimethypyridinium bromide and (PMe2)3CBr. (PMe2)3CBr was determined to be pure as revealed by 31P{1H} NMR. It is expected that oxidation of the bromide should yield the 6pi-cationic ligand. In the next strategy, density function theory calculations (DFT) were used to predict the possibility that the 6pi-cationic ligand of guanidinium analog would coordinate with a group 6B metal carbonyl. However, attempts to synthesize the predicted complex were unsuccessful; when neodymium nitrate was reacted with the 6pi-cationic ligand of guanidinium salt, a completely novel diguanidinium diaquapentakis(nitrato)neodymiate(III) was produced, as characterized by X-ray analysis, NMR, elemental analysis, and infrared spectroscopy. In the next approach, the synthesis of the 6pi-cationic ligand of guanidinium analog tripiperidine carbenium tetrafluoroborate was attempted; again the ligand could not be obtained; however, other novel compounds, 1-tritylpiperidine and diphenyldipiperidin-1-ylmethane were obtained as indicated by single crystal X-ray analysis. The last strategy was to synthesize a 6pi-anionic phosphorus-based complex using 2,4,6-tri-tert-butylaniline and PI5. While the desired complex was not obtained, another novel compound, 2,4,6-tri- tert-butylbenzenaminium iodide, was produced and characterized by single crystal X-ray analysis and 1H NMR. In conclusion, new strategies that combine DFT with novel synthetic approaches will be required to successfully produce coordination complexes containing 6pi-cationic ligands. Abstract II. The goal of this study was to assess effectiveness of using Calibrated Peer Review (CPR) for submitting post-lab reports. According to the literature the use of CPR could help improve students' writing skills (WS), conceptual understanding (CU) and critical thinking (CT). The first strategy of this study was to divide all students into two groups and required one group to use CPR for writing post-lab reports. The performances of the post-lab between the two groups were then compared. In second strategy I used an essay (pretest/posttest) to objectively assess students' writing skills that showed an improvement of 19% from students' who used CPR and 11% from students' who did not use CPR. When we compared the percentage of students who were not proficient in any areas (WS, CU, or CT) between the pre- and post-test, the CPR group has more improvement (22%) over the non-CPR group, which is 17%. Statistical analyses (t-test and ANOVA) for pretest and posttest scores have also shown significant differences in means and variances for CPR and non CPR students. In the third strategy we collected feedback from students through survey questions regarding the usefulness of CPR from their point of view. We have obtained low rating (2 on a five point Likert scale) about the use of CPR for writing post-lab report from students.

Photophysical analysis of 1,10-phenanthroline-embedded porphyrin analogues and their magnesium(II) complexes.

PubMed

Ishida, Masatoshi; Lim, Jong Min; Lee, Byung Sun; Tani, Fumito; Sessler, Jonathan L; Kim, Dongho; Naruta, Yoshinori

2012-11-05

The synthesis, characterization, photophysical properties, and theoretical analysis of a series of tetraaza porphyrin analogues (H-Pn: n=1-4) containing a dipyrrin subunit and an embedded 1,10-phenanthroline subunit are described. The meso-phenyl-substituted derivative (H-P1) interacts with a Mg(2+) salt (e.g., MgCl(2), MgBr(2), MgI(2), Mg(ClO(4))(2), and Mg(OAc)(2)) in MeCN solution, thereby giving rise to a cation-dependent red-shift in both the absorbance- and emission maxima. In this system, as well as in the other H-Pn porphyrin analogues used in this study, the four nitrogen atoms of the ligand interact with the bound magnesium cation to form Mg(2+)-dipyrrin-phenanthroline complexes of the general structure MgX-Pn (X=counteranion). Both single-crystal X-ray diffraction analysis of the corresponding zinc-chloride derivative (ZnCl-P1) and fluorescence spectroscopy of the Mg-adducts that are formed from various metal salts provide support for the conclusion that, in complexes such as MgCl-P1, a distorted square-pyramidal geometry persists about the metal cation wherein a chloride anion acts as an axial counteranion. Several analogues (HPn) that contain electron-donating and/or electron-withdrawing dipyrrin moieties were prepared in an effort to understand the structure-property relationships and the photophysical attributes of these Mg-dipyrrin complexes. Analysis of various MgX-Pn (X=anion) systems revealed significant substitution effects on their chemical, electrochemical, and photophysical properties, as well as on the Mg(2+)-cation affinities. The fluorescence properties of MgCl-Pn reflected the effect of donor-excited photoinduced electron transfer (d-PET) processes from the dipyrrin subunit (as a donor site) to the 1,10-phenanthroline acceptor subunit. The proposed d-PET process was analyzed by electron paramagnetic resonance (EPR) spectroscopy and by femtosecond transient absorption (TA) spectroscopy, as well as by theoretical DFT calculations. Taken together, these studies provide support for the suggestion that a radical species is produced as the result of an intramolecular charge-transfer process, following photoexcitation. These photophysical effects, combined with a mixed dipyrrin-phenanthroline structure that is capable of effective Mg(2+)-cation complexation, lead us to suggest that porphyrin-inspired systems, such as HPn, have a role to play as magnesium-cation sensors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-phosphate binders

DOEpatents

Howe, Beth Ann [Lewistown, IL; Chaps-Cabrera, Jesus Guadalupe [Coahuila, MX

2009-05-12

A metal-phosphate binder is provided. The binder may include an aqueous phosphoric acid solution, a metal-cation donor including a metal other than aluminum, an aluminum-cation donor, and a non-carbohydrate electron donor.

Studies on the electrodeposition of tin from acidic chloride-gluconate solutions

NASA Astrophysics Data System (ADS)

Rudnik, Ewa; Włoch, Grzegorz

2013-01-01

Electrodeposition of tin from acidic chloride-gluconate baths was investigated. Equilibrium distribution of tin(II) species showed domination of Sn(II)-gluconate complexes, but for Sn2+ concentrations 50 mM or higher increased percentage of Sn(II)-chloride complexes was found. Cyclic voltammetry, anodic stripping analysis and potentiostatic measurements indicated that rate of the cathodic process is determined by the release of metal cations from gluconate complexes in diluted bath (5 mM), but for more concentrated solutions reduction of Sn(II) ions run under diffusion control. Studies of anodic response showed that it depends on the Sn(II)/Glu ratio in the bath and deposition potential due to development of different planes of metal crystal. Average effective diffusion coefficients of metal species were determined. Morphology and structure tin deposits were also presented.

Investigating the pharmacodynamic and magnetic properties of pyrophosphate-bridged coordination complexes

NASA Astrophysics Data System (ADS)

Ikotun, Oluwatayo (Tayo) F.

The multidentate nature of pyrophosphate makes it an attractive ligand for complexation of metal cations. The participation of pyrophosphate in a variety of biological pathways and its metal catalyzed hydrolysis has driven our investigation into its coordination chemistry. We have successfully synthesized a library of binuclear pyrophosphate bridge coordination complexes. The problem of pyrophosphate hydrolysis to phosphate in the presence of divalent metal ions was overcome by incorporating capping ligands such as 1,10-phenanthroline and 2,2'-bipyridine prior to the addition of the pyrophosphate. The magnetic properties of these complexes was investigated and magneto-structural analysis was conducted. The biological abundance of pyrophosphate and the success of metal based drugs such as cisplatin, prompted our investigation of the cytotoxic properties of M(II) pyrophosphate dimeric complexes (where M(II) is CoII, CuII, and NiII) in adriamycin resistant human ovarian cancer cells. Thess compounds were found to exhibit toxicity in the nanomolar to picomolar range. We conducted in vitro stability studies and the mechanism of cytoxicity was elucidated by performing DNA mobility and binding assays, enzyme inhibition assays, and in vitro oxidative stress studies.

Parts per billion detection of uranium with a porphyrinoid-containing nanoparticle and in vivo photoacoustic imaging

DOE PAGES

Ho, I-Ting; Sessler, Jonathan L.; Gambhir, Sanjiv Sam; ...

2015-04-01

Chemical tools that can report radioactive isotopes would be of interest to the defense community. Here in this paper we report –250 nm polymeric nanoparticles containing porphyrinoid macrocycles with and without pre-complexed depleted uranium and demonstrate that the latter species may be detected easily and with high sensitivity via photoacoustic imaging. The porphyrinoid macrocycles used in the present study are non-aromatic in the absence of the uranyl cation, but aromatic after cation complexation. We solubilized both the freebase and metalated forms of the macrocycles in poly(lactic-co-glycolic acid) and found a peak in the photoacoustic spectrum at 910 nm excitation inmore » the case of the uranyl complex. The signal was stable for at least 15 minutes and allowed detection of uranium concentrations down to 6.2 ppb (5.7 nM) in vitro and 0.57 ppm (19 fCi; 0.52 μM) in vivo. Furthermore, to the best of our knowledge, this is the first report of a nanoparticle that detects an actinide cation via photoacoustic imaging.« less

Ga(+) Basicity and Affinity Scales Based on High-Level Ab Initio Calculations.

PubMed

Brea, Oriana; Mó, Otilia; Yáñez, Manuel

2015-10-26

The structure, relative stability and bonding of complexes formed by the interaction between Ga(+) and a large set of compounds, including hydrocarbons, aromatic systems, and oxygen-, nitrogen-, fluorine and sulfur-containing Lewis bases have been investigated through the use of the high-level composite ab initio Gaussian-4 theory. This allowed us to establish rather accurate Ga(+) cation affinity (GaCA) and Ga(+) cation basicity (GaCB) scales. The bonding analysis of the complexes under scrutiny shows that, even though one of the main ingredients of the Ga(+) -base interaction is electrostatic, it exhibits a non-negligible covalent character triggered by the presence of the low-lying empty 4p orbital of Ga(+) , which favors a charge donation from occupied orbitals of the base to the metal ion. This partial covalent character, also observed in AlCA scales, is behind the dissimilarities observed when GaCA are compared with Li(+) cation affinities, where these covalent contributions are practically nonexistent. Quite unexpectedly, there are some dissimilarities between several Ga(+) -complexes and the corresponding Al(+) -analogues, mainly affecting the relative stability of π-complexes involving aromatic compounds. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intriguing mechanistic labyrinths in gold(i) catalysis

PubMed Central

Obradors, Carla

2014-01-01

Many mechanistically intriguing reactions have been developed in the last decade using gold(i) as catalyst. Here we review the main mechanistic proposals in gold-catalysed activation of alkynes and allenes, in which this metal plays a central role by stabilising a variety of complex cationic intermediates. PMID:24176910

Conformational effects on cationization of poly(ethylene glycol) by alkali metal ions in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

NASA Astrophysics Data System (ADS)

Shimada, Kayori; Matsuyama, Shigetomo; Saito, Takeshi; Kinugasa, Shinichi; Nagahata, Ritsuko; Kawabata, Shin-Ichirou

2005-12-01

Conformational effects of polymer chains on matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) were studied by using an equimolar mixture of uniform poly(ethylene glycol)s (PEGs) and by molecular dynamics simulations. Uniform PEGs with degrees of polymerization n = 8-39 were separated from commercial PEG samples by preparative supercritical fluid chromatography. MALDI-TOFMS spectra of an equimolar mixture of the uniform PEGs in aqueous ethanol were measured by adding a mixture of 2,5-dihydroxybenzoic acid (as a matrix reagent) and five alkali metal chlorides (LiCl, NaCl, KCl, RbCl, and CsCl). After optimization of the matrix concentration and laser power, five types of adduct cationized by Li+, Na+, K+, Rb+, and Cs+ could be identified simultaneously in the same spectrum. In the lower molecular-mass region around 103, the spectral intensity increase rapidly with increasing molecular mass of PEG; this rapid increase in the spectral intensity started at a lower molecular mass for smaller adduct cations. Molecular dynamics simulations were used to calculated the affinity of PEG for the adduct cations. These experimental and simulated results showed that the observed spectral intensities in MALDI-TOFMS were markedly affected by the species of adduct cations and the degree of polymerization of the PEG, and that they were dependent on the stability of the PEG-cation complex.

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

PubMed

Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

2018-02-19

The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

NO.sub.x catalyst and method of suppressing sulfate formation in an exhaust purification system

DOEpatents

Balmer-Millar, Mari Lou [Chillicothe, IL; Park, Paul W [Peoria, IL; Panov, Alexander G [Peoria, IL

2007-06-26

The activity and durability of a zeolite lean-burn NOx catalyst can be increased by loading metal cations on the outer surface of the zeolite. However, the metal loadings can also oxidize sulfur dioxide to cause sulfate formation in the exhaust. The present invention is a method of suppressing sulfate formation in an exhaust purification system including a NO.sub.x catalyst. The NO.sub.x catalyst includes a zeolite loaded with at least one metal. The metal is selected from among an alkali metal, an alkaline earth metal, a lanthanide metal, a noble metal, and a transition metal. In order to suppress sulfate formation, at least a portion of the loaded metal is complexed with at least one of sulfate, phosphate, and carbonate.

NO.sub.x catalyst and method of suppressing sulfate formation in an exhaust purification system

DOEpatents

Balmer-Millar, Mari Lou; Park, Paul W.; Panov, Alexander G.

2006-08-22

The activity and durability of a zeolite lean-bum NOx catalyst can be increased by loading metal cations on the outer surface of the zeolite. However, the metal loadings can also oxidize sulfur dioxide to cause sulfate formation in the exhaust. The present invention is a method of suppressing sulfate formation in an exhaust purification system including a NO.sub.x catalyst. The NO.sub.x catalyst includes a zeolite loaded with at least one metal. The metal is selected from among an alkali metal, an alkaline earth metal, a lanthanide metal, a noble metal, and a transition metal. In order to suppress sulfate formation, at least a portion of the loaded metal is complexed with at least one of sulfate, phosphate, and carbonate.

Synthesis of electroactive ionic liquids for flow battery applications

DOEpatents

Anderson, Travis Mark; Ingersoll, David; Staiger, Chad; Pratt, Harry

2015-09-01

The present disclosure is directed to synthesizing metal ionic liquids with transition metal coordination cations, where such metal ionic liquids can be used in a flow battery. A cation of a metal ionic liquid includes a transition metal and a ligand coordinated to the transition metal.

Identification of number and type of cations in water-soluble Cs+ and Na+ calix[4]arene-bis-crown-6 complexes by using ESI-TOF-MS.

PubMed

Kumagai, Shogo; Hayashi, Kotaro; Kameda, Tomohito; Morohashi, Naoya; Hattori, Tetsutaro; Yoshioka, Toshiaki

2018-04-01

The treatment of cesium-contaminated wastewater has become one of the biggest issues. The selective Cs + removal from wastewater containing competitive alkali metal ions such as Na + is desired to reduce the volume of sludge. Therefore, the present work focused on water-soluble calix[4]arene-bis-crown-6 (W-BisC6) to selectively capture Cs + . For characterization of the complex, UV-vis spectroscopy is commonly used, however, due to the limited availability of information it can be hard to quickly identify the specific structures of some complexes. In this work, the electrospray ionization time of flight spectrometry (ESI-TOF-MS) is successfully utilized to identify the number and type of cations in W-BisC6-cation complexes. ESI-TOF-MS accurately recognized 4 types of complex (W-BisC6-Na + , W-BisC6-Cs + , W-BisC6-2Na + , W-BisC6-Na + -Cs + ), and the experimental and simulated results were almost perfectly matched. It also revealed the difficulty of W-BisC6-2Cs + complex formation under the present conditions. Thus, this technique is significantly helpful for rapid identification of the specific structures of complexes during Cs + -contaminated wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Interaction between transition metals and phenylalanine: a combined experimental and computational study.

PubMed

Elius Hossain, Md; Mahmudul Hasan, Md; Halim, M E; Ehsan, M Q; Halim, Mohammad A

2015-03-05

Some transition metal complexes of phenylalanine of general formula [M(C9H10NO2)2]; where M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) are prepared in aqueous medium and characterized by spectroscopic, thermo-gravimetric (TG) and magnetic susceptibility analysis. Density functional theory (DFT) has been employed calculating the equilibrium geometries and vibrational frequencies of those complexes at B3LYP level of theory using 6-31G(d) and SDD basis sets. In addition, frontier molecular orbital and time-dependent density functional theory (TD-DFT) calculations are performed with CAM-B3LYP/6-31+G(d,p) and B3LYP/SDD level of theories. Thermo-gravimetric analysis confirms the composition of the complexes by comparing the experimental and calculated data for C, H, N and metals. Experimental and computed IR results predict a significant change in vibrational frequencies of metal-phenylalanine complexes compared to free ligand. DFT calculation confirms that Mn, Co, Ni and Cu complexes form square planar structure whereas Zn adopts distorted tetrahedral geometry. The metal-oxygen bonds in the optimized geometry of all complexes are shorter compared to the metal-nitrogen bonds which is consistent with a previous study. Cation-binding energy, enthalpy and Gibbs free energy indicates that these complexes are thermodynamically stable. UV-vis and TD-DFT studies reveal that these complexes demonstrate representative metal-to-ligand charge transfer (MLCT) and d-d transitions bands. TG analysis and IR spectra of the metal complexes strongly support the absence of water in crystallization. Magnetic susceptibility data of the complexes exhibits that all except Zn(II) complex are high spin paramagnetic. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Palmieri, M.D.; Fritz, J.S.

Metal ions are determined by adding N-methylfurohydroxamic acid to an aqueous sample and then separating the metal chelates by direct injection onto a liquid chromatographic column. Separations on a C/sub 8/ silica column and a polystyrene-divinylbenzene column are compared, with better separations seen on the polymeric column. The complexes formed at low pH values are cationic and are separated by an ion pairing mechanism. Retention times and selectivity of the metal complexes can be varied by changing the pH. Several metal ions can be separated and quantified; separation conditions, linear calibration curve ranges, and detection limits are presented for Zr(IV),more » Hf(IV), Fe(III), Nb(V), Al(III), and Sb(III). Interferences due to the presence of other ions in solution are investigated. Finally, an antiperspirant sample is analyzed for zirconium by high-performance liquid chromatography.« less

Structure, bonding, and reactivity of reactant complexes and key intermediates.

PubMed

Soriano, Elena; Marco-Contelles, José

2011-01-01

Complexes of Pt and Au (gold(III) and cationic gold(I)) have shown an exceptional ability to promote a variety of organic transformations of unsaturated precursors due to their peculiar Lewis acid properties: the alkynophilic character of these soft metals and the π-acid activation of unsaturated groups promotes the intra- or intermolecular attack of a nucleophile. In this chapter we summarize the computational data reported on the structure, bonding, and reactivity of the reactant π-complexes and also on the key intermediate species.

Gas-phase and solution-phase polymerization of epoxides by Cr(salen) complexes: evidence for a dinuclear cationic mechanism.

PubMed

Schön, Eva; Zhang, Xiangyang; Zhou, Zhiping; Chisholm, Malcolm H; Chen, Peter

2004-11-15

The gas-phase reactions of a series of mass-selected mononuclear and dinuclear Cr(salen) complexes with propylene oxide suggest that the enhanced reactivity of the dinuclear complexes in gas-phase and in solution may derive from a dicationic mechanism in which the alkoxide chain is mu(2)-coordinated to two Lewis acidic metal centers. The double coordination is proposed to suppress backbiting, and hence chain-transfer in the gas-phase homopolymerization of epoxides.

Complex oxides: Intricate disorder

DOE PAGES

Uberuaga, Blas Pedro

2016-02-29

In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore,more » how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations 1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder 2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought 4.« less

Pi-metal complexes of tetrapyrrolic systems. A novel coordination mode in "porphyrin-like" chemistry.

PubMed

Cuesta, Luciano; Sessler, Jonathan L

2009-09-01

The coordination chemistry of porphyrins and related tetrapyrrolic ligands has traditionally centered around the ability of these systems to form pyrrole N-ligated complexes via the formation of sigma bonds, either within the N(4) core or displaced above it. In fact, such sigma-complexes are known with almost every metal cation in the periodic table. However, a growing number of pi-complexes derived from tetrapyrrolic ligands have been reported in recent years. The underlying coordination mode, while still novel in the context of "porphyrin-like" chemistry, is already being recognized for the effects it can impart over the reactivity, as well as the spectroscopic, redox, electronic, and optical properties of various oligopyrrolic macrocycles. This critical review summarizes accomplishments made in this fast-emerging field (59 references).

Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Shock, Everetr L.; Koretsky, Carla M.

1995-04-01

Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( overlineSo) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of overlineSo provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( Δ -Sro) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

Involvement of the exomer complex in the polarized transport of Ena1 required for Saccharomyces cerevisiae survival against toxic cations.

PubMed

Anton, Carlos; Zanolari, Bettina; Arcones, Irene; Wang, Congwei; Mulet, Jose Miguel; Spang, Anne; Roncero, Cesar

2017-12-01

Exomer is an adaptor complex required for the direct transport of a selected number of cargoes from the trans -Golgi network (TGN) to the plasma membrane in Saccharomyces cerevisiae However, exomer mutants are highly sensitive to increased concentrations of alkali metal cations, a situation that remains unexplained by the lack of transport of any known cargoes. Here we identify several HAL genes that act as multicopy suppressors of this sensitivity and are connected to the reduced function of the sodium ATPase Ena1. Furthermore, we find that Ena1 is dependent on exomer function. Even though Ena1 can reach the plasma membrane independently of exomer, polarized delivery of Ena1 to the bud requires functional exomer. Moreover, exomer is required for full induction of Ena1 expression after cationic stress by facilitating the plasma membrane recruitment of the molecular machinery involved in Rim101 processing and activation of the RIM101 pathway in response to stress. Both the defective localization and the reduced levels of Ena1 contribute to the sensitivity of exomer mutants to alkali metal cations. Our work thus expands the spectrum of exomer-dependent proteins and provides a link to a more general role of exomer in TGN organization. © 2017 Anton et al. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

New Metal Niobate and Silicotitanate Ion Exchangers: Development and Characterization

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

Alexandra Navrotsky; Mary Lou Balmer; Tina M. Nenoff

2003-12-05

This renewal proposal outlines our current progress and future research plans for ion exchangers: novel metal niobate and silicotitanate ion exchangers and their ultimate deployment in the DOE complex. In our original study several forms (including Cs exchanged) of the heat treated Crystalline Silicotitanates (CSTs) were fully characterized by a combination of high temperature synthesis and phase identification, low temperature synthesis and phase identification, and thermodynamics. This renewal proposal is predicated on work completed in our current EMSP program: we have shown preliminary data of a novel class of niobate-based molecular sieves (Na/Nb/M/O, M = transition metals), which show exceptionallymore » high selectivity for divalent cations under extreme conditions (acid solutions, competing cations), in addition to novel silicotitanate phases which are also selective for divalent cations. Furthermore, these materials are easily converted by a high temperature in-situ heat treatment into a refractory ceramic waste form with low cation leachability. The new waste form is a perovskite phase, which is also a major component of Synroc, a titanate ceramic waste form used for sequestration of HLW wastes from reprocessed, spent nuclear fuel. These new niobate ion exchangers also shown orders of magnitude better selectivity for Sr2+ under acid conditions than any other material. The goal of the program is to reduce the costs associated with divalent cation waste removal and disposal, to minimize the risk of contamination to the environment during ion exchanger processing, and to provide DOE with materials for near-term lab-bench stimulant testing, and eventual deployment. The proposed work will provide information on the structure/property relationship between ion exchanger frameworks and selectivity for specific ions, allowing for the eventual ''tuning'' of framework for specific ion exchange needs. To date, DOE sites have become interested in on-site testing of these materials; ongoing discussions and initial experiments are occurring with Dr. Dean Peterman, Idaho National Engineering and Environmental Laboratory (INEEL) (location of the DOE/EM Waste Treatment Focus Area), and Dr. John Harbour, Savannah River Site (SRS). Yet the materials have not been optimized, and further research and development of the novel ion exchangers and testing conditions with simulants are needed. In addition, studies of the ion exchanger composition versus ion selectivity, ion exchange capacity and durability of final waste form are needed. This program will bring together three key institutions to address scientific hurdles of the separation process associated with metal niobate and silicotitanate ion exchangers, in particular for divalent cations (e.g., Sr2+). The program involves a joint effort between researchers at Pacific Northwest National Laboratory, who are leaders in structure/property relations in silicotitanates and in waste form development and performance assessment, Sandia National Laboratories, who discovered and developed crystalline silicotitanate ion exchangers (with Texas A&M and UOP) and also the novel class of divalent metal niobate ion exchangers, and the Thermochemistry Facility at UC Davis, who are world renowned experts in calorimetry and have already performed extensive thermodynamic studies on silicotitanate materials. In addition, Dr. Rodney Ewing of University of Michigan, an expert in radiation effects on materials, and Dr. Robert Roth of the National Institute of Standards and Technology and The Viper Group, a leader in phase equilibria development, will be consultants for radiation and phase studies. The research team will focus on three tasks that will provide both the basic research necessary for the development of highly selective ion exchange materials and also materials for short-term deployment within the DOE complex: (1) Structure/property relationships of a novel class of niobate-based molecular sieves (Na/Nb/M/O, M = transition metals), which show exceptionally high selectivity for divalent cations under extreme conditions (acid solutions, competing cations), (2) the role of ion exchanger structure change (both niobates and silicotitanates) on the exchange capacity (for elements such as Sr and actinide-surrogates) which results from exposure to DOE complex waste simulants, (3) thermodynamic stability of metal niobates and silicotitanate ion exchangers.« less

On the structure of transition metals complexes with the new tridentate dye of thiazole series: Theoretical and experimental studies

NASA Astrophysics Data System (ADS)

Fizer, Maksym; Sidey, Vasyl; Tupys, Andrii; Ostapiuk, Yurii; Tymoshuk, Oleksandr; Bazel, Yaroslav

2017-12-01

The 1-[(5-Benzyl-1,3-thiazol-2-yl)diazenyl]naphthalene-2-ol (BnTAN) is a recently synthesized azo dye that can act as a tridentate ligand in complexes with transition metals. In a series of previous works, this analytical reagent was shown to be applicable for selective, reliable, express and relatively inexpensive determination of heavy metals in different objects through the spectrophotometric technique. Although the action of 1-(2-thiazolylazo)-2-naphthol (TAN) dyes as tridentate ligands has been suggested in the literature long time ago, due to the lack of experimental data, it was necessary to investigate the mechanism of formation and the structure of BnTAN complexes with the such transition metals as Cu(II), Zn(II) and Cd(II). Furthermore, the reactivity and properties of different acidity forms and conformers of BnTAN and related TAN dyes were not fully defined, so the determination of these properties by analysis of wavefunction was also necessary. Two standard spectrophotometric methods and voltammetric technique were used to determine the composition of complex of BnTAN with metals ions. All three experimental methods indicate that coordination ratio of metal:dye is equal to 1:2. Moreover, this study reports the stability and geometry of conformers of different forms (anionic/neutral/cationic) of BnTAN, along with a detailed analysis of electronic properties, reactivity and aromaticity of the most stable conformers of BnTAN forms. Each of the above forms has some difference in position of benzyl ring against the thiazole moiety, which is explained in terms of attraction and repulsion of these two fragments induced by partial atomic charges. The crucial influence of hydrogen bond and weak non-covalent interactions between naphthyl, aza- and thiazolyl fragments has been established. The quantum chemical calculations have shown that partial atomic charges of anionic, neutral and cationic forms can explain the reactivity of each BnTAN form, and have also clarified the mechanism of formation of metal complex through the connection of metal with phenol oxygen, thiazolyl nitrogen and one nitrogen of aza group - thus giving two five-membered metal-containing cycles and confirming that BnTAN acts as a tridentate ligand. The obtained results introduce novel and crucial information which can assist in understanding the mechanism of complex formation of BnTAN and display the strength and level of detail of applying quantum chemical methods to reveal the reactivity, energy properties, and electronic properties of this new dye.

Efficient adsorption of multiple heavy metals with tailored silica aerogel-like materials.

PubMed

Vareda, João P; Durães, Luisa

2017-11-10

Recently developed tailored adsorbents for heavy metal uptake are studied in batch tests with Cu, Pb, Cd, Ni, Cr and Zn, in order to decontaminate polluted environments where these heavy metals are found in solution - water courses and groundwater. The adsorbents feature mercapto or amine-mercapto groups that are capable of complexating the cations. Through the use of equilibrium tests it is found that a remarkably high heavy metal uptake is obtained for all metals (ranging from 84 to 140 mg/g). These uptake values are quite impressive when compared to other adsorbents reported in the literature, which is also due to the double functionalization present in one of the adsorbents. For the best adsorbent, adsorption capacities followed the order Cu(II) > Pb(II) > Zn(II) > Cr(III) > Cd(II) > Ni(II). With these adsorbents, the removal process was fast with most of the metals being removed in less than 1 h. Competitive sorption tests were performed in tertiary mixtures that were based on real world polluted sites. It was found that although competitive sorption occurs, affecting the individual removal of each metal, all the cations in solution still interact with the adsorbent, achieving removal values that make this type of material very interesting for its proposed application.

Reactions of Copper and Silver Cations with Carbon Dioxide: An Infrared Photodissociation Spectroscopic and Theoretical Study.

PubMed

Zhao, Zhi; Kong, Xiangtao; Yang, Dong; Yuan, Qinqin; Xie, Hua; Fan, Hongjun; Zhao, Jijun; Jiang, Ling

2017-05-04

The reaction of copper and silver cations with carbon dioxide was studied by mass-selected infrared photodissociation spectroscopy. Quantum chemical calculations were performed on these products, which aided the experimental assignments of the infrared spectra and helped to elucidate the geometrical and electronic structures. The Cu + and Ag + cations bind to an oxygen atom of CO 2 in an end-on configuration via a charge-quadrupole electrostatic interaction in the [M(CO 2 ) n ] + complexes. The formation of oxide-carbonyl and carbonyl-carbonate structures is not favored for the interaction of CO 2 with Cu + and Ag + . For n = 3 and 4, the n + 0 structure is preferred. [Note on the nomenclature: Using i + j, i denotes the number of CO 2 molecules in the first coordination shell, and j denotes the number of CO 2 molecules in the second coordination shell.] The two nearly energy-identical n + 0 and (n - 1) + 1 structures coexist in n = 5 and 6. While the six-coordinated structure is favored for [Cu(CO 2 ) n=7,8 ] + , the n + 0 configuration is dominated in [Ag(CO 2 ) n=7,8 ] + . The reaction of CO 2 with the cationic metal atoms has been compared to that with the neutral and anionic metal atoms, which would have important implications for understanding the interaction of CO 2 with reduction catalysts and rationally designing catalysts for CO 2 reduction based on cost-effective transition metals.

Eu(III) Complexes of Octadentate 1-Hydroxy-2-pyridinones: Stability and Improved Photophysical Performance[].

PubMed

Moore, Evan G; D'Aléo, Anthony; Xu, Jide; Raymond, Kenneth N

2009-10-13

The luminescence properties of lanthanoid ions can be dramatically enhanced by coupling them to antenna ligands that absorb light in the UV/visible and then efficiently transfer the energy to the lanthanoid center. The synthesis and the complexation of Ln(III) cations (Ln=Eu; Gd) for a ligand based on four 1-hydroxy-2-pyridinone (1,2-HOPO) chelators appended to a ligand backbone derived by linking two L-lysine units (3LI-bis-LYS) is described. This octadentate Eu(III) complex ([Eu(3LI-bis-LYS-1,2-HOPO)](-)) has been evaluated in terms of its thermodynamic stability, UV/visible absorption and luminescence properties. For this complex the conditional stability constant (pM) is 19.9, which is an order of magnitude higher than diethylenetriaminepentacetic acid (DTPA) at pH= 7.4. This Eu(III) complex also shows an almost two-fold increase in its luminescence quantum yield in aqueous solution (pH= 7.4) when compared to other octadentate ligands. Hence, despite a slight decrease of the molar absorption coefficient, a much higher brightness is obtained for [Eu(3LI-bis-LYS-1,2-HOPO)](-). This overall improvement was achieved by saturating the coordination sphere of the Eu(III) cation, yielding an increased metal centered efficiency by excluding solvent water molecules from the metal's inner sphere.

Impact of metal cations on the electrocatalytic properties of Pt/C nanoparticles at multiple phase interfaces.

PubMed

Durst, Julien; Chatenet, Marian; Maillard, Frédéric

2012-10-05

Proton-exchange membrane fuel cells (PEMFCs) use carbon-supported nanoparticles based on platinum and its alloys to accelerate the rate of the sluggish oxygen-reduction reaction (ORR). The most common metals alloyed to Pt include Co, Ni and Cu, and are thermodynamically unstable in the PEMFC environment. Their dissolution yields the formation and redistribution of metal cations (M(y+)) within the membrane electrode assembly (MEA). Metal cations can also contaminate the MEA when metallic bipolar plates are used as current collectors. In each case, the electrical performance of the PEMFC severely decreases, an effect that is commonly attributed to the poisoning of the sulfonic acid groups of the perfluorosulfonated membrane (PEM) and the resulting decrease of the proton transport properties. However, the impact of metal cations on the kinetics of electrochemical reactions involving adsorption/desorption and bond-breaking processes remains poorly understood. In this paper, we use model electrodes to highlight the effect of metal cations on Pt/C nanoparticles coated or not with a perfluorosulfonated ionomer for the CO electrooxidation reaction and the oxygen reduction reaction. We show that metal cations negatively impact the ORR kinetics and the mass-transport resistance of molecular oxygen. However, the specific adsorption of sulfonate groups of the Nafion® ionomer locally modifies the double layer structure and increases the tolerance to metal cations, even in the presence of sulphate ions in the electrolyte. The survey is extended by using an ultramicroelectrode with cavity and a solid state cell (SSC) specifically developed for this study.

Bacterio-electric leaching of metals

DOEpatents

Lazaroff, Norman; Dugan, Patrick R.

1992-07-07

The separation of cationic materials from an ore body is assisted by the application of an electric potential, and resulting current, to the ore body, in association with iron or sulphur oxidizing bacteria. The combined process induces migration of cationic metals to a cathode suspended within the ore body so that the cationic metal can be preferentially separated from the ore body.

Bacterio-electric leaching of metals

DOEpatents

Lazaroff, Norman; Dugan, Patrick R.

1992-01-01

The separation of cationic materials from an ore body is assisted by the application of an electric potential, and resulting current, to the ore body, in association with iron or sulphur oxidizing bacteria. The combined process induces migration of cationic metals to a cathode suspended within the ore body so that the cationic metal can be preferentially separated from the ore body.

Structures and unimolecular chemistry of M(Pro2-H)(+) (M = Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn) by IRMPD spectroscopy, SORI-CID, and theoretical studies.

PubMed

Jami-Alahmadi, Yasaman; Fridgen, Travis D

2016-01-21

M(Pro2-H)(+) complexes were electrosprayed and isolated in an FTICR cell where their unimolecular chemistries and structures were explored using SORI-CID and IRMPD spectroscopy. These experiments were augmented by computational methods such as electronic structure, simulated annealing, and atoms in molecules (AIM) calculations. The unimolecular chemistries of the larger metal cation (Ca(2+), Sr(2+) and Ba(2+)) complexes predominantly involve loss of neutral proline whereas the complexes involving the smaller Mg(2+) and transition metal dications tend to lose small neutral molecules such as water and carbon dioxide. Interestingly, all complexes involving transition metal dications except for Cu(Pro2-H)(+) lose H2 upon collisional or IRMPD activation. IRMPD spectroscopy shows that the intact proline in the transition metal complexes and Cu(Pro2-H)(+) is predominantly canonical (charge solvated) while for the Ca(2+), Sr(2+), and Ba(2+) complexes, proline is in its zwitterionic form. The IRMPD spectra for both Mg(Pro2-H)(+) and Mn(Pro2-H)(+) are concluded to have contributions from both charge-solvated and canonical structures.

Interaction between alkaline earth cations and oxo-ligands. DFT study of the affinity of the Ca2+ cation for carbonyl ligands.

PubMed

da Costa, Leonardo Moreira; Carneiro, José Walkimar de Mesquita; Romeiro, Gilberto Alves; Paes, Lilian Weitzel Coelho

2011-02-01

The affinity of the Ca(2+) ion for a set of substituted carbonyl ligands was analyzed with both the DFT (B3LYP/6-31+G(d)) and semi-empirical (PM6) methods. Two types of ligands were studied: a set of monosubstituted [O=CH(R)] and a set of disubstituted ligands [O=C(R)(2)] (R=H, F, Cl, Br, OH, OCH(3), CH(3), CN, NH(2) and NO(2)), with R either directly bound to the carbonyl carbon atom or to the para position of a phenyl ring. The interaction energy was calculated to quantify the affinity of the Ca(2+) cation for the ligands. Geometric and electronic parameters were correlated with the intensity of the metal-ligand interaction. The electronic nature of the substituent is the main parameter that determines the interaction energy. Donor groups make the interaction energy more negative (stabilizing the complex formed), while acceptor groups make the interaction energy less negative (destabilizing the complex formed).

Single Sublattice Endotaxial Phase Separation Driven by Charge Frustration in a Complex Oxide

PubMed Central

2013-01-01

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation. PMID:23750709

Distinct roles of beta1 metal ion-dependent adhesion site (MIDAS), adjacent to MIDAS (ADMIDAS), and ligand-associated metal-binding site (LIMBS) cation-binding sites in ligand recognition by integrin alpha2beta1.

PubMed

Valdramidou, Dimitra; Humphries, Martin J; Mould, A Paul

2008-11-21

Integrin-ligand interactions are regulated in a complex manner by divalent cations, and previous studies have identified ligand-competent, stimulatory, and inhibitory cation-binding sites. In collagen-binding integrins, such as alpha2beta1, ligand recognition takes place exclusively at the alpha subunit I domain. However, activation of the alphaI domain depends on its interaction with a structurally similar domain in the beta subunit known as the I-like or betaI domain. The top face of the betaI domain contains three cation-binding sites: the metal-ion dependent adhesion site (MIDAS), the ADMIDAS (adjacent to MIDAS), and LIMBS (ligand-associated metal-binding site). The role of these sites in controlling ligand binding to the alphaI domain has yet to be elucidated. Mutation of the MIDAS or LIMBS completely blocked collagen binding to alpha2beta1; in contrast mutation of the ADMIDAS reduced ligand recognition but this effect could be overcome by the activating monoclonal antibody TS2/16. Hence, the MIDAS and LIMBS appear to be essential for the interaction between alphaI and betaI, whereas occupancy of the ADMIDAS has an allosteric effect on the conformation of betaI. An activating mutation in the alpha2 I domain partially restored ligand binding to the MIDAS and LIMBS mutants. Analysis of the effects of Ca(2+), Mg(2+), and Mn(2+) on ligand binding to these mutants showed that the MIDAS is a ligand-competent site through which Mn(2+) stimulates ligand binding, whereas the LIMBS is a stimulatory Ca(2+)-binding site, occupancy of which increases the affinity of Mg(2+) for the MIDAS.

Chemistry in acetone complexes of metal dications: a remarkable ethylene production pathway.

PubMed

Wu, Jianhua; Liu, Dan; Zhou, Jian-Ge; Hagelberg, Frank; Park, Sung Soo; Shvartsburg, Alexandre A

2007-06-07

Electrospray ionization can generate microsolvated multiply charged metal ions for various metals and ligands, allowing exploration of chemistry within such clusters. The finite size of these systems permits comparing experimental results with accurate calculations, creating a natural laboratory to research ion solvation. Mass spectrometry has provided much insight into the stability and dissociation of ligated metal cations. While solvated singly charged ions tend to shrink by ligand evaporation, solvated polycations below a certain size exhibit charge reduction and/or ligand fragmentation due to organometallic reactions. Here we investigate the acetone complexes of representative divalent metals (Ca, Mn, Co, Ni, and Cu), comparing the results of collision-induced dissociation with the predictions of density functional theory. As for other solvated dications, channels involving proton or electron transfer compete with ligand loss and become dominant for smaller complexes. The heterolytic C-C bond cleavage is common, like in DMSO and acetonitrile complexes. Of primary interest is the unanticipated neutral ethylene loss, found for all metals studied except Cu and particularly intense for Ca and Mn. We focus on understanding that process in the context of competing dissociation pathways, as a function of metal identity and number of ligands. According to first-principles modeling, ethylene elimination proceeds along a complex path involving two intermediates. These results suggest that chemistry in microsolvated multiply charged ions may still hold major surprises.

The reduction mechanism of chromite in the presence of a silica flux

NASA Astrophysics Data System (ADS)

Weber, P.; Eric, R. H.

1993-12-01

The reduction behavior of a natural chromite from the Bushveld Complex of South Africa was studied at 1300 °C to 1500 °C. Reduction was by graphite in the presence of silica. Thermo-gravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis were the experimental techniques used. Silica affected the reduction at and above 1400 °C. A two-stage reduction mechanism was established. The first stage, up to a reduction level of about 40 pct, is primarily confined to iron metallization, and zoning is observed in partially reduced chromites. In this stage, silica does not interfere with the reduction, which proceeds by an outward diffusion of Fe2+ ions and an inward diffusion of Mg2+ and Cr2+ ions. The second stage is primarily confined to chromium metallization, and formation of a silicate slag alters the reduction mechanism. The slag phase agglomerates and even embeds partially reduced chromite particles. An ion-exchange reaction between the re-ducible cations (Cr3+ and Fe2+) in the spinel and the dissolved cations (Al3+ and Mg2+) in the slag allows further reduction. Once the reducible cations are dissolved in the slag phase, they are reduced to the metallic state at sites where there is contact with the reductant.

Cation-enhanced capillary electrophoresis separation of atropoisomer anions.

PubMed

Na, Yun-Cheol; Berthod, Alain; Armstrong, Daniel W

2015-12-01

CE was used to study the separation of the atropoisomers of four phosphoric acids and two sulfonic acids and the enantiomers of two phosphoric acids. All solutes are in their anionic forms in aqueous electrolytes. The chiral additives were two hydroxypropyl cyclodextrins (CDs) and cyclofructan 6 (CF6). The CDs were able to separate four solutes and the CF6 additive could separate only one: 1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (BHP). Since CF6 is able to bind with cations, nitrate of alkaline metals, Ba(2+) , and Pb(2+) were added, greatly improving the BHP separation at the expense of longer migration times. There seems to be a link between CF6-cation-binding constants and BHP resolution factors. Cation additions were also performed with CD selectors that are less prone to form complexes with cations. Significant improvements of enantiomer or atropoisomer separations were observed also associated with longer migration times. It is speculated that the anionic solutes associate with the added cations forming larger entities better differentiated by CDs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nucleotide cleaving agents and method

DOEpatents

Que, Jr., Lawrence; Hanson, Richard S.; Schnaith, Leah M. T.

2000-01-01

The present invention provides a unique series of nucleotide cleaving agents and a method for cleaving a nucleotide sequence, whether single-stranded or double-stranded DNA or RNA, using and a cationic metal complex having at least one polydentate ligand to cleave the nucleotide sequence phosphate backbone to yield a hydroxyl end and a phosphate end.

Polymer-grafted QCM chemical sensor and application to heavy metalions real time detection.

PubMed

Sartore, Luciana; Barbaglio, Marzia; Borgese, Laura; Bontempi, Elza

2011-07-20

A flow type quartz crystal microbalance (QCM) chemical sensor was developed for monitoring of heavy metal ions in aqueous solutions (that is suitable for environmental monitoring). The sensor is based upon surface chelation of the metal ions at multifunctional polymer modified gold electrodes on 9 MHz AT-cut quartz resonators, functioning as a QCM. New processes have been developed which enable to obtain surface-modified gold electrodes with high heavy metal ions complexing ability. These polymer grafted QCM sensors can selectively adsorb heavy metal ions, such as copper lead chrome and cadmium, from solution over a wide range from 0.01 to 1000 ppm concentration by complexation with functional groups in the polymers. Cations typically present in natural water did not interfere with the detection of heavy metals. X-Ray Reflectivity (XRR) and Total Reflection X-ray Fluorescence (TXRF) were carried out to characterise the unmodified and modified gold surfaces as well as to verify the possibility to selectively bond and remove metal ions.

Interaction of In(I) and Tl(I) cations with 2,6-diaryl pyridine ligands: cation encapsulation within a very weakly interacting N/arene host environment.

PubMed

Mansaray, Hassanatu B; Tang, Christina Y; Vidovic, Dragoslav; Thompson, Amber L; Aldridge, Simon

2012-12-03

The interaction of 2,6-dimesitylpyridine with Tl(I) and In(I) cations has been investigated with a view to developing tractable molecular M(I) compounds which are soluble in organic media. In stark contrast to isosteric and isoelectronic terphenyl systems, complexes featuring the [(2,6-Mes(2)py)M](+) fragment feature very weak metal-ligand interactions in the solid state, as revealed by M-N distances of the order of 2.45 Å (M = In) and 2.64 Å (M = Tl). While additional weak π interactions are observed with arene solvate molecules in these systems, the related 2:1 complex [(2,6-Mes(2)py)(2)In][BAr(f)(4)] features an In(I) center wholly encapsulated by the bulky Mes(2)py donors, and even longer In-N distances [2.586(6) and 2.662(5) Å]. These contacts are about 0.5 Å greater than the sum of the respective covalent radii (2.13 Å) and provide evidence for an effectively "naked" In(I) cation stabilized to a minor extent by orbital interactions.

Evolution of organo-cyanometallate cages: supramolecular architectures and new Cs+-specific receptors.

PubMed

Boyer, Julie L; Kuhlman, Matthew L; Rauchfuss, Thomas B

2007-04-01

The ability of inorganic cyanometallate polymers to form interesting and useful complexes is well-known. This Account summarizes work, especially in our laboratories, aimed at replicating aspects of this inorganic chemistry in homogeneous solution using organometallic building blocks. A library of molecular organometallic cyanides and Lewis acids, with varying charges and labilities, are shown to give families of neutral and charged cages. Neutral and anionic cages, often molecular boxes, bind larger alkali metals tightly. Cubic frameworks show an unparalleled affinity for cesium cations over potassium cations. Noncubic cages are described including tetrahedranes, defect boxes, trigonal prisms, and hexagonal prisms.

Anion-π interaction in metal-organic networks formed by metal halides and tetracyanopyrazine

NASA Astrophysics Data System (ADS)

Rosokha, Sergiy V.; Kumar, Amar

2017-06-01

Co-crystallization of tetracyanopyrazine, TCP, with the tetraalkylammonium salts of linear [CuBr2]-, planar [PtCl4]2- or [Pt2Br6]2-, or octahedral [PtBr6]2- complexes resulted in formation of the alternating [MlXn]m-/TCP stacks separated by the Alk4N+ cations. These hybrid stacks showed multiple short contacts between halide ligands of the [MlXn]m- complexes and carbon atoms of the TCP acceptor indicating strong anion-π bonding between these species. It confirmed that the anion-π interaction is sufficiently strong to bring together such disparate components as ionic metal complexes and neutral aromatic molecules regardless of the geometry of the coordination compound. Structural features of the solid-state stacks and [MlXn]m-·TCP dyads resulted from the quantum-mechanical computations suggests that the molecular-orbital (weakly-covalent) component play an important role in association of the [MlXn]m- complexes with the TCP acceptor.

Sorption of Sr, Co and Zn on illite: Batch experiments and modelling including Co in-diffusion measurements on compacted samples

NASA Astrophysics Data System (ADS)

Montoya, V.; Baeyens, B.; Glaus, M. A.; Kupcik, T.; Marques Fernandes, M.; Van Laer, L.; Bruggeman, C.; Maes, N.; Schäfer, T.

2018-02-01

Experimental investigations on the uptake of divalent cations (Sr, Co and Zn) onto illite (Illite du Puy, Le-Puy-en-Velay, France) were carried out by three different international research groups (Institute for Nuclear Waste Disposal, KIT (Germany), Group Waste & Disposal, SCK-CEN, (Belgium) and Laboratory for Waste Management, PSI (Switzerland)) in the framework of the European FP7 CatClay project. The dependence of solid-liquid distribution ratios (Rd values) on pH at trace metal conditions (sorption edges) and on the metal ion concentration (sorption isotherms) was determined in dilute suspensions of homo-ionic Na-illite (Na-IdP) under controlled N2 atmosphere. The experimental results were modelled using the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) sorption model. The sorption of Sr depends strongly on ionic strength, while a rather weak pH dependence is observed in a pH range between 3 and 11. The data were modelled with cation exchange reactions, taking into account competition with H, K, Ca, Mg and Al, and surface complexation on weak amphotheric edge sites at higher pH values. The sorption of Co on Na-IdP, however, is strongly pH dependent. Cation exchange on the planar sites and surface complexation on strong and weak amphoteric edge sites were used to describe the Co sorption data. Rd values for Co derived from in-diffusion measurements on compacted Na-IdP samples (bulk-dry density of 1700 kg m-3) between pH 5.0 and 9.0 are in good agreement with the batch sorption data. The equivalence of both approaches to measure sorption was thus confirmed for the present test system. In addition, the results highlight the importance of both major and minor surface species for the diffusive transport behaviour of strongly sorbing metal cations. While surface complexes at the edge sites determine largely the Rd value, the diffusive flux may be governed by those species bound to the planar sites, even at low fractional occupancies. The pH dependent sorption determined for trace Zn concentrations showed large Rd values across the entire pH range with almost no dependence on the background electrolyte concentration. Additional sorption experiments carried out at substantial fractional Zn loadings demonstrated that the selectivity for the exchange of Na+ for Zn2+ at the planar sites could not explain the large Rd values measured at low pH and trace Zn concentrations. This suggests that another mechanism is ruling Zn uptake under these conditions.

Charge-separated and molecular heterobimetallic rare earth-rare earth and alkaline earth-rare earth aryloxo complexes featuring intramolecular metal-pi-arene interactions.

PubMed

Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Ruhlandt-Senge, Karin; St Prix, Courtney; Zuniga, Maria F

2009-01-01

Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

Structures of the dehydrogenation products of methane activation by 5d transition metal cations revisited: Deuterium labeling and rotational contours

NASA Astrophysics Data System (ADS)

Owen, Cameron J.; Boles, Georgia C.; Chernyy, Valeriy; Bakker, Joost M.; Armentrout, P. B.

2018-01-01

A previous infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT) study explored the structures of the [M,C,2H]+ products formed by dehydrogenation of methane by four, gas-phase 5d transition metal cations (M+ = Ta+, W+, Ir+, and Pt+). Complicating the analysis of these spectra for Ir and Pt was observation of an extra band in both spectra, not readily identified as a fundamental vibration. In an attempt to validate the assignment of these additional peaks, the present work examines the gas phase [M,C,2D]+ products of the same four metal ions formed by reaction with perdeuterated methane (CD4). As before, metal cations are formed in a laser ablation source and react with methane pulsed into a reaction channel downstream, and the resulting products are spectroscopically characterized through photofragmentation using the free-electron laser for intracavity experiments in the 350-1800 cm-1 range. Photofragmentation was monitored by the loss of D for [Ta,C,2D]+ and [W,C,2D]+ and of D2 in the case of [Pt,C,2D]+ and [Ir,C,2D]+. Comparison of the experimental spectra and DFT calculated spectra leads to structural assignments for all [M,C,2H/2D]+ systems that are consistent with previous identifications and allows a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy. Further, full rotational contours are simulated for each vibrational band and explain several observations in the present spectra, such as doublet structures in several bands as well as the observed linewidths. The prominent extra bands in the [Pt,C,2D/2H]+ spectra appear to be most consistent with an overtone of the out-of-plane bending vibration of the metal carbene cation structure.

Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

PubMed

Audras, Matthieu; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Dumas, Thomas; Illy, Marie-Claire; Martin, Nicolas; Zilbermann, Israel; Moiseev, Yulia; Ben-Eliyahu, Yeshayahu; Bettelheim, Armand; Cammelli, Sebastiano; Hennig, Christoph; Moisy, Philippe

2017-10-16

The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am 3+ and Pu 3+ ) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H 2 O)] - , where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.

High capacity nickel battery material doped with alkali metal cations

DOEpatents

Jackovitz, John F.; Pantier, Earl A.

1982-05-18

A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

Metal Ion Binding at the Catalytic Site Induces Widely Distributed Changes in a Sequence Specific Protein–DNA Complex

PubMed Central

2016-01-01

Metal ion cofactors can alter the energetics and specificity of sequence specific protein–DNA interactions, but it is unknown if the underlying effects on structure and dynamics are local or dispersed throughout the protein–DNA complex. This work uses EcoRV endonuclease as a model, and catalytically inactive lanthanide ions, which replace the Mg2+ cofactor. Nuclear magnetic resonance (NMR) titrations indicate that four Lu3+ or two La3+ cations bind, and two new crystal structures confirm that Lu3+ binding is confined to the active sites. NMR spectra show that the metal-free EcoRV complex with cognate (GATATC) DNA is structurally distinct from the nonspecific complex, and that metal ion binding sites are not assembled in the nonspecific complex. NMR chemical shift perturbations were determined for 1H–15N amide resonances, for 1H–13C Ile-δ-CH3 resonances, and for stereospecifically assigned Leu-δ-CH3 and Val-γ-CH3 resonances. Many chemical shifts throughout the cognate complex are unperturbed, so metal binding does not induce major conformational changes. However, some large perturbations of amide and side chain methyl resonances occur as far as 34 Å from the metal ions. Concerted changes in specific residues imply that local effects of metal binding are propagated via a β-sheet and an α-helix. Both amide and methyl resonance perturbations indicate changes in the interface between subunits of the EcoRV homodimer. Bound metal ions also affect amide hydrogen exchange rates for distant residues, including a distant subdomain that contacts DNA phosphates and promotes DNA bending, showing that metal ions in the active sites, which relieve electrostatic repulsion between protein and DNA, cause changes in slow dynamics throughout the complex. PMID:27786446

Use of grape seed and its natural polyphenol extracts as a natural organic coagulant for removal of cationic dyes.

PubMed

Jeon, Jong-Rok; Kim, Eun-Ju; Kim, Young-Mo; Murugesan, Kumarasamy; Kim, Jae-Hwan; Chang, Yoon-Seok

2009-11-01

Natural organic coagulants (NOCs) such as chitosan and Moringa oleifera seeds have been extensively characterized for potential application in water treatment as an alternative to metal-based coagulants. However, the action of both chitosan and M. oleifera seeds is mainly restricted to anionic organic pollutants because of their cationic functional groups affording poor cationic pollutant coagulation by electrostatic repulsion. In this study, we employed ethanolic grape seed extract (GSE) and grape seed-derived polyphenols such as tannic acid and catechin in an effort to find novel NOCs showing stable anionic forms for removal of cationic organic pollutants. The target substances tested were malachite green (MG) and crystal violet (CV), both mutagenic cationic dyes. Polyphenol treatment induced fast decolorization followed by gradual floc formation concomitant with red or blue shifts in maximum absorbance wavelengths of the cationic dyes. Liquid chromatography analysis of flocs formed by polyphenols directly showed that initial supramolecular complexes attributed mainly to electrostatic attraction between polyphenol hydroxyphenyl groups and cationic dyes further progressed into stronger aggregates, leading to precipitation of dye-polyphenol complexes. Consistent with the results obtained using catechin and tannic acid, use of GSE also resulted in effective decolorization and coagulation of soluble MG and CV in aqueous solutions. Screening of several organic GSE components for NOC activity strongly suggested that natural polyphenols are the main organic ingredients causing MG and CV removal via gradual floc formation. The treatment by natural polyphenols and GSE decreased toxicity of MG- or CV-contaminated water.

Mechanisms of metal sorption by biochars: Biochar characteristics and modifications.

PubMed

Li, Hongbo; Dong, Xiaoling; da Silva, Evandro B; de Oliveira, Letuzia M; Chen, Yanshan; Ma, Lena Q

2017-07-01

Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production. Published by Elsevier Ltd.

Pillared-layer microporous metal-organic frameworks constructed by robust hydrogen bonds. Synthesis, characterization, and magnetic and adsorption properties of 2,2'-biimidazole and carboxylate complexes.

PubMed

Ding, Bing-Bing; Weng, Yan-Qin; Mao, Zong-Wan; Lam, Chi-Keung; Chen, Xiao-Ming; Ye, Bao-Hui

2005-11-28

Two new isostructural complexes [M(H2biim)3][M(btc)(Hbiim)].2H2O (M = Co, (1); M = Ni, (2)) (btc = 1,3,5-benzenetricarboxylate; H2biim = 2,2'-biimidazole) have been synthesized and characterized by single-crystal X-ray diffraction. They present a unique structure consisting of two distinct units: the monomeric cations [M(H2biim)3]2+ and the two-dimensional (2D) anionic polymer [M(Hbiim)(btc)]2-. In the anionic moiety, the Hbiim- monoanion is simultaneously coordinated to one metal atom in a bidentate mode and further to another metal atom in a monodentate mode. The imidazolate groups bridge the two adjacent metal ions into a helical chain which is further arranged in left- and right-handed manners. These chains are bridged by btc ligands into a 2D brick wall structure. The most interesting aspect is that the [M(H2biim)3]2+ cations act as pillars and link the anionic layers via robust heteromeric hydrogen-bonded synthons (9) and (7) formed by the uncoordinated oxygen atoms of carboxylate groups and the H2biim ligands, resulting in a microporous metal-organic framework with one-dimensional (1D) channels (ca. 11.85 angstroms x 11.85 angstroms for 1 and 11.43 angstroms x 11.43 angstroms for 2). Magnetic properties of these two complexes have also been studied in the temperature range of 2-300 K, and their magnetic susceptibilities obey the Curie-Weiss law in the temperature range of 20-300 K (for 1) and 2-300 K (for 2), respectively, showing anti-ferromagnetic coupling through imidazolate bridging. Taking into consideration the Heisenberg infinite chain model as well as the possibility of chain-to-chain and chain-to-cation interactions, the anti-ferromagnetic exchange of 2 is analyzed via a correction for the molecular field, giving the values of g(cat) = 2.296, g(Ni) = 2.564, J = -13.30 cm(-1), and zJ' = -0.017 cm(-1). The microporous frameworks are stable at ca. 350 degrees C. They do not collapse after removal of the guest water molecules in the channels, and they adsorb methanol molecules selectively.

The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid - Synthesis and structural studies

NASA Astrophysics Data System (ADS)

Drzewiecka-Antonik, Aleksandra; Ferenc, Wiesława; Wolska, Anna; Klepka, Marcin T.; Cristóvão, Beata; Sarzyński, Jan; Rejmak, Paweł; Osypiuk, Dariusz

2017-01-01

The Co(II), Ni(II) and Cu(II) complexes with herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) were synthesized and structurally characterized. The geometry of metal-ligand interaction was refined using XAFS and DFT studies. The Co(2,4-D)2·6H2O and Ni(2,4-D)2·4H2O complexes have octahedral geometry with two carboxylate groups of 2,4-D anions and four water molecules in the coordination sphere. The square planar geometry around metal cations formed by the carboxylate groups from two monodentate ligands and two water molecules, is observed for Cu(2,4-D)2·4H2O complex. In the recrystallized Ni(II) complex dinuclear 'Chinese lantern' structures with bridging carboxylate groups of 2,4-D were observed.

DFT study of the active site of the XoxF-type natural, cerium-dependent methanol dehydrogenase enzyme.

PubMed

Bogart, Justin A; Lewis, Andrew J; Schelter, Eric J

2015-01-19

Rare-earth metal cations have recently been demonstrated to be essential co-factors for the growth of the methanotrophic bacterium Methylacidiphilum fumariolicum SolV. A crystal structure of the rare-earth-dependent methanol dehydrogenase (MDH) includes a cerium cation in the active site. Herein, the Ce-MDH active site has been analyzed through DFT calculations. The results show the stability of the Ce(III)-pyrroloquinoline quinone (PQQ) semiquinone configuration. Calculations on the active oxidized form of this complex indicate a 0.81 eV stabilization of the PQQ(0) LUMO at cerium versus calcium, supporting the observation that the cerium cation in the active site confers a competitive advantage to Methylacidiphilum fumariolicum SolV. Using reported aqueous electrochemical data, a semi-empirical correlation was established based on cerium(IV/III) redox potentials. The correlation allowed estimation of the cerium oxidation potential of +1.35 V versus saturated calomel electrode (SCE) in the active site. The results are expected to guide the design of functional model complexes and alcohol-oxidation catalysts based on lanthanide complexes of biologically relevant quinones. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Metals and Breast Cancer

PubMed Central

Byrne, Celia; Divekar, Shailaja D.; Storchan, Geoffrey B.; Parodi, Daniela A.; Martin, Mary Beth

2014-01-01

Metalloestrogens are metals that activate the estrogen receptor in the absence of estradiol. The metalloestrogens fall into two subclasses: metal/metalloid anions and bivalent cationic metals. The metal/metalloid anions include compounds such as arsenite, nitrite, selenite, and vanadate while the bivalent cations include metals such as cadmium, calcium, cobalt, copper, nickel, chromium, lead, mercury, and tin. The best studied metalloestrogen is cadmium. It is a heavy metal and a prevalent environmental contaminant with no known physiological function. This review addresses our current understanding of the mechanism by which cadmium and the bivalent cationic metals activate estrogen receptor-α. The review also summarizes the in vitro and in vivo evidence that cadmium functions as an estrogen and the potential role of cadmium in breast cancer. PMID:23338949

Metal ion influence on eumelanin fluorescence and structure.

PubMed

Sutter, Jens-Uwe; Birch, David J S

2014-04-10

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

Metal ion influence on eumelanin fluorescence and structure

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

Removal of heavy metal cations by biogenic magnetite nanoparticles produced in Fe(III)-reducing microbial enrichment cultures.

PubMed

Iwahori, Keisuke; Watanabe, Jun-ichi; Tani, Yukinori; Seyama, Haruhiko; Miyata, Naoyuki

2014-03-01

The biogenic magnetite nanoparticles presented here had a high capacity of adsorbing metal cations, which was approximately 30- to 40-fold greater than commercially available magnetite. These results suggest the potential application of microbial magnetite formation in the removal of toxic metal cations from water. Copyright © 2013 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Insight into Oxide-Bridged Heterobimetallic Al/Zr Olefin Polymerization Catalysts.

PubMed

Boulho, Cédric; Zijlstra, Harmen S; Hofmann, Alexander; Budzelaar, Peter H M; Harder, Sjoerd

2016-11-21

Reaction of (TBBP)AlMe⋅THF with [Cp* 2 Zr(Me)OH] gave [(TBBP)Al(THF)-O-Zr(Me)Cp* 2 ] (TBBP=3,3',5,5'-tetra-tBu-2,2'-biphenolato). Reaction of [DIPPnacnacAl(Me)-O-Zr(Me)Cp 2 ] with [PhMe 2 NH] + [B(C 6 F 5 ) 4 ] - gave a cationic Al/Zr complex that could be structurally characterized as its THF adduct [(DIPPnacnac)Al(Me)-O-Zr(THF)Cp 2 ] + [B(C 6 F 5 ) 4 ] - (DIPPnacnac=HC[(Me)C=N(2,6-iPr 2 -C 6 H 3 )] 2 ). The first complex polymerizes ethene in the presence of an alkylaluminum scavenger but in the absence of methylalumoxane (MAO). The adduct cation is inactive under these conditions. Theoretical calculations show very high energy barriers (ΔG=40-47 kcal mol -1 ) for ethene insertion with a bridged AlOZr catalyst. This is due to an unfavorable six-membered-ring transition state, in which the methyl group bridges the metal and ethene with an obtuse metal-Me-C angle that prevents synchronized bond-breaking and making. A more-likely pathway is dissociation of the Al-O-Zr complex into an aluminate and the active polymerization catalyst [Cp* 2 ZrMe] + . © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-organic frameworks in cadmium(II) complexes with 5-methoxyindole-2-carboxylic acid: structure, vibrational spectra and DFT calculations

NASA Astrophysics Data System (ADS)

Morzyk-Ociepa, Barbara; Szmigiel, Ksenia; Dysz, Karolina; Turowska-Tyrk, Ilona; Michalska, Danuta

2016-11-01

Two new complexes of Cd(II) with an O-deprotonated anion of 5-methoxyindole-2-carboxylic acid (5-MeOI2CA), of the formulas [Cd(5-MeOI2CA)2(H2O)2]n (1) and [Cd3(5-MeOI2CA)6(H2O)4(DMSO)4]ṡ2DMSO (2) were synthesized. In the polymeric complex 1, the 5-MeOI2CA anion acts as a bidentate bridging ligand and the coordination environment around the Cd(II) ion can be described as a distorted octahedron. Single crystal X-ray diffraction analysis of 2 has revealed that this complex is a trimer and it crystallizes in the monoclinic system (space group P21/c with a = 20.3403(4), b = 14.3079(2), c = 15.0603(3) Å, β = 92.4341(17)°, V = 4379.00(14) Å3 and Z = 2). In 2, the 5-MeOI2CA anions act as bidentate bridging and bidentate chelating ligands. The asymmetric unit of 2 contains two crystallographically independent Cd(II) cations. One of the cations is coordinated to six oxygen atoms and shows an octahedral geometry with a rhombic deformation. The other Cd(II) cation adopts a distorted seven-coordinate pentagonal-bipyramidal geometry involving seven oxygen atoms. In 2, the DMSO solvent molecules play a key role in the formation of metal-organic frameworks by filling voids, which are created by the bridging and chelating 5-MeOI2CA anions, the cadmium cations and the other DMSO molecules coordinated to cadmium. Comprehensive theoretical calculations (including the optimized structural parameters, harmonic frequencies and vibrational intensities) were performed for 2 using the B3LYP method with the 6-311++G(d,p)/LanL2DZ basis sets. The infrared and Ramana spectra were measured and a detailed assignment of the experimental spectra of 2 was performed. All cadmium-oxygen stretching vibrations occur in the range below 400 cm-1.

Mechanisms governing the leaching of soil metals as a result of disposal of olive mill wastewater on agricultural soils.

PubMed

Aharonov-Nadborny, R; Tsechansky, L; Raviv, M; Graber, E R

2018-07-15

Olive mill wastewater (OMWW) is an acidic, saline, and organic matter-rich aqueous byproduct of olive oil production that is usually disposed of by spreading on agricultural soils. This study tested whether spreading OMWW can release indigenous soil metals (Fe, Mn, Cu and Zn) through pH, redox, and DOM complexation-related mechanisms, using three agricultural soils having different textures and chemical properties, and controlled pH and redox conditions (pH5.6 or 8.4; ORP from -200 to +250mV). Comparison treatments included a solution having the same salt content and composition as OMWW but lacking OM, and deionized water (DW). In all three soils and under all pH and redox conditions, the model salt solution and DW treatments solubilized considerably fewer metal cations than did OMWW. Overall, the primary factor in metals release from the soils by OMWW was the DOM fraction. pH, redox and soil type played secondary but important roles in solubilization of the various metals. pH had a major impact on Mn leaching but no impact on Fe and Cu leaching. Conversely, redox did not affect Mn leaching, but lower redox conditions contributed to elevated release of both Fe and Cu. For the most part, released metals were sourced from water soluble, exchangeable, easily reducible, and moderately reducible soil metals pools. Fe, Mn and Cu released from the soils by OMWW featured mainly as metal-organic complexes, and OMWW generally caused Zn precipitation in the soils. Soils rich in clay and organic matter under reduced pH and low redox conditions released substantially more metal cations than did a sand-rich soil. Spreading OMWW may result in sequestration of essential micronutrients like Zn, and increased availability of other micronutrients such as Fe, Mn and Cu. Copyright © 2018 Elsevier B.V. All rights reserved.

The rhizotoxicity of metal cations is related to their strength of binding to hard ligands.

PubMed

Kopittke, Peter M; Menzies, Neal W; Wang, Peng; McKenna, Brigid A; Wehr, J Bernhard; Lombi, Enzo; Kinraide, Thomas B; Blamey, F Pax C

2014-02-01

Mechanisms whereby metal cations are toxic to plant roots remain largely unknown. Aluminum, for example, has been recognized as rhizotoxic for approximately 100 yr, but there is no consensus on its mode of action. The authors contend that the primary mechanism of rhizotoxicity of many metal cations is nonspecific and that the magnitude of toxic effects is positively related to the strength with which they bind to hard ligands, especially carboxylate ligands of the cell-wall pectic matrix. Specifically, the authors propose that metal cations have a common toxic mechanism through inhibiting the controlled relaxation of the cell wall as required for elongation. Metal cations such as Al(3+) and Hg(2+), which bind strongly to hard ligands, are toxic at relatively low concentrations because they bind strongly to the walls of cells in the rhizodermis and outer cortex of the root elongation zone with little movement into the inner tissues. In contrast, metal cations such as Ca(2+), Na(+), Mn(2+), and Zn(2+) , which bind weakly to hard ligands, bind only weakly to the cell wall and move farther into the root cylinder. Only at high concentrations is their weak binding sufficient to inhibit the relaxation of the cell wall. Finally, different mechanisms would explain why certain metal cations (for example, Tl(+), Ag(+), Cs(+), and Cu(2+)) are sometimes more toxic than expected through binding to hard ligands. The data presented in the present study demonstrate the importance of strength of binding to hard ligands in influencing a range of important physiological processes within roots through nonspecific mechanisms. © 2013 SETAC.

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.

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

DOE PAGES

Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra; ...

2017-07-24

The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

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

Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra

The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

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

Precise spectroscopic analysis of solar-type stars with moderate and fast rotation

NASA Astrophysics Data System (ADS)

Tsantaki, Maria

In the present work the performance and applicability of the thin mercury film electrode (TMFE) in the dynamic speciation of trace metals was investigated. Two different electroanalytical stripping techniques were used: the classical anodic stripping voltammetry (ASV) and a recent developed technique, scanning stripping chronopotentiometry (SSCP). The ion-exchange and the mass transport features of novel mixed coatings of two sulfonated cation-exchange polymers with dissimilar characteristics, Nafion (NA) and poly(sodium 4-styrenesulfonate) (PSS) were evaluated, prior to its application in the field of trace metal analysis. Suitable NA-PSS polymer coatings could be used in the modification of TMFE, presenting a high sensitivity, reproducibility, mechanical stability and adequate antifouling properties in the ASV determination of trace metal cations in complex media. Also the features of the PSS polyelectrolyte layers for ion-exchange voltammetry (IEV) were evaluated. The goal was to search for the best conditions to obtain stable PSS coated electrodes, which could present high negative charge densities in order to enhance the electrostatic accumulation of cations within the film, thus enlarging the ASV signal. The applicability and performance of the TMFE in the trace metal speciation studies, by SSCP, were for the first time exploited. The optimized TMFE presented a high sensitivity and resolution, being an excellent complement to the conventional mercury electrodes and could be use for 1-day term with no significant variation in the SCP analytical signal and no apparent degradation. The calculated SSCP curves were in excellent agreement with experimental data at the TMFE and the stability constant (K), calculated from the shift in the SSCP half-wave potential, of two labile metal-complex systems were in good agreement with the ones obtained using the conventional Hanging mercury drop electrode (HMDE) and those predicted by theory. Additionally, the experimental lability diagnosis inherent to the SSCP technique was validated and a rigorous quantification of the lability degree was made. Due to the well defined hydrodynamic conditions at the thin mercury film rotating disk electrode (TMF-RDE), during the deposition step, this electrode is quite valuable in the determination of kinetic parameters, like the association rate constants (ka).

The correlation of adsorption behavior between ciprofloxacin hydrochloride and the active sites of Fe-doped MCM-41

NASA Astrophysics Data System (ADS)

Wu, Ying; Tang, Yiming; Li, Laisheng; Liu, Peihong; Li, Xukai; Chen, Weirui; Xue, Ying

2018-02-01

Fe-MCM-41s with various molar ratios of silicon to iron (20, 40, 80 and 160) were prepared to investigate adsorption properties of ciprofloxacin hydrochloride (CPX) in aqueous solutions. Fe-MCM-41s were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption isotherms and infrared spectroscopy (FT-IR). Effects of silicon–iron ratio, adsorbent dosage, pH and temperature were conducted to explore the adsorption mechanism of CPX on Fe-MCM-41. The results showed that the introduction of iron facilitated the absorption quantity for CPX from 20.04 to 83.33 mg g-1 at 120 min of reaction time, which was mainly attributed to surface complexation. The promotion of hydrophobic effect, electrostatic interactions and π-π electron donor–acceptor interaction also played coordinate roles in the adsorption process. The experimental kinetic data followed both the pseudo-second-order and intra-particle diffusion models, while the adsorption isotherm data fit well to Freundlich model at high temperature. Thermodynamic study showed that the adsorption was spontaneous. Under the effect of electrostatic interaction, pH of the solution strongly affected CPX adsorption. Five representative metal cations (Ca, Cu, Ni, Pb and Cd) were chosen to study the effects on CPX adsorption and their complexation. The inhibiting effect of metal cations on CPX adsorption was sequenced in the order of Cu > Ni > Pb > Cd > Ca, which followed the same order as the complexation stability constants between CPX and cations. The Fe-MCM-41 adsorbent possessed excellent reusability for 4 cycles use, suggesting a potential applicability of Fe-MCM-41 to remove CPX in water.

Metal-air cell with performance enhancing additive

DOEpatents

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.

Metal fate and partitioning in soils under bark beetle-killed trees.

PubMed

Bearup, Lindsay A; Mikkelson, Kristin M; Wiley, Joseph F; Navarre-Sitchler, Alexis K; Maxwell, Reed M; Sharp, Jonathan O; McCray, John E

2014-10-15

Recent mountain pine beetle infestation in the Rocky Mountains of North America has killed an unprecedented acreage of pine forest, creating an opportunity to observe an active re-equilibration in response to widespread land cover perturbation. This work investigates metal mobility in beetle-impacted forests using parallel rainwater and acid leaches to estimate solid-liquid partitioning coefficients and a complete sequential extraction procedure to determine how metals are fractionated in soils under trees experiencing different phases of mortality. Geochemical model simulations analyzed in consideration with experimental data provide additional insight into the mechanisms controlling metal complexation. Metal and base-cation mobility consistently increased in soils under beetle-attacked trees relative to soil under healthy trees. Mobility increases were more pronounced on south facing slopes and more strongly correlated to pH under attacked trees than under healthy trees. Similarly, soil moisture was significantly higher under dead trees, related to the loss of transpiration and interception. Zinc and cadmium content increased in soils under dead trees relative to living trees. Cadmium increases occurred predominantly in the exchangeable fraction, indicating increased mobilization potential. Relative increases of zinc were greatest in the organic fraction, the only fraction where increases in copper were observed. Model results reveal that increased organic complexation, not changes in pH or base cation concentrations, can explain the observed differences in metal partitioning for zinc, nickel, cadmium, and copper. Predicted concentrations would be unlikely to impair human health or plant growth at these sites; however, higher exchangeable metals under beetle-killed trees relative to healthy trees suggest a possible decline in riverine ecosystem health and water quality in areas already approaching criteria limits and drinking water standards. Impairment of water quality in important headwater streams from the increased potential for metal mobilization and storage will continue to change as beetle-killed trees decompose and forests begin to recover. Copyright © 2014 Elsevier B.V. All rights reserved.

Sorption mechanism of enrofloxacin on humic acids extracted from Brazilian soils.

PubMed

Martínez-Mejía, Mónica J; Sato, Isabela; Rath, Susanne

2017-07-01

Veterinary antimicrobials are emerging environmental contaminants of concern. In this study, the sorption of enrofloxacin (ENR) onto humic acids (HAs) extracted from three Brazilian soils was evaluated. HAs were characterized by elemental analysis and solid 13 C nuclear magnetic resonance spectroscopy. The sorption of ENR onto HAs was at least 20-fold higher than onto the soils from which they were separated. Ionic and cation bridging are the primary interactions involved. The interactions driven by cation exchange are predominant on HAs, which appear to have abundant carboxylic groups and a relatively high proportion of H-bond donor moieties with carbohydrate-like structures. Interactions explained by cation bridging and/or surface complexation on HAs are facilitated by moieties containing conjugated ligands, significant content of oxygen-containing functional groups, such as phenolic-OH or lignin-like structures. HAs containing electron-donating phenolic moieties and carboxylic acid ligand groups exhibit a sorption mechanism that is primarily driven by strong metal binding, favoring the formation of ternary complexes between functional groups of the organic matter and drugs.

A Class of Multiresponsive Colorimetric and Fluorescent pH Probes via Three Different Reaction Mechanisms of Salen Complexes: A Selective and Accurate pH Measurement.

PubMed

Cheng, Jinghui; Gou, Fei; Zhang, Xiaohong; Shen, Guangyu; Zhou, Xiangge; Xiang, Haifeng

2016-09-19

We report a class of multiresponsive colorimetric and fluorescent pH probes based on three different reaction mechanisms including cation exchange, protonation, and hydrolysis reaction of K(I), Ca(II), Zn(II), Cu(II), Al(III), and Pd(II) Salen complexes. Compared with traditional pure organic pH probes, these complex-based pH probes exhibited a much better selectivity due to the shielding function of the filled-in metal ion in the complex. Their pH sensing performances were affected by the ligand structure and the central metal ion. This work is the first report of "off-on-on'-off" colorimetric and fluorescent pH probes that possess three different reaction mechanisms and should inspire the design of multiple-responsive probes for important analytes in biological systems.

ADSORPTION METHOD FOR SEPARATING METAL CATIONS

DOEpatents

Khym, J.X.

1959-03-10

The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

Molecular Dynamics Study of Crystalline Swelling of Montmorillonite as Affected by Interlayer Cation Hydration

NASA Astrophysics Data System (ADS)

Li, Hongliang; Song, Shaoxian; Dong, Xianshu; Min, Fanfei; Zhao, Yunliang; Peng, Chenliang; Nahmad, Yuri

2018-04-01

Swelling of montmorillonite (Mt) is an important factor for many industrial applications. In this study, crystalline swelling of alkali-metal- and alkaline-earth-metal-Mt has been studied through energy optimization and molecular dynamics simulations using the clay force field by Materials Studio 8.0. The delamination and exfoliation of Mt are primarily realized by crystalline swelling caused by the enhanced interlayer cation hydration. The initial position of the interlayer cations and water molecules is the dominated factor for the accuracy of the Mt simulations. Crystalline swelling can be carried out in alkali-metal-Mt and Mg-Mt but with difficulty in Ca-Mt, Sr-Mt and Ba-Mt. The crystalline swelling capacity values are in the order Na-Mt > K-Mt > Cs-Mt > Mg-Mt. This order of crystalline swelling of Mt in the same group can be attributed to the differences between the interlayer cation hydration strengths. In addition, the differences in the crystalline swelling between the alkali-metal-Mt and alkaline-earth-metal-Mt can be primarily attributed to the valence of the interlayer cations.

Syntheses, structures and luminescent properties of zero-/two-dimensional Cd(II) and Eu(III) complexes

NASA Astrophysics Data System (ADS)

Fan, Rui-Qing; Wang, Li-Yuan; Wang, Ping; Chen, Hong; Sun, Cun-fa; Yang, Yu-Lin; Su, Qing

2012-12-01

Three metal-organic complexes Cd(HBIDC)(phen)2·4H2O (1), [Cd(BIC)(phen)]n (2) and {[Eu(HBIDC)(H2BIDC)(H2O)]·H2O}n (3) (H3BIDC=benzimidazole-5,6-dicarboxylic acid, H2BIC=benzimidazole-6-carboxylic acid, phen=1,10-phenanthroline) have been synthesized under hydro(solvo)thermal conditions and structurally characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. With similar reaction conditions, reactions of the same ligand with different metal cations selected from different blocks (d-block and f-block) result in different coordination modes of carboxylate groups and final frameworks of complexes 1 and 3. The decarboxylation was observed in complex 2 and resulted in the formation of BIC2- ligand. Complexes 1-3 have intense fluorescent emissions at room temperature in dimethylsulfoxide (DMSO) solution and in the solid-state, which indicate they are potential fluorescence materials. The quantum yields and fluorescence lifetimes of these three complexes were systematically studied.

S/G-1: an ab initio force-field blending frozen Hermite Gaussian densities and distributed multipoles. Proof of concept and first applications to metal cations.

PubMed

Chaudret, Robin; Gresh, Nohad; Narth, Christophe; Lagardère, Louis; Darden, Thomas A; Cisneros, G Andrés; Piquemal, Jean-Philip

2014-09-04

We demonstrate as a proof of principle the capabilities of a novel hybrid MM'/MM polarizable force field to integrate short-range quantum effects in molecular mechanics (MM) through the use of Gaussian electrostatics. This lead to a further gain in accuracy in the representation of the first coordination shell of metal ions. It uses advanced electrostatics and couples two point dipole polarizable force fields, namely, the Gaussian electrostatic model (GEM), a model based on density fitting, which uses fitted electronic densities to evaluate nonbonded interactions, and SIBFA (sum of interactions between fragments ab initio computed), which resorts to distributed multipoles. To understand the benefits of the use of Gaussian electrostatics, we evaluate first the accuracy of GEM, which is a pure density-based Gaussian electrostatics model on a test Ca(II)-H2O complex. GEM is shown to further improve the agreement of MM polarization with ab initio reference results. Indeed, GEM introduces nonclassical effects by modeling the short-range quantum behavior of electric fields and therefore enables a straightforward (and selective) inclusion of the sole overlap-dependent exchange-polarization repulsive contribution by means of a Gaussian damping function acting on the GEM fields. The S/G-1 scheme is then introduced. Upon limiting the use of Gaussian electrostatics to metal centers only, it is shown to be able to capture the dominant quantum effects at play on the metal coordination sphere. S/G-1 is able to accurately reproduce ab initio total interaction energies within closed-shell metal complexes regarding each individual contribution including the separate contributions of induction, polarization, and charge-transfer. Applications of the method are provided for various systems including the HIV-1 NCp7-Zn(II) metalloprotein. S/G-1 is then extended to heavy metal complexes. Tested on Hg(II) water complexes, S/G-1 is shown to accurately model polarization up to quadrupolar response level. This opens up the possibility of embodying explicit scalar relativistic effects in molecular mechanics thanks to the direct transferability of ab initio pseudopotentials. Therefore, incorporating GEM-like electron density for a metal cation enable the introduction of nonambiguous short-range quantum effects within any point-dipole based polarizable force field without the need of an extensive parametrization.

Biochar immobilizes soil-borne arsenic but not cationic metals in the presence of low-molecular-weight organic acids.

PubMed

Alozie, Nneka; Heaney, Natalie; Lin, Chuxia

2018-07-15

A batch experiment was conducted to examine the effects of biochar on the behaviour of soil-borne arsenic and metals that were mobilized by three low-molecular-weight organic acids. In the presence of citric acid, oxalic acid and malic acid at a molar concentration of 0.01M, the surface of biochar was protonated, which disfavours adsorption of the cationic metals released from the soil by organic acid-driven mobilization. In contrast, the oxyanionic As species were re-immobilized by the protonated biochar effectively. Biochar could also immobilize oxyanionic Cr species but not cationic Cr species. The addition of biochar increased the level of metals in the solution due to the release of the biochar-borne metals under attack by LMWOAs via cation exchange. Biochar could also have the potential to enhance reductive dissolution of iron and manganese oxides in the soil, leading to enhanced release of trace elements bound to these oxides. The findings obtained from this study have implications for evaluating the role of biochar in immobilizing trace elements in rhizosphere. Adsorption of cationic heavy metals on biochar in the presence of LMWOAs is unlikely to be a mechanism responsible for the impeded uptake of heavy metals by plants growing in heavy metal-contaminated soils. Copyright © 2018 Elsevier B.V. All rights reserved.

Tunable Catalysis of Water to Peroxide with Anionic, Cationic, and Neutral Atomic Au, Ag, Pd, Rh, and Os

NASA Astrophysics Data System (ADS)

Suggs, K.; Kiros, F.; Tesfamichael, A.; Felfli, Z.; Msezane, A. Z.

2015-05-01

Fundamental anionic, cationic, and neutral atomic metal predictions utilizing density functional theory calculations validate the recent discovery identifying the interplay between Regge resonances and Ramsauer-Townsend minima obtained through complex angular momentum analysis as the fundamental atomic mechanism underlying nanoscale catalysis. Here we investigate the optimization of the catalytic behavior of Au, Ag, Pd, Rh, and Os atomic systems via polarization effects and conclude that anionic atomic systems are optimal and therefore ideal for catalyzing the oxidation of water to peroxide, with anionic Os being the best candidate. The discovery that cationic systems increase the transition energy barrier in the synthesis of peroxide could be important as inhibitors in controlling and regulating catalysis. These findings usher in a fundamental and comprehensive atomic theoretical framework for the generation of tunable catalytic systems. The ultimate aim is to design giant atomic catalysts and sensors, in the context of the recently synthesized tri-metal Ag@Au@Pt and bimetal Ag@Au nanoparticles for greatly enhanced plasmonic properties and improved chemical stability for chemical and biological sensing. Research was supported by U.S. DOE Office of Basic Energy Sciences.

Ortho-para interconversion in cation-water complexes: The case of V + (H 2 O) and Nb + (H 2 O) clusters

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

Ward, T. B.; Miliordos, E.; Carnegie, P. D.

Vanadium and niobium cation-water complexes, V+(H2O) and Nb+(H2O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O–H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. The A rotational constants are smaller than expected and the normal 1:3 intensity ratios for K = even:odd levels for independent ortho:para nuclearmore » spin states are missing for some complexes. We relied on highly correlated internally contracted Multi-Reference Configuration Interaction (icMRCI) and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to quasi-C2v symmetry with significant probability off the C2 axis, thus explaining the reduced A values. Both vanadium and iobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 106 sec-1).« less

Ortho-para interconversion in cation-water complexes: The case of V+(H2O) and Nb+(H2O) clusters.

PubMed

Ward, T B; Miliordos, E; Carnegie, P D; Xantheas, S S; Duncan, M A

2017-06-14

Vanadium and niobium cation-water complexes, V + (H 2 O) and Nb + (H 2 O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O-H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. The A rotational constants are smaller than expected and the normal 3:1 intensity ratios for K = odd:even levels for independent ortho:para nuclear spin states are missing for some complexes. We relied on highly correlated internally contracted multi-reference configuration interaction and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to the quasi-C 2v symmetry with a significant probability off the C 2 axis, thus explaining the reduced A values. Both vanadium and niobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 10 6 s -1 ).

Ortho-para interconversion in cation-water complexes: The case of V+(H2O) and Nb+(H2O) clusters

NASA Astrophysics Data System (ADS)

Ward, T. B.; Miliordos, E.; Carnegie, P. D.; Xantheas, S. S.; Duncan, M. A.

2017-06-01

Vanadium and niobium cation-water complexes, V+(H2O) and Nb+(H2O), are produced by laser vaporization in a pulsed supersonic expansion, mass selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy using rare gas atom (Ar, Ne) complex predissociation. The vibrational bands measured in the O-H stretching region contain K-type rotational sub-band structure, which provides insight into the structures of these complexes. However, rotational sub-bands do not exhibit the simple patterns seen previously for other metal ion-water complexes. The A rotational constants are smaller than expected and the normal 3:1 intensity ratios for K = odd:even levels for independent ortho:para nuclear spin states are missing for some complexes. We relied on highly correlated internally contracted multi-reference configuration interaction and Coupled Cluster [CCSD(T)] electronic structure calculations of those complexes with and without the rare gas atoms to investigate these anomalies. Rare gas atoms were found to bind via asymmetric motifs to the hydrated complexes undergoing large amplitude motions that vibrationally average to the quasi-C2v symmetry with a significant probability off the C2 axis, thus explaining the reduced A values. Both vanadium and niobium cations exhibit unusually strong nuclear spin coupling to the hydrogen atoms of water, the values of which vary with their electronic state. This catalyzes ortho-para interconversion in some complexes and explains the rotational patterns. The rate of ortho-para relaxation in the equilibrated complexes must therefore be greater than the collisional cooling rate in the supersonic expansion (about 106 s-1).

Cation and anion sequences in dark-adapted Balanus photoreceptor

PubMed Central

1977-01-01

Anion and cation permeabilities in dark-adapted Balanus photoreceptors were determined by comparing changes in the membrane potential in response to replacement of the dominant anion (Cl-) or cation (Na+) by test anions or cations in the superfusing solution. The anion permeability sequence obtained was PI greater than PSO4 greater than PBr greater than PCl greater than Pisethionate greater than Pmethanesulfonate. Gluconate, glucuronate, and glutamate generally appeared more permeable and propionate less permeable than Cl-. The alkali-metal cation permeability sequence obtained was PK greater than PRb greater than PCx greater than PNa approximately PLi. This corresponds to Eisenman's IV which is the same sequencethat has been obtained for other classes of nerve cells in the resting state. The values obtained for the permeability ratios of the alkali-metal cations are considered to be minimal. The membrane conductance measured by passing inward current pulses in the different test cations followed the sequence, GK greater than GRb greater than GCs greater than GNa greater than GLi. The conductance ratios obtained for a full substitution of the test cation agreed quite well with permeability ratios for all the alkali-metal cations except K+ which was generally higher. PMID:199688

Biotic ligand modeling approach: Synthesis of the effect of major cations on the toxicity of metals to soil and aquatic organisms.

PubMed

Ardestani, Masoud M; van Straalen, Nico M; van Gestel, Cornelis A M

2015-10-01

The biotic ligand model (BLM) approach is used to assess metal toxicity, taking into account the competition of other cations with the free metal ions for binding to the biotic ligand sites of aquatic and soil organisms. The bioavailable fraction of metals, represented by the free metal ion, is a better measure than the total concentration for assessing their potential risk to the environment. Because BLMs are relating toxicity to the fraction of biotic ligands occupied by the metal, they can be useful for investigating factors affecting metal bioaccumulation and toxicity. In the present review, the effects of major cations on the toxicity of metals to soil and aquatic organisms were comprehensively studied by performing a meta-analysis of BLM literature data. Interactions at the binding sites were shown to be species- and metal-specific. The main factors affecting the relationships between toxicity and conditional binding constants for metal binding at the biotic ligand appeared to be Ca(2+) , Mg(2+) , and protons. Other important characteristics of the exposure medium, such as levels of dissolved organic carbon and concentrations of other cations, should also be considered to obtain a proper assessment of metal toxicity to soil and aquatic organisms. © 2015 SETAC.

Design and synthesis of metal complexes of (2E)-2-[(2E)-3-phenylprop-2-en-1-ylidene]hydrazinecarbothioamide and their photocatalytic degradation of methylene blue.

PubMed

Krishna, P Murali; Reddy, N B Gopal; Kottam, Nagaraju; Yallur, B C; Katreddi, Hussain Reddy

2013-01-01

The photocatalytic degradation has been considered to be an efficient process for the degradation of organic pollutants, which are present in the effluents released by industries. The photocatalytic bleaching of cationic dye methylene blue was carried out spectrometrically on irradiation of UV light using Cu(II), Ni(II), and Co(II) complexes of (2E)-2-[(2E)-3-phenylprop-2-en-1-ylidene]hydrazinecarbothioamide (HL). The effects of pH and metal ion were studied on the efficiency of the reaction. Cu(II) complex shows better catalytic activity and the highest percentage degradation (~88.8%) of methylene blue was observed at pH 12. A tentative mechanism has also been proposed for the photocatalytic degradation of methylene blue.

Structure and gas phase stability of complexes L . .. M, where M = Li+, Na+, Mg2+ and L is formaldehyde, formic acid, formate anion, formamide and their sila derivatives

NASA Astrophysics Data System (ADS)

Remko, Milan

Ab initio SCF and DFT methods were used to characterize the gas-phase complexes of selected carbonyl and silacarbonyl bases with Li+ , Na+ and Mg2+ . Geometries were optimized at the Hartree-Fock ab initio and Becke 3LYP DFT levels with the 6-31G* basis set. Frequency computations were performed at the RHF/6-31G* level of theory. Interaction energies of the cation-coordinated systems also were determined with the MP2/6-31G* method. The effect of extension of basis set (to the 6-31+ G* basis) on the computed properties of anion-metal cation complexes was investigated. Calculated energies of formation vary as Mg2+ > Li+ > Na+ . The Becke 3LYP DFT binding energies were comparable with those obtained at the correlated MP2 level and are in good agreement with available experimental data.

Voltammetry of ion transfer across a polarized room-temperature ionic liquid membrane facilitated by valinomycin: theoretical aspects and application.

PubMed

Langmaier, Jan; Samec, Zdenek

2009-08-01

Cyclic voltammetry is used to investigate the transfer of alkali-metal cations, protons, and ammonium ions facilitated by the complex formation with valinomycin at the interface between an aqueous electrolyte solution and a room-temperature ionic liquid (RTIL) membrane. The membrane is made of a thin (approximately 112 microm) microporous filter impregnated with an RTIL that is composed of tridodecylmethylammonium cations and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anions. An extension of the existing theory of voltammetry of ion transfer across polarized liquid membranes makes it possible to evaluate the standard ion-transfer potentials for the hydrophilic cations studied, as well as the stability constants (K(i)) of their 1:1 complexes with valinomycin, as log K(i) = 9.0 (H(+)), 11.1 (Li(+)), 12.8 (Na(+)), 17.2 (K(+)), 15.7 (Rb(+)), 15.1 (Cs(+)), and 14.7 (NH(4)(+)). These data point to the remarkably enhanced stability of the valinomycin complexes within RTIL, and to the enhanced selectivity of valinomycin for K(+) over all other univalent ions studied, compared to the conventional K(+) ion-selective liquid-membrane electrodes. Selective complex formation allows one to resolve voltammetric responses of K(+) and Na(+) in the presence of an excess of Mg(2+) or Ca(2+), which is demonstrated by determination of K(+) and Na(+) in the table and tap water samples.

Interactions of carbon nanotubes with aqueous/aquatic media containing organic/inorganic contaminants and selected organisms of aquatic ecosystems--A review.

PubMed

Boncel, Sławomir; Kyzioł-Komosińska, Joanna; Krzyżewska, Iwona; Czupioł, Justyna

2015-10-01

Due to their unique molecular architecture translating into numerous every-day applications, carbon nanotubes (CNTs) will be ultimately an increasingly significant environmental contaminant. This work reviews qualitative/quantitative analyses of interactions of various types of CNTs and their chemically modified analogues with aqueous/aquatic media containing organic and inorganic contaminants and selected organisms of aquatic ecosystems. A special emphasis was placed on physicochemical interactions between CNTs as adsorbents of heavy metal cations and aromatic compounds (dyes) with its environmental consequences. The studies revealed CNTs as more powerful adsorbents of aromatic compounds (an order of magnitude higher adsorption capacity) than metal cations. Depending on the presence of natural organic matter (NOM) and/or co-contaminants, CNTs may act as Trojan horse while passing through biological membranes (in the absence of NOM coordinating metal ions). Nanotubes, depending on flow conditions and their morphology/surface chemistry, may travel with natural waters or sediment with immobilized PAHs or metals and/or increase cyto- and ecotoxicity of PAHs/metal ions by their release via competitive complexation, or cause synergic ecotoxicity while adsorbing nutrients. Additionally, toxicity of CNTs against exemplary aquatic microorganisms was reviewed. It was found for Daphnia magna that longer exposures to CNTs led to higher ecotoxicity with a prolonged CNTs excretion. SWCNTs were more toxic than MWCNTs, while hydrophilization of CNTs via oxidation or anchoring thereto polar/positively charged polymer chains enhanced stability of nanotubes dispersion in aqueous media. On the other hand, bioavailability of functionalized CNTs was improved leading to more complex both mechanisms of uptake and cytotoxic effects. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrostatically driven resonance energy transfer in "cationic" biocompatible indium phosphide quantum dots.

PubMed

Devatha, Gayathri; Roy, Soumendu; Rao, Anish; Mallick, Abhik; Basu, Sudipta; Pillai, Pramod P

2017-05-01

Indium Phosphide Quantum Dots (InP QDs) have emerged as an alternative to toxic metal ion based QDs in nanobiotechnology. The ability to generate cationic surface charge, without compromising stability and biocompatibility, is essential in realizing the full potential of InP QDs in biological applications. We have addressed this challenge by developing a place exchange protocol for the preparation of cationic InP/ZnS QDs. The quaternary ammonium group provides the much required permanent positive charge and stability to InP/ZnS QDs in biofluids. The two important properties of QDs, namely bioimaging and light induced resonance energy transfer, are successfully demonstrated in cationic InP/ZnS QDs. The low cytotoxicity and stable photoluminescence of cationic InP/ZnS QDs inside cells make them ideal candidates as optical probes for cellular imaging. An efficient resonance energy transfer ( E ∼ 60%) is observed, under physiological conditions, between the cationic InP/ZnS QD donor and anionic dye acceptor. A large bimolecular quenching constant along with a linear Stern-Volmer plot confirms the formation of a strong ground state complex between the cationic InP/ZnS QDs and the anionic dye. Control experiments prove the role of electrostatic attraction in driving the light induced interactions, which can rightfully form the basis for future nano-bio studies between cationic InP/ZnS QDs and anionic biomolecules.

Impact of wine production on the fractionation of copper and iron in Chardonnay wine: Implications for oxygen consumption.

PubMed

Rousseva, Michaela; Kontoudakis, Nikolaos; Schmidtke, Leigh M; Scollary, Geoffrey R; Clark, Andrew C

2016-07-15

Copper and iron in wine can influence oxidative, reductive and colloidal stability. The current study utilises a solid phase extraction technique to fractionate these metals into hydrophobic, cationic and residual forms, with quantification by ICP-OES. The impact of aspects of wine production on the metal fractions was examined, along with the relationship between metal fractions and oxygen decay rates. Addition of copper and iron to juice, followed by fermentation, favoured an increase in all of their respective metal fractions in the wine, with the largest increase observed for the cationic form of iron. Bentonite fining of the protein-containing wines led to a significant reduction in the cationic fraction of copper and an increase in the cationic form of iron. Total copper correlated more closely with oxygen consumption in the wine compared to total iron, and the residual and cationic forms of copper provided the largest contribution to this impact. Copyright © 2016 Elsevier Ltd. All rights reserved.

A heterobimetallic Ga/Yb-Schiff base complex for catalytic asymmetric alpha-addition of isocyanides to aldehydes.

PubMed

Mihara, Hisashi; Xu, Yingjie; Shepherd, Nicholas E; Matsunaga, Shigeki; Shibasaki, Masakatsu

2009-06-24

Development of a new heterobimetallic Ga(O-iPr)(3)/Yb(OTf)(3)/Schiff base 2d complex for catalytic asymmetric alpha-additions of isocyanides to aldehydes is described. Schiff base 2d derived from o-vanillin was suitable to utilize cationic rare earth metal triflates with good Lewis acidity in bimetallic Schiff base catalysis. The Ga(O-iPr)(3)/Yb(OTf)(3)/Schiff base 2d complex promoted asymmetric alpha-additions of alpha-isocyanoacetamides to aryl, heteroaryl, alkenyl, and alkyl aldehydes in good to excellent enantioselectivity (88-98% ee).

Hydrocolloid liquid-core capsules for the removal of heavy-metal cations from water.

PubMed

Nussinovitch, A; Dagan, O

2015-12-15

Liquid-core capsules with a non-crosslinked alginate fluidic core surrounded by a gellan membrane were produced in a single step to investigate their ability to adsorb heavy metal cations. The liquid-core gellan-alginate capsules, produced by dropping alginate solution with magnesium cations into gellan solution, were extremely efficient at adsorbing lead cations (267 mg Pb(2+)/g dry alginate) at 25 °C and pH 5.5. However, these capsules were very weak and brittle, and an external strengthening capsule was added by using magnesium cations. The membrane was then thinned with the surfactant lecithin, producing capsules with better adsorption attributes (316 mg Pb(+2)/g dry alginate vs. 267 mg Pb(+2)/g dry alginate without lecithin), most likely due to the thinner membrane and enhanced mass transfer. The capsules' ability to adsorb other heavy-metal cations - copper (Cu(2+)), cadmium (Cd(2+)) and nickel (Ni(2+)) - was tested. Adsorption efficiencies were 219, 197 and 65 mg/g, respectively, and were correlated with the cation's affinity to alginate. Capsules with the sorbed heavy metals were regenerated by placing in a 1M nitric acid suspension for 24h. Capsules could undergo three regeneration cycles before becoming damaged. Copyright © 2015 Elsevier B.V. All rights reserved.

Interaction of d(10) metal ions with thioether ligands: a thermodynamic and theoretical study.

PubMed

Melchior, Andrea; Peralta, Elena; Valiente, Manuel; Tavagnacco, Claudio; Endrizzi, Francesco; Tolazzi, Marilena

2013-05-07

Thermodynamic parameters of complex formation between d(10) metal ions, such as Zn(2+), Cd(2+), Hg(2+) and Ag(+), and the macrocyclic thioether 1,4,7-trithiacyclononane ([9]AneS3) or the monodentate diethylsulfide (Et(2)S), in acetonitrile (AN) at 298.15 K, were studied by a systematic methodology including potentiometry, calorimetry and polarography. [9]AneS3 is able to form complexes with all the target cations, Et(2)S only reacts with Hg(2+) and Ag(+). Mononuclear ML(j) (j = 1, 2) complexes are formed with all the metal ions investigated, where the affinity order is Hg(2+) > Ag(+) > Cd(2+) ≈ Zn(2+) when L = [9]AneS3 and Hg(2+) > Ag(+) when L = Et(2)S. Enthalpy and entropy values are generally negative, as a consequence of both metal ion interactions with neutral ligands, the reagents' loss of degrees of freedom and the release of solvating molecules. DFT calculations on the complexes formed with [9]AneS3 in vacuum and in AN are also carried out, to correlate experimental and theoretical thermodynamic values and to highlight the interplay between the direct metal-thioether interaction and the solvation effects. Trends obtained for the stability constants and enthalpies of the 1 : 1 and 1 : 2 complexes in solvent well reproduce the experimental ones for all the divalent metal ion complexes with [9]AneS3 and indicate the release of 3 AN molecules in the formation of each consecutive octahedral complex. In addition, calculated and experimental values for Ag(+) complex formation in solution suggest that in AgL(2) species [9]AneS3 ligands are not both tridentate.

Self-Assembly of Porphyrin J-Aggregates

NASA Astrophysics Data System (ADS)

Snitka, Valentinas; Rackaitis, Mindaugas; Navickaite, Gintare

2006-03-01

The porphyrin nanotubes were built by ionic self-assembly of two oppositely charged porphyrins in aqueous solution. The porphyrins in the acid aqueous solution self-assemble into J-aggregates, wheels or other structures. The electrostatic forces between these porphyrin blocks contribute to the formation of porphyrin aggregates in the form of nanotubes, enhance the structural stability of these nanostructures. The nanotubes were composed mixing aqueous solutions of the two porphyrins - anionic Meso-tetra(4- sulfonatophrnyl)porhine dihydrochloride (TPPS4) and cationic Meso-tetra(4-pyridyl)porphine (T4MPyP). The porphyrin nanotubes obtained are hollow structures with the length of 300 nm and diameter 50 nm. Photocatalytic porphyrins are used to reduce metal complexes from aqueous solution and to control the deposition of Au from AuHCl4 and Au nanoparticles colloid solutions onto porphyrin nanotubes. Porphyrin nanotubes are shown to reduce metal complexes and deposit the metal selectively onto the inner or outer surface of the tubes, leading to nanotube-metal composite structures.

Spectroscopic studies of transition metal ions in molten alkali metal carboxylates

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

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

Electronic absorption and C-13 NMR spectroscopic studies were carried out to investigate the structure of (i) alkali metal formate (Fm) and acetate (Ac) eutectic melts and (ii) solutions of 3d transition metal (TM) cations in these eutectics. Measurements were made over the temperature range 90..-->..190/sup 0/C. The most stable oxidation states of the individual TMs in the Fm and Ac eutectics were: Ti/sup 3 +/, V/sup 3 +/, VO/sup 2 +/, Cr/sup 3 +/, Mn/sup 2 +/, Fe/sup 2 +/, Co/sup 2 +/, Ni/sup 2 +/, and Cu/sup 2 +/. The ligand field absorption spectra obtained in these carboxylate meltsmore » bore a consistent resemblance to the spectra of these same cations in aqueous media, but the absorptivities were generally higher than are observed for the hexaquo complexes. The results were interpreted in terms of the existence of bidentate coordination in some (if not all) cases, leading to noncentrosymmetric complexation geometries. Key results of the NMR measurements included the apparent observation of two different carboxylate anion environments in Ni/sup 2 +/ solutions. C-13 spin-lattice relaxation of the carboxylate anions in the TM-free eutectics was found to be controlled by dipolar coupling to another nucleus. In the TM-containing solutions, the spin-lattice relaxation times were reduced by a factor of 10 to 1000, evidencing the expected shift to electron-nuclear dipolar coupling. Activation energies for viscous flow derived from the spin-lattice relaxation measurements on TM-free melts were in the 10..-->..11 kcal/mol range, reflecting the highly ordered, glassy nature of the eutectics studied.« less

Understanding the Effect of Cation Disorder on the Voltage Profile of Lithium Transition-Metal Oxides

DOE PAGES

Abdellahi, Aziz; Urban, Alexander; Dacek, Stephen; ...

2016-07-13

Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO 2) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dV/dx u )is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (~4.5-4.7 V). In this study, we develop a lattice model based on first principles to understand andmore » quantify the voltage slope of cation-disordered LiMO 2. We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of highvoltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disorder is generally smaller for highvoltage transition metals than for low-voltage transition metals due to a more effective screening of Li-M interactions by oxygen electrons. Short-range order in practical disordered compounds is found to further mitigate the voltage slope increase upon disorder. In conclusion, our analysis shows that the additional high-voltage tetrahedral capacity induced by disorder is smaller in Liexcess compounds than in stoichiometric LiMO 2 compounds.« less

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

PubMed Central

2016-01-01

Electrostatics are central to all aspects of nucleic acid behavior, including their folding, condensation, and binding to other molecules, and the energetics of these processes are profoundly influenced by the ion atmosphere that surrounds nucleic acids. Given the highly complex and dynamic nature of the ion atmosphere, understanding its properties and effects will require synergy between computational modeling and experiment. Prior computational models and experiments suggest that cation occupancy in the ion atmosphere depends on the size of the cation. However, the computational models have not been independently tested, and the experimentally observed effects were small. Here, we evaluate a computational model of ion size effects by experimentally testing a blind prediction made from that model, and we present additional experimental results that extend our understanding of the ion atmosphere. Giambasu et al. developed and implemented a three-dimensional reference interaction site (3D-RISM) model for monovalent cations surrounding DNA and RNA helices, and this model predicts that Na+ would outcompete Cs+ by 1.8–2.1-fold; i.e., with Cs+ in 2-fold excess of Na+ the ion atmosphere would contain an equal number of each cation (Nucleic Acids Res.2015, 43, 8405). However, our ion counting experiments indicate that there is no significant preference for Na+ over Cs+. There is an ∼25% preferential occupancy of Li+ over larger cations in the ion atmosphere but, counter to general expectations from existing models, no size dependence for the other alkali metal ions. Further, we followed the folding of the P4–P6 RNA and showed that differences in folding with different alkali metal ions observed at high concentration arise from cation–anion interactions and not cation size effects. Overall, our results provide a critical test of a computational prediction, fundamental information about ion atmosphere properties, and parameters that will aid in the development of next-generation nucleic acid computational models. PMID:27479701

Study of quantitative interactions of potato and corn starch granules with ions in diluted solutions of heavy metal salts.

PubMed

Szymońska, Joanna; Molenda, Marcin; Wieczorek, Jerzy

2015-12-10

Interactions of potato and corn starch granules with ions in diluted solutions of silver, lead, copper or iron salts were investigated. It was shown experimentally that granules accumulated the cations in amounts depending on the granule structure and water content as well as a type of both metal and counter-ions present in solution. Potato starch retained almost three times more cations compared to corn starch what was proportional to the total phosphorous content in these starches. Quantity of milligrams of cations bound by 1g of starch was inversely correlated with the cation hydration. Ag(+), Pb(2+) and Cu(2+) were connected in stoichiometric amounts of moles to semicrystalline and amorphous parts of the granules. Fe(3+) ions were accumulated in higher than stoichiometric quantities mainly in granule amorphous regions. Metal ions penetrated into granules together with anions except nitrates which remained on surface of potato starch granules. Cations facilitated the starch thermal decomposition in accordance with values of their standard redox potentials. Nitrates supported this process only in the presence of base metal cations. Copyright © 2015 Elsevier Ltd. All rights reserved.

Formation of novel transition metal hydride complexes with ninefold hydrogen coordination

PubMed Central

Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-ichi

2017-01-01

Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9]3−), tungsten ([WH9]3−), niobium ([NbH9]4−) and tantalum ([TaH9]4−) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature. PMID:28287143

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

PubMed

Asakawa, Yoshiki; Yamamoto, Eiichi; Asakawa, Naoki

2014-10-01

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

[DNA complexes, formed on aqueous phase surfaces: new planar polymeric and composite nanostructures].

PubMed

Antipina, M N; Gaĭnutdinov, R V; Rakhnianskaia, A A; Sergeev-Cherenkov, A N; Tolstikhina, A L; Iurova, T V; Kislov, V V; Khomutov, G B

2003-01-01

The formation of DNA complexes with Langmuir monolayers of the cationic lipid octadecylamine (ODA) and the new amphiphilic polycation poly-4-vinylpyridine with 16% of cetylpyridinium groups (PVP-16) on the surface of an aqueous solution of native DNA of low ionic strength was studied. Topographic images of Langmuir-Blodgett films of DNA/ODA and DNA/PVP-16 complexes applied to micaceous substrates were investigated by the method of atomic force microscopy. It was found that films of the amphiphilic polycation have an ordered planar polycrystalline structure. The morphology of planar DNA complexes with the amphiphilic cation substantially depended on the incubation time and the phase state of the monolayer on the surface of the aqueous DNA solution. Complex structures and individual DNA molecules were observed on the surface of the amphiphilic monolayer. Along with quasi-linear individual bound DNA molecules, characteristic extended net-like structures and quasi-circular toroidal condensed conformations of planar DNA complexes were detected. Mono- and multilayer films of DNA/PVP-16 complexes were used as templates and nanoreactors for the synthesis of inorganic nanostructures via the binding of metal cations from the solution and subsequent generation of the inorganic phase. As a result, ultrathin polymeric composite films with integrated DNA building blocks and quasi-linear arrays of inorganic semiconductor (CdS) and iron oxide nanoparticles and nanowires were obtained. The nanostructures obtained were characterized by scanning probe microscopy and transmission electron microscopy techniques. The methods developed are promising for investigating the mechanisms of structural organization and transformation in DNA and polyelectrolyte complexes at the gas-liquid interface and for the design of new extremely thin highly ordered planar polymeric and composite materials, films, and coatings with controlled ultrastructure for applications in nanoelectronics and nanobiotechnology.

Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

PubMed

Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2016-10-04

Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

Effect of nitroso complexes of some transition metals on the activity of soluble guanylate cyclase.

PubMed

Severina, I S; Bussygina, O G; Grigorjev, N B

1992-03-01

Effects of nitroso complexes of some transition metals (Fe, Co, Cr), differing in the character of NO oxidation on the activity of human and rat platelet guanylate cyclase were studied. 3 types of nitroso complexes were used: (1) NO group carries a positive charge--a nitrosonium cation (Na2[FeNO + (CN)5]-nitroprusside); (2) NO is neutral--(K3[CrNO(CN)5 and [CoNO(NH3)5]SO4) and (3) NO is coordinated as anion NO- (K3[CoNO-(CN)5]. It is shown that the highest stimulatory effect is produced by sodium nitroprusside, whose activating action is due to the interaction of its NO group with the guanylate cyclase heme. Nitroso complexes (Co and Cr) the NO group of which is neutral stimulated guanylate cyclase activity insignificantly and this activation was not guanylate cyclase heme directed. Nitroso complex (Co) with NO coordinated as anion NO(-)--is a guanylate cyclase inhibitor. In contrast to nitroprusside, the nitroso complexes used (Co and Cr) have no hypotensive effect. It was concluded that the essential requirement for the realization of the hypotensive effect of transition metals' nitroso complexes is the ability of these compounds to activate soluble guanylate cyclase solely by the heme-dependent mechanism.

Metallomics for Alzheimer's disease treatment: Use of new generation of chelators combining metal-cation binding and transport properties.

PubMed

D'Acunto, Cosimo Walter; Kaplánek, Robert; Gbelcová, Helena; Kejík, Zdeněk; Bříza, Tomáš; Vasina, Liudmila; Havlík, Martin; Ruml, Tomáš; Král, Vladimír

2018-04-25

Alzheimer's disease (AD) is a progressive neurodegenerative disorder affecting tens of million people. Currently marketed drugs have limited therapeutic efficacy and only slowing down the neurodegenerative process. Interestingly, it has been suggested that biometal cations in the amyloid beta (Aβ) aggregate deposits contribute to neurotoxicity and degenerative changes in AD. Thus, chelation therapy could represent novel mode of therapeutic intervention. Here we describe the features of chelators with therapeutically relevant mechanism of action. We have found that the tested compounds effectively reduce the toxicity of exogenous Aβ and suppress its endogenous production as well as decrease oxidative stress. Cholyl hydrazones were found to be the most active compounds. In summary, our data show that cation complexation, together with improving transport efficacy may represent basis for eventual treatment strategy in AD. Copyright © 2018. Published by Elsevier Masson SAS.

Acid-base-controlled stereoselective metalation of overhanging carboxylic acid porphyrins: consequences for the formation of heterobimetallic complexes.

PubMed

Le Gac, Stéphane; Najjari, Btissam; Dorcet, Vincent; Roisnel, Thierry; Fusaro, Luca; Luhmer, Michel; Furet, Eric; Halet, Jean-François; Boitrel, Bernard

2013-08-12

Overhanging carboxylic acid porphyrins have revealed promising ditopic ligands offering a new entry in the field of supramolecular coordination chemistry of porphyrinoids. Notably, the adjunction of a so-called hanging-atop (HAT) Pb(II) cation to regular Pb(II) porphyrin complexes allowed a stereoselective incorporation of the N-core bound cation, and an allosterically controlled Newton's cradle-like motion of the two Pb(II) ions also emerged from such bimetallic complexes. In this contribution, we have extended this work to other ligands and metal ions, aiming at understanding the parameters that control the HAT Pb(II) coordination. The nature of the N-core bound metal ion (Zn(II), Cd(II)), the influence of the deprotonation state of the overhanging COOH group and the presence of a neutral ligand on the opposite side (exogenous or intramolecular), have been examined through (1)H NMR spectroscopic experiments with the help of radiocrystallographic structures and DFT calculations. Single and bis-strap ligands have been considered. They all incorporate a COOH group hung over the N-core on one side. For the bis-strap ligands, either an ester or an amide group has been introduced on the other side. In the presence of a base, the mononuclear Zn(II) or Cd(II) complexes incorporate the carbonyl of the overhanging carboxylate as apical ligand, decreasing its availability for the binding of a HAT Pb(II). An allosteric effector (e.g., 4-dimethylaminopyridine (DMAP), in the case of a single-strap ligand) or an intramolecular ligand (e.g., an amide group), strong enough to compete with the carbonyl of the hung COO(-), is required to switch the N-core bound cation to the opposite side with concomitant release of the COO(-), thereby allowing HAT Pb(II) complexation. In the absence of a base, Zn(II) or Cd(II) binds preferentially the carbonyl of the intramolecular ester or amide groups in apical position rather than that of the COOH. This better preorganization, with the overhanging COOH fully available, is responsible for a stronger binding of the HAT Pb(II). Thus, either allosteric or acid-base control is achieved through stereoselective metalation of Zn(II) or Cd(II). In the latter case, according to the deprotonation state of the COOH group, the best electron-donating ligand is located on one or the other side of the porphyrin (COO(-)>CONHR>COOR>COOH): the lower affinity of COOH for Zn(II) and Cd(II), the higher for a HAT Pb(II). These insights provide new opportunities for the elaboration of innovative bimetallic molecular switches. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Persister cells, the biofilm matrix and tolerance to metal cations in biofilm and planktonic Pseudomonas aeruginosa.

PubMed

Harrison, Joe J; Turner, Raymond J; Ceri, Howard

2005-07-01

In this study, we examined Pseudomonas aeruginosa ATCC 27853 biofilm and planktonic cell susceptibility to metal cations. The minimum inhibitory concentration (MIC), the minimum bactericidal concentration (MBC) required to eradicate 100% of the planktonic population (MBC 100), and the minimum biofilm eradication concentration (MBEC) were determined using the MBEC trade mark-high throughput assay. Six metals - Co(2+), Ni(2+), Cu(2+), Zn(2+), Al(3+) and Pb(2+)- were each tested at 2, 4, 6, 8, 10 and 27 h of exposure to biofilm and planktonic cultures grown in rich or minimal media. With 2 or 4 h of exposure, biofilms were approximately 2-25 times more tolerant to killing by metal cations than the corresponding planktonic cultures. However, by 27 h of exposure, biofilm and planktonic bacteria were eradicated at approximately the same concentration in every instance. Viable cell counts evaluated at 2 and 27 h of exposure revealed that at high concentrations, most of the metals assayed had killed greater than 99.9% of biofilm and planktonic cell populations. The surviving cells were propogated in vitro and gave rise to biofilm and planktonic cultures with normal sensitivity to metals. Further, retention of copper by the biofilm matrix was investigated using the chelator sodium diethlydithiocarbamate. Formation of visible brown metal-chelates in biofilms treated with Cu(2+) suggests that the biofilm matrix may coordinate and sequester metal cations from the aqueous surroundings. Overall, our data suggest that both metal sequestration in the biofilm matrix and the presence of a small population of 'persister' cells may be contributing factors in the time-dependent tolerance of both planktonic cells and biofilms to high concentrations of metal cations.

Esterification of phenyl acetic acid with p-cresol using metal cation exchanged montmorillonite nanoclay catalysts.

PubMed

Bhaskar, M; Surekha, M; Suma, N

2018-02-01

The liquid phase esterification of phenyl acetic acid with p -cresol over different metal cation exchanged montmorillonite nanoclays yields p -cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (M n +  = Al 3+ , Zn 2+ , Mn 2+ , Fe 3+ , Cu 2+ ) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al 3+ -montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p -cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1 H NMR and 13 C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation.

Investigation of the mineralogy and the sorption mechanism of Ni, Cu, Co and Mo by turbostratic phyllomanganates of Mn-nodules from the eastern equatorial Pacific Ocean using XAS

NASA Astrophysics Data System (ADS)

Wegorzewski, A.; Webb, S.; Grangeon, S.; Kuhn, T.

2016-12-01

Mn-nodules are Mn-Fe (oxy)hydroxides bearing high amounts of economically important metals such as Ni, Cu, Co, Mo, as well as high field strength elements. According to that nodules are interesting for science and industry. Especially the sorption sites of metals (Ni, Cu, Mo) by the mineral phases are important to understand their coordination environment and further to tailor a specific metallurgical treatment in order to optimize the metal extraction procedure. Nodules used for this study were sampled from the German license area within the Clarion Clipperton Zone in the Pacific. These nodules grow on the seafloor in 4200 m depth by metal precipitation from oxic (hydrogenetic growth) and/or suboxic waters (suboxic diagenetic growth; Halbach et al., 1988). They show a complex texture characterized by irregular, concentrically banded nm- to µm-thick layered growth structures (LGS). Electronmicroprobe and X-ray diffraction analyses reveal: suboxic diagenetic LGS have high Mn/Fe ratios (9-826; Mn ≈ 40 wt. %; Fe ≈ 0.5 wt %), high Ni (0.3-2.6 wt %) and Cu (0.5-3.0 wt %) contents but low Co content (0.02±0.01 wt %). Mineralogically those LGS are turbostratic phyllomanganates (vernadite), which consist of [MnO6]-octahedral layers, separated from each other by cations (e.g., Na, Mg) and water in the interlayer, forming 7 and 10 Å phyllomanganates (Bode et al., 2007). In contrast hydrogenetic LGS show low Mn/Fe ratios (<5), low Ni+Cu content (<1 wt%) but enrichment in Co (≤0.5 wt%). Those LGS are of δ-MnO2, which is epitaxially intergrown with an amorphous FeOOH phase. In general, phyllomanganates have a high opportunity to incorporate metals due to their negative layer charge deficit cause by abundant isomorphic substitution of Mn4+ by Mn3+ and vacancies within MnO2 sheets. The negative charge deficit can be balanced by hydrated interlayer cations (e.g., Na, Mg) or due to metals adsorption at cation vacancy sites, incorporation into the MnO2 sheet and/or adsorption at lateral edge surfaces (Peacock, 2009; Pena et al., 2015). A special emphasis of this study was to determine the boundings of Ni, Cu, Co and Mo by the Mn-mineral phases of nodules. X-ray absorption spectroscopy analyses show that metals such as Ni, Cu, Co are rather incorporated into MnO2 sheets than adsorbed as inner-sphere complexes over/below vacancies, like Mo.

A primer on trace metal-sediment chemistry

USGS Publications Warehouse

Horowitz, Arthur J.

1985-01-01

In most aquatic systems, concentrations of trace metals in suspended sediment and the top few centimeters of bottom sediment are far greater than concentrations of trace metals dissolved in the water column. Consequently, the distribution, transport, and availability of these constituents can not be intelligently evaluated, nor can their environmental impact be determined or predicted solely through the sampling and analysis of dissolved phases. This Primer is designed to acquaint the reader with the basic principles that govern the concentration and distribution of trace metals associated with bottom and suspended sediments. The sampling and analysis of suspended and bottom sediments are very important for monitoring studies, not only because trace metal concentrations associated with them are orders of magnitude higher than in the dissolved phase, but also because of several other factors. Riverine transport of trace metals is dominated by sediment. In addition, bottom sediments serve as a source for suspended sediment and can provide a historical record of chemical conditions. This record will help establish area baseline metal levels against which existing conditions can be compared. Many physical and chemical factors affect a sediment's capacity to collect and concentrate trace metals. The physical factors include grain size, surface area, surface charge, cation exchange capacity, composition, and so forth. Increases in metal concentrations are strongly correlated with decreasing grain size and increasing surface area, surface charge, cation exchange capacity, and increasing concentrations of iron and manganese oxides, organic matter, and clay minerals. Chemical factors are equally important, especially for differentiating between samples having similar bulk chemistries and for inferring or predicting environmental availability. Chemical factors entail phase associations (with such sedimentary components as interstitial water, sulfides, carbonates, and organic matter) and ways in which the metals are entrained by the sediments (such as adsorption, complexation, and within mineral lattices).

Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal

PubMed Central

Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

2014-01-01

The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes, or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70% molar yield toward citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide. PMID:24790972

Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids

NASA Astrophysics Data System (ADS)

Romero, F. Denis; Pitcher, M. J.; Hiley, C. I.; Whitehead, G. F. S.; Kar, S.; Ganin, A. Y.; Antypov, D.; Collins, C.; Dyer, M. S.; Klupp, G.; Colman, R. H.; Prassides, K.; Rosseinsky, M. J.

2017-07-01

Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid-solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure.

An Operationally Simple Method for Separating the Rare-Earth Elements Neodymium and Dysprosium.

PubMed

Bogart, Justin A; Lippincott, Connor A; Carroll, Patrick J; Schelter, Eric J

2015-07-06

Rare-earth metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare earths. To incentivize recycling there is a clear need for simple methods for targeted separations of mixtures of rare-earth metal salts. Metal complexes of a tripodal nitroxide ligand [{(2-(t) BuNO)C6 H4 CH2 }3 N](3-) (TriNOx(3-) ), feature a size-sensitive aperture formed of its three η(2) -(N,O) ligand arms. Exposure of metal cations in the aperture induces a self-associative equilibrium comprising [M(TriNOx)thf]/ [M(TriNOx)]2 (M=rare-earth metal). Differences in the equilibrium constants (Keq ) for early and late metals enables simple Nd/Dy separations through leaching with a separation ratio SNd/Dy =359. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic Identification of the Carbyne Hydride Structure of the Dehydrogenation Product of Methane Activation by Osmium Cations

NASA Astrophysics Data System (ADS)

Armentrout, P. B.; Kuijpers, Stach E. J.; Lushchikova, Olga V.; Hightower, Randy L.; Boles, Georgia C.; Bakker, Joost M.

2018-04-01

The present work explores the structures of species formed by dehydrogenation of methane (CH4) and perdeuterated methane (CD4) by the 5d transition metal cation osmium (Os+). Using infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT), the structures of the [Os,C,2H]+ and [Os,C,2D]+ products are explored. This study complements previous work on the related species formed by dehydrogenation of methane by four other 5d transition metal cations (M+ = Ta+, W+, Ir+, and Pt+). Osmium cations are formed in a laser ablation source, react with methane pulsed into a reaction channel downstream, and the resulting products spectroscopically characterized through photofragmentation using the Free-Electron Laser for IntraCavity Experiments (FELICE) in the 300-1800 cm-1 range. Photofragmentation was monitored by the loss of H2/D2. Comparison of the experimental spectra and DFT calculated spectra leads to identification of the ground state carbyne hydride, HOsCH+ (2A') as the species formed, as previously postulated theoretically. Further, a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy, is achieved. A full rotational contour analysis explains the observed linewidths as well as the observation of doublet structures in several bands, consistent with previous observations for HIrCH+ (2A'). [Figure not available: see fulltext.

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

DOE PAGES

Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J.; ...

2016-12-01

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normalmore » alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R •), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

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

Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J.

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normalmore » alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R •), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less

Investigating the synthesis of ligated metal clusters in solution using a flow reactor and electrospray ionization mass spectrometry.

PubMed

Olivares, Astrid; Laskin, Julia; Johnson, Grant E

2014-09-18

The scalable synthesis of ligated subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic, and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth, and postreduction etching are still not well understood. Herein, we demonstrate a prototype temperature-controlled flow reactor for qualitatively studying cluster formation in solution at steady-state conditions. Employing this technique, methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand, and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with a known length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates, and products synthesized in real time was characterized qualitatively using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged organometallic complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged organometallic complexes while reducing the abundance of triply charged species. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of batch reduction synthesis in solution.

Photoemission spectra and density functional theory calculations of 3d transition metal-aqua complexes (Ti-Cu) in aqueous solution.

PubMed

Yepes, Diana; Seidel, Robert; Winter, Bernd; Blumberger, Jochen; Jaque, Pablo

2014-06-19

Photoelectron spectroscopy measurements and density functional calculations are combined to determine the lowest electron binding energies of first-row transition-metal aqua ions, titanium through copper, with 3d(1) through 3d(9) electronic configurations, in their most common oxidation states. Vertical ionization energies are found to oscillate considerably between 6.76 and 9.65 eV for the dications and between 7.05 and 10.28 eV for the respective trivalent cations. The metal cations are modeled as [M(H2O)n](q+) clusters (q = 2, 3, and 4; n = 6 and 18) surrounded by continuum solvent. The performance of 10 exchange-correlation functionals, two GGAs, three MGGAs, two HGGAs and three HMGGAs, combined with the MDF10(ECP)/6-31+G(d,p) basis set is assessed for 11 M-O bond distances, 10 vertical ionization energies, 6 adiabatic ionization energies, and the associated reorganization free energies. We find that for divalent cations the HGGA and HMGGA functionals in combination with the 18 water model show the best agreement with experimental vertical ionization energies and geometries; for trivalent ions, the MGGA functionals perform best. The corresponding reorganization free energies (λo) of the oxidized ions are significantly underestimated with all DFT functionals and cluster models. This indicates that the structural reorganization of the solvation shell upon ionization is not adequately accounted for by the simple solvation models used, emphasizing the importance of extended sampling of thermally accessible solvation structures for an accurate computation of this quantity. The photoelectron spectroscopy measurements reported herein provide a comprehensive set of transition-metal redox energetic quantities for future electronic structure benchmarks.

Reduction potentials of heterometallic manganese–oxido cubane complexes modulated by redox-inactive metals

PubMed Central

Tsui, Emily Y.; Agapie, Theodor

2013-01-01

Understanding the effect of redox-inactive metals on the properties of biological and heterogeneous water oxidation catalysts is important both fundamentally and for improvement of future catalyst designs. In this work, heterometallic manganese–oxido cubane clusters [MMn3O4] (M = Sr2+, Zn2+, Sc3+, Y3+) structurally relevant to the oxygen-evolving complex (OEC) of photosystem II were prepared and characterized. The reduction potentials of these clusters and other related mixed metal manganese–tetraoxido complexes are correlated with the Lewis acidity of the apical redox-inactive metal in a manner similar to a related series of heterometallic manganese–dioxido clusters. The redox potentials of the [SrMn3O4] and [CaMn3O4] clusters are close, which is consistent with the observation that the OEC is functional only with one of these two metals. Considering our previous studies of [MMn3O2] moieties, the present results with more structurally accurate models of the OEC ([MMn3O4]) suggest a general relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidities of incorporated cations that applies to diverse structural motifs. These findings support proposals that one function of calcium in the OEC is to modulate the reduction potential of the cluster to allow electron transfer. PMID:23744039

Gas-phase fragmentation of coordination compounds: loss of CO(2) from inorganic carbonato complexes to give metal oxide ions

PubMed

Dalgaard; McKenzie

1999-10-01

Using electrospray ionization mass spectrometry, novel transition metal oxide coordination complex ions are proposed as the products of the collision-induced dissociation (CID) of some carbonato complex ions through the loss of a mass equivalent to CO(2). CID spectra of [(tpa)CoCO(3)](+) (tpa = tris(2-pyridylmethyl)methylamine), [(bispicMe(2)en)Fe(&mgr;-O)(&mgr;-CO(3))Fe(bispicMe(2)en)]2+ (bispicMe(2)en = N,N'-dimethyl-N,N'-bis(2-pyridylmethy)eth- ane-1, 2-diamine) and [(bpbp)Cu(2)CO(3)](+) (bpbp(-) = bis[(bis-(2-pyridylmethyl)amino)methyl]-4-tertbutylpheno-lato(1-)), show peaks assigned to the mono- and dinuclear oxide cations, [(tpa)CoO](+), [(bispicMe(2)en)(2)Fe(2)(O)(2)]2+ and [(bpbp)Cu(2)O](+), as the dominant species. These results can be likened to the reverse of typical synthetic reactions in which metal hydroxide compounds react with CO(2) to give metal carbonato compounds. Because of the lack of available protons in the gas phase, novel oxide species rather than the more common hydroxide ions are generated. These oxide ions are relevant to the highly oxidizing species proposed in oxygenation reactions catalysed by metal oxides and metalloenzymes. Copyright 1999 John Wiley & Sons, Ltd.

Interaction of metal ions and amino acids - Possible mechanisms for the adsorption of amino acids on homoionic smectite clays

NASA Technical Reports Server (NTRS)

Gupta, A.; Loew, G. H.; Lawless, J.

1983-01-01

A semiempirical molecular orbital method is used to characterize the binding of amino acids to hexahydrated Cu(2+) and Ni(2+), a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays. Five alpha-amino acids, beta-alanine, and gamma-aminobutyric acid were used to investigate the metal ion and amino acid specificity in binding. It was assumed that the alpha, beta, and gamma-amino acids would bind as bidentate anionic ligands, forming either 1:1 or 1:2 six-coordinated five, six, and seven-membered-ring chelate complexes, respectively. Energies of complex formation, optimized geometries, and electron and spin distribution were determined; and steric constraints of binding of the amino acids to the ion-exchanged cations in the interlamellar spacing of a clay were examined. Results indicate that hexahydrated Cu(2+) forms more stable complexes than hexahydrated Ni(2+) with all the amino acids studied. However, among these amino acids, complex formation does not favor the adsorption of the biological subset. Calculated energetics of complex formation and steric constraints are shown to predict that 1:1 rather than 1:2 metal-amino acid complexes are generally favored in the clay.

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

Uberuaga, Blas Pedro

In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore,more » how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations 1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder 2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought 4.« less

Ultrasound enhances in vivo tumor expression of plasmid DNA by PEG-introduced cationized dextran.

PubMed

Hosseinkhani, Hossein; Tabata, Yasuhiko

2005-11-28

This study is an investigation to experimentally confirm whether or not ultrasound (US) irradiation is effective in enhancing the in vivo gene expression of plasmid DNA in tumor. Dextran was cationized by introducing spermine to the hydroxyl groups to allow to polyionically complex with a plasmid DNA. The cationized dextran prepared was additionally modified with poly(ethylene glycol) (PEG) molecules which have an active ester and methoxy groups at each terminal, to obtain cationized dextran with different percentages of PEG introduced. Various cationized dextrans with or without PEG introduction were mixed with a plasmid DNA of LacZ to form cationized dextran-plasmid DNA complexes. Electrophoretical examination revealed that the plasmid DNA was complexed both with the cationized dextran and PEG-introduced cationized dextran, irrespective of the PEG introduction percentage, although the higher N/P ratio was needed for plasmid DNA complexation with the latter. By complexation with the cationized dextran, the zeta potential of plasmid DNA was changed to be positive. The charge of PEG-introduced cationized dextran-plasmid DNA complexes became close to 0 mV as their percentage of PEG introduced increased, although the molecular size was about 250 nm, irrespective of the PEG introduction. When cationized dextran-plasmid DNA complexes with or without PEG introduction were intravenously injected to mice carrying a subcutaneous Meth-AR-1 fibrosarcoma mass and the subsequent US irradiation to the tumor mass percutaneously, the PEG-introduced cationized dextran-plasmid DNA complex plus US irradiation enhanced the tumor level of gene expression to a significantly high extent compared with the cationized dextran-plasmid DNA complex and free plasmid DNA with or without US irradiation. The enhanced level depended on the time period and timing of US irradiation. Fluorescent microscopic studies revealed that the localization of plasmid DNA and the gene expression were observed in the tumor tissue injected with the PEG-introduced cationized dextran-plasmid DNA complex plus the subsequent US irradiation. We conclude that complexation with the PEG-introduced cationized dextran combined with US irradiation is a promising way to target the plasmid DNA to the tumor for gene expression.

PEGylation enhances tumor targeting of plasmid DNA by an artificial cationized protein with repeated RGD sequences, Pronectin.

PubMed

Hosseinkhani, Hossein; Tabata, Yasuhiko

2004-05-31

The objective of this study is to investigate feasibility of a non-viral gene carrier with repeated RGD sequences (Pronectin F+) in tumor targeting for gene expression. The Pronectin F+ was cationized by introducing spermine (Sm) to the hydroxyl groups to allow to polyionically complex with plasmid DNA. The cationized Pronectin F+ prepared was additionally modified with poly(ethylene glycol) (PEG) molecules which have active ester and methoxy groups at the terminal, to form various PEG-introduced cationized Pronectin F+. The cationized Pronectin F+ with or without PEGylation at different extents was mixed with a plasmid DNA of LacZ to form respective cationized Pronectin F+-plasmid DNA complexes. The plasmid DNA was electrophoretically complexed with cationized Pronectin F+ and PEG-introduced cationized Pronectin F+, irrespective of the PEGylation extent, although the higher N/P ratio of complexes was needed for complexation with the latter Pronectin F+. The molecular size and zeta potential measurements revealed that the plasmid DNA was reduced in size to about 250 nm and the charge was changed to be positive by the complexation with cationized Pronectin F+. For the complexation with PEG-introduced cationized Pronectin F+, the charge of complex became neutral being almost 0 mV with the increasing PEGylation extents, while the molecular size was similar to that of cationized Pronectin F+. When cationized Pronectin F+-plasmid DNA complexes with or without PEGylation were intravenously injected to mice carrying a subcutaneous Meth-AR-1 fibrosarcoma mass, the PEG-introduced cationized Pronectin F+-plasmid DNA complex specifically enhanced the level of gene expression in the tumor, to a significantly high extent compared with the cationized Pronectin F+-plasmid DNA complexes and free plasmid DNA. The enhanced level of gene expression depended on the percentage of PEG introduced, the N/P ratio, and the plasmid DNA dose. A fluorescent microscopic study revealed that the localization of plasmid DNA in the tumor tissue was observed only for the PEG-introduced cationized Pronectin F+-plasmid DNA complex injected. We conclude that the PEGylation of cationized Pronectin F+ is a promising way to enable the plasmid DNA to target to the tumor for gene expression. Coyright 2004 Elsevier B.V.

First-Row Transition Metal Doping in Calcium Phosphate Bioceramics: A Detailed Crystallographic Study

PubMed Central

Renaudin, Guillaume; Gomes, Sandrine; Nedelec, Jean-Marie

2017-01-01

Doped calcium phosphate bioceramics are promising materials for bone repair surgery because of their chemical resemblance to the mineral constituent of bone. Among these materials, BCP samples composed of hydroxyapatite (Ca10(PO4)6(OH)2) and β-TCP (Ca3(PO4)2) present a mineral analogy with the nano-multi-substituted hydroxyapatite bio-mineral part of bones. At the same time, doping can be used to tune the biological properties of these ceramics. This paper presents a general overview of the doping mechanisms of BCP samples using cations from the first-row transition metals (from manganese to zinc), with respect to the applied sintering temperature. The results enable the preparation of doped synthetic BCP that can be used to tailor biological properties, in particular by tuning the release amounts upon interaction with biological fluids. Intermediate sintering temperatures stabilize the doping elements in the more soluble β-TCP phase, which favors quick and easy release upon integration in the biological environment, whereas higher sintering temperatures locate the doping elements in the weakly soluble HAp phase, enabling a slow and continuous supply of the bio-inspired properties. An interstitial doping mechanism in the HAp hexagonal channel is observed for the six investigated cations (Mn2+, Fe3+, Co2+, Ni2+, Cu2+ and Zn2+) with specific characteristics involving a shift away from the center of the hexagonal channel (Fe3+, Co2+), cationic oxidation (Mn3+, Co3+), and also cationic reduction (Cu+). The complete crystallochemical study highlights a complex HAp doping mechanism, mainly realized by an interstitial process combined with calcium substitution for the larger cations of the series leading to potentially calcium deficient HAp. PMID:28772452

Multicolor fluorescence of a styrylquinoline dye tuned by metal cations.

PubMed

Shiraishi, Yasuhiro; Ichimura, Chizuru; Sumiya, Shigehiro; Hirai, Takayuki

2011-07-18

A styrylquinoline dye with a dipicolylamine (DPA) moiety (1) has been synthesized. The dye 1 in acetonitrile demonstrates multicolor fluorescence upon addition of different metal cations. Compound 1 shows a green fluorescence without cations. Coordination of 1 with Cd(2+) shows a blue emission, while with Hg(2+) and Pb(2+) exhibits yellow and orange emissions, respectively. The different fluorescence spectra are due to the change in intramolecular charge transfer (ICT) properties of 1 upon coordination with different cations. The DPA and quinoline moieties of 1 behave as the electron donor and acceptor units, respectively, and both units act as the coordination site for metal cations. Cd(2+) coordinates with the DPA unit. This reduces the donor ability of the unit and decreases the energy level of HOMO. This results in an increase in HOMO-LUMO gap and blue shifts the emission. Hg(2+) or Pb(2+) coordinate with both DPA and quinoline units. The coordination with the quinoline unit decreases the energy level of LUMO. This results in a decrease in HOMO-LUMO gap and red shifts the emission. Addition of two different metal cations successfully creates intermediate colors; in particular, the addition of Cd(2+) and Pb(2+) at once creates a bright white fluorescence. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trinuclear Lanthanoid Complexes of 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol with a Unique, Sandwich-Type Cage Structure(1).

PubMed

Hedinger, Roman; Ghisletta, Michele; Hegetschweiler, Kaspar; Tóth, Eva; Merbach, André E.; Sessoli, Roberta; Gatteschi, Dante; Gramlich, Volker

1998-12-28

A variety of trinuclear complexes [M(3)(H(-)(3)L)(2)](3+) [M = Y, La, Eu, Gd, Dy; L = 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci)] was prepared as solid materials of the composition M(3)(H(-)(3)L)(2)X(3).pH(2)O.qEtOH (X = Cl, NO(3); 2.5

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes.

PubMed

Wang, Dawei; Kou, Ronghui; Ren, Yang; Sun, Cheng-Jun; Zhao, Hu; Zhang, Ming-Jian; Li, Yan; Huq, Ashifia; Ko, J Y Peter; Pan, Feng; Sun, Yang-Kook; Yang, Yong; Amine, Khalil; Bai, Jianming; Chen, Zonghai; Wang, Feng

2017-10-01

Nickel-rich layered transition metal oxides, LiNi 1- x (MnCo) x O 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7 Mn 0.15 Co 0.15 O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

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

Wang, Dawei; Kou, Ronghui; Ren, Yang

Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strongmore » temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs« less

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

DOE PAGES

Wang, Dawei; Kou, Ronghui; Ren, Yang; ...

2017-08-25

Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strongmore » temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs« less

Liquid-liquid distribution of ion associates of tetrabromoindate(III) with quaternary ammonium counter ions.

PubMed

Yamamoto, K; Matsumoto, A

1997-11-01

The solvent extraction of an ion associate of tetrabromoindate(III) ion, InBr(-)(4), with quaternary ammonium cations (Q(+)) has been studied. The extraction constant (K(ex)) were determined for the ion associates of InBr(-)(4) with Q(+) between an aqueous phase and several organic phases (chloroform, chlorobenzene, benzene and toluene). A linear relationship was found between log K(ex) and the total number of carbon atoms in Q(+); from the slope of the lines, the contribution of a methylene group to log K(ex) was calculated to be 0.91 for the chloroform extraction system and 0.52 for the other extraction systems. The extractability with alkyltrimethylammonium cations was larger than that with symmetrical tetraalkylammonium cations and the mean difference in log K(ex) for two cations (one of each type) with the same number of carbon atoms was about 1.3. From the extraction constant obtained, the extractability of InBr(-)(4) among metal-halogeno complex anions was in the order TlBr(-)(4) > BiI(-)(4) > AuBr(-)(4) > AuCl(-)(4) > TlCl(-)(4) > InBr(-)(4) > CuCl(-)(2).

Tunable intraparticle frameworks for creating complex heterostructured nanoparticle libraries

NASA Astrophysics Data System (ADS)

Fenton, Julie L.; Steimle, Benjamin C.; Schaak, Raymond E.

2018-05-01

Complex heterostructured nanoparticles with precisely defined materials and interfaces are important for many applications. However, rationally incorporating such features into nanoparticles with rigorous morphology control remains a synthetic bottleneck. We define a modular divergent synthesis strategy that progressively transforms simple nanoparticle synthons into increasingly sophisticated products. We introduce a series of tunable interfaces into zero-, one-, and two-dimensional copper sulfide nanoparticles using cation exchange reactions. Subsequent manipulation of these intraparticle frameworks yielded a library of 47 distinct heterostructured metal sulfide derivatives, including particles that contain asymmetric, patchy, porous, and sculpted nanoarchitectures. This generalizable mix-and-match strategy provides predictable retrosynthetic pathways to complex nanoparticle features that are otherwise inaccessible.

Electrocatalytic reduction of CO2 with CCC-NHC pincer nickel complexes.

PubMed

Cope, James D; Liyanage, Nalaka P; Kelley, Paul J; Denny, Jason A; Valente, Edward J; Webster, Charles Edwin; Delcamp, Jared H; Hollis, T Keith

2017-08-22

A CCC-NHC pincer Ni(ii)Cl complex was prepared according to the metallation/transmetallation methodology. It was fully characterized by electrochemical, NMR spectroscopic, theoretical, and X-ray crystallographic methods. The complex and its cation were evaluated for electrocatalytic reduction of CO 2 under a variety of conditions and found to provide some of the fastest catalytic rates and highest substrate selectivities (CO 2 vs. H + ) reported. Rates improved in the presence of water and, significantly, catalysis occurred at the first reduction potential, presumably at the Ni(i) state. Controlled potential electrolysis (CPE) was found to yield CO at 34% and formate at 47% Faradaic efficiency (FE).

Use of Carboxymethyl-beta-cyclodextrin (CMCD) as Flushing Agent for Remediation of Metal Contaminated Soil

NASA Astrophysics Data System (ADS)

Skold, M. E.; Thyne, G. D.; McCray, J. E.; Drexler, J. W.

2005-12-01

One of the major challenges in remediating soil and ground water is the presence of mixed organic and inorganic contaminants. Due to their very different behavior, research has to a large extent focused on remediation of either organic or inorganic contaminants rather than mixed waste. Cyclodextrins (CDs) are a group of non-toxic sugar based molecules that do not sorb to soil particles and do not experience pore size exclusion. Thus, they have good hydraulic properties. CDs enhance the solubility of organic compounds by forming inclusion complexes between organic contaminants and the non-polar cavity at the center of the CD. By substituting functional groups to the cyclodextrin molecule it can form complexes with heavy metals. Previous studies have shown that carboxymethyl-beta-cyclodextrin (CMCD) can simultaneously complex organic and inorganic contaminants. The aim of this study is to compare how strongly CMCD complexes several common heavy metals, radioactive elements and a common divalent cation. Results from batch experiments show that CMCD has the ability to complex a wide array of heavy metals and radioactive elements. The solubility of metal oxalates and metal oxides clearly increased in the presence of CMCD. Logarithmic conditional formation constants ranged from 3.5 to 6 for heavy metals and from 3 to 6 for radioactive elements. Calcium, which may compete for binding sites, has a logarithmic conditional formation constant of 3.1. Batch experiments performed at 10 and 25 degrees C showed little temperature effect on conditional formation constants. Results from batch experiments were compared to results from column experiments where Pb was sorbed onto hydrous ferric oxide coated sand and subsequently removed by a CMCD solution. The results indicate that CMCD is a potential flushing agent for remediation of mixed waste sites.

Substituting Fe for two of the four Mn ions in photosystem II-effects on water-oxidation.

PubMed

Semin, Boris K; Seibert, Michael

2016-06-01

We have investigated the interaction of Fe(II) cations with Ca-depleted PSII membranes (PSII[-Ca,4Mn]) in the dark and found that Fe(II) incubation removes 2 of 4 Mn ions from the tetranuclear Mn cluster of the photosynthetic O2-evolving complex (OEC). The reduction of Mn ions in PSII(-Ca,4Mn) by Fe(II) and the concomitant release of two Mn(II) cations is accompanied by the binding of newly generated Fe(III) in at least one vacated Mn site. Flash-induced chlorophyll (Chl) fluorescence yield measurements of this new 2Mn/nFe cluster (PSII[-Ca,2Mn,nFe]) show that charge recombination in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) occurs between Qa (-) and the remaining Mn/Fe cluster (but not YZ (●)) in the OEC, and extraction of 2 Mn occurs uniformly in all PSII complexes. No O2 evolution is observed, but the heteronuclear metal cluster in PSII(-Ca,2Mn,nFe) samples is still able to supply electrons for reduction of the exogenous electron acceptor, 2,6-dichlorophrenolindophenol, by photooxidizing water and producing H2O2 in the absence of an exogenous donor as seen previously with PSII(-Ca,4Mn). Selective extraction of Mn or Fe cations from the 2Mn/nFe heteronuclear cluster demonstrates that the high-affinity Mn-binding site is occupied by one of the iron cations. It is notable that partial water-oxidation function still occurs when only two Mn cations are present in the PSII OEC.

Unravelling metal mobility under complex contaminant signatures.

PubMed

de Souza Machado, Anderson Abel; Spencer, Kate L; Zarfl, Christiane; O'Shea, Francis T

2018-05-01

Metals are concerning pollutants in estuaries, where contamination can undergo significant remobilisation driven by physico-chemical forcing. Environmental concentrations of metals in estuarine sediments are often higher than natural backgrounds, but show no contiguity to potential sources. Thus, better understanding the metal mobility in estuaries is essential to improve identification of pollution sources and their accountability for environmental effects. This study aims to identify the key biogeochemical drivers of metal mobilisation on contaminated estuarine sediments through (1) evaluation of the potential mobilisation under controlled conditions, and (2) investigation of the relevance of metal mobilisation for in situ pollution levels in an area with multiple contaminant sources. Sediments from a saltmarsh adjacent to a coastal landfill, a marina, and a shipyard on the Thames Estuary (Essex, UK) were exposed in the laboratory (24h, N=96, 20°C) to water under various salinity, pH, and redox potential. Major cations, Fe(II), and trace metal concentrations were analysed in the leachate and sediment. Salinity, pH and redox had a significant effect on metal mobilisation (p<0.001), e.g. under certain conditions Fe(II) leaching was increased ~1000-fold. Measurements in situ of surface and subsurface sediment cores revealed that landfill proximity poorly explained metal spatial distribution. However, physicochemical parameters explained up to 97% of geochemically normalized metal concentrations in sediments. Organic matter and pH were dominant factors for most of the metal concentrations at the sediment surface. At subsurface, major cations (Ca, Na, Mg and K) were determinant predictors of metal concentrations. Applying the empirical model obtained in the laboratory to geochemical conditions of the studied saltmarsh it was possible to demonstrate that Fe mobilisation regulates the fate of this (and other) metal in that area. Thus, present results highlight the importance of metal mobility to control sediment pollution and estuarine fate of metals. Copyright © 2017 Elsevier B.V. All rights reserved.

Selective Reduction of CO2 to a Formate Equivalent with Heterobimetallic Gold- - -Copper Hydride Complexes.

PubMed

Hicken, Alexandra; White, Andrew J P; Crimmin, Mark R

2017-11-20

A series of heterobimetallic complexes containing three-center, two-electron Au-H-Cu bonds have been prepared from addition of a parent gold hydride to a bent d 10 copper(I) fragment. These highly unusual heterobimetallic complexes represent a missing link in the widely investigated series of neutral and cationic coinage metal hydride complexes containing Cu-H-Cu and M-H-M + moieties (M=Cu, Ag). The well-defined heterobimetallic hydride complexes act as precatalysts for the conversion of CO 2 into HCO 2 Bpin with HBpin as the reductant. The selectivity of the heterobimetallic complexes for the catalytic production of a formate equivalent surpasses that of the parent monomeric Group 11 complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of a lead mining-smelting complex on the forest-floor litter arthropod fauna in the new lead belt region of southeast Missouri

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

Watson, A.P.; Van Hook, R.I.; Jackson, D.R.

1976-07-01

Studies of biological activity within the litter horizons of a watershed contaminated by emissions from a lead-ore processing complex focused on the litter-arthropod food chain as a means of detecting perturbations in a heavy-metal contaminated ecosystem. Both point sources (smelter stack emissions) and fugitive sources (ore-handling processes, yard dusts, and exposed concentrate piles) contributed to the Pb, Zn, Cu, and Cd levels in the study area. Arthropod trophic level density, biomass, and heavy metal content were determined by analysis of specimens removed from litter by von Tullgren funnel extraction, taxonomically classified, and segregated into the trophic categories. Changes in littermore » decomposition were reflected in the dynamics of the litter arthropod community. Food-chain dilution of Pb, Zn, Cu, and Cd from litter to litter consumer was occurring, as indicated by the mean concentration factors. Accumulation of Pb by litter consumers was much less than that found for the other three heavy metals. In contrast, predatory arthropods on Crooked Creek Watershed either concentrated or equilibrated with respect to Pb, Zn, and Cd from their prey, as indicated by mean total predator concentration factors. A significant depression of the Ca, Mg, and K content litter occurred relative to the control within 0.8 km of the stack. Two mechanisms were postulated to explain this result: increased leaching of cations through the litter induced by a loss of cation exchange capacity, a decrease in pH, and a decrease in microbial immobilization of macronutrients; and a decreased uptake of macronutrients due to root damage produced by heavy-metal concentrations.« less

Towards Rational Design of Functional Fluoride and Oxyfluoride Materials from First Principles

NASA Astrophysics Data System (ADS)

Charles, Nenian

Complex transition metal compounds (TMCs) research has produced functional materials with a range of properties, including ferroelectricity, colossal magnetoresistance, nonlinear optical activity and high-temperature superconductivity. Conventional routes to tune properties in transition metal oxides, for example, have relied primarily on cation chemical substitution and interfacial effects in thin film heterostructures. In heteroanionic TMCs, exhibiting two chemically distinct anions coordinating the same or different cations, engineering of the anion sub-lattice for property control is a promising alternative approach. The presence of multiple anions provides additional design variables, such as anion order, that are absent in homoanionic counterparts. The more complex structural and chemical phase space of heteroanionic materials provides a unique opportunity to realize enhanced or unanticipated electronic, optical, and magnetic responses. Although there is growing interest in heteroanionic materials, and synthetic and characterization advances are occurring for these materials, the crystal-chemistry principles for realizing structural and property control are only slowing emerging. This dissertation employs anion engineering to investigate phenomena in transition metal fluorides and oxyfluorides compounds using first principles density functional theory calculations. Oxyfluorides are particularly intriguing owing their tendency to stabilize highly ordered anion sublattices as well as the potential to combine the advantageous properties of transition metal oxides and fluorides. This work 1) addresses the challenges of studying fluorides and oxyfluorides using first principles calculations; 2) evaluates the feasibility of using external stimuli, such as epitaxial strain and hydrostatic pressure, to control properties of fluorides and oxyfluorides; and 3) formulates a computational workflow based on multiple levels of theory and computation to elucidate structure-property relationships and anion-order descriptors. The insights gained in this work advance the understanding of oxide-fluoride anion engineered materials and we anticipate that it will motivate novel experimental efforts and materials by design in the future.

Leaching heavy metals from the surface soil of reclaimed tidal flat by alternating seawater inundation and air drying.

PubMed

Guo, Shi-Hong; Liu, Zhen-Ling; Li, Qu-Sheng; Yang, Ping; Wang, Li-Li; He, Bao-Yan; Xu, Zhi-Min; Ye, Jin-Shao; Zeng, Eddy Y

2016-08-01

Leaching experiments were conducted in a greenhouse to simulate seawater leaching combined with alternating seawater inundation and air drying. We investigated the heavy metal release of soils caused by changes associated with seawater inundation/air drying cycles in the reclaimed soils. After the treatment, the contents of all heavy metals (Cd, Pb, Cr, and Cu), except Zn, in surface soil significantly decreased (P < 0.05), with removal rates ranging from 10% to 51%. The amounts of the exchangeable, carbonate, reducible, and oxidizable fractions also significantly decreased (P < 0.05). Moreover, prolonged seawater inundation enhanced the release of heavy metals. Measurement of diffusive gradients in thin films indicated that seawater inundation significantly increased the re-mobility of heavy metals. During seawater inundation, iron oxide reduction induced the release of heavy metals in the reducible fraction. Decomposition of organic matter, and complexation with dissolved organic carbon decreased the amount of heavy metals in the oxidizable fraction. Furthermore, complexation of chloride ions and competition of cations during seawater inundation and/or leaching decreased the levels of heavy metals in the exchangeable fraction. By contrast, air drying significantly enhanced the concentration of heavy metals in the exchangeable fraction. Therefore, the removal of heavy metals in the exchangeable fraction can be enhanced during subsequent leaching with seawater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal resistance in acidophilic microorganisms and its significance for biotechnologies.

PubMed

Dopson, Mark; Holmes, David S

2014-10-01

Extremely acidophilic microorganisms have an optimal pH of <3 and are found in all three domains of life. As metals are more soluble at acid pH, acidophiles are often challenged by very high metal concentrations. Acidophiles are metal-tolerant by both intrinsic, passive mechanisms as well as active systems. Passive mechanisms include an internal positive membrane potential that creates a chemiosmotic gradient against which metal cations must move, as well as the formation of metal sulfate complexes reducing the concentration of the free metal ion. Active systems include efflux proteins that pump metals out of the cytoplasm and conversion of the metal to a less toxic form. Acidophiles are exploited in a number of biotechnologies including biomining for sulfide mineral dissolution, biosulfidogenesis to produce sulfide that can selectively precipitate metals from process streams, treatment of acid mine drainage, and bioremediation of acidic metal-contaminated milieux. This review describes how acidophilic microorganisms tolerate extremely high metal concentrations in biotechnological processes and identifies areas of future work that hold promise for improving the efficiency of these applications.

The effects of the macrotetralide actin antibiotics on the equilibrium extraction of alkali metal salts into organic solvents.

PubMed

Eisenman, G; Ciani, S; Szabo, G

1969-12-01

In order to clarify the mechanism by which neutral molecules such as the macrotetralide actin antibiotics make phospholipid bilayer membranes selectively permeable to cations, we have studied, both theoretically and experimentally, the extraction by these antibiotics of cations from aqueous solutions into organic solvents. The experiments involve merely shaking an organic solvent phase containing the antibiotic with aqueous solutions containing various cationic salts of a lipid-soluble colored anion. The intensity of color of the organic phase is then measured spectrophotometrically to indicate how much salt has been extracted. From such measurements of the equilibrium extraction of picrate and dinitrophenolate salts of Li, Na, K, Rb, Cs, and NH4 into n-hexane, dichloromethane, and hexane-dichloromethane mixtures, we have verified that the chemical reactions are as simple as previously postulated, at least for nonactin, monactin, dinactin, and trinactin. The equilibrium constant for the extraction of each cation by a given macrotetralide actin antibiotic was also found to be measurable with sufficient precision for meaningful differences among the members of this series of antibiotics to be detected. It is noteworthy that the ratios of selectivities among the various cations were discovered to be characteristic of a given antibiotic and to be completely independent of the solvent used. This finding and others reported here indicate that the size and shape of the complex formed between the macrotetralide and a given cation is the same, regardless of the species of cation bound. For such "isosteric" complexes, notable simplifications of the theory become possible which enable us to predict not only the electrical properties of a membrane made of the same solvent and having the thinness of the phospholipid bilayer but also, and more importantly, the electrical properties of the phospholipid bilayer membrane itself. These predictions will be compared with experimental data for phospholipid bilayer membranes in the accompanying paper.

Capture of Pb2+ and Cu2+ Metal Cations by Neisseria meningitidis-type Capsular Polysaccharides.

PubMed

Ghimire, Sujan; McCarthy, Pumtiwitt C

2018-05-05

Heavy metal pollution of water is a significant environmental and public health concern. Current biological strategies for heavy metal removal from water are performed using microbial biopolymers, including polysaccharides, that are already fully formed. This creates limitations in adapting polysaccharides to increase binding affinity for specific metals. We propose that altering the specificity of polysaccharide-producing enzymes could be beneficial to improving metal capture by modified polysaccharides. We assess binding of Cu 2+ and Pb 2+ metal cations to Neisseria meningitidis -type polysaccharides. All concentrations of metal cations tested were able to completely bind to colominic acid. This polymer is equivalent to the capsular polysaccharide of N. meningitidis serogroup B comprised of a homopolymer of negatively charged sialic acid. There was slightly less binding observed with N. meningitidis serogroup W, which contains repeating units of the neutral sugar galactose and sialic acid. Our work represents the first assessment of the metal-binding properties of these capsular polysaccharides. Future work will seek to optimize metal-binding with Neisseria meningitidis serogroup W polysaccharide.

Roles of Cationic and Elemental Calcium in the Electro-Reduction of Solid Metal Oxides in Molten Calcium Chloride

NASA Astrophysics Data System (ADS)

Qiu, Guohong; Jiang, Kai; Ma, Meng; Wang, Dihua; Jin, Xianbo; Chen, George Z.

2007-06-01

Previous work, mainly from this research group, is re-visited on electrochemical reduction of solid metal oxides, in the form of compacted powder, in molten CaCl2, aiming at further understanding of the roles of cationic and elemental calcium. The discussion focuses on six aspects: 1.) debate on two mechanisms proposed in the literature, i. e. electro-metallothermic reduction and electro-reduction (or electro-deoxidation), for the electrolytic removal of oxygen from solid metals or metal oxides in molten CaCl2; 2.) novel metallic cavity working electrodes for electrochemical investigations of compacted metal oxide powders in high temperature molten salts assisted by a quartz sealed Ag/AgCl reference electrode (650 ºC- 950 ºC); 3.) influence of elemental calcium on the background current observed during electrolysis of solid metal oxides in molten CaCl2; 4.) electrochemical insertion/ inclusion of cationic calcium into solid metal oxides; 5.) typical features of cyclic voltammetry and chronoamperometry (potentiostatic electrolysis) of metal oxide powders in molten CaCl2; and 6.) some kinetic considerations on the electrolytic removal of oxygen.

Is Electronegativity a Useful Descriptor for the "Pseudo-Alkali-Metal" NH4?

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

Whiteside, Alexander; Xantheas, Sotiris S.; Gutowski, Maciej S.

2011-11-18

Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined the electronegativity of the "pseudo-alkali metal" ammonium (NH4) and evaluated its reliability as a descriptor in comparison to the electronegativities of the alkali metals. The computed properties of its binary complexes with astatine and of selected borohydrides confirm the similarity of NH4 to the alkali metal atoms, although the electronegativity of NH4 is relatively large in comparison to its cationic radius. We paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation, andmore » reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the polyatomic nature of NH4.« less

Is electronegativity a useful descriptor for the pseudo-alkali metal NH4?

PubMed

Whiteside, Alexander; Xantheas, Sotiris S; Gutowski, Maciej

2011-11-18

Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined one such property--the electronegativity--for the "pseudo-alkali metal" ammonium (NH(4)), and evaluated its reliability as a descriptor versus the electronegativities of the alkali metals. The computed properties of ammonium's binary complexes with astatine and of selected borohydrides confirm the similarity of NH(4) to the alkali metal atoms, although the electronegativity of NH(4) is relatively large in comparison to its cationic radius. We have paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation and reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the molecular nature of NH(4). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Speciation of cadmium and zinc with application to soil solutions

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

Holm, P.E.; Christensen, T.H.; Tjell, J.C.

1995-01-01

A two-part method has been developed for determination of Cd and Zn species in 50-mL soil solution samples containing low concentrations of Cd and Zn (1-10 {mu}g Cd L{sup -1} and 50-1000 {mu}g Zn L{sup -1}). The method uses two cation exchange resins (Amberlite CG 120 and Chelex 100) in a batch-column-batch procedure and relies on analytical determinations of Cd and Zn by graphite furnace atomic absorption spectrophotometry. The first part (batch) of the method allows determination of free divalent Cd{sup 2+} and Zn{sup 2+}. This part is experimentally sensitive to cation concentrations and ionic strength and these parameters shouldmore » be controlled during the experimental procedures. However, it is shown that Cd and Zn concentrations and pH do not influence the method. Speciations performed on samples containing chloride and sulfate were in accordance with theoretical calculations. The second part (column-batch) of the method operationally separates the complexed fraction into labile complexes, slowly labile complexes, and stable complexes. Chloro complexes were identified as labile complexes, while EDTA complexes were identified as stable complexes. The method works well with relatively small volumes of sample solutions and at low metal concentrations and may be useful in characterization of Cd and Zn in soil solutions. 12 refs., 6 figs., 3 tabs.« less

Phenyl substitution of cationic bis-cyclometalated iridium(iii) complexes for iTMC-LEECs.

PubMed

Suhr, Kristin J; Bastatas, Lyndon D; Shen, Yulong; Mitchell, Lauren A; Frazier, Gary A; Taylor, David W; Slinker, Jason D; Holliday, Bradley J

2016-11-28

A series of seven cationic bis-cyclometalated iridium(iii) complexes of the form [(C^N) 2 (N^N)Ir][PF 6 ] has been designed in order to examine the effect of bulky, hydrophobic phenyl substituents on the structure-property relationship of these ionic transition metal complexes (iTMCs) in light-emitting electrochemical cells (LEECs). Capping phenyl substituents on the cyclometalating and ancillary ligands allows for individual tuning of the HOMO and LUMO energy levels, respectively, yielding an emission range from yellow to red. The complexes in this series exhibit increased quantum yields, up to 70% higher than the unoptimized, archetypal [(2-phenylpyridine) 2 (2,2'-bipyridine)Ir][PF 6 ]. Among these, one complex, C3, was recently reported to produce devices with superior luminance and efficiency. Simultaneous measure of the series of complexes enabled the clear discernment of trends in device performance connected to fundamental structure-property relationships that elucidate the origin of enhanced luminance. In general, phenyl substitution of the 2-phenylpyridine ligands of the parent complex produced higher luminance and faster device response than phenyl substitution of the 2,2'-bipyridine ligand. Overall, complex design and device engineering produce competitive LEECs from simple, single-layer architectures. The synthesis, crystallographic, photophysical, and electrochemical properties of the iTMCs, along with the electroluminescence properties of the LEEC devices are reported herein.

Synthesis and Reactivity toward H2 of (η(5)-C5Me5)Rh(III) Complexes with Bulky Aminopyridinate Ligands.

PubMed

Zamorano, Ana; Rendón, Nuria; Valpuesta, José E V; Álvarez, Eleuterio; Carmona, Ernesto

2015-07-06

Electrophilic, cationic Rh(III) complexes of composition [(η(5)-C5Me5)Rh(Ap)](+), (1(+)), were prepared by reaction of [(η(5)-C5Me5)RhCl2]2 and LiAp (Ap = aminopyridinate ligand) followed by chloride abstraction with NaBArF (BArF = B[3,5-(CF3)2C6H3]4). Reactions of cations 1(+) with different Lewis bases (e.g., NH3, 4-dimethylaminopyridine, or CNXyl) led in general to monoadducts 1·L(+) (L = Lewis base; Xyl = 2,6-Me2C6H3), but carbon monoxide provided carbonyl-carbamoyl complexes 1·(CO)2(+) as a result of metal coordination and formal insertion of CO into the Rh-Namido bond of complexes 1(+). Arguably, the most relevant observation reported in this study stemmed from the reactions of complexes 1(+) with H2. (1)H NMR analyses of the reactions demonstrated a H2-catalyzed isomerization of the aminopyridinate ligand in cations 1(+) from the ordinary κ(2)-N,N' coordination to a very uncommon, formally tridentate κ-N,η(3) pseudoallyl bonding mode (complexes 3(+)) following benzylic C-H activation within the xylyl substituent of the pyridinic ring of the aminopyridinate ligand. The isomerization entailed in addition H-H and N-H bond activation and mimicked previous findings with the analogous iridium complexes. However, in dissimilarity with iridium, rhodium complexes 1(+) reacted stoichiometrically at 20 °C with excess H2. The transformations resulted in the hydrogenation of the C5Me5 and Ap ligands with concurrent reduction to Rh(I) and yielded complexes [(η(4)-C5Me5H)Rh(η(6)-ApH)](+), (2(+)), in which the pyridinic xylyl substituent is η(6)-bonded to the rhodium(I) center. New compounds reported were characterized by microanalysis and NMR spectroscopy. Representative complexes were additionally investigated by X-ray crystallography.

A theoretical study of complexes formed between cations and curved aromatic systems: electrostatics does not always control cation-π interaction.

PubMed

Carrazana-García, Jorge A; Cabaleiro-Lago, Enrique M; Rodríguez-Otero, Jesús

2017-04-19

The present work studies the interaction of two extended curved π-systems (corannulene and sumanene) with various cations (sodium, potassium, ammonium, tetramethylammonium, guanidinium and imidazolium). Polyatomic cations are models of groups found in important biomolecules in which cation-π interaction plays a fundamental role. The results indicate an important size effect: with extended π systems and cations of the size of potassium and larger, dispersion is much more important than has been generally recognized for cation-π interactions. In most of the systems studied here, the stability of the cation-π complexes is the result of a balanced combination of electrostatic, induction and dispersion contributions. None of the systems studied here owes its stability to the electrostatic interaction more than 42%. Induction dominates stabilization in complexes with sodium, and in some of the potassium and ammonium complexes. In complexes with large cations and with flat cations dispersion is the major stabilizing contribution and can provide more than 50% of the stabilization energy. This implies that theoretical studies of the cation-π interaction involving large or even medium-size fragments require a level of calculation capable of properly modelling dispersion. The separation between the cation and the π system is another important factor to take into account, especially when the fragments of the cation-π complex are bound (for example, to a protein backbone) and cannot interact at the most favourable distance.

Esterification of phenyl acetic acid with p-cresol using metal cation exchanged montmorillonite nanoclay catalysts

PubMed Central

Bhaskar, M.; Surekha, M.; Suma, N.

2018-01-01

The liquid phase esterification of phenyl acetic acid with p-cresol over different metal cation exchanged montmorillonite nanoclays yields p-cresyl phenyl acetate. Different metal cation exchanged montmorillonite nanoclays (Mn+ = Al3+, Zn2+, Mn2+, Fe3+, Cu2+) were prepared and the catalytic activity was studied. The esterification reaction was conducted by varying molar ratio of the reactants, reaction time and catalyst amount on the yield of the ester. Among the different metal cation exchanged catalysts used, Al3+-montmorillonite nanoclay was found to be more active. The characterization of the material used was studied under different techniques, namely X-ray diffraction, scanning electron microscopy and thermogravimetric analysis. The product obtained, p-cresyl phenyl acetate, was identified by thin-layer chromotography and confirmed by Fourier transform infrared, 1H NMR and 13C NMR. The regeneration activity of used catalyst was also investigated up to fourth generation. PMID:29515855

Homoleptic 2,2'-bipyridine metalates(-I) of iron and cobalt, one cocrystallized with an anthracene radical anion and the other with neutral anthracene.

PubMed

Brennessel, William W; Ellis, John E

2014-08-01

Homoleptic 2,2'-bipyridine (bipy) metalates of iron and cobalt have been synthesized directly from the corresponding homoleptic anthracene metalates. In the iron structure, bis[([2.2.2]cryptand)potassium(I)] tris(2,2'-bipyridine)ferrate(-I) anthracene(-I), [K(C18H36N2O6)]2[Fe(C10H8N2)3](C14H10), the asymmetric unit contains one potassium complex cation in a general position, the Fe center and one and a half bipy ligands of the ferrate complex on a crystallographic twofold axis that includes the Fe atom, and one half of an anthracene radical anion whose other half is generated by a crystallographic inversion center. The cations and anions are well separated and the geometry about the Fe center is essentially octahedral. In the cobalt structure, ([2.2.2]cryptand)potassium(I) bis(2,2'-bipyridine)cobaltate(-I) anthracene hemisolvate tetrahydrofuran (THF) disolvate, [K(C18H36N2O6)][Co(C10H8N2)2]·0.5C14H10·2C4H8O, the asymmetric unit contains the cation, anion, and both cocrystallized THF solvent molecules in general positions, and one half of a cocrystallized anthracene molecule whose other half is generated by a crystallographic inversion center. The cation and anion are well separated and the ligand planes in the cobaltate anion are periplanar. Each anthracene molecule is midway between and is oriented perpendicular to a pair of symmetry-related bipy ligands such that aromatic donor-acceptor interactions may play a role in the packing arrangement. The lengths of the bonds that connect the bipy rings support the assertion that the ligands are bipy radical anions in the iron structure. However, in the case of cobalt, these lengths are between the known ranges for a bipy radical anion and a bipy dianion, and therefore no conclusion can be made from the crystallography alone. One cocrystallized THF solvent molecule in the cobalt structure was modeled as disordered over three positions with appropriate geometric and thermal restraints, which resulted in a refined component mass ratio of 0.412 (4):0.387 (3):0.201 (3).

Synthesis and Elucidation Structure of Tetrakis-diphenylaminecopper(II) Chloride Hexahydrate

NASA Astrophysics Data System (ADS)

Syaima, H.; Rahardjo, S. B.; Suciningrum, E.

2017-11-01

CuCl2·2H2O with diphenylamine formed a complex compound in 1:4-mole ratio of metal to the ligand in methanol. Its structural properties were investigated by employing metal content analysis by Atomic Absorption Spectroscopy (AAS), magnetic susceptibility, UV-vis and FTIR spectroscopy. The forming of the complex was indicated by shifting of UV-Vis spectra. The result of analysis Cu(II) in the complex showed empirical formula of the complex were Cu(diphenylamine)4Cl2(H2O)6. The electrical conductivity of complex showed the charge ratio of cation and anion = 2:1. Finally, the proposed formula of the complex was [Cu(diphenylamine)4]Cl2·6H2O. Based on infrared spectra, it was revealed that diphenylamine existed as monodentate bind to copper(II) through the functional group of N-H. The electronic spectral study of the complex showed three transition peaks on 861, 592, and 419 nm corresponding to the 2B1g → 2A1g, 2B1g → 2B2g dan 2B1g → 2Eg transitions. The complex was paramagnetic and indicated that ligands form square planar geometry around the Cu(II).

The Gellyfish: An In-Situ Equilibrium-Based Sampler for Determining Multiple Free Metal Ion Concentrations in Marine Ecosystems

PubMed Central

Dong, Zhao; Lewis, Christopher G.; Burgess, Robert M.; Shine, James P.

2016-01-01

Free metal ions are usually the most bioavailable and toxic metal species to aquatic organisms, but they are difficult to measure due to their extremely low concentrations in the marine environment. Many of the current methods for determining free metal ions are complicated, time-consuming, and can only measure one metal at a time. We developed a new version of the ‘Gellyfish’, an in-situ equilibrium-based sampler, with significantly reduced equilibration time and the capability of measuring multiple free metal ions simultaneously. By calibrating the Gellyfish to account for its uptake of cationic metal complexes and validating them in multi-metal competition experiments, we were able to determine free metal ion concentrations previously collected over ten months at five locations in Boston Harbor for Cu, Zn, Pb, Ni, and Cd. This work generated one of the largest free metal ion datasets and demonstrated the applicability of the Gellyfish as an easy-to-use and inexpensive tool for monitoring free ion concentrations of metal mixtures in marine ecosystems. PMID:25598362

Poly[4,4'-(propane-1,3-diyl)dipyridinium bis{tetraaquabis(μ2-5-carboxybenzene-1,2,4-tricarboxylato)bis[μ2-1,3-bis(4-pyridyl)propane]dicobalt(II)} pentahydrate].

PubMed

Atria, Ana María; Corsini, Gino; Garland, Maria Teresa; Baggio, Ricardo

2011-11-01

The title polymeric compound, {(C(13)H(16)N(2))[Co(C(10)H(3)O(8))(C(13)H(14)N(2))(H(2)O)(2)](2)·5H(2)O}(n), is an ionic structure comprising an anionic two-dimensional mesh characterized by a {[Co(Hbtc)(bpp)(H(2)O)(2)](-)}(2) motif [Hbtc is 5-carboxybenzene-1,2,4-tricarboxylate and bpp is 1,3-bis(4-pyridyl)propane], with interspersed 4,4'-(propane-1,3-diyl)dipyridinium cations, denoted (H(2)bpp)(2+), and water molecules providing the charge balance and structure stabilization. The reticular mesh consists of two independent types of [Co(H(2)O)(2)](2+) cationic nodes (lying on inversion centres), interconnected in the [101] direction by two independent sets of neutral bridging bpp ligands, both types of ligands being split by non-equivalent twofold axes. One set is formed by genuinely symmetric moieties, while those in the second set are only symmetric by disorder in the central propane bridge. These chains contain only one type of Co(II) centre and one type of bpp ligand; the metal cations therein are laterally bridged by Hbtc anions, thus forming transverse chains of alternating types of Co(II) cations. The elemental motif of the resulting grid is a highly distorted parallelogram, with metal-metal distances of 13.5242 (14) Å in the bpp direction and 9.105 (2) Å in the Hbtc direction, and a large internal angle of 138.42 (18)°. These two-dimensional structures have a profusion of hydrogen-bonding interactions with each other, either directly (with the aqua molecules as donors and the Hbtc anions as acceptors) or mediated by the unbound (H(2)bpp)(2+) cations and water molecules of hydration. These interactions generate a very complex hydrogen-bonding scheme involving all of the available N-H and O-H groups and which links these two-dimensional grids into a three-dimensional network.

Niobate-based octahedral molecular sieves

DOEpatents

Nenoff, Tina M.; Nyman, May D.

2006-10-17

Niobate-based octahedral molecular sieves having significant activity for multivalent cations and a method for synthesizing such sieves are disclosed. The sieves have a net negatively charged octahedral framework, comprising niobium, oxygen, and octahedrally coordinated lower valence transition metals. The framework can be charge balanced by the occluded alkali cation from the synthesis method. The alkali cation can be exchanged for other contaminant metal ions. The ion-exchanged niobate-based octahedral molecular sieve can be backexchanged in acidic solutions to yield a solution concentrated in the contaminant metal. Alternatively, the ion-exchanged niobate-based octahedral molecular sieve can be thermally converted to a durable perovskite phase waste form.

Niobate-based octahedral molecular sieves

DOEpatents

Nenoff, Tina M.; Nyman, May D.

2003-07-22

Niobate-based octahedral molecular sieves having significant activity for multivalent cations and a method for synthesizing such sieves are disclosed. The sieves have a net negatively charged octahedral framework, comprising niobium, oxygen, and octahedrally coordinated lower valence transition metals. The framework can be charge balanced by the occluded alkali cation from the synthesis method. The alkali cation can be exchanged for other contaminant metal ions. The ion-exchanged niobate-based octahedral molecular sieve can be backexchanged in acidic solutions to yield a solution concentrated in the contaminant metal. Alternatively, the ion-exchanged niobate-based octahedral molecular sieve can be thermally converted to a durable perovskite phase waste form.

Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon–carbon bond forming reactions

PubMed Central

Jouffroy, Matthieu; Gramage-Doria, Rafael; Sémeril, David; Oberhauser, Werner; Toupet, Loïc

2014-01-01

Summary The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2. PMID:25383109

Electrochemical Removal of Metal Cations from Wastewater Monitored by Differential Pulse Polarography

ERIC Educational Resources Information Center

Bruce, Delphine; Kuhn, Alexander; Sojic, Neso

2004-01-01

Electrodeposition eliminates wastewater pollutants such as electrochemically active metal cations, with different pulse polarography (DPP) scrutinizing the kinetics of the treatment process. These mechanisms produce qualitative and quantitative data about the removal process, while students appreciate the use of electrochemistry in resolving…

Hexakis(N,N-dimethyl­formamide-κO)cobalt(II) bis­(perchlorate)

PubMed Central

Eissmann, Frank; Böhle, Tony; Mertens, Florian O. R. L.; Weber, Edwin

2010-01-01

The asymmetric unit of the title complex, [Co(DMF)6](ClO4)2 (DMF = N,N-dimethyl­formamide, C3H7NO), consists of two half complex cations with the Co2+ metal ions located on centers of inversion and two perchlorate anions. In the crystal packing, each Co2+ ion is coordinated by six mol­ecules of DMF in a slightly distorted octa­hedral geometry. The crystal structure is mainly stabilized by coordinative, ionic and C—H⋯O hydrogen-bonding inter­actions. PMID:21580225

Carbonic anhydrase inhibitors. A general approach for the preparation of water-soluble sulfonamides incorporating polyamino-polycarboxylate tails and of their metal complexes possessing long-lasting, topical intraocular pressure-lowering properties.

PubMed

Scozzafava, Andrea; Menabuoni, Luca; Mincione, Francesco; Supuran, Claudiu T

2002-03-28

Reaction of polyamino-polycarboxylic acids or their dianhydrides with aromatic/heterocyclic sulfonamides possessing a free amino/imino/hydrazino/hydroxy group afforded mono- and bis-sulfonamides containing polyamino-polycarboxylic acid moieties in their molecule. The acids/anhydrides used in synthesis included IDA, NTA, EDDA, EDTA and EDTA dianhydride, DTPA and DTPA dianhydride, EGTA and EGTA dianhydride, and EDDHA, among others. All the newly prepared derivatives showed strong affinity toward isozymes I, II, and IV of carbonic anhydrase (CA). Metal complexes of the new compounds have also been prepared. Metal ions used in such preparations included di- and trivalent main-group and transition cations, such as Zn(II), Cu(II), Al(III), etc. Some of the new sulfonamides/disulfonamides obtained in this way, as well as their metal complexes, behaved as nanomolar CA inhibitors against isozymes II and IV, being slightly less effective in inhibiting isozyme I. Some of these sulfonamides as well as their metal complexes strongly lowered intraocular pressure (IOP) when applied topically, directly into the normotensive/glaucomatous rabbit eye, as 1-2% water solutions/suspensions. The good water solubility of these sulfonamide CA inhibitors, correlated with the neutral pH of their water solutions used in the ophthalmologic applications and the long duration of action of the IOP-lowering effect, makes them interesting candidates for developing novel types of antiglaucoma drugs devoid of serious topical side effects.

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

Abdellahi, Aziz; Urban, Alexander; Dacek, Stephen

Cation disorder is a phenomenon that is becoming increasingly important for the design of high-energy lithium transition metal oxide cathodes (LiMO 2) for Li-ion batteries. Disordered Li-excess rocksalts have recently been shown to achieve high reversible capacity, while in operando cation disorder has been observed in a large class of ordered compounds. The voltage slope (dV/dx u )is a critical quantity for the design of cation-disordered rocksalts, as it controls the Li capacity accessible at voltages below the stability limit of the electrolyte (~4.5-4.7 V). In this study, we develop a lattice model based on first principles to understand andmore » quantify the voltage slope of cation-disordered LiMO 2. We show that cation disorder increases the voltage slope of Li transition metal oxides by creating a statistical distribution of transition metal environments around Li sites, as well as by allowing Li occupation of highvoltage tetrahedral sites. We further demonstrate that the voltage slope increase upon disorder is generally smaller for highvoltage transition metals than for low-voltage transition metals due to a more effective screening of Li-M interactions by oxygen electrons. Short-range order in practical disordered compounds is found to further mitigate the voltage slope increase upon disorder. In conclusion, our analysis shows that the additional high-voltage tetrahedral capacity induced by disorder is smaller in Liexcess compounds than in stoichiometric LiMO 2 compounds.« less

Binding in alkali and alkaline-earth tetrahydroborates: Special position of magnesium tetrahydroborate

NASA Astrophysics Data System (ADS)

Łodziana, Zbigniew; van Setten, Michiel J.

2010-01-01

Compounds of light elements and hydrogen are currently extensively studied due to their potential application in the field of hydrogen or energy storage. A number of new interesting tetrahydroborates that are especially promising due to their very high gravimetric hydrogen content were recently reported. However, the determination and understanding of their complex crystalline structures has created considerable debate. Metal tetrahydroborates, in general, form a large variety of structures ranging from simple for NaBH4 to very complex for Mg(BH4)2 . Despite the extensive discussion in the literature no clear explanation has been offered for this variety so far. In this paper we analyze the structural and electronic properties of a broad range of metal tetrahydroborates and reveal the factors that determine their structure: ionic bonding, the orientation of the BH4 groups, and the coordination number of the metal cation. We show, in a simple way, that the charge transfer in the metal tetrahydroborates rationally explains the structural diversity of these compounds. Being ionic systems, the metal tetrahydroborates fall into the classification of Linus Pauling. By using the ionic radius for the BH4 group as determined in this paper, this allows for structural predictions for new and mixed compounds.

New donor-acceptor conjugates based on a trifluorenylporphyrin linked to a redox-switchable ruthenium unit.

PubMed

Merhi, Areej; Zhang, Xu; Yao, Dandan; Drouet, Samuel; Mongin, Olivier; Paul, Frédéric; Williams, J A Gareth; Fox, Mark A; Paul-Roth, Christine O

2015-05-28

Reactions of the 16-electron ruthenium complex [Ru(dppe)2Cl][PF6] with metal-free and zinc ethynylphenyltrifluorenylporphyrins and respectively, gave the new dyads and with ethynylruthenium group as a potential electron donor and the porphyrin as a potential electron acceptor. The redox properties of the porphyrins were investigated by cyclic voltammetry and UV spectroelectrochemistry (SEC), which reveal that the monocation and monoanion of metal-free porphyrin are stable under these conditions whereas the formation of the corresponding radical cation or anion of the zinc porphyrin was accompanied by partial decomplexation of the zinc ion. Oxidations of the dyads and gave stable radical cations as probed using IR, NIR and UV SEC methods. These cations show similar NIR and IR bands to those reported for the known 17-electron [Ru(dppe)2(C[triple bond, length as m-dash]CPh)Cl](+) radical cation. Remarkably, the dyad has four stable redox states +2/+1/0/-1 where the second oxidation and first reduction processes take place at the porphyrin unit. Simulated absorption spectra on at optimised geometries obtained by TD-DFT computations with the CAM-B3LYP functional are shown to be in very good agreement with the observed UV absorption spectra of . The spectra of and their oxidised and reduced species were interpreted with the aid of the TD-DFT data. Fluorescence measurements reveal that the dyads and are only weakly emitting compared to and , indicative of quenching of the porphyrinic singlet excited state by the ruthenium centre.

Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation.

PubMed

Nishiura, Masayoshi; Guo, Fang; Hou, Zhaomin

2015-08-18

The search for new catalysts for more efficient, selective chemical transformations and for the synthesis of new functional materials has been a long-standing research subject in both academia and industry. To develop new generations of catalysts that are superior or complementary to the existing ones, exploring the potential of untapped elements is an important strategy. Rare-earth elements, including scandium, yttrium, and the lanthanides (La-Lu), constitute one important frontier in the periodic table. Rare-earth elements possess unique chemical and physical properties that are different from those of main-group and late-transition metals. The development of rare-earth-based catalysts by taking the advantage of these unique properties is of great interest and importance. The most stable oxidation state of rare-earth metals is 3+, which is difficult to change under many reaction conditions. The oxidative addition and reductive elimination processes often observed in catalytic cycles involving late transition metals are generally difficult in the case of rare-earth complexes. The 18-electron rule that is applicable to late-transition-metal complexes does not fit rare-earth complexes, whose structures are mainly governed by the sterics (rather than the electron numbers) of the ligands. In the lanthanide series (La-Lu), the ionic radius gradually decreases with increasing atomic number because of the influence of the 4f electrons, which show poor shielding of nuclear charge. Rare-earth metal ions generally show strong Lewis acidity and oxophilicity. Rare-earth metal alkyl and hydride species are highly reactive, showing both nucleophilicity and basicity. The combination of these features, such as the strong nucleophilicity and moderate basicity of the alkyl and hydride species and the high stability, strong Lewis acidity, and unsaturated C-C bond affinity of the 3+ metal ions, can make rare-earth metals unique candidates for the formation of excellent single-site catalysts. This Account is intended to give an overview of our recent studies on organo rare-earth catalysis, in particular the synthesis and application of half-sandwich rare-earth alkyl complexes bearing monocyclopentadienyl ligands for olefin polymerization, carbometalation, and hydroarylation. Treatment of half-sandwich rare-earth dialkyl complexes having the general formula CpMR2 with an equimolar amount of an appropriate borate compound such as [Ph3C][B(C6F5)4] can generate the corresponding cationic monoalkyl species, which serve as excellent single-site catalysts for the polymerization and copolymerization of a wide range of olefin monomers such as ethylene, 1-hexene, styrene, conjugated and nonconjugated dienes, and cyclic olefins. The cationic half-sandwich rare-earth alkyl complexes can also catalyze the regio- and stereoselective alkylative alumination of alkenes and alkynes through insertion of the unsaturated C-C bond into the metal-alkyl bond followed by transmetalation between the resulting new alkyl or alkenyl species and an alkylaluminum compound. Moreover, a combination of deprotonative C-H bond activation of appropriate organic compounds such as anisoles and pyridines by the rare-earth alkyl species and insertion of alkenes into the resulting new metal-carbon bond can lead to catalytic C-H bond alkylation of the organic substrates. Most of these transformations are unique to the rare-earth catalysts with selectivity and functional group tolerance different from those of late-transition-metal catalysts.

Does Metal Ion Complexation Make Radical Clocks Run Fast? An Experimental Perspective.

PubMed

Abdel Latif, Marwa K; Spencer, Jared N; Paradzinsky, Mark; Tanko, James M

2017-12-28

The rate constant for the β-scission of the cumyloxyl radical (k β ) was measured in the presence of various added electrolytes in acetonitrile and DMSO solvent. The results show that in CH 3 CN, k β increases in the presence of added electrolyte, roughly paralleling the size of the cation: Li + > Mg 2+ ≈ Na + > n Bu 4 N + > no added electrolyte. As suggested by Bietti et al. earlier, this effect is attributable to stabilizing ion-dipole interactions in the transition state of the developing carbonyl group, a conclusion further amplified by MO calculations (gas phase) reported herein. Compared to the gas phase predictions, however, this effect is seriously attenuated in solution because complexation of the cation to the electrophilic alkoxyl radical (relative to the solvent, CH 3 CN) is very weak. Because the interaction of Li + and Na + is much stronger with DMSO than with CH 3 CN, addition of these ions has no effect on the rate of β-scission.

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb).

PubMed

Cary, Samantha K; Livshits, Maksim; Cross, Justin N; Ferrier, Maryline G; Mocko, Veronika; Stein, Benjamin W; Kozimor, Stosh A; Scott, Brian L; Rack, Jeffrey J

2018-04-02

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction-or find alternatives-because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV (TTA) 4 . Meanwhile, +3 metals formed anionic M III (TTA) 4 - species. Characterization of these M(TTA) 4 x- ( x = 0, 1) compounds by UV-vis-NIR, IR, 1 H and 19 F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV (TTA) 4 and Pu IV (TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV (TTA) 4 and M III (TTA) 4 - are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV , Hf IV , and Zr IV .

Methods and energy storage devices utilizing electrolytes having surface-smoothing additives

DOEpatents

Xu, Wu; Zhang, Jiguang; Graff, Gordon L; Chen, Xilin; Ding, Fei

2015-11-12

Electrodeposition and energy storage devices utilizing an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and anode surface. For electrodeposition of a first metal (M1) on a substrate or anode from one or more cations of M1 in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second metal (M2), wherein cations of M2 have an effective electrochemical reduction potential in the solution lower than that of the cations of M1.

Cation-π interaction of the univalent sodium cation with [2.2.2]paracyclophane: Experimental and theoretical study

NASA Astrophysics Data System (ADS)

Makrlík, Emanuel; Sýkora, David; Böhm, Stanislav; Vaňura, Petr

2018-02-01

By employing electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent sodium cation (Na+) forms with [2.2.2]paracyclophane (C24H24) the cationic complex [Na(C24H24)]+. Further, applying quantum chemical DFT calculations, the most probable structure of the [Na(C24H24)]+ complex was derived. In the resulting complex with a symmetry very close to C3, the "central" cation Na+, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered cation-π complex [Na(C24H24)]+ was found to be -267.3 kJ/mol, confirming the formation of this fascinating complex species as well.

Electrochemical Reduction of Oxygen in Aprotic Ionic Liquids Containing Metal Cations: A Case Study on the Na-O2 system.

PubMed

Azaceta, Eneko; Lutz, Lukas; Grimaud, Alexis; Vicent-Luna, Jose Manuel; Hamad, Said; Yate, Luis; Cabañero, German; Grande, Hans-Jurgen; Anta, Juan A; Tarascon, Jean-Marie; Tena-Zaera, Ramon

2017-04-10

Metal-air batteries are intensively studied because of their high theoretical energy-storage capability. However, the fundamental science of electrodes, electrolytes, and reaction products still needs to be better understood. In this work, the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) was chosen to study the influence of a wide range of metal cations (M n+ ) on the electrochemical behavior of oxygen. The relevance of the theory of Lewis hard and soft acids and bases to predict satisfactorily the reduction potential of oxygen in electrolytes containing metal cations is demonstrated. Systems with soft and intermediate M n+ acidity are shown to facilitate oxygen reduction and metal oxide formation, whereas oxygen reduction is hampered by hard acid cations such as sodium and lithium. Furthermore, DFT calculations on the energy of formation of the resulting metal oxides rationalize the effect of M n+ on oxygen reduction. A case study on the Na-O 2 system is described in detail. Among other things, the Na + concentration of the electrolyte is shown to control the electrochemical pathway (solution precipitation vs. surface deposition) by which the discharge product grows. All in all, fundamental insights for the design of advanced electrolytes for metal-air batteries, and Na-air batteries in particular, are provided. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substituent and Solvent Effects on the Absorption Spectra of Cation-π Complexes of Benzene and Borazine: A Theoretical Study.

PubMed

Sarmah, Nabajit; Bhattacharyya, Pradip Kr; Bania, Kusum K

2014-05-29

Time-dependent density functional theory (TDDFT) has been used to predict the absorption spectra of cation-π complexes of benzene and borazine. Both polarized continuum model (PCM) and discrete solvation model (DSM) and a combined effect of PCM and DSM on the absorption spectra have been elucidated. With decrease in size of the cation, the π → π* transitions of benzene and borazine are found to undergo blue and red shift, respectively. A number of different substituents (both electron-withdrawing and electron-donating) and a range of solvents (nonpolar to polar) have been considered to understand the effect of substituent and solvents on the absorption spectra of the cation-π complexes of benzene and borazine. Red shift in the absorption spectra of benzene cation-π complexes are observed with both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The same trend has not been observed in the case of substituted borazine cation-π complexes. The wavelength of the electronic transitions corresponding to cation-π complexes correlates well with the Hammet constants (σ p and σ m ). This correlation indicates that the shifting of spectral lines of the cation-π complexes on substitution is due to both resonance and inductive effect. On incorporation of solvent phases, significant red or blue shifting in the absorption spectra of the complexes has been observed. Kamlet-Taft multiparametric equation has been used to explain the effect of solvent on the absorption spectra of complexes. Polarity and polarizability are observed to play an important role in the solvatochromism of the cation-π complexes.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

PubMed

Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N

2016-03-15

Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values<3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with (55)Fe and (26)Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (>70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. Copyright © 2015 Elsevier B.V. All rights reserved.

Understanding metallic bonding: Structure, process and interaction by Rasch analysis

NASA Astrophysics Data System (ADS)

Cheng, Maurice M. W.; Oon, Pey-Tee

2016-08-01

This paper reports the results of a survey of 3006 Year 10-12 students on their understandings of metallic bonding. The instrument was developed based on Chi's ontological categories of scientific concepts and students' understanding of metallic bonding as reported in the literature. The instrument has two parts. Part one probed into students' understanding of metallic bonding as (a) a submicro structure of metals, (b) a process in which individual metal atoms lose their outermost shell electrons to form a 'sea of electrons' and octet metal cations or (c) an all-directional electrostatic force between delocalized electrons and metal cations, that is, an interaction. Part two assessed students' explanation of malleability of metals, for example (a) as a submicro structural rearrangement of metal atoms/cations or (b) based on all-directional electrostatic force. The instrument was validated by the Rasch Model. Psychometric assessment showed that the instrument possessed reasonably good properties of measurement. Results revealed that it was reliable and valid for measuring students' understanding of metallic bonding. Analysis revealed that the structure, process and interaction understandings were unidimensional and in an increasing order of difficulty. Implications for the teaching of metallic bonding, particular through the use of diagrams, critiques and model-based learning, are discussed.

Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

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

Johnson, Gregory R.; Bell, Alexis T.

2016-06-17

Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH 4 and increase the selectivity toward C 5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becomingmore » insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C 5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and dissociation.« less

Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

DOE PAGES

Johnson, Gregory R.; Bell, Alexis T.

2016-03-31

Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH 4 and increase the selectivity toward C 5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM-EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becomingmore » insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. We found a strong positive correlation between the C 5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid-base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir-Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. Our results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and dissociation.« less

Relative abundance of chemical forms of Cu(II) and Cd(II) on soybean roots as influenced by pH, cations and organic acids

PubMed Central

Zhou, Qin; Liu, Zhao-dong; Liu, Yuan; Jiang, Jun; Xu, Ren-kou

2016-01-01

Little information is available on chemical forms of heavy metals on integrate plant roots. KNO3 (1 M), 0.05M EDTA at pH6 and 0.01 M HCl were used sequentially to extract the exchangeable, complexed and precipitated forms of Cu(II) and Cd(II) from soybean roots and then to investigate chemical form distribution of Cu(II) and Cd(II) on soybean roots. Cu(II) and Cd(II) adsorbed on soybean roots were mainly exchangeable form, followed by complexed form, while their precipitated forms were very low under acidic conditions. Soybean roots had a higher adsorption affinity to Cu(II) than Cd(II), leading to higher toxic of Cu(II) than Cd(II). An increase in solution pH increased negative charge on soybean and thus increased exchangeable Cu(II) and Cd(II) on the roots. Ca2+, Mg2+ and NH4+ reduced exchangeable Cu(II) and Cd(II) levels on soybean roots and these cations showed greater effects on Cd(II) than Cu(II) due to greater adsorption affinity of the roots to Cu(II) than Cd(II). L-malic and citric acids decreased exchangeable and complexed Cu(II) on soybean roots. In conclusion, Cu(II) and Cd(II) mainly existed as exchangeable and complexed forms on soybean roots. Ca2+ and Mg2+ cations and citric and L-malic acids can potentially alleviate Cu(II) and Cd(II) toxicity to plants. PMID:27805020

Determination of labile copper, cobalt, and chromium in textile mill wastewater

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

Crain, J.S.; Essling, A.M.; Kiely, J.T.

1997-01-01

Copper, chromium, and cobalt species present in filtered wastewater effluent were separated by cation exchange and reverse phase chromatography. Three sample fractions were obtained: one containing metal cations (i.e., trivalent Cr, divalent Cu, and divalent Co), one containing organic species (including metallized dyes), and one containing other unretained species. The metal content of each fraction was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The sum of the corrected data was compared to the metal content of a filtered effluent aliquot digested totally with fuming sulfuric acid. Other aliquots of the filtered effluent were spiked with the metals ofmore » interest and digested to confirm chemical yield and accuracy. Method detection limits were consistently below 20 {mu}g L{sup -1} for Cu, 30 {mu}g L{sup -1} for Co, and 10 {mu}g L{sup -1} for Cr. Spike recoveries for undifferentiated Cu and Cr were statistically indistinguishable from unity; although Co spike recoveries were slightly low ({approximately}95%), its chemical yield was 98%. Copper retention on the sodium sulfonate cation exchange resin was closely correlated with the [EDTA]/[Cu] ratio, suggesting that metals retained upon the cation exchange column were assignable to labile metal species; however, mass balances for all three elements, though reasonable ({approximately}90%), were significantly different from unity. Mechanical factors may have contributed to the material loss, but other data suggest that some metal species reacted irreversibly with the reverse phase column. 3 refs., 2 figs., 4 tabs.« less

PNacPNacE: (E = Ga, In, Tl) - monomeric group 13 metal(i) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide.

PubMed

Sindlinger, Christian P; Lawrence, Samuel R; Acharya, Shravan; Ohlin, C André; Stasch, Andreas

2017-12-12

The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L - = HC(Ph 2 P[double bond, length as m-dash]NDip) 2 - , Dip = 2,6- i Pr 2 C 6 H 3 ; M = Li, Na, K) with "GaI", InBr or TlBr afforded the monomeric group 13 metal(i) complexes LE:, E = Ga (1), In (2) and Tl (3) in moderate yields, and small quantities of LGaI 2 4 in the case of Ga, respectively. The molecular structures of LE: 1-3 from X-ray single crystal diffraction show them to contain puckered six-membered rings with N,N'-chelating methanide ligands and two-coordinated metal(i) centres. Reduction reactions of LAlI 2 5, prepared by iodination of LAlMe 2 , were not successful and no aluminium(i) congener could be prepared so far. DFT studies on LE:, E = Al-Tl, were carried out and support the formulation as an anionic, N,N'-chelating methanide ligand coordinating to group 13 metal(i) cations. The HOMOs of the molecules for E = Al-In show a dominant contribution from a metal-based lone pair that is high in s-character.

Spectroscopic evidence of 3-hydroxyflavone sorption within MFI type zeolites: ESIPT and metal complexation.

PubMed

Moissette, A; Hureau, M; Kokaislova, A; Le Person, A; Cornard, J P; De Waele, I; Batonneau-Gener, I

2015-10-21

Due to its chemical and photochemical properties and potential applications in numerous domains as a molecular probe, 3-hydroxyflavone (3HF) is a molecule of high interest. In particular, the processes of intramolecular proton transfer in the excited state and metallic complexation are known to be dependent on the chemical environment. In this context, the particular properties of zeolites make these microporous materials an environment adapted to study the reactivity of isolated molecules adsorbed in their porous void space. Thus, this report investigates the incorporation without any solvent of 3HF into the internal volume of various channel-type MFI zeolites. Using complementary techniques (diffuse reflectance UV-vis absorption, Raman scattering, FTIR, fluorescence emission and molecular modelling), very different spectral behaviours are observed in totally dealuminated silicalite-1 and in Al rich MZSM-5 (M = H(+), Na(+), Zn(2+)). In silicalite-1, the non-polar and non-protic internal micro-environment does not induce any valuable interaction between 3HF and the channel walls. Therefore, the molecule shows easy tautomer formation upon excitation. Within HZSM-5, 3HF is adsorbed in close proximity of the acid proton of the zeolite which inhibits the intramolecular proton transfer and then, only the normal form is observed at the excited state. For NaZSM-5, the spectral data show an intermediary behaviour due to the aprotic but polar environment, in agreement with 3HF sorption in close proximity of the Na(+) extra framework cation. After mixing 3HF and ZnZSM-5, the spectral features clearly indicate metallic complexation of the guest molecule. The zeolite dependent reactivity reported here demonstrates the adsorption of the guest within the internal volume because the charge balancing cations which clearly control the reaction are principally located in the zeolite channels. The 3HF incorporation into the internal volume is proved by the decrease of the microporous volume observed by nitrogen adsorption-desorption isotherm measurements. The experimental data are confirmed by Monte Carlo molecular modelling which also predicts 3HF sorption in the zeolite channels in the proximity of charge compensating cations. Consequently, as the molecule dimensions are assumed to be slightly larger than the channel size, the flexibility of the molecule and the lattice deformation have to be considered to allow 3HF penetration into the zeolite void space.

Cd(II) and Pb(II) complexes of the polyether ionophorous antibiotic salinomycin

PubMed Central

2011-01-01

Background The natural polyether ionophorous antibiotics are used for the treatment of coccidiosis in poultry and ruminants. They are effective agents against infections caused by Gram-positive microorganisms. On the other hand, it was found that some of these compounds selectively bind lead(II) ions in in vivo experiments, despite so far no Pb(II)-containing compounds of defined composition have been isolated and characterized. To assess the potential of polyether ionophores as possible antidotes in the agriculture, a detailed study on their in vitro complexation with toxic metal ions is required. In the present paper we report for the first time the preparation and the structure elucidation of salinomycin complexes with ions of cadmium(II) and lead(II). Results New metal(II) complexes of the polyether ionophorous antibiotic salinomycin with Cd(II) and Pb(II) ions were prepared and structurally characterized by IR, FAB-MS and NMR techniques. The spectroscopic information and elemental analysis data reveal that sodium salinomycin (SalNa) undergoes a reaction with heavy metal(II) ions to form [Cd(Sal)2(H2O)2] (1) and [Pb(Sal)(NO3)] (2), respectively. Abstraction of sodium ions from the cavity of the antibiotic is occurring during the complexation reaction. Salinomycin coordinates with cadmium(II) ions as a bidentate monoanionic ligand through the deprotonated carboxylic moiety and one of the hydroxyl groups to yield 1. Two salinomycin anions occupy the equatorial plane of the Cd(II) center, while two water molecules take the axial positions of the inner coordination sphere of the metal(II) cation. Complex 2 consists of monoanionic salinomycin acting in polydentate coordination mode in a molar ratio of 1: 1 to the metal ion with one nitrate ion for charge compensation. Conclusion The formation of the salinomycin heavy metal(II) complexes indicates a possible antidote activity of the ligand in case of chronic/acute intoxications likely to occur in the stock farming. PMID:21906282

Versatile nature of hetero-chitosan based derivatives as biodegradable adsorbent for heavy metal ions; a review.

PubMed

Ahmad, Mudasir; Manzoor, Kaiser; Ikram, Saiqa

2017-12-01

The polyfunctional chitosan can act as the biological macromolecule ligand not only for the adsorption and the recovery of metal ions from an aqueous media, but also for the fabrication of novel adsorbents which shows selectivity and better adsorption properties. The unmodified chitosan itself, a single cationic polysaccharide, has hydroxyl and amine groups carrying complex properties with the metal ions. In addition, the selectivity of metal ions, the adsorption efficiency and adsorption capacity of the adsorbent can be modified chemically. This review covers the synthetic strategies of chitosan towards the synthesis of hetero-chitosan based adsorbents via chemical modifications in past two decades. It also includes how chemical modification influences the metal adsorption with N, O, S and P containing chitosan derivatives. Hope this review article provides an opportunity for researchers in the future to explore the potential of chitosan as an adsorbent for removal of metal ions from wastewater. Copyright © 2017 Elsevier B.V. All rights reserved.

Structure and Bonding analysis of the cationic electrophilic phosphinidene complexes of iron, ruthenium, and osmium [(η(5)-C5Me5)(CO)2M{PN(i)Pr2}]+, [(η(5)-C5H5)(CO)2M{PNR2}]+ (R = Me, (i)Pr), and [(η(5)-C5H5)(PMe3)2M{PNMe2}]+ (M = Fe, Ru, Os).

PubMed

Pandey, Krishna K; Tiwari, Pradeep; Patidar, Pankaj

2012-11-29

Quantum-chemical DFT calculations for the electronic, molecular structure and M-PNR(2) bonding analyses of the experimentally known cationic electrophilic phosphinidene complexes [(η(5)-C(5)Me(5))(CO)(2)M{PN(i)Pr(2)}](+) and of the model complexes [(η(5)-C(5)H(5))(CO)(2)M{PNR(2)}](+) (R = (i)Pr, Me) and [(η(5)-C(5)H(5))(PMe(3))(2)M{PNMe(2)}](+) were carried out using BP86/TZ2P/ZORA level of theory. The calculated geometrical parameters of the studied complexes are in good agreement with the reported experimental values. The short M-P bond distances and calculated Pauling bond orders (range of 1.23-1.68), suggest the presence of M-P multiple bond characters. The Hirshfeld charge analysis shows that the overall charge flows from phosphinidene ligand to metal fragment. The M-P σ-bonding orbitals are well-occupied (>1.80e). The energy decomposition analysis revealed that the contribution of the electrostatic interaction ΔE(elstat) is, in all studied complexes, significantly larger (55.2-62.6%) than the orbital interactions ΔE(orb). The orbital interactions between metal and PNR(2) in [(η(5)-C(5)H(5))(L)(2)M{PNR(2)}](+) arise mainly from M ← PNR(2) σ-donation. The π-bonding contribution (19-36%) is much smaller than the σ-bonding. The interaction energies, as well as bond dissociation energies, depend on the auxiliary ligand framework around the metal and decrease in the order (η(5)-C(5)H(5)) > (η(5)-C(5)Me(5)) and CO > PMe(3). Upon substitution of R = (i)Pr with smaller group R = Me, the M-PNR(2) bond strength slightly decreases.

Adsorption studies of heavy metal ions on mesoporous aluminosilicate, novel cation exchanger.

PubMed

Sepehrian, H; Ahmadi, S J; Waqif-Husain, S; Faghihian, H; Alighanbari, H

2010-04-15

Mesoporous aluminosilicates, have been prepared with various mole ratios of Si/Al and Cethyltrimethylammonium bromide (CTAB). They have been characterized by XRD, nitrogen adsorption/desorption measurements, FT-IR and thermogravimetry. Adsorption behavior of heavy metal ions on this adsorbent have been studied and discussed. The results show that incorporation of aluminum ions in the framework of the mesoporous MCM-41 has transformed it into an effective cation exchanger. The K(d) values of several metal ions have been increased. Separation of Sr(II)-Ce(III), Sr(II)-U(VI) and Cd(II)-Ce(III) has been developed on columns of this novel mesoporous cation exchanger. 2009 Elsevier B.V. All rights reserved.

EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides

PubMed Central

Bencivenni, Giorgio; Cesari, Riccardo; Nanni, Daniele; El Mkami, Hassane

2010-01-01

Summary The reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium, gallium and indium trichlorides with phenyl azides containing a variety of substituents. Analysis of the spectra showed that 4-methoxy-, 3-methoxy- and 2-methoxyphenyl azides all gave ‘dimer’ radical cations [ArNHC6H4NH2]+• and trimers [ArNHC6H4NHC6H4NH2]+• followed by polymers. 4-Azidobenzonitrile, with its electron-withdrawing substituent, did not react. In general the aromatic azides appeared to react most rapidly with AlCl3 but this reagent tended to generate much polymer. InCl3 was the least reactive group 13 halide. DFT computations of the radical cations provided corroborating evidence and suggested that the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposed. PMID:21049080

Effects of Ca, Cu, Al and La on pectin gel strength: implications for plant cell walls.

PubMed

McKenna, Brigid A; Nicholson, Timothy M; Wehr, J Bernhard; Menzies, Neal W

2010-06-16

Rheology of Ca-pectate gels is widely studied, but the behaviour of pectate gels formed by Cu, Al and La is largely unknown. It is well known that gel strength increases with increasing Ca concentration, and it is hypothesised that this would also be the case for other cations. Pectins are a critical component of plant cell walls, imparting various physicochemical properties. Furthermore, the mechanism of metal toxicity in plants is hypothesised to be, in the short term, related to metal interactions with cell wall pectin. This study investigated the influence of Ca, Cu, Al and La ion concentrations at pH 4 on the storage modulus as a function of frequency for metal-pectin gels prepared from pectin (1%) with a degree of esterification of 30%. Gels were formed in situ over 6d in metal chloride solution adjusted daily to pH 4. Cation concentration was varied to develop a relationship between gel strength and cation concentration. At similar levels of cation saturation, gel strength increased in the order of La

Sorption of chlorophenols on microporous minerals: mechanism and influence of metal cations, solution pH, and humic acid.

PubMed

Yang, Hui; Hu, Yuanan; Cheng, Hefa

2016-10-01

Sorption of 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) on a range of dealuminated zeolites were investigated to understand the mechanism of their sorption on microporous minerals, while the influence of common metal cations, solution pH, and humic acid was also studied. Sorption of chlorophenols was found to increase with the hydrophobicity of the sorbates and that of the microporous minerals, indicating the important role of hydrophobic interactions, while sorption was also stronger in the micropores of narrower sizes because of greater enhancement of the dispersion interactions. The presence of metal cations could enhance chlorophenol sorption due to the additional electrostatic attraction between metal cations exchanged into the mineral micropores and the chlorophenolates, and this effect was apparent on the mineral sorbent with a high density of surface cations (2.62 sites/nm(2)) in its micropores. Under circum-neutral or acidic conditions, neutral chlorophenol molecules adsorbed into the hydrophobic micropores through displacing the "loosely bound" water molecules, while their sorption was negligible under moderately alkaline conditions due to electrostatic repulsion between the negatively charged zeolite framework and anionic chlorophenolates. The influence of humic acid on sorption of chlorophenols on dealuminated Y zeolites suggests that its molecules did not block the micropores but created a secondary sorption sites by forming a "coating layer" on the external surface of the zeolites. These mechanistic insights could help better understand the interactions of ionizable chlorophenols and metal cations in mineral micropores and guide the selection and design of reusable microporous mineral sorbents for sorptive removal of chlorophenols from aqueous stream.

Yarrowia lipolytica possesses two plasma membrane alkali metal cation/H+ antiporters with different functions in cell physiology.

PubMed

Papouskova, Klara; Sychrova, Hana

2006-04-03

The family of Nha antiporters mediating the efflux of alkali metal cations in exchange for protons across the plasma membrane is conserved in all yeast species. Yarrowia lipolytica is a dimorphic yeast, phylogenetically very distant from the model yeast Saccharomyces cerevisiae. A search in its sequenced genome revealed two genes (designated as YlNHA1 and YlNHA2) with homology to the S. cerevisiae NHA1 gene, which encodes a plasma membrane alkali metal cation/H+ antiporter. Upon heterologous expression of both YlNHA genes in S. cerevisiae, we showed that Y. lipolytica antiporters differ not only in length and sequence, but also in their affinity for individual substrates. While the YlNha1 protein mainly increased cell tolerance to potassium, YlNha2p displayed a remarkable transport capacity for sodium. Thus, Y. lipolytica is the first example of a yeast species with two plasma membrane alkali metal cation/H+ antiporters differing in their putative functions in cell physiology; cell detoxification vs. the maintenance of stable intracellular pH, potassium content and cell volume.

Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes

PubMed Central

Devaraj, A.; Gu, M.; Colby, R.; Yan, P.; Wang, C. M.; Zheng, J. M.; Xiao, J.; Genc, A.; Zhang, J. G.; Belharouak, I.; Wang, D.; Amine, K.; Thevuthasan, S.

2015-01-01

The distribution of cations in Li-ion battery cathodes as a function of cycling is a pivotal characteristic of battery performance. The transition metal cation distribution has been shown to affect cathode performance; however, Li is notoriously challenging to characterize with typical imaging techniques. Here laser-assisted atom probe tomography (APT) is used to map the three-dimensional distribution of Li at a sub-nanometre spatial resolution and correlate it with the distribution of the transition metal cations (M) and the oxygen. As-fabricated layered Li1.2Ni0.2Mn0.6O2 is shown to have Li-rich Li2MO3 phase regions and Li-depleted Li(Ni0.5Mn0.5)O2 regions. Cycled material has an overall loss of Li in addition to Ni-, Mn- and Li-rich regions. Spinel LiNi0.5Mn1.5O4 is shown to have a uniform distribution of all cations. APT results were compared to energy dispersive spectroscopy mapping with a scanning transmission electron microscope to confirm the transition metal cation distribution. PMID:26272722

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

PubMed

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

2017-01-01

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

Inhibition of palm oil oxidation by zeolite nanocrystals.

PubMed

Tan, Kok-Hou; Awala, Hussein; Mukti, Rino R; Wong, Ka-Lun; Rigaud, Baptiste; Ling, Tau Chuan; Aleksandrov, Hristiyan A; Koleva, Iskra Z; Vayssilov, Georgi N; Mintova, Svetlana; Ng, Eng-Poh

2015-05-13

The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species.

Properties of complexes formed by Na(+), Mg(2+), and Fe(2+) binding with benzene molecules.

PubMed

Kolakkandy, Sujitha; Pratihar, Subha; Aquino, Adelia J A; Wang, Hai; Hase, William L

2014-10-09

A theoretical investigation was performed to study cation-π interactions in complexes of benzene (Bz) with cations, that is, M(z+)(Bz)n for M(z+) = Na(+), Mg(2+), Fe(2+) and n = 1-3, using MP2 theory with the 6-31+G* and 6-311++G** basis sets and the DFT/(B3LYP and B3LYP-D)/6-311++G** methods. Binding energies and structures of the complexes are reported. The splitting between the quintet and single states of the Fe(2+) complexes was found to depend on the number of benzene molecules in the complex and the complex's structure. All of the M(z+)(Bz) complexes prefer a half-sandwich geometry. A geometry with the cation sandwiched between the two benzene rings was found for the M(z+)(Bz)2 complexes, with the benzene rings either in an eclipsed or staggered conformation. An approximate cyclic structure, with the cation at its center, was found for three benzene molecules interacting with the cation. The cation-benzene binding energy is substantial and equal to 22, 108, and 151 kcal/mol for the Na(+)(Bz), Mg(2+)(Bz), and Fe(2+)(Bz) complexes, respectively. The strength of the interaction of the cation with an individual benzene molecule decreases as the number of benzene molecules bound to the cation increases; for example, it is 108 kcal/mol for Mg(2+)(Bz), but only 71 kcal/mol for Mg(2+)(Bz)3. There is a range of values for the M(z+)(Bz)n intermolecular vibrational frequencies; for example, they are ∼230-360 and ∼10-330 cm(-1) for the Mg(2+)(Bz) and Mg(2+)(Bz)3 complexes, respectively. Binding of the cation to benzene both red and blue shifts the benzene vibrational frequencies. This shifting is larger for the Mg(2+) and Fe(2+) complexes, as compared to those for Na(+), as a result of the former's stronger cation-benzene binding. The present study is an initial step to understand the possible importance of cation-π interactions for polycyclic aromatic hydrocarbon aggregation processes during soot formation.

Study of the adsorption of Cd and Zn onto an activated carbon: Influence of pH, cation concentration, and adsorbent concentration

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

Seco, A.; Marzal, P.; Gabaldon, C.

1999-06-01

The single adsorption of Cd and Zn from aqueous solutions has been investigated on Scharlau Ca 346 granular activated carbon in a wide range of experimental conditions: pH, metal concentration, and carbon concentration. The results showed the efficiency of the activated carbon as sorbent for both metals. Metal removals increase on raising the pH and carbon concentration, and decrease on raising the initial metal concentration. The adsorption processes have been modeled using the surface complex formation (SCF) Triple Layer Model (TLM). The adsorbent TLM parameters were determined. Modeling has been performed assuming a single surface bidentate species or an overallmore » surface species with fractional stoichiometry. The bidentate stoichiometry successfully predicted cadmium and zinc removals in all the experimental conditions. The Freundlich isotherm has been also checked.« less

Synthesis, magnetic, spectral, and antimicrobial studies of Cu(II), Ni(II) Co(II), Fe(III), and UO 2(II) complexes of a new Schiff base hydrazone derived from 7-chloro-4-hydrazinoquinoline

NASA Astrophysics Data System (ADS)

El-Behery, Mostafa; El-Twigry, Haifaa

2007-01-01

A new hydrazone ligand, HL, was prepared by the reaction of 7-chloro-4-hydrazinoquinoline with o-hydroxybenzaldehyde. The ligand behaves as monoprotic bidentate. This was accounted for as the ligand contains a phenolic group and its hydrogen atom is reluctant to be replaced by a metal ion. The ligand reacted with Cu(II), Ni(II), Co(II), Fe(III), and UO 2(II) ions to yield mononuclear complexes. In the case of Fe(III) ion two complexes, mono- and binuclear complexes, were obtained in the absence and presence of LiOH, respectively. Also, mixed ligand complexes were obtained from the reaction of the metal cations Cu(II), Ni(II) and Fe(III) with the ligand (HL) and 8-hydroxyquinoline (8-OHqu) in the presence of LiOH, in the molar ratio 1:1:1:1. It is clear that 8-OHqu behaves as monoprotic bidentate ligand in such mixed ligand complexes. The ligand, HL, and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass, and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square-planar geometry, while Ni(II) mixed complex has also formed a tetrahedral configuration and UO 2(II) complex which formed a favorable pentagonal biprymidial geometry. Magnetic moment of the binuclear Fe(III) complex is quite low compared to calculated value for two iron ions complex and thus shows antiferromagnetic interactions between the two adjacent ferric ions. The HL and metal complexes were tested against one stain Gram positive bacteria ( Staphylococcus aureus), Gram negative bacteria ( Escherichia coli), and fungi ( Candida albicans). The tested compounds exhibited higher antibacterial acivities.

Iodide Ion Pairing with Highly Charged Ruthenium Polypyridyl Cations in CH3CN.

PubMed

Swords, Wesley B; Li, Guocan; Meyer, Gerald J

2015-05-04

A series of three highly charged cationic ruthenium(II) polypyridyl complexes of the general formula [Ru(deeb)3-x(tmam)x](PF6)2x+2, where deeb is 4,4'-diethyl ester-2,2'-bipyridine and tmam is 4,4'-bis[(trimethylamino)methyl]-2,2'-bipyridine, were synthesized and characterized and are referred to as 1, 2, or 3 based on the number of tmam ligands. Crystals suitable for X-ray crystallography were obtained for the homoleptic complex 3, which was found to possess D3 symmetry over the entire ruthenium complex. The complexes displayed visible absorption spectra typical of metal-to-ligand charge-transfer (MLCT) transitions. In acetonitrile, quasi-reversible waves were assigned to Ru(III/II) electron transfer, with formal reduction potentials that shifted negative as the number of tmam ligands was increased. Room temperature photoluminescence was observed in acetonitrile with quantum yields of ϕ ∼ 0.1 and lifetimes of τ ∼ 2 μs. The spectroscopic and electrochemical data were most consistent with excited-state localization on the deeb ligand for 1 and 2 and on the tmam ligand for 3. The addition of tetrabutylammonium iodide to the complexes dissolved in a CH3CN solution led to changes in the UV-vis absorption spectra consistent with ion pairing. A Benesi-Hildebrand-type analysis of these data revealed equilibrium constants that increased with the cationic charge 1 < 2 < 3 with K = 4000, 4400, and 7000 M(-1). (1)H NMR studies in CD3CN also revealed evidence for iodide ion pairs and indicated that they occur predominantly with iodide localization near the tmam ligand(s). The diastereotopic H atoms on the methylene carbon that link the amine to the bipyridine ring were uniquely sensitive to the presence of iodide; analysis revealed that an iodide "binding pocket" exists wherein iodide forms an adduct with the 3 and 3' bipyridyl H atoms and the quaternized amine. The MLCT excited states were efficiently quenched by iodide. Time-resolved photoluminescence measurements of 1 revealed a static component consistent with rapid electron transfer from iodide in the "binding pocket" to the Ru metal center in the excited state, ket > 10(8) s(-1). The possible relevance of this work to solar energy conversion and dye-sensitized solar cells is discussed.

New coordination polymers from 1D chain, 2D layer to 3D framework constructed from 1,2-phenylenediacetic acid and 1,3-bis(4-pyridyl)propane flexible ligands

NASA Astrophysics Data System (ADS)

Xin, Ling-Yun; Liu, Guang-Zhen; Wang, Li-Ya

2011-06-01

The hydrothermal reactions of Cd, Zn, or Cu(II) acetate salts with H 2PHDA and BPP flexible ligands afford three new coordination polymers, including [Cd(PHDA)(BPP)(H 2O)] n(1), [Zn(PHDA)(BPP)] n(2), and [Cu 2(PHDA) 2(BPP)] n(3) (H 2PHDA=1,2-phenylenediacetic acid, BPP=1,3-bis(4-pyridyl)propane). The single-crystal X-ray diffractions reveal that all three complexes feature various metal carboxylate subunits extended further by the BPP ligands to form a diverse range of structures, displaying a remarked structural sensitivity to metal(II) cation. Complex 1 containing PHDA-bridged binuclear cadmium generates 1D double-stranded chain, complex 2 results in 2D→2D interpenetrated (4,4) grids, and complex 3 displays a 3D self-penetrated framework with 4 86 68 rob topology. In addition, fluorescent analyses show that both 1 and 2 exhibit intense blue-violet photoluminescence in the solid state.

Study of the reaction of tungsten carbide in molten alkali metal nitrates. Syntheses of divalent (s and d blocks) metal tungstates

NASA Astrophysics Data System (ADS)

Deloume, Jean-Pierre; Marote, Pedro; Sigala, Catherine; Matei, Cristian

2003-08-01

WC is tested as precursor to synthesize metal tungstates by reaction in molten alkali metal nitrates. This constitutes a complex redox system with two reducing agents, W and C, and an oxidizer having several oxidation states. The mass loss due to the evolution of gases reveals the reaction steps. The infrared analyses of the gas phase show what kind of reaction develops according to the temperature. WC produces a water-soluble alkali metal tungstate. The reaction of a mixture of WC and a divalent metal chloride (Mg, Ca, Ba, Ni, Cu, Zn) leads to water-insoluble metal tungstates. As the reactivity of the cations increases in the order Zn, Ni, Cu, the reaction of WC is modified by their presence. The physico-chemical characterizations of the products show that some of them are contaminated either by WC or by metal oxide. Some others are rather pure products. These differences, in relationship with the other analyses, allow to propose first reaction pathways of the tungsten carbide in molten salts.

Raman spectroscopy of DNA-metal complexes. II. The thermal denaturation of DNA in the presence of Sr2+, Ba2+, Mg2+, Ca2+, Mn2+, Co2+, Ni2+, and Cd2+.

PubMed

Duguid, J G; Bloomfield, V A; Benevides, J M; Thomas, G J

1995-12-01

Differential scanning calorimetry, laser Raman spectroscopy, optical densitometry, and pH potentiometry have been used to investigate DNA melting profiles in the presence of the chloride salts of Ba2+, Sr2+, Mg2+, Ca2+, Mn2+, Co2+, Ni2+, and Cd2+. Metal-DNA interactions have been observed for the molar ratio [M2+]/[PO2-] = 0.6 in aqueous solutions containing 5% by weight of 160 bp mononucleosomal calf thymus DNA. All of the alkaline earth metals, plus Mn2+, elevate the melting temperature of DNA (Tm > 75.5 degrees C), whereas the transition metals Co2+, Ni2+, and Cd2+ lower Tm. Calorimetric (delta Hcal) and van't Hoff (delta HVH) enthalpies of melting range from 6.2-8.7 kcal/mol bp and 75.6-188.6 kcal/mol cooperative unit, respectively, and entropies from 17.5 to 24.7 cal/K mol bp. The average number of base pairs in a cooperative melting unit () varied from 11.3 to 28.1. No dichotomy was observed between alkaline earth and transition DNA-metal complexes for any of the thermodynamic parameters other than their effects on Tm. These results complement Raman difference spectra, which reveal decreases in backbone order, base unstacking, distortion of glycosyl torsion angles, and rupture of hydrogen bonds, which occur after thermal denaturation. Raman difference spectroscopy shows that transition metals interact with the N7 atom of guanine in duplex DNA. A broader range of interaction sites with single-stranded DNA includes ionic phosphates, the N1 and N7 atoms of purines, and the N3 atom of pyrimidines. For alkaline earth metals, very little interaction was observed with duplex DNA, whereas spectra of single-stranded complexes are very similar to those of melted DNA without metal. However, difference spectra reveal some metal-specific perturbations at 1092 cm-1 (nPO2-), 1258 cm-1 (dC, dA), and 1668 cm-1 (nC==O, dNH2 dT, dG, dC). Increased spectral intensity could also be observed near 1335 cm-1 (dA, dG) for CaDNA. Optical densitometry, employed to detect DNA aggregation, reveals increased turbidity during the melting transition for all divalent DNA-metal complexes, except SrDNA and BaDNA. Turbidity was not observed for DNA in the absence of metal. A correlation was made between DNA melting, aggregation, and the ratio of Raman intensities I1335/I1374. At room temperature, DNA-metal interactions result in a pH drop of 1.2-2.2 units for alkaline earths and more than 2.5 units for transition metals. Sr2+, Ba2+, and Mg2+ cause protonated sites on the DNA to become thermally labile. These results lead to a model that describes DNA aggregation and denaturation during heating in the presence of divalent metal cations; 1) The cations initially interact with the DNA at phosphate and/or base sites, resulting in proton displacement. 2) A combination of metal-base interactions and heating disrupts the base pairing within the DNA duplex. This allows divalent metals and protons to bind to additional sites on the DNA bases during the aggregation/melting process. 3) Strands whose bases have swung open upon disruption are linked to neighboring strands by metal ion bridges. 4) Near the midpoint of the melting transition, thermal energy breaks up the aggregate. We have no evidence to indicate whether metal ion cross-bridges or direct base-base interactions rupture first. 5) Finally, all cross-links break, resulting in single-stranded DNA complexed with metal ions.

Diverse reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) towards alkali metal, group 9 metal, and coinage metal precursors† †Electronic supplementary information (ESI) available: Experimental and calculation details, and crystallographic information for 2, 3, 4, 6, 8. CCDC 1038665, 1038666, 1038667, 1011534, and 1011533. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00404g Click here for additional data file. Click here for additional data file.

PubMed Central

Kong, Lingbing; Ganguly, Rakesh; Li, Yongxin

2015-01-01

The reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) 1 towards metal precursors and its coordination chemistry were comprehensively studied. While the boron center in 1 is reluctant to coordinate to the alkali metals in their trifluoromethanesulfonate salts (MOTf) (M = Li, Na, K), the unprecedented compound 2 containing two L2PhB: units linked by a cyclic Li(OTf)2Li spacer was obtained from the reaction of 1 with LiOTf. Treatment of 1 with group 9 metal complexes [MCl(COD)]2 (M = Rh, Ir) afforded the first zwitterionic rhodium(i)–boronium complex 3 and the iridium(iii)–borane complex 4, respectively. The reaction pathway may involve C–H activation followed by proton migration from the metals to the boron center, demonstrating the first example of the deprotonation of metal hydrides by a basic boron. In the reactions with coinage metals, 1 could act as a two-electron reducing agent towards the metal chlorides MCl (M = Cu, Ag, Au). Meanwhile, the reaction of 1 with gold chloride supported by a N-heterocyclic carbene (NHC) produced a heteroleptic cationic gold complex [(L2PhB)Au(NHC)]Cl (6) featuring both carbene and L2PhB: ligands on the gold atom. In contrast, an isolable gold chloride complex (L2PhB)AuCl (8) was obtained by direct complexation between 1 and triphenylphosphine-gold chloride via ligand exchange. X-ray diffraction analysis and computational studies revealed the nature of the B:→Au bonding interaction in complexes 6 and 8. Natural Population Analysis (NPA) and Natural Bond Orbital (NBO) analysis support the strong σ-donating property of the L2PhB: ligand. Moreover, preliminary studies showed that complex 8 can serve as an efficient precatalyst for the addition of X–H (X = N, O, C) to alkynes under ambient conditions, demonstrating the first application of a metal complex featuring a neutral boron-based ligand in catalysis. PMID:29308167

[2.2.2]Paracyclophane as a receptor for the cesium cation in the gas phase

NASA Astrophysics Data System (ADS)

Makrlík, Emanuel; Sýkora, David; Böhm, Stanislav; Vaňura, Petr

2017-10-01

By using electrospray ionisation mass spectrometry, it was proven experimentally that the cesium cation (Cs+) forms with [2.2.2]paracyclophane (C24H24) the cationic complex [Cs(C24H24)]+. Further, applying quantum chemical calculations, the most probable structure of the [Cs(C24H24)]+ complex was derived. In the resulting complex with a symmetry very close to C3, the 'central' cation Cs+, fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is bound to all three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered cation-π complex [Cs(C24H24)]+ was found to be -73.2 kJ/mol, confirming the formation of this fascinating complex species as well. This means that [2.2.2]paracyclophane can be considered as a receptor for the Cs+ cation in the gas phase.

Sterically Hindered Chiral Organometallic Complexes: AN X-Ray Crystallographic, NMR Spectroscopic and Ehmo Study.

NASA Astrophysics Data System (ADS)

Malisza, Krisztina Laura

Sterically crowded organometallic complexes present fascinating problems of structure and molecular dynamics. Tetrahedral clusters such as (RCequivCR ^')rm(C_5H_5)_2M _2(CO)_4, where M = Mo or W, crystallize in conformations possessing three terminal carbonyls while the fourth is semi-bridging. However, these ligands undergo a rapid exchange process which can be followed by variable -temperature NMR spectroscopy. When the R substituent is derived from a chiral natural product, the low temperature NMR spectra reveal the presence of diastereomers which are interconvertible via rotations of the organometallic vertices. The fluxional behaviour of tetrahedral clusters containing such vertices as Co(CO)_3, Fe(CO)_3 or rm(C_5H _5)Mo(CO)_2 can be rationalized by means of molecular orbital calculations at the extended Huckel level of approximation. These studies show that the barriers to vertex rotation can usually be traced to one principal orbital interaction in each case. However, in rm(C_5H_5)_2Mo_2(CO) _4(R-CequivC-R) clusters, the barriers are primarily steric in character. The ability of transition metal clusters to delocalize electronic charge is well known and, in principle, could be used to stabilize intermediates of biochemical significance. Treatment of 2-methylcyclopentanone with an alkyne anion was carried out in order to generate 1-alkynyl-2-methylcyclopentanols in which the methyl and alkynyl groups are trans diaxial; the aim was to mimic the "D"-ring of the steroidal contraceptive mestranol. In fact, the major epimer was the one in which the methyl and alkynyl substituents were disposed in a cis manner. The conformation of 2-methyl-1-phenylethynylcyclopentanol 47 was elucidated by two-dimensional NMR techniques. Moreover, the structure of 47 and also of its rm Co _2(CO)_6 derivative have been determined crystallographically. Protonation of the dicobalt or dimolybdenum complexes of 47 lead to stable cations; treatment of these cations with nucleophiles results in elimination of water to yield 2-methylcyclopentene derivatives of which the dimolybdenum cluster has been characterized by x-ray crystallography. The sterically crowded complexes rm(C _6H_5)_3SiOH[ Cr(CO)_3 ]_{n}, where n = 1,2,3, have also been characterized X-ray crystallographically and all three have propellor-type geometries. The question of whether the phenyl ring rotations are correlated has been studied by variable-temperature NMR spectroscopy. These systems do not yield stable silicenium cations, but the analogous Cr(CO)_3 complex of triphenylcarbinol not only shows fluxional behaviour but also yields a metal -stabilized cation. The pathway for phenyl rotations in such systems can be followed via a Dunitz-type trajectory approach in which a number of x-ray structures were analyzed.

Charge transfer complexes of metal-free phthalocyanine radical anions with decamethylmetallocenium cations: (Cp*2Co+)(H2Pc˙-)·solvent and (Cp*2Cr+)(H2Pc˙-)·4C6H4Cl2.

PubMed

Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2017-03-14

Charge transfer complexes (Cp* 2 Co + )(H 2 Pc˙ - )·0.5C 6 H 4 Cl 2 ·0.7C 6 H 5 CN·0.3C 6 H 14 (1) and (Cp* 2 Cr + )(H 2 Pc˙ - )·4C 6 H 4 Cl 2 (2) have been obtained as single crystals. Both complexes contain metal-free phthalocyanine (Pc) radical anions and decamethylmetallocenium cations. Reduction of the Pc macrocycle leads to the appearance of new bands at 1026-1030 nm in the NIR range and blue shifts of both Soret and Q-bands of H 2 Pc in the spectra of 1 and 2. The geometry of the Pc macrocycles supports the formation of H 2 Pc˙ - by the alternation of shorter and longer C-N(imine) bonds in the macrocycles in 2. Complex 1 contains pairs of H 2 Pc˙ - having effective π-π interactions with two sandwiched Cp* 2 Co + cations, whereas complex 2 contains stacks composed of alternating Cp* 2 Cr + and H 2 Pc˙ - ions. The magnetic moment of 1 is 1.64 μ B at 300 K due to the contribution of the H 2 Pc˙ - spins with the S = 1/2 state and diamagnetism of Cp* 2 Co + . This is supported by the observation of a narrow EPR signal of 1 with g = 2.0032-2.0036 characteristic of H 2 Pc˙ - . Strong antiferromagnetic coupling of spins with a Weiss temperature of -23 K is observed between H 2 Pc˙ - in 1. This coupling is probably mediated by the Cp* 2 Co + cations. The magnetic moment of 2 is 4.18 μ B at 300 K indicating the contribution of both paramagnetic H 2 Pc˙ - (S = 1/2) and Cp* 2 Cr + (S = 3/2) species. In spite of the presence of stacks of alternating ions in 2, only weak magnetic coupling is observed with a Weiss temperature of -4 K most probably due to ineffective π-π interactions between Cp* 2 Cr + and H 2 Pc˙ - . The EPR spectrum of 2 contains an asymmetric signal attributed to Cr III (g 1 = 3.9059-3.9220) and a narrow Lorentzian signal from H 2 Pc˙ - with g 2 = 1.9943-1.9961. In addition to these signals, a broad EPR signal grows in intensity below 80 K with g 4 = 2.1085-2.2438 which can be attributed to both paramagnetic Cp* 2 Cr + and H 2 Pc˙ - species having exchange interactions.

Sequestering ability to Cu2+ of a new bodipy-based dye and its behavior as in vitro fluorescent sensor.

PubMed

Papalia, Teresa; Barattucci, Anna; Barreca, Davide; Bellocco, Ersilia; Bonaccorsi, Paola; Minuti, Lucio; Nicolò, Marco Sebastiano; Temperini, Andrea; Foti, Claudia

2017-02-01

A Bodipy (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) derivative has been conceived and synthesized starting from l-aspartic acid, as a selective turn-off sensor of Cu 2+ ions. Its acid-base properties were determined to study the formation of metal/sensor complex species by titration of solutions each containing a different metal ion, such as Cu 2+ , Ca 2+ , Zn 2+ , Pb 2+ and Hg 2+ and different metal/sensor ratios. The speciation models allowed us to simulate the distribution of the metal/sensor complex species at the normal concentrations of the corresponding metals present in biological fluids. The distribution diagrams, obtained by varying the concentration of sensor 1, clearly indicate that sensor 1 responds selectively to Cu 2+ at micromolar concentrations, even in the presence of other more abundant metal cations Ca 2+ . Finally, we analyzed the cellular uptake of sensor 1 on human erythrocytes and its ability to chelate Cu 2+ in the cellular environment. Results indicate that it crosses the plasmatic membrane and colors the cells of a bright fluorescent red. Exposing the fluorescent cells to Cu 2+ results in a complete cellular photobleaching of the red fluorescence, indicating that sensor 1 is able to detect metal changes in the cytosolic environment. Copyright © 2016 Elsevier Inc. All rights reserved.

Removal of contaminants from landfill leachates by filtration through glauconitic greensands

USGS Publications Warehouse

Spoljaric, N.; Crawford, W.A.

1979-01-01

Passing landfill leachate through glauconitic greensand filters reduces the heavy metal cation content, lessens the unpleasant odor, and diminishes the murkiness of the leachate. The capability of the greensand to trap metal cations is increased by prolonging the contact time between the leachate and the greensand. Flushing the charged greensand filter with water does not cause significant release of cations back into solution, suggesting that polluted greensand might be disposed of at landfill sites without endangering the quality of either ground or surface water. ?? 1979 Springer Verlag New York Inc.

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

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

Wu, Hui, E-mail: huiwu@nist.gov; Zhou, Xiuquan; Rodriguez, Efrain E.

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH{sub 4}·nCN{sub 3}H{sub 5}, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH{sub 4}){sub 2}·6CN{sub 3}H{sub 5} is composed of large complex Mg[CN{sub 3}H{sub 5}]{sub 6}{sup 2+} cations and surrounding BH{sub 4}{sup -} ions, while Ca(BH{sub 4}){sub 2}·2CN{sub 3}H{sub 5} possesses layers of corner-sharing Ca[BH{sub 4}]{sub 4}(CN{sub 3}H{sub 5}){sub 2} octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be releasedmore » from MBH{sub 4}·nCN{sub 3}H{sub 5} (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH{sub 4}){sub 2}·nCN{sub 3}H{sub 5} can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release. - Graphical abstract: A new family of complex hydrides: borohydride guanidinates, was developed with diverse crystal structures and remarkable hydrogen storage properties. - Highlights: • A new family of complex hydrides, borohydride guanidinate complexes, are synthesized. • Their diverse crystal structures are determined using combined characterizations. • These compounds can release ~10 wt% pure H{sub 2} at moderate temperatures. • Dehydrogenation thermodynamics and H{sub 2} purity can be tuned by varying cation species.« less

Metal interferences and their removal prior to the determination of As(T) and As(III) in acid mine waters by hydride generation atomic absorption spectrometry

USGS Publications Warehouse

McCleskey, R. Blaine; Nordstrom, D. Kirk; Ball, James W.

2003-01-01

Hydride generation atomic absorption spectrometry (HGAAS) is a sensitive and selective method for the determination of total arsenic (arsenic(III) plus arsenic(V)) and arsenic(III); however, it is subject to metal interferences for acid mine waters. Sodium borohydride is used to produce arsine gas, but high metal concentrations can suppress arsine production. This report investigates interferences of sixteen metal species including aluminum, antimony(III), antimony(V), cadmium, chromium(III), chromium(IV), cobalt, copper(II), iron(III), iron(II), lead, manganese, nickel, selenium(IV), selenium(VI), and zinc ranging in concentration from 0 to 1,000 milligrams per liter and offers a method for removing interfering metal cations with cation exchange resin. The degree of interference for each metal without cation-exchange on the determination of total arsenic and arsenic(III) was evaluated by spiking synthetic samples containing arsenic(III) and arsenic(V) with the potential interfering metal. Total arsenic recoveries ranged from 92 to 102 percent for all metals tested except antimony(III) and antimony(V) which suppressed arsine formation when the antimony(III)/total arsenic molar ratio exceeded 4 or the antimony(V)/total arsenic molar ratio exceeded 2. Arsenic(III) recoveries for samples spiked with aluminum, chromium(III), cobalt, iron(II), lead, manganese, nickel, selenium(VI), and zinc ranged from 84 to 107 percent over the entire concentration range tested. Low arsenic(III) recoveries occurred when the molar ratios of metals to arsenic(III) were copper greater than 120, iron(III) greater than 70, chromium(VI) greater than 2, cadmium greater than 800, antimony(III) greater than 3, antimony(V) greater than 12, or selenium(IV) greater than 1. Low recoveries result when interfering metals compete for available sodium borohydride, causing incomplete arsine production, or when the interfering metal oxidizes arsenic(III). Separation of interfering metal cations using cation-exchange prior to hydridegeneration permits accurate arsenic(III) determinations in acid mine waters containing high concentrations of interfering metals. Stabilization of the arsenic redox species for as many as 15 months is demonstrated for samples that have been properly filtered and acidified with HCl in the field. The detection limits for the method described in this report are 0.1 micrograms per liter for total arsenic and 0.8 micrograms per liter for arsenic(III).

Research and Technology Development Activities to Address the DOE-EM Environmental Mercury Challenge

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

Pierce, Eric M; Peterson, Mark J

Human activities have altered trace metal distributions globally. This is especially true for the trace metal mercury (Hg), a pervasive global pollutant that can be methylated to form highly toxic methylmercury (MeHg), which bioaccumulates in aquatic food webs, endangering humans and other biota. Currently there are more than 3,000 mercury-contaminated sites identified worldwide and the United Nations Environment Programme has recently highlighted the risk of this contamination to human health [1, 2]. The Oak Ridge Reservation (ORR) represents an example of one of these mercury-contaminated sites. Unlike other contaminants metals, radionuclides, and organic solvents that impact the Department of Energymore » Office of Environmental Management (DOE-EM) cleanup program at the ORR and other DOE sites, mercury has several unique characteristics that make environmental remediation of the Y-12 National Security Complex one of the most formidable challenges ever encountered. These distinctive physicochemical properties for mercury include the following: it is a liquid at ambient temperature and pressure; it is the only metal that biomagnifies; and it is the only contaminant transported as a cation, as a dissolved or gaseous elemental metal (similar to an organic solvent), or as both a cation and a dissolved or gaseous elemental metal under environmental conditions. Because of these complexities, implementing cost effective and sustainable solutions that reduce mercury flux from various primary and secondary contamination sources will require linking basic science understanding and applied research advancements into Oak Ridge Office of Environmental Management s (OREM) cleanup process. Currently, DOE is investing in mercury-related research through a variety of programs, including the Office of Science sponsored Critical Interfaces Science Focus Area, EM headquarters sponsored Applied Field Research Initiative, OREM-sponsored Lower East Fork Poplar Creek (LEFPC) Mercury Technology Development Program, Small Business Innovative Research (SBIR), and EM s Minority Serving Institutions Partnership Program. Collectively, these multi-institutional and multidisciplinary programs are generating new tools, knowledge, and remediation approaches that will enable efficient cleanup of mercury contaminated systems locally and globally. In this talk we will highlight the progress made to date in addressing key knowledge gaps required to solve this watershed-scale conundrum.« less

A smart T(1)-weighted MRI contrast agent for uranyl cations based on a DNAzyme-gadolinium conjugate.

PubMed

Xu, Weichen; Xing, Hang; Lu, Yi

2013-11-07

Rational design of smart MRI contrast agents with high specificity for metal ions remains a challenge. Here, we report a general strategy for the design of smart MRI contrast agents for detecting metal ions based on conjugation of a DNAzyme with a gadolinium complex. The 39E DNAzyme, which has high selectivity for UO2(2+), was conjugated to Gd(III)-DOTA and streptavidin. The binding of UO2(2+) to its 39E DNAzyme resulted in the dissociation of Gd(III)-DOTA from the large streptavidin, leading to a decrease of the T1 correlation time, and a change in the MRI signal.

Cation-induced coagulation of aquatic plant-derived dissolved organic matter: Investigation by EEM-PARAFAC and FT-IR spectroscopy

USDA-ARS?s Scientific Manuscript database

Interaction and coagulation of plant-derived dissolved organic matter (DOM) by metal cations are important biogeochemical processes of organic matter in lake systems. Thus, coagulation and fractionation of plant-derived DOM by di- and tri-valent Ca, Al, and Fe ions were investigated. Metal ion-induc...

Synthesis of phthalide-fused indoline by microwave irradiation and preliminary binding study with metal cations

NASA Astrophysics Data System (ADS)

Ling, Sheryn Wong Shue; Latip, Jalifah; Hassan, Nurul Izzaty; Hasbullah, Siti Aishah

2018-04-01

An efficient and green method of synthesizing phthalide-fused indoline, 3-[(1,3,3-trimethylindolin-2-ylidene)methyl]isobenzofuran-1(3H)-one (3) has been developed by the coupling reaction of 1,3,3-trimethyl-2-methyleneindoline, 1 and phthalaldehydic acid, 2 under solvent-free domestic microwave irradiation. The compound was produced with an excellent yield (98 %) and at a shorter reaction time (5 min) as compared to the conventional method. Compound 3 was fully characterized by analytical and spectral methods. Preliminary binding study of 3 towards different types of metal cations was done by "naked eye" colorimetric detection and UV-vis spectrophotometer. Compound 3 exhibits good selectivity and sensitivity for Sn2+ compared to other metal cations.

Brilliant Sm, Eu, Tb, and Dy Chiral Lanthanide Complexes with Strong Circularly Polarized Luminescence

PubMed Central

Petoud, Stéphane; Muller, Gilles; Moore, Evan G.; Xu, Jide; Sokolnicki, Jurek; Riehl, James P.; Le, Uyen N.; Cohen, Seth M.; Raymond, Kenneth N.

2009-01-01

The synthesis, characterization, and luminescent behavior of trivalent Sm, Eu, Dy, and Tb complexes of two enantiomeric, octadentate, chiral, 2-hydroxyisophthalamide ligands are reported. These complexes are highly luminescent in solution. Functionalization of the achiral parent ligand with a chiral 1-phenylethylamine substituent on the open face of the complex in close proximity to the metal center yields complexes with strong circularly polarized luminescence (CPL) activity. This appears to be the first example of a system utilizing the same ligand architecture to sensitize four different lanthanide cations and display CPL activity. The luminescence dissymmetry factor, glum, recorded for the Eu(III) complex is one of the highest values reported, and this is the first time the CPL effect has been demonstrated for a Sm(III) complex with a chiral ligand. The combination of high luminescence intensity with CPL activity should enable new bioanalytical applications of macromolecules in chiral environments. PMID:17199285

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

NASA Astrophysics Data System (ADS)

Wu, Hui; Zhou, Xiuquan; Rodriguez, Efrain E.; Zhou, Wei; Udovic, Terrence J.; Yildirim, Taner; Rush, John J.

2016-10-01

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH4·nCN3H5, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH4)2·6CN3H5 is composed of large complex Mg[CN3H5]62+ cations and surrounding BH4- ions, while Ca(BH4)2·2CN3H5 possesses layers of corner-sharing Ca[BH4]4(CN3H5)2 octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be released from MBH4·nCN3H5 (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH4)2·nCN3H5 can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release.

Cation-exchanged SAPO-34 for adsorption-based hydrocarbon separations: predictions from dispersion-corrected DFT calculations.

PubMed

Fischer, Michael; Bell, Robert G

2014-10-21

The influence of the nature of the cation on the interaction of the silicoaluminophosphate SAPO-34 with small hydrocarbons (ethane, ethylene, acetylene, propane, propylene) is investigated using periodic density-functional theory calculations including a semi-empirical dispersion correction (DFT-D). Initial calculations are used to evaluate which of the guest-accessible cation sites in the chabazite-type structure is energetically preferred for a set of ten cations, which comprises four alkali metals (Li(+), Na(+), K(+), Rb(+)), three alkaline earth metals (Mg(2+), Ca(2+), Sr(2+)), and three transition metals (Cu(+), Ag(+), Fe(2+)). All eight cations that are likely to be found at the SII site (centre of a six-ring) are then included in the following investigation, which studies the interaction with the hydrocarbon guest molecules. In addition to the interaction energies, some trends and peculiarities regarding the adsorption geometries are analysed, and electron density difference plots obtained from the calculations are used to gain insights into the dominant interaction types. In addition to dispersion interactions, electrostatic and polarisation effects dominate for the main group cations, whereas significant orbital interactions are observed for unsaturated hydrocarbons interacting with transition metal (TM) cations. The differences between the interaction energies obtained for pairs of hydrocarbons of interest (such as ethylene-ethane and propylene-propane) deliver some qualitative insights: if this energy difference is large, it can be expected that the material will exhibit a high selectivity in the adsorption-based separation of alkene-alkane mixtures, which constitutes a problem of considerable industrial relevance. While the calculations show that TM-exchanged SAPO-34 materials are likely to exhibit a very high preference for alkenes over alkanes, the strong interaction may render an application in industrial processes impractical due to the large amount of energy required for regeneration. In this respect, SAPOs exchanged with alkaline earth cations could provide a better balance between selectivity and energy cost of regeneration.

Structural basis for the metal-selective activation of the manganese transport regulator of Bacillus subtilis.

PubMed

Kliegman, Joseph I; Griner, Sarah L; Helmann, John D; Brennan, Richard G; Glasfeld, Arthur

2006-03-21

The manganese transport regulator (MntR) of Bacillus subtilis is activated by Mn(2+) to repress transcription of genes encoding transporters involved in the uptake of manganese. MntR is also strongly activated by cadmium, both in vivo and in vitro, but it is poorly activated by other metal cations, including calcium and zinc. The previously published MntR.Mn(2+) structure revealed a binuclear complex of manganese ions with a metal-metal separation of 3.3 A (herein designated the AB conformer). Analysis of four additional crystal forms of MntR.Mn(2+) reveals that the AB conformer is only observed in monoclinic crystals at 100 K, suggesting that this conformation may be stabilized by crystal packing forces. In contrast, monoclinic crystals analyzed at room temperature (at either pH 6.5 or pH 8.5), and a second hexagonal crystal form (analyzed at 100 K), all reveal the shift of one manganese ion by 2.5 A, thereby leading to a newly identified conformation (the AC conformer) with an internuclear distance of 4.4 A. Significantly, the cadmium and calcium complexes of MntR also contain binuclear complexes with a 4.4 A internuclear separation. In contrast, the zinc complex of MntR contains only one metal ion per subunit, in the A site. Isothermal titration calorimetry confirms the stoichiometry of Mn(2+), Cd(2+), and Zn(2+) binding to MntR. We propose that the specificity of MntR activation is tied to productive binding of metal ions at two sites; the A site appears to act as a selectivity filter, determining whether the B or C site will be occupied and thereby fully activate MntR.

Effects of Cations on Corrosion of Inconel 625 in Molten Chloride Salts

NASA Astrophysics Data System (ADS)

Zhu, Ming; Ma, Hongfang; Wang, Mingjing; Wang, Zhihua; Sharif, Adel

2016-04-01

Hot corrosion of Inconel 625 in sodium chloride, potassium chloride, magnesium chloride, calcium chloride and their mixtures with different compositions is conducted at 900°C to investigate the effects of cations in chloride salts on corrosion behavior of the alloy. XRD, SEM/EDS were used to analyze the compositions, phases, and morphologies of the corrosion products. The results showed that Inconel 625 suffers more severe corrosion in alkaline earth metal chloride molten salts than alkaline metal chloride molten salts. For corrosion in mixture salts, the corrosion rate increased with increasing alkaline earth metal chloride salt content in the mixture. Cations in the chloride molten salts mainly affect the thermal and chemical properties of the salts such as vapor pressure and hydroscopicities, which can affect the basicity of the molten salt. Corrosion of Inconel 625 in alkaline earth metal chloride salts is accelerated with increasing basicity.

DISTINCT ROLES OF β1 MIDAS, ADMIDAS AND LIMBS CATION-BINDING SITES IN LIGAND RECOGNITION BY INTEGRIN α2β1*

PubMed Central

Valdramidou, Dimitra; Humphries, Martin J.; Mould, A. Paul

2012-01-01

Integrin-ligand interactions are regulated in a complex manner by divalent cations, and previous studies have identified ligand-competent, stimulatory, and inhibitory cation-binding sites. In collagen-binding integrins, such as α2β1, ligand recognition takes place exclusively at the α subunit I domain. However, activation of the αI domain depends on its interaction with a structurally similar domain in the β subunit known as the I-like or βI domain. The top face of the βI domain contains three cation-binding sites: the metal-ion dependent adhesion site (MIDAS), the ADMIDAS (adjacent to MIDAS) and LIMBS (ligand-associated metal binding site). The role of these sites in controlling ligand binding to the αI domain has yet to be elucidated. Mutation of the MIDAS or LIMBS completely blocked collagen binding to α2β1; in contrast mutation of the ADMIDAS reduced ligand recognition but this effect could be overcome by the activating mAb TS2/16. Hence, the MIDAS and LIMBS appear to be essential for the interaction between αI and βI whereas occupancy of the ADMIDAS has an allosteric effect on the conformation of βI. An activating mutation in the α2 I domain partially restored ligand binding to the MIDAS and LIMBS mutants. Analysis of the effects of Ca2+, Mg2+ and Mn2+ on ligand binding to these mutants showed that the MIDAS is a ligand-competent site through which Mn2+ stimulates ligand binding, whereas the LIMBS is a stimulatory Ca2+-binding site, occupancy of which increases the affinity of Mg2+ for the MIDAS. PMID:18820259

Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures

PubMed Central

Bogart, Justin A.; Cole, Bren E.; Boreen, Michael A.; Lippincott, Connor A.; Manor, Brian C.; Carroll, Patrick J.; Schelter, Eric J.

2016-01-01

Rare earth (RE) metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare REs. To incentivize recycling, there is a clear need for the development of simple methods for targeted separations of mixtures of RE metal salts. Metal complexes of a tripodal hydroxylaminato ligand, TriNOx3–, featured a size-sensitive aperture formed of its three η2-(N,O) ligand arms. Exposure of cations in the aperture induced a self-associative equilibrium comprising RE(TriNOx)THF and [RE(TriNOx)]2 species. Differences in the equilibrium constants Kdimer for early and late metals enabled simple separations through leaching. Separations were performed on RE1/RE2 mixtures, where RE1 = La–Sm and RE2 = Gd–Lu, with emphasis on Eu/Y separations for potential applications in the recycling of phosphor waste from compact fluorescent light bulbs. Using the leaching method, separations factors approaching 2,000 were obtained for early–late RE combinations. Following solvent optimization, >95% pure samples of Eu were obtained with a 67% recovery for the technologically relevant Eu/Y separation. PMID:27956636

Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures.

PubMed

Bogart, Justin A; Cole, Bren E; Boreen, Michael A; Lippincott, Connor A; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

2016-12-27

Rare earth (RE) metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare REs. To incentivize recycling, there is a clear need for the development of simple methods for targeted separations of mixtures of RE metal salts. Metal complexes of a tripodal hydroxylaminato ligand, TriNOx 3- , featured a size-sensitive aperture formed of its three η 2 -(N,O) ligand arms. Exposure of cations in the aperture induced a self-associative equilibrium comprising RE(TriNOx)THF and [RE(TriNOx)] 2 species. Differences in the equilibrium constants K dimer for early and late metals enabled simple separations through leaching. Separations were performed on RE1/RE2 mixtures, where RE1 = La-Sm and RE2 = Gd-Lu, with emphasis on Eu/Y separations for potential applications in the recycling of phosphor waste from compact fluorescent light bulbs. Using the leaching method, separations factors approaching 2,000 were obtained for early-late RE combinations. Following solvent optimization, >95% pure samples of Eu were obtained with a 67% recovery for the technologically relevant Eu/Y separation.

Mechanisms and dynamics of protonation and lithiation of ferrocene.

PubMed

Sharma, Nishant; Ajay, Jayanth K; Venkatasubbaiah, Krishnan; Lourderaj, Upakarasamy

2015-09-14

By elucidating the mechanism of the simplest electrophilic substitution reaction of ferrocene, it was found that the verification of the protonation reaction has been a difficulty. In the work reported here, ab initio chemical dynamics simulations were performed at B3LYP/DZVP level of theory to understand the atomic level mechanisms of protonation and lithiation of ferrocene. Protonation of ferrocene resulted in the agostic and metal-protonated forms. Trajectory calculations revealed that protonation of ferrocene occurs by exo and endo mechanisms, with exo being the major path. H(+) was found to be mobile and hopped from the Cp ring to the metal center and vice versa after the initial attack on ferrocene, with the metal-complex having a shorter lifetime. These results remove the ambiguity surrounding the mechanism, as proposed in earlier experimental and computational studies. Lithiation of ferrocene resulted in the formation of cation-π and metal-lithiated complexes. Similar to protonation, trajectory results revealed that both exo and endo paths were followed, with the exo path being the major one. In addition, lithiated-ferrocene exhibited planetary motion. The major path (exo) followed in the protonation and lithiation of ferrocene is consistent with the observations in earlier experimental studies for other hard electrophiles.

Bridging the gap between ionic liquids and molten salts: group 1 metal salts of the bistriflamide anion in the gas phase.

PubMed

Leal, João P; da Piedade, Manuel E Minas; Canongia Lopes, José N; Tomaszowska, Alina A; Esperança, José M S S; Rebelo, Luís Paulo N; Seddon, Kenneth R

2009-03-19

Fourier transform ion cyclotron resonance mass spectrometry experiments showed that liquid Group 1 metal salts of the bistriflamide anion undergoing reduced-pressure distillation exhibit a remarkable behavior that is in transition between that of the vapor-liquid equilibrium characteristics of aprotic ionic liquids and that of the Group 1 metal halides: the unperturbed vapors resemble those of aprotic ionic liquids, in the sense that they are essentially composed of discrete ion pairs. However, the formation of large aggregates through a succession of ion-molecule reactions is closer to what might be expected for Group 1 metal halides. Similar experiments were also carried out with bis{(trifluoromethyl)sulfonyl}amine to investigate the effect of H(+), which despite being the smallest Group 1 cation, is generally regarded as a nonmetal species. In this case, instead of the complex ion-molecule reaction pattern found for the vapors of Group 1 metal salts, an equilibrium similar to those observed for aprotic ionic liquids was observed.

Stable powders made from photosensitive polycrystalline complexes of heterocyclic monomers and their polymers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor); Hodko, Dalibor (Inventor)

1999-01-01

The present invention relates to a low electronic conductivity polymer composition having well dispersed metal granules, a stable powder made from photosensitive polycrystalline complexes of pyrrole, or its substituted derivatives and silver cations for making the polymer composition, and methods of forming the stable powder and polymer composition, respectively. A polycrystalline complex of silver and a monomer, such as pyrrole, its substituted derivatives or combinations thereof, is precipitated in the form of a stable photosensitive powder upon addition of the monomer to a solvent solution, such as toluene containing an electron acceptor. The photosensitive powder can be stored in the dark until needed. The powder may be dissolved in a solvent, cast onto a substrate and photopolymerized.

Quantitative and Comprehensive Decomposition of the Ion Atmosphere around Nucleic Acids

PubMed Central

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

2011-01-01

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

Molecular-dynamics simulations of alkaline-earth metal cations in water by atom-bond electronegativity equalization method fused into molecular mechanics.

PubMed

Yang, Zhong-Zhi; Li, Xin

2005-09-01

Intermolecular potential for alkaline-earth metal (Be(2+), Mg(2+), and Ca(2+)) cations in water has been derived using the atom-bond electronegativity equalization method fused into molecular mechanics (ABEEM/MM), and it is consistent with what was previously applied to the hydration study of the monovalent cations. Parameters for the effective interaction between a cation and a water molecule were determined, reproducing the ab initio results. The static, dynamic, and thermodynamic properties of Be(2+)(aq), Mg(2+)(aq), and Ca(2+)(aq) were studied using these potential parameters. Be(2+) requires a more complicated form of the potential function than Mg(2+) and Ca(2+) in order to obtain better fits. Strong influences of the twofold charged cations on the structures of the hydration shells and some other properties of aqueous ionic solutions are discussed and compared with the results of a previous study of monovalent cations in water. At the same time, comparative study of the hydration properties of each cation is also discussed. This work demonstrates that ABEEM/MM provides a useful tool in the exploration of the hydration of double-charged cations in water.

Zeolite A synthesized from alkaline assisted pre-activated halloysite for efficient heavy metal removal in polluted river water and industrial wastewater.

PubMed

Meng, Qingpeng; Chen, Hong; Lin, Junzhong; Lin, Zhang; Sun, Junliang

2017-06-01

High quality zeolite A was synthesized through a hydrothermal process using alkaline-assisted pre-activated halloysite mineral as the alumina and silica source. The synthesis conditions employed in this study were finely tuned by varying the activating temperature, sodium hydroxide content, water content and Si/Al ratio. The obtained zeolite A showed excellent adsorption properties for both single metal cation solutions and mixed cation solutions when the concentrations of the mixed cations were comparable with those in polluted natural river water and industrial wastewater. High adsorptive capacities for Ag + (123.05mg/g) and Pb 2+ (227.70mg/g) were achieved using the synthesized zeolite A. This observation indicates that the zeolite A synthesized from alkaline-assisted pre-activated halloysite can be used as a low-cost and relatively effective adsorbent to purify heavy metal cation polluted natural river water and industrial wastewater. Copyright © 2016. Published by Elsevier B.V.

Insights into dynamic processes of cations in pyrochlores and other complex oxides

DOE PAGES

Uberuaga, Blas Pedro; Perriot, Romain

2015-08-26

Complex oxides are critical components of many key technologies, from solid oxide fuel cells and superionics to inert matrix fuels and nuclear waste forms. In many cases, understanding mass transport is important for predicting performance and, thus, extensive effort has been devoted to understanding mass transport in these materials. However, most work has focused on the behavior of oxygen while cation transport has received relatively little attention, even though cation diffusion is responsible for many phenomena, including sintering, radiation damage evolution, and deformation processes. Here, we use accelerated molecular dynamics simulations to examine the kinetics of cation defects in onemore » class of complex oxides, A₂B₂O₇ pyrochlore. In some pyrochlore chemistries, B cation defects are kinetically unstable, transforming to A cation defects and antisites at rates faster than they can diffuse. When this occurs, transport of B cations occurs through defect processes on the A sublattice. Further, these A cation defects, either interstitials or vacancies, can interact with antisite disorder, reordering the material locally, though this process is much more efficient for interstitials than vacancies. Whether this behavior occurs in a given pyrochlore depends on the A and B chemistry. Pyrochlores with a smaller ratio of cation radii exhibit this complex behavior, while those with larger ratios exhibit direct migration of B interstitials. Similar behavior has been reported in other complex oxides such as spinels and perovskites, suggesting that this coupling of transport between the A and B cation sublattices, while not universal, occurs in many complex oxide.« less

Development of a novel device to trap heavy metal cations: application of the specific interaction between heavy metal cation and mismatch DNA base pair.

PubMed

Torigoe, Hidetaka; Miyakawa, Yukako; Fukushi, Miyako; Ono, Akira; Kozasa, Tetsuo

2009-01-01

We have already found that Hg(II) cation specifically binds to T:T mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving T:T mismatch base pair by about 4 degrees C. We have also found that Ag(I) cation specifically binds to C:C mismatch base pair in heteroduplex DNA, which increases the melting temperature of heteroduplex DNA involving C:C mismatch base pair by about 4 degrees C. Using the specific interaction, we developed a novel device to trap each of Hg(II) and Ag(I) cation. The device is composed of 5'-biotinylated T-rich or C-rich DNA oligonucleotides, BIO-T20: 5'-Bio-T(20)-3' or BIO-C20: 5'-Bio-C(20)-3' (Bio is a biotin), immobilized on streptavidin-coated polystylene beads. When the BIO-T20-immobilized beads were added to a solution containing Hg(II) cation, and the beads trapping Hg(II) cation were collected by centrifugation, almost all of Hg(II) cation were removed from the solution. Also, when the BIO-C20-immobilized beads were added to a solution containing Ag(I) cation, and the beads trapping Ag(I) cation were collected by centrifugation, almost all of Ag(I) cation were removed from the solution. We conclude that, using the novel device developed in this study, Hg(II) and Ag(I) cation can be effectively removed from the solution.

Cationic metal complex, carbonatobis(1,10-phenanthroline)cobalt(III) as anion receptor: Synthesis, characterization, single crystal X-ray structure and packing analysis of [Co(phen) 2CO 3](3,5-dinitrobenzoate)·5H 2O

NASA Astrophysics Data System (ADS)

Sharma, Raj Pal; Singh, Ajnesh; Brandão, Paula; Felix, Vitor; Venugopalan, Paloth

2009-03-01

To explore the potential of [Co(phen) 2CO 3] + as anion receptor, red coloured single crystals of [Co(phen) 2CO 3](dnb)·5H 2O (dnb = 3,5-dinitrobenzoate) were obtained by recrystallizing the red microcrystalline product synthesised by the reaction of carbonatobis (1,10-phenanthroline)cobalt(III)chloride with sodium salt of 3,5-dinitrobenzoic acid in aqueous medium (1:1 molar ratio). The newly synthesized complex salt has been characterized by elemental analysis, spectroscopic studies (IR, UV/visible, 1H and 13C NMR), solubility and conductance measurements. The complex salt crystallizes in the triclinic crystal system with space group P1¯, having the cell dimensions a = 10.3140(8), b = 12.2885(11), c = 12.8747(13), α = 82.095(4), β = 85.617(4), γ = 79.221(4)°, V = 1585.6(2) Å 3, Z = 2. Single crystal X-ray structure determination revealed ionic structure consisting of cationic carbonatobis(1,10-phenanthroline)cobalt(III), dnb anion and five lattice water molecule. In the complex cation [Co(phen) 2CO 3] +, the cobalt(III) is bonded to four nitrogen atoms, originating from two phenanthroline ligands and two oxygen atoms from the bidentate carbonato group showing an octahedral geometry around cobalt(III) center. Supramolecular networks between ionic groups [ CHphen+⋯Xanion-] by second sphere coordination i.e. C sbnd H⋯O (benzoate), C sbnd H⋯O (nitro), C sbnd H⋯O (water) besides electrostatic forces of attraction alongwith π-π interactions stabilize the crystal lattice.

Enhancing tonoplast Cd/H antiport activity increases Cd, Zn, and Mn tolerance, and impacts root/shoot Cd partitioning in Nicotiana tabacum L.

USDA-ARS?s Scientific Manuscript database

Sequestration mechanisms that prevent high concentrations of free metal ions from persisting in metabolically active compartments of cells are thought to be central in tolerance of plants to high levels of divalent cation metals. Expression of "AtCAX2" or "AtCAX4", which encode divalent cation/proto...

Comparison of the One-electron Oxidations of CO-Bridged vs Unbridged Bimetallic Complexes: Electron-transfer Chemistry of Os2Cp2(CO)4 and Os2Cp*2(μ-CO)2(CO)2 (Cp = η5-C5H5, Cp* = η5-C5Me5)

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

Laws, Derek R.; Bullock, R. Morris; Lee, Richmond

The one-electron oxidations of two dimers of half-sandwich osmium carbonyl complexes have been examined by electrochemistry, spectro-electrochemistry, and computational methods. The all-terminal carbonyl complex Os2Cp2(CO)4 (1, Cp = η5-C5H5) undergoes a reversible one-electron anodic reaction at E1/2 = 0.41 V vs ferrocene in CH2Cl2/0.05 M [NBu4][B(C6F5)4], giving a rare example of a metal-metal bonded radical cation unsupported by bridging ligands. The IR spectrum of 1+ is consistent with an approximately 1:1 mixture of anti and gauche structures for the 33 e- radical cation in which it has retained all-terminal bonding of the CO ligands. DFT calculations, including orbital-occupancy-perturbed Mayer bond-ordermore » analyses, show that the HOMOs of anti-1 and gauche-1 are metal-ligand delocalized. Removal of an electron from 1 has very little effect on the Os-Os bond order, accounting for the resistance of 1+ to heterolytic cleavage. The Os-Os bond distance is calculated to decrease by 0.10 Å and 0.06 Å as a consequence of one-electron oxidation of anti-1 and gauche-1, respectively. The CO-bridged complex Os2Cp*2(μ-CO)2(CO)2 (Cp* = η5-C5Me5), trans-2, undergoes a more facile oxidation, E1/2 = - 0.11 V, giving a persistent radical cation shown by solution IR analysis to preserve its bridged-carbonyl structure. However, ESR analysis of frozen solutions of 2+ is interpreted in terms of the presence of two isomers, most likely anti-2+ and trans-2+, at low temperature. Calculations show that the HOMO of trans-2 is highly delocalized over the metal-ligand framework, with the bridging carbonyls accounting for about half of the orbital makeup. The Os-Os bond order again changes very little with removal of an electron, and the Os-Os bond length actually undergoes minor shortening. Calculations suggest that the second isomer of 2+ has both the trans CO-bridged and the anti all-terminal CO structures. DRL and WEG acknowledge the support of the National Science Foundation under grant CHE-0808909. K-WH acknowledges financial support from KAUST. RMB thanks the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences for support. Pacific Northwest National Laboratory is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. We thank Dr. S. I. Gorelsky for the discussion on the OOP analysis.« less

Metal Cations in G-Quadruplex Folding and Stability

NASA Astrophysics Data System (ADS)

Bhattacharyya, Debmalya; Mirihana Arachchilage, Gayan; Basu, Soumitra

2016-09-01

This review is focused on the structural and physico-chemical aspects of metal cation coordination to G-Quadruplexes (GQ) and their effects on GQ stability and conformation. G-Quadruplex structures are non-canonical secondary structures formed by both DNA and RNA. G-quadruplexes regulate a wide range of important biochemical processes. Besides the sequence requirements, the coordination of monovalent cations in the GQ is essential for its formation and determines the stability and polymorphism of GQ structures. The nature, location and dynamics of the cation coordination and their impact on the overall GQ stability are dependent on several factors such as the ionic radii, hydration energy and the bonding strength to the O6 of guanines. The intracellular monovalent cation concentration and the localized ion concentrations determine the formation of GQs and can potentially dictate their regulatory roles. A wide range of biochemical and biophysical studies on an array of GQ enabling sequences have generated at a minimum the knowledge base that allows us to often predict the stability of GQs in presence of the physiologically relevant metal ions, however, prediction of conformation of such GQs is still out of the realm.

Recovery process for electroless plating baths

DOEpatents

Anderson, Roger W.; Neff, Wayne A.

1992-01-01

A process for removing, from spent electroless metal plating bath solutions, accumulated byproducts and counter-ions that have deleterious effects on plating. The solution, or a portion thereof, is passed through a selected cation exchange resin bed in hydrogen form, the resin selected from strong acid cation exchangers and combinations of intermediate acid cation exchangers with strong acid cation exchangers. Sodium and nickel ions are sorbed in the selected cation exchanger, with little removal of other constituents. The remaining solution is subjected to sulfate removal through precipitation of calcium sulfate hemihydrate using, sequentially, CaO and then CaCO.sub.3. Phosphite removal from the solution is accomplished by the addition of MgO to form magnesium phosphite trihydrate. The washed precipitates of these steps can be safely discarded in nontoxic land fills, or used in various chemical industries. Finally, any remaining solution can be concentrated, adjusted for pH, and be ready for reuse. The plating metal can be removed from the exchanger with sulfuric acid or with the filtrate from the magnesium phosphite precipitation forming a sulfate of the plating metal for reuse. The process is illustrated as applied to processing electroless nickel plating baths.

Recovery process for electroless plating baths

DOEpatents

Anderson, R.W.; Neff, W.A.

1992-05-12

A process is described for removing, from spent electroless metal plating bath solutions, accumulated byproducts and counter-ions that have deleterious effects on plating. The solution, or a portion thereof, is passed through a selected cation exchange resin bed in hydrogen form, the resin selected from strong acid cation exchangers and combinations of intermediate acid cation exchangers with strong acid cation exchangers. Sodium and nickel ions are sorbed in the selected cation exchanger, with little removal of other constituents. The remaining solution is subjected to sulfate removal through precipitation of calcium sulfate hemihydrate using, sequentially, CaO and then CaCO[sub 3]. Phosphite removal from the solution is accomplished by the addition of MgO to form magnesium phosphite trihydrate. The washed precipitates of these steps can be safely discarded in nontoxic land fills, or used in various chemical industries. Finally, any remaining solution can be concentrated, adjusted for pH, and be ready for reuse. The plating metal can be removed from the exchanger with sulfuric acid or with the filtrate from the magnesium phosphite precipitation forming a sulfate of the plating metal for reuse. The process is illustrated as applied to processing electroless nickel plating baths. 18 figs.

Metal chalcogenide nanoparticle gel networks: Their formation mechanism and application for novel material generation and heavy metal water remediation via cation exchange reactions

NASA Astrophysics Data System (ADS)

Palhares, Leticia F.

The dissertation research is focused on (1) uncovering the mechanism of metal chalcogenide nanoparticle gel formation; (2) extending the cation exchange reaction protocol to zinc sulfide gel networks, with the goal of accessing new aerogel chemistries and understanding the factors that drive the process; and (3) conducting a quantitative analysis of the ability of ZnS aerogels to remove heavy metal ions from aqueous solutions. The mechanism of metal chalcogenide nanoparticle gel formation was investigated using Raman spectroscopy and X-ray Photoelectron Spectroscopy to probe the chemical changes that occur during the gelation process. These techniques suggest that the bonding between the particles in the CdSe nanoparticle gels is due to the oxidation of surface selenide species, forming covalent Se--Se bonds. Treating the gel networks with a suitable reducing agent, such as a thiol, breaks the covalent bond and disperses the gel network. The addition of sodium borohydride, a "pure" reducing agent, also breaks down the gel network, strengthening the hypothesis that the reducing character of the thiols, not their ligation ability, is responsible for the gel network breakdown. UV-Vis spectroscopy, Transmission Electron Microscopy and Powder X-ray Diffraction were used to analyze the particles after successive gelation-dispersion cycles. The primary particle size decreases after repeated oxidation-reduction cycles, due to nanoparticle surface etching. This trend is observed for CdSe and CdS gel networks, allowing for the proposition that the oxidative-reductive mechanism responsible for the formation-dispersion of the gels is general, applying to other metal chalcogenide nanocrystals as well. The cation exchange reaction previously demonstrated for CdSe gels was extended to ZnS gel networks. The exchange occurs under mild reaction conditions (room temperature, methanol solvent) with exchanging ions of different size, charge and mobility (Ag+, Pb2+, Cd2+ , Cu2+). The overall reaction is kinetically controlled, since systems with similar solubility, and thus similar thermodynamic driving force (e.g. PbS and CdS) exchange at very different rates. A correlation exists between the speed of the reaction and the difference between the reduction potential of the incoming cation and that of Zn2+; the larger the difference, the faster the exchange. At the same time, the porosity of the aerogels and the surfactant-free surfaces hold great importance for the exchange reactions, allowing for exchange between cations of similar size and charge (i.e. Pb2+ for Zn2+), a phenomenon that was previously reported as impossible in ligand-capped metal chalcogenide nanoparticles. These observations allowed for a better understanding of the factors governing the cation exchange reaction in nanoscale metal chalcogenides. Quaternary ZnS-CuInS2 gels were obtained by cation exchange with Cu+ and In3+, but the pure CuInS2 phase was not obtained under the mild reaction conditions used, probably due to the very different mobility of the two exchanging cations. The kinetically fast cation exchange process and the propensity of the soft chalcogenide gel networks to bind heavy metal ions selectively, suggest that these materials could also be suitable for the removal of heavy metal ions from the environment. The dissertation research studied the capacity of ZnS aerogels to sequester heavy metal ions such as Pb2+ and Hg2+ from water. The materials are efficient in removing the heavy metal ions from aqueous solutions with a wide range of initial concentrations. For initial concentrations that mimic an environmental spill (i.e. 100 ppb Pb2+), the treatment with the aerogel affords a final concentration lower than the 15 ppm action level recommended by the EPA. Under thermodynamically forcing conditions, the water remediation capacity of the ZnS nanoparticle aerogels was determined to be 14.2 mmol Pb2+ / g ZnS aerogel, which is the highest value reported to date.

Relevant role of dissolved humic matter in phosphorus bioavailability in natural and agronomical ecosystems through the formation of Humic-(Metal)-Phosphate complexes

NASA Astrophysics Data System (ADS)

Baigorri, Roberto; Urrutia, Óscar; Erro, Javier; Pazos-Pérez, Nicolás; María García-Mina, José

2016-04-01

Natural Organic Matter (NOM) and the NOM fraction present in soil solution (dissolved organic matter: DOM) are currently considered as fundamental actors in soil fertility and crop mineral nutrition. Indeed, decreases in crop yields as well as soil erosion are closely related to low values of NOM and, in fact, the use of organic amendments as both soil improvers and plant growth enhancers is very usual in countries with soils poor in NOM. This role of NOM (and DOM) seems to be associated with the presence of bio-transformed organic molecules (humic substances) with high cation chelating-complexing ability. In fact, bioavailable micronutrients with metallic character in soil solutions of alkaline and calcareous soils are forming stable complexes with DOM. This beneficial action of DOM also concerns other plant nutrients such as inorganic phosphate (Pi). Among the different mechanisms involved in the beneficial action of DOM on P bioavailability, the possible formation of poly-nuclear complexes including stable chemical bonds between negative binding sites in humic substances and Pi through metal bridges in soil solution might be relevant, especially in acidic soils. In fact, several studies have proven that these complexes can be obtained in the laboratory and are very efficient in prevent Pi soil fixation and improve Pi root uptake. However, clear experimental evidence about their presence in soil solutions of natural and agronomical soil ecosystems has not published yet. We present here experimental results supporting the real presence of stable Pi-metal-Humic (PMH) complexes in the soil solution of several acidic soils. The study is based on the physico-chemical characterization (31P-NMR, FTIR, TEM-EDAX, ICP-OES) of the DOM fraction isolated by ultrafiltration from the soil solution of several representative acidic soils. In average, more than 60 % of Pi was found in the soil solution humic fraction forming stable humic-metal (Fe, Al) complexes.

Fourier transform Raman spectroscopic characterisation of cells of the plant-associated soil bacterium Azospirillum brasilense Sp7

NASA Astrophysics Data System (ADS)

Kamnev, A. A.; Tarantilis, P. A.; Antonyuk, L. P.; Bespalova, L. A.; Polissiou, M. G.; Colina, M.; Gardiner, P. H. E.; Ignatov, V. V.

2001-05-01

Structural and compositional features of bacterial cell samples and of lipopolysaccharide-protein complex isolated from the cell surface of the plant-growth-promoting rhizobacterium Azospirillum brasilense (wild-type strain Sp7) were characterised using Fourier transform (FT) Raman spectroscopy. The structural spectroscopic information obtained is analysed and considered together with analytical data on the content of metal cations (Co 2+, Cu 2+ and Zn 2+) in the bacterial cells grown in a standard medium as well as in the presence of each of the cations (0.2 mM). The latter, being taken up by bacterial cells from the culture medium in significant amounts, were shown to induce certain metabolic changes in the bacterium revealed in FT-Raman spectra, which is discussed from the viewpoint of bacterial response to environmental stresses.

Structural and Magnetic Properties of M(mnt)(2) Salts (M = Ni, Pt, Cu) with a Ferrocene-Based Cation, [FcCH(2)N(CH(3))(3)](+). Interplay between M.M and M.S Intermolecular Interactions.

PubMed

Pullen, Anthony E.; Faulmann, Christophe; Pokhodnya, Konstantin I.; Cassoux, Patrick; Tokumoto, Madoka

1998-12-28

A series of metal bis-mnt complexes (mnt = 1,2-dithiolatomaleonitrile) with the trimethylammonium methylferrocene cation have been synthesized and characterized using X-ray diffraction, magnetic susceptibility, and differential scanning calorimetry measurements. The complexes have the formulas (FcCH(2)NMe(3))[Ni(mnt)(2)] (2), (FcCH(2)NMe(3))[Pt(mnt)(2)] (3), and (FcCH(2)NMe(3))(2)[Cu(mnt)(2)] (4) (where Fc = ferrocene). At 300 K, the crystal structures of 1:1 complexes 2 and 3 are very similar. They consist of pairs of [M(mnt)(2)](-) in a slipped configuration packed in stacks. Each [M(mnt)(2)](-) stack is separated from adjacent stacks by two columns of cations. Within the pairs, the [M(mnt)(2)](-) anions interact via short M.S contacts, while there are no short contacts between the pairs. Complex 4, which has a 2:1 stoichiometry, exhibits a markedly different packing arrangement of the anionic units. Due to the special position of the Cu atom in the asymmetric unit cell, [Cu(mnt)(2)](2)(-) dianions are completely isolated from each other. The magnetic susceptibility behavior of the nickel complex is consistent with the presence of magnetically isolated, antiferromagnetically (AF) coupled [Ni(mnt)(2)](-) pairs with the AF exchange parameter, J = -840 cm(-)(1). The platinum complex undergoes an endothermic structural phase transition (T(p)) at 247 K. Below T(p) its structure is characterized by the formation of magnetically isolated [Pt(mnt)(2)](2)(2)(-) dimers in an eclipsed configuration with short Pt.Pt and S.S contacts between monomers. In the magnetic properties, the structural changes reveal themselves as an abrupt susceptibility drop implying a substantial increase of the AF exchange parameter. A mechanism of the phase transition in the platinum compound is proposed. For compound 4, paramagnetic behavior is observed.

Influence of Copper Resistance Determinants on Gold Transformation by Cupriavidus metallidurans Strain CH34

PubMed Central

Wiesemann, Nicole; Mohr, Juliane; Grosse, Cornelia; Herzberg, Martin; Hause, Gerd; Reith, Frank

2013-01-01

Cupriavidus metallidurans is associated with gold grains and may be involved in their formation. Gold(III) complexes influence the transcriptome of C. metallidurans (F. Reith et al., Proc. Natl. Acad. Sci. U. S. A. 106:17757–17762, 2009), leading to the upregulation of genes involved in the detoxification of reactive oxygen species and metal ions. In a systematic study, the involvement of these systems in gold transformation was investigated. Treatment of C. metallidurans cells with Au(I) complexes, which occur in this organism's natural environment, led to the upregulation of genes similar to those observed for treatment with Au(III) complexes. The two indigenous plasmids of C. metallidurans, which harbor several transition metal resistance determinants, were not involved in resistance to Au(I/III) complexes nor in their transformation to metallic nanoparticles. Upregulation of a cupA-lacZ fusion by the MerR-type regulator CupR with increasing Au(III) concentrations indicated the presence of gold ions in the cytoplasm. A hypothesis stating that the Gig system detoxifies gold complexes by the uptake and reduction of Au(III) to Au(I) or Au(0) reminiscent to detoxification of Hg(II) was disproven. ZupT and other secondary uptake systems for transition metal cations influenced Au(III) resistance but not the upregulation of the cupA-lacZ fusion. The two copper-exporting P-type ATPases CupA and CopF were also not essential for gold resistance. The copABCD determinant on chromosome 2, which encodes periplasmic proteins involved in copper resistance, was required for full gold resistance in C. metallidurans. In conclusion, biomineralization of gold particles via the reduction of mobile Au(I/III) complexes in C. metallidurans appears to primarily occur in the periplasmic space via copper-handling systems. PMID:23475973

Structural elucidation, EPR and magnetic property of a Co(III) complex salt incorporating 4,4‧-bipyridine and 5-sulfoisophthalate

NASA Astrophysics Data System (ADS)

Das, Kuheli; Datta, Amitabha; Pevec, Andrej; Mane, Sandeep B.; Rameez, Mohammad; Garribba, Eugenio; Akitsu, Takashiro; Tanka, Shinnosuke

2018-01-01

The cobalt(III) derivative [Co3(sip)4(bipy)2(H2O)10][Co(bipy)2(H2O)4]3(sip)2·20H2O (1) has been hydro(solvo) thermally synthesized by combining sodium 5-sulfoisophthalate (sipH2Na) as organic linker, divalent cobalt nitrate hexahydrate as metal salt and the flexible N-donor ancillary ligand bipy (4,4‧-bipyridine). Compound 1 is an ionic solid consisting of both cobalt containing cations and anions and also in addition 5-sulfoisophthalate anions. Cobalt containing cations in the crystal structure are mononuclear complex while cobalt containing anion is a discrete trinuclear species. The π-π interaction present in 1 results in chain supramolecular structure. The encapsulation of the cobalt compound displays a moderate luminescent property. On temperature dependent magnetic study, it is revealed that the corresponding effective magnetic moment is 5.27 B.M. at 300 K, which suggests isolated Co(III) species with S = 2 (theoretical value is 4.90 B M.) and thus 1 shows a rare paramagnetic behavior.

Syntheses, crystal and band structures, and optical properties of a selenidoantimonate and an iron polyselenide

NASA Astrophysics Data System (ADS)

Liu, Guang-Ning; Zhu, Wen-Juan; Zhang, Ming-Jian; Xu, Bo; Liu, Qi-Sheng; Zhang, Zhen-Wei; Li, Cuncheng

2014-10-01

A new selenidoantimonate (CH3NH4)[Mn(phen)2](SbSe4)·phen (1, phen=1,10-phenanthroline) and an iron polyselenide [Fe(phen)2](Se4) (2) were obtained under hydro(solvo)thermal conditions. Compound 1 represents the first example of a selenidoantimonate anion as a ligand to a transition-metal π-conjugated ligand complex cation. Compound 2 containing a κ2Se1,Se4 chelating tetraselenide ligand, represents the only example of a tetraselenide ligand to a Fe complex cation. Compounds 1 and 2 exhibit optical gaps of 1.71 and 1.20 eV, respectively and their thermal stabilities have been investigated by thermogravimetric analyses. The electronic band structure along with the density of states calculated by the DFT method indicate that the optical absorptions mainly originate from the charge transitions from the Se 4p and Mn 3d states to the phen p-π* orbital for 1 and the Se 4p and Fe 3d states to the phen p-π* orbital for 2.

Malonate-containing manganese(III) complexes: synthesis, crystal structure, and magnetic properties of AsPh4[Mn(mal)2(H2O)2].

PubMed

Delgado, Fernando S; Kerbellec, Nicolas; Ruiz-Pérez, Catalina; Cano, Joan; Lloret, Francesc; Julve, Miguel

2006-02-06

The novel manganese(III) complexes PPh4[Mn(mal)2(H2O)2] (1) and AsPh4[Mn(mal)2(H2O)2] (2) (PPh4+ = tetraphenylphosphonium cation, AsPh4+ = tetraphenylarsonium cation, and H2mal = malonic acid) have been prepared, and the structure of 2 was determined by X-ray diffraction analysis. 2 is a mononuclear complex whose structure is made up of trans-diaquabis(malonato)manganate(III) units and tetraphenylarsonium cations. Two crystallographically independent manganese(III) ions (Mn(1) and Mn(2)) occur in 2 that exhibit elongated octahedral surroundings with four oxygen atoms from two bidentate malonate groups in equatorial positions (Mn(1)-O = 1.923(6) and 1.9328(6) A and Mn(2)-O = 1.894(6) and 1.925(6) A) and two trans-coordinated water molecules in the axial sites (Mn(1)-Ow = 2.245(6) A and Mn(2)-Ow = 2.268(6) A). The [Mn(mal)2(H2O)2]- units are linked through hydrogen bonds involving the free malonate-oxygen atoms and the coordinated water molecules to yield a quasi-square-type anionic layer growing in the ab plane. The shortest intralayer metal-metal separations are 7.1557(7) and 7.1526(7) A (through the edges of the square). The anionic sheets are separated from each other by layers of AsPh4+ where sextuple- and double-phenyl embraces occur. The magnetic behavior of 1 and 2 in the temperature range 1.9-290 K reveals the occurrence of weak intralayer ferromagnetic interactions (J = +0.081(1) (1) and +0.072(2) cm(-1) (2)). These values are compared to those of the weak antiferromagnetic coupling [J = -0.19(1) cm(-1)], which is observed in the chain compound K2[Mn(mal)2(MeOH)2][Mn(mal)2] (3), where the exchange pathway involves the carboxyate-malonate bridge in the anti-syn conformation. The structure of 3 was reported elsewhere. Theoretical calculations on fragment models of 2 and 3 were performed to analyze and substantiate both the nature and magnitude of the magnetic couplings observed.

Cationic cluster formation versus disproportionation of low-valent indium and gallium complexes of 2,2'-bipyridine

PubMed Central

Lichtenthaler, Martin R.; Stahl, Florian; Kratzert, Daniel; Heidinger, Lorenz; Schleicher, Erik; Hamann, Julian; Himmel, Daniel; Weber, Stefan; Krossing, Ingo

2015-01-01

Group 13 MI compounds often disproportionate into M0 and MIII. Here, however, we show that the reaction of the MI salt of the weakly coordinating alkoxyaluminate [GaI(C6H5F)2]+[Al(ORF)4]− (RF=C(CF3)3) with 2,2'-bipyridine (bipy) yields the paramagnetic and distorted octahedral [Ga(bipy)3]2+•{[Al(ORF)4]−}2 complex salt. While the latter appears to be a GaII compound, both, EPR and DFT investigations assign a ligand-centred [GaIII{(bipy)3}•]2+ radical dication. Surprisingly, the application of the heavier homologue [InI(C6H5F)2]+[Al(ORF)4]− leads to aggregation and formation of the homonuclear cationic triangular and rhombic [In3(bipy)6]3+, [In3(bipy)5]3+ and [In4(bipy)6]4+ metal atom clusters. Typically, such clusters are formed under strongly reductive conditions. Analysing the unexpected redox-neutral cationic cluster formation, DFT studies suggest a stepwise formation of the clusters, possibly via their triplet state and further investigations attribute the overall driving force of the reactions to the strong In−In bonds and the high lattice enthalpies of the resultant ligand stabilized [M3]3+{[Al(ORF)4]−}3 and [M4]4+{[Al(ORF)4]−}4 salts. PMID:26478464

FRET study of G-quadruplex forming fluorescent oligonucleotide probes at the lipid monolayer interface.

PubMed

Swiatkowska, Angelika; Kosman, Joanna; Juskowiak, Bernard

2016-01-05

Spectral properties and G-quadruplex folding ability of fluorescent oligonucleotide probes at the cationic dioctadecyldimethylammonium bromide (DODAB) monolayer interface are reported. Two oligonucleotides, a 19-mer bearing thrombin binding aptamer sequence and a 21-mer with human telomeric sequence, were end-labeled with fluorescent groups (FAM and TAMRA) to give FRET probes F19T and F21T, respectively. The probes exhibited abilities to fold into a quadruplex structure and to bind metal cations (Na(+) and K(+)). Fluorescence spectra of G-quadruplex FRET probes at the monolayer interface are reported for the first time. Investigations included film balance measurements (π-A isotherms) and fluorescence spectra recording using a fiber optic accessory interfaced with a spectrofluorimeter. The effect of the presence of DODAB monolayer, metal cations and the surface pressure of monolayer on spectral behavior of FRET probes were examined. Adsorption of probe at the cationic monolayer interface resulted in the FRET signal enhancement even in the absence of metal cations. Variation in the monolayer surface pressure exerted rather modest effect on the spectral properties of probes. The fluorescence energy transfer efficiency of monolayer adsorbed probes increased significantly in the presence of sodium or potassium ion in subphase, which indicated that the probes retained their cation binding properties when adsorbed at the monolayer interface. Copyright © 2015 Elsevier B.V. All rights reserved.

Physical characteristics of lanthanide complexes that act as magnetization transfer (MT) contrast agents

NASA Astrophysics Data System (ADS)

Zhang, Shanrong; Sherry, A. Dean

2003-02-01

Rapid water exchange is normally considered a prerequisite for efficient Gd3+-based MRI contrast agents. Yet recent measures of exchange rates in some Gd3+ complexes have shown that water exchange can become limiting when such complexes are attached to larger macromolecular structures. A new class of lanthanide complexes that display unusually slow water exchange (bound water lifetimes (τM298) > 10 μs) has recently been reported. This apparent disadvantage may be taken advantage of by switching the metal ion from gadolinium(III) to a lanthanide that shifts the bound water resonance substantially away from bulk water. Given appropriate water exchange kinetics, one can then alter the intensity of the bulk water signal by selective presaturation of this highly shifted, Ln3+-bound water resonance. This provides the basis of a new method to alter MR image contrast in tissue. We have synthesized a variety of DOTA-tetra(amide) ligands to evaluate as potential magnetization transfer (MT) contrast agents and found that the bound water lifetimes in these complexes are sensitive to both ligand structure (a series of Eu3+ complexes have τM298 values that range from 1 to 1300 μs) and the identity of the paramagnetic Ln3+ cation (from 3 to 800 μs for a single ligand). This demonstrates that it may be possible either to fine-tune the ligand structure or to select proper lanthanide cation to create an optimal MT agent for any clinical imaging field.

Selectivity of externally facing ion-binding sites in the Na/K pump to alkali metals and organic cations

PubMed Central

Ratheal, Ian M.; Virgin, Gail K.; Yu, Haibo; Roux, Benoît; Gatto, Craig; Artigas, Pablo

2010-01-01

The Na/K pump is a P-type ATPase that exchanges three intracellular Na+ ions for two extracellular K+ ions through the plasmalemma of nearly all animal cells. The mechanisms involved in cation selection by the pump's ion-binding sites (site I and site II bind either Na+ or K+; site III binds only Na+) are poorly understood. We studied cation selectivity by outward-facing sites (high K+ affinity) of Na/K pumps expressed in Xenopus oocytes, under voltage clamp. Guanidinium+, methylguanidinium+, and aminoguanidinium+ produced two phenomena possibly reflecting actions at site III: (i) voltage-dependent inhibition (VDI) of outwardly directed pump current at saturating K+, and (ii) induction of pump-mediated, guanidinium-derivative–carried inward current at negative potentials without Na+ and K+. In contrast, formamidinium+ and acetamidinium+ induced K+-like outward currents. Measurement of ouabain-sensitive ATPase activity and radiolabeled cation uptake confirmed that these cations are external K+ congeners. Molecular dynamics simulations indicate that bound organic cations induce minor distortion of the binding sites. Among tested metals, only Li+ induced Na+-like VDI, whereas all metals tested except Na+ induced K+-like outward currents. Pump-mediated K+-like organic cation transport challenges the concept of rigid structural models in which ion specificity at site I and site II arises from a precise and unique arrangement of coordinating ligands. Furthermore, actions by guanidinium+ derivatives suggest that Na+ binds to site III in a hydrated form and that the inward current observed without external Na+ and K+ represents cation transport when normal occlusion at sites I and II is impaired. These results provide insights on external ion selectivity at the three binding sites. PMID:20937860

C-1s NEXAFS spectroscopy reveals chemical fractionation of humic acid by cation-induced coagulation

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

Christl,I.; Kretzschmar, R.

2007-01-01

The influence of cation-induced coagulation on the chemical composition of dissolved and coagulated fractions of humic acid was investigated in batch coagulation experiments for additions of aluminum at pH 4 and 5, iron at pH 4, and calcium and lead at pH 6. The partitioning of organic carbon and metals was determined by analyzing total organic carbon and total metal contents of the dissolved phase. Both the dissolved and the coagulated humic acid fractions were characterized using synchrotron scanning transmission X-ray microscopy (STXM) and C-1s near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Intensities of {pi}* transitions of carboxyl carbon andmore » {sigma}* transitions of alkyl, O-alkyl, and carboxyl carbon decreased with increasing metal concentration for the dissolved humic acid fractions. This decrease was accompanied by an increase of the respective intensities in the coagulated fraction as shown for lead. Intensities of aromatic and phenolic carbon were affected to a larger extent only by aluminum and iron additions. The changes observed in the C-1s NEXAFS spectra coincided with an increasing removal of organic carbon from the dissolved phase with increasing total metal concentrations. We conclude that humic acid was chemically fractionated by cation-induced coagulation, which preferentially removed functional groups involved in metal-cation binding from solution.« less

Citrate mediated synthesis and tuning of luminescence in Eu3+ incorporated Gd2O3 nanophosphors

NASA Astrophysics Data System (ADS)

Abhilash Kumar, R. G.; Gopchandran, K. G.

2015-02-01

Gd1.9Eu0.1O3 nanophosphors were prepared successfully by a large-scale facile solution based citrate-metal complex controlled combustion method and was systematically studied by varying the citric acid to metal cation ratio. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) measurements and radiative properties were done to evaluate the crystal structure, phase formation, phase composition, surface morphology, radiative and luminescent properties of the prepared nanophosphors. Photoluminescent emission intensity of the samples can be correlated with the amount of citric acid, improved crystallinity, uniform morphology, particle size, reduced defects, and proper diffusion of Eu3+ in to the crystal structure of Gd2O3. Higher asymmetricity results in intense red emission (612 nm) due to 5D0-7F2 forced electric dipole transition and found that photoluminescence intensity is highest for the sample prepared with citric acid to metal cation ratio of 2:1. The existence of strong red emission from Gd1.9Eu0.1O3 nanophosphor corresponding to 5D0-7F2 transition (612 nm) of Eu3+ under UV light excitation make it a promising candidate for applications in bio assays, magnetic resonance imaging, deep uv LED's, solid state lighting, fluorescent lamps and flat panel displays.

Synthesis, characterization and extraction studies of some metal (II) complexes containing (hydrazoneoxime and bis-acylhydrazone) moieties

NASA Astrophysics Data System (ADS)

Al-Ne'aimi, Mohammed Mahmmod; Al-Khuder, Mohammed Moudar

2013-03-01

In this study, diacetylmonoximebenzoylhydrazone (L1H2) and 1,4-diacetylbenzene bis(benzoyl hydrazone) (L2H2) were synthesized by the condensation of benzohydrazide with diacetyl monoxime and 1,4-diacetylbenzene, respectively. Complexes of these ligands with Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) inos were prepared with a metal:ligand ratio of 1:2 for L1H2 ligand, and 1:1 for L2H2 ligand. The ligands and their complexes were elucidated on the basis of elemental analyses CHN, AAS, FT-IR, 1H- and 13C NMR spectra, UV-vis spectra and magnetic susceptibility measurements. Results show the L1H2 ligand act as monoanionic O,N,N-tridentate and coordination takes place in the enol form through the oxime nitrogen, the imine nitrogen and the enolate oxygen atoms with a N4O2 donor environment, while the L2H2 ligand act as a dianionic O,N,N,O-tetradentate and coordination takes place in the enol form through the enolate oxygen and the azomethine nitrogen atoms with a N2O2 donor environment. These results are consistent with the formation of mononuclear metal (II) complexes [M(L1H)2], and binuclear polymeric metal (II) complexes [{M2(L2)}n]. The extraction ability of both ligands were examined in chloroform by the liquid-liquid extraction of selected transition metal [Co2+, Ni2+, Cu2+, Zn2+ and Pb2+] cations. The effects of pH and contact time on the percentage extraction of metal (II) ions were studied under the optimum extraction conditions. The (L1H2) ligand shows strong binding ability toward copper(II) and lead(II) ions, while the (L2H2) ligand shows strong binding ability toward nickel(II) and zinc(II) ions.

Synthesis, characterization and extraction studies of some metal (II) complexes containing (hydrazoneoxime and bis-acylhydrazone) moieties.

PubMed

Al-Ne'aimi, Mohammed Mahmmod; Al-Khuder, Mohammed Moudar

2013-03-15

In this study, diacetylmonoximebenzoylhydrazone (L(1)H(2)) and 1,4-diacetylbenzene bis(benzoyl hydrazone) (L(2)H(2)) were synthesized by the condensation of benzohydrazide with diacetyl monoxime and 1,4-diacetylbenzene, respectively. Complexes of these ligands with Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) inos were prepared with a metal:ligand ratio of 1:2 for L(1)H(2) ligand, and 1:1 for L(2)H(2) ligand. The ligands and their complexes were elucidated on the basis of elemental analyses CHN, AAS, FT-IR, (1)H- and (13)C NMR spectra, UV-vis spectra and magnetic susceptibility measurements. Results show the L(1)H(2) ligand act as monoanionic O,N,N-tridentate and coordination takes place in the enol form through the oxime nitrogen, the imine nitrogen and the enolate oxygen atoms with a N(4)O(2) donor environment, while the L(2)H(2) ligand act as a dianionic O,N,N,O-tetradentate and coordination takes place in the enol form through the enolate oxygen and the azomethine nitrogen atoms with a N(2)O(2) donor environment. These results are consistent with the formation of mononuclear metal (II) complexes [M(L(1)H)(2)], and binuclear polymeric metal (II) complexes [{M(2)(L(2))}(n)]. The extraction ability of both ligands were examined in chloroform by the liquid-liquid extraction of selected transition metal [Co(2+), Ni(2+), Cu(2+), Zn(2+) and Pb(2+)] cations. The effects of pH and contact time on the percentage extraction of metal (II) ions were studied under the optimum extraction conditions. The (L(1)H(2)) ligand shows strong binding ability toward copper(II) and lead(II) ions, while the (L(2)H(2)) ligand shows strong binding ability toward nickel(II) and zinc(II) ions. Copyright © 2012 Elsevier B.V. All rights reserved.

X-ray crystal structure of divalent metal-activated ß-xyloisdase, RS223BX

USDA-ARS?s Scientific Manuscript database

We report the first X-ray structure of a glycoside hydrolase family 43 ß-xylosidase, RS223BX, which is strongly activated by the addition of divalent metal cations. The 2.69 Å structure reveals that the Ca2+ cation is located at the back of the active site pocket. The Ca2+ coordinates to H274 to sta...

Electrostatically driven resonance energy transfer in “cationic” biocompatible indium phosphide quantum dots† †Electronic supplementary information (ESI) available: Detailed experimental methods, the synthesis and characterization of QDs, bioimaging, stability studies, control experiments, and the calculation of various parameters involved in the resonance energy transfer process etc. See DOI: 10.1039/c7sc00592j Click here for additional data file.

PubMed Central

Devatha, Gayathri; Roy, Soumendu; Rao, Anish; Mallick, Abhik; Basu, Sudipta

2017-01-01

Indium Phosphide Quantum Dots (InP QDs) have emerged as an alternative to toxic metal ion based QDs in nanobiotechnology. The ability to generate cationic surface charge, without compromising stability and biocompatibility, is essential in realizing the full potential of InP QDs in biological applications. We have addressed this challenge by developing a place exchange protocol for the preparation of cationic InP/ZnS QDs. The quaternary ammonium group provides the much required permanent positive charge and stability to InP/ZnS QDs in biofluids. The two important properties of QDs, namely bioimaging and light induced resonance energy transfer, are successfully demonstrated in cationic InP/ZnS QDs. The low cytotoxicity and stable photoluminescence of cationic InP/ZnS QDs inside cells make them ideal candidates as optical probes for cellular imaging. An efficient resonance energy transfer (E ∼ 60%) is observed, under physiological conditions, between the cationic InP/ZnS QD donor and anionic dye acceptor. A large bimolecular quenching constant along with a linear Stern–Volmer plot confirms the formation of a strong ground state complex between the cationic InP/ZnS QDs and the anionic dye. Control experiments prove the role of electrostatic attraction in driving the light induced interactions, which can rightfully form the basis for future nano-bio studies between cationic InP/ZnS QDs and anionic biomolecules. PMID:28626557

Synthesis, Properties, and Light-Emitting Electrochemical Cell (LEEC) Device Fabrication of Cationic Ir(III) Complexes Bearing Electron-Withdrawing Groups on the Cyclometallating Ligands

PubMed Central

2016-01-01

The structure–property relationship study of a series of cationic Ir(III) complexes in the form of [Ir(C^N)2(dtBubpy)]PF6 [where dtBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine and C^N = cyclometallating ligand bearing an electron-withdrawing group (EWG) at C4 of the phenyl substituent, i.e., −CF3 (1), −OCF3 (2), −SCF3 (3), −SO2CF3 (4)] has been investigated. The physical and optoelectronic properties of the four complexes were comprehensively characterized, including by X-ray diffraction analysis. All the complexes exhibit quasireversible dtBubpy-based reductions from −1.29 to −1.34 V (vs SCE). The oxidation processes are likewise quasireversible (metal + C^N ligand) and are between 1.54 and 1.72 V (vs SCE). The relative oxidation potentials follow a general trend associated with the Hammett parameter (σ) of the EWGs. Surprisingly, complex 4 bearing the strongest EWG does not adhere to the expected Hammett behavior and was found to exhibit red-shifted absorption and emission maxima. Nevertheless, the concept of introducing EWGs was found to be generally useful in blue-shifting the emission maxima of the complexes (λem = 484–545 nm) compared to that of the prototype complex [Ir(ppy)2(dtBubpy)]PF6 (where ppy = 2-phenylpyridinato) (λem = 591 nm). The complexes were found to be bright emitters in solution at room temperature (ΦPL = 45–66%) with microsecond excited-state lifetimes (τe = 1.14–4.28 μs). The photophysical properties along with density functional theory (DFT) calculations suggest that the emission of these complexes originates from mixed contributions from ligand-centered (LC) transitions and mixed metal-to-ligand and ligand-to-ligand charge transfer (LLCT/MLCT) transitions, depending on the EWG. In complexes 1, 3, and 4 the 3LC character is prominent over the mixed 3CT character, while in complex 2, the mixed 3CT character is much more pronounced, as demonstrated by DFT calculations and the observed positive solvatochromism effect. Due to the quasireversible nature of the oxidation and reduction waves, fabrication of light-emitting electrochemical cells (LEECs) using these complexes as emitters was possible with the LEECs showing moderate efficiencies. PMID:27681985

Water insoluble and soluble lipids for gene delivery.

PubMed

Mahato, Ram I

2005-04-05

Among various synthetic gene carriers currently in use, liposomes composed of cationic lipids and co-lipids remain the most efficient transfection reagents. Physicochemical properties of lipid/plasmid complexes, such as cationic lipid structure, cationic lipid to co-lipid ratio, charge ratio, particle size and zeta potential have significant influence on gene expression and biodistribution. However, most cationic lipids are toxic and cationic liposomes/plasmid complexes do not disperse well inside the target tissues because of their large particle size. To overcome the problems associated with cationic lipids, we designed water soluble lipopolymers for gene delivery to various cells and tissues. This review provides a critical discussion on how the components of water insoluble and soluble lipids affect their transfection efficiency and biodistribution of lipid/plasmid complexes.

Synthesis and SMM behaviour of trinuclear versus dinuclear 3d-5f uranyl(v)-cobalt(ii) cation-cation complexes.

PubMed

Chatelain, Lucile; Tuna, Floriana; Pécaut, Jacques; Mazzanti, Marinella

2017-05-02

Trinuclear versus dinuclear heterodimetallic U V O 2 + Co 2+ complexes were selectively assembled via a cation-cation interaction by tuning the ligand. The trimeric complex 2, with a linear [Co-O[double bond, length as m-dash]U[double bond, length as m-dash]O-Co] core, exhibits magnetic exchange and slow relaxation with a reversal barrier of 30.5 ± 0.9 K providing the first example of a U-Co exchange-coupled SMM.

Design of Nickel-Based Cation-Disordered Rock-Salt Oxides: The Effect of Transition Metal (M = V, Ti, Zr) Substitution in LiNi0.5M0.5O2 Binary Systems.

PubMed

Cambaz, Musa Ali; Vinayan, Bhaghavathi P; Euchner, Holger; Johnsen, Rune E; Guda, Alexander A; Mazilkin, Andrey; Rusalev, Yury V; Trigub, Alexander L; Gross, Axel; Fichtner, Maximilian

2018-06-20

Cation-disordered oxides have been ignored as positive electrode material for a long time due to structurally limited lithium insertion/extraction capabilities. In this work, a case study is carried out on nickel-based cation-disordered Fm3 ̅m LiNi 0.5 M 0.5 O 2 positive electrode materials. The present investigation targets tailoring the electrochemical properties for nickel-based cation-disordered rock-salt by electronic considerations. The compositional space for binary LiM +3 O 2 with metals active for +3/+4 redox couples is extended to ternary oxides with LiA 0.5 B 0.5 O 2 with A = Ni 2+ and B = Ti 4+ , Zr 4+ , and V +4 to assess the impact of the different transition metals in the isostructural oxides. The direct synthesis of various new unknown ternary nickel-based Fm3̅ m cation-disordered rock-salt positive electrode materials is presented with a particular focus on the LiNi 0.5 V 0.5 O 2 system. This positive electrode material for Li-ion batteries displays an average voltage of ∼2.55 V and a high discharge capacity of 264 mAhg -1 corresponding to 0.94 Li. For appropriate cutoff voltages, a long cycle life is achieved. The charge compensation mechanism is probed by XANES, confirming the reversible oxidation and reduction of V 4+ /V 5+ . The enhancement in the electrochemical performances within the presented compounds stresses the importance of mixed cation-disordered transition metal oxides with different electronic configuration.

Adsorption of tetracycline on Fe (hydr)oxides: effects of pH and metal cation (Cu2+, Zn2+ and Al3+) addition in various molar ratios

PubMed Central

Hsu, Liang-Ching; Liu, Yu-Ting; Syu, Chien-Hui; Huang, Mei-Hsia; Teah, Heng Yi

2018-01-01

Iron (Fe) (hydr)oxides control the mobility and bioavailability of tetracycline (TC) in waters and soils. Adsorption of TC on Fe (hydr)oxides is greatly affected by polyvalent metals; however, impacts of molar metal/TC ratios on TC adsorptive behaviours on Fe (hydr)oxides remain unclear. Results showed that maximum TC adsorption on ferrihydrite and goethite occurred at pH 5–6. Such TC adsorption was generally promoted by the addition of Cu2+, Zn2+ and Al3+. The greatest increase in TC adsorption was found in the system with molar Cu/TC ratio of 3 due to the formation of Fe hydr(oxide)–Cu–TC ternary complexes. Functional groups on TC that were responsible for the complexation with Cu2+shifted from phenolic diketone groups at Cu/TC molar ratio < 1 to amide groups at Cu/TC molar ratio ≥ 1. For the addition of Al3+, the complexation only took place with phenolic diketone groups, resulting in the enhanced TC adsorption at a molar Al/TC ratio of 1. However, TC adsorption decreased for Al/TC molar ratio > 1 as excess Al3+ led to the competitive adsorption with Al/TC complexes. For the Zn2+ addition, no significant correlation was found between TC adsorption capacity and molar Zn/TC ratios. PMID:29657795

Predictions of diagenetic reactions in the presence of organic acids

NASA Astrophysics Data System (ADS)

Harrison, Wendy J.; Thyne, Geoffrey D.

1992-02-01

Stability constants have been estimated for cation complexes with anions of monofunctional and difunctional acids (combinations of Ca, Mg, Fe, Al, Sr, Mn, U, Th, Pb, Cu, Zn with formate, acetate, propionate, oxalate, malonate, succinate, and salicylate) between 0 and 200°C. Difunctional acid anions form much more stable complexes than monofunctional acid anions with aluminum; the importance of the aluminum-acetate complex is relatively minor in comparison to aluminum oxalate and malonate complexes. Divalent metal cations such as Mg, Ca, and Fe form more stable complexes with acetate than with difunctional acid anions. Aluminum-oxalate can dominate the species distribution of aluminum under acidic pH conditions, whereas the divalent cation-acetate and oxalate complexes rarely account for more than 60% of the total dissolved cation, and then only in more alkaline waters. Mineral thermodynamic affinities were calculated using the reaction path model EQ3/6 for waters having variable organic acid anion (OAA) contents under conditions representative of those found during normal burial diagenesis. The following scenarios are possible: 1) K-feldspar and albite are stable, anorthite dissolves 2) All feldpars are stable 3) Carbonates can be very unstable to slightly unstable, but never increase in stability. Organic acid anions are ineffective at neutral to alkaline pH in modifying stabilities of aluminosilicate minerals whereas the anions are variably effective under a wide range of pH in modifying carbonate mineral stabilities. Reaction path calculations demonstrate that the sequence of mineral reactions occurring in an arkosic sandstone-fluid system is only slightly modified by the presence of OAA. A spectrum of possible sandstone alteration mineralogies can be obtained depending on the selected boundary conditions: EQ3/6 predictions include quartz overgrowth, calcite replacement of plagioclase, albitization of plagioclase, and the formation of porosity-occluding calcite cement, smectite, and illite, all of which are commonly documented in rocks. Under some circumstances, OAA-bearing waters are less effective at producing porosity in an arkosic sandstone than are OAA-free waters. In the scenarios modeled in this study the role of OAA in fluid-rock interactions is to contribute to the total alteration assemblage but not necessarily to dominate it, except under exceptional circumstances that might include, for example, hydrocarbon contaminant plumes in aquifers, wetland environments, and within hydrocarbon source-rocks.

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex.

PubMed

Aly, Shawkat M; Goswami, Subhadip; Alsulami, Qana A; Schanze, Kirk S; Mohammed, Omar F

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

Structural, energetic, spectroscopic and QTAIM analyses of cation-π interactions involving mono- and bi-cyclic ring fused benzene systems.

PubMed

Hassan, Ayorinde; Dinadayalane, Tandabany C; Grabowski, Sławomir J; Leszczynski, Jerzy

2013-12-28

The effect of increasing the number of monocyclic six-membered rings or bicyclic rings of bicyclo[2.1.1]hexenyl fused to benzene on cation-π interactions involving alkali metal ions (Li(+), Na(+), and K(+)) has been investigated. The binding energy data at the B3LYP/6-311+G(2d,2p) level clearly indicate that the binding affinity of the metal ion with benzene is enhanced by increasing the number of rings fused irrespective of a monocyclic or a bicyclic ring. Calculated binding energies are in good agreement with the available experimental results. The binding strength of cations with ligands decreases in the order Li(+) > Na(+) > K(+). Our study establishes that trisannelation of bicyclo[2.1.1]hexene to benzene facilitates a very strong interaction between benzene and cations. Infrared (IR) frequencies and nuclear magnetic resonance (NMR) chemical shifts are shown to be valuable in characterizing cation-π interactions. The C-C bonds of the central six-membered rings are weakened due to metal ion binding. Based on the Quantum Theory of Atoms in Molecules (QTAIM), we have observed the presence of stabilizing H∙∙∙H interactions in two of the considered systems as opposed to the frequent description of these interactions as non-bonded repulsive interactions. Alkali metal ion binding with those two ligands slightly reduces the strength of such H∙∙∙H interactions.

New cobalt(II) and nickel(II) complexes of benzyl carbazate Schiff bases: Syntheses, crystal structures, in vitro DNA and HSA binding studies.

PubMed

Nithya, Palanivelu; Helena, Sannasi; Simpson, Jim; Ilanchelian, Malaichamy; Muthusankar, Aathi; Govindarajan, Subbiah

2016-12-01

In the present study, new Schiff base complexes with the composition [M(NCS) 2 (L1) 2 ]·nH 2 O, where M=Co (n=0) (1) and Ni (n=2) (2); [M(NCS) 2 (L2) 2 ], M=Co (3) and Ni (4) as well as [M(NCS) 2 (L3) 2 ], M=Co (5) and Ni (6); (L1=benzyl 2-(propan-2-ylidene)hydrazinecarboxylate, L2=benzyl 2-(butan-2-ylidene)hydrazinecarboxylate and L3=benzyl 2-(pentan-3-ylidene)hydrazinecarboxylate) have been synthesized by a template method. The complexes were characterised by analytical methods, spectroscopic studies, thermal and X-ray diffraction techniques. The structures of all the complexes explore that the metal(II) cation has a trans-planar coordination environment, the monomeric units containing a six-coordinated metal center in octahedral geometry with N-bound isothiocyanate anions coordinated as terminal ligands. Furthermore, the binding of the two Schiff base ligands to the metal centers involves the azomethine nitrogen and the carbonyl oxygen in mutually trans configuration. The binding interactions of all the complexes with Calf thymus-deoxyribonucleic acid (CT-DNA) and human serum albumin (HSA) have been investigated using absorption and emission spectral techniques. The CT-DNA binding properties of these complexes reveal that they bind to CT-DNA through a partial intercalation mode and the binding constant values were calculated using the absorption and emission spectral data. The binding constant values (~10×10 6 moldm -3 ) indicate strong binding of metal complexes with CT-DNA. HSA binding interaction studies showed that the cobalt and nickel complexes can quench the intrinsic fluorescence of HSA through static quenching process. Also, molecular docking studies were supported out to apprehend the binding interactions of these complexes with DNA and HSA which offer new understandings into the experimental model observations. Copyright © 2016 Elsevier B.V. All rights reserved.

Immune complexes with cationic antibodies deposit in glomeruli more effectively than cationic antibodies alone.

PubMed

Mannik, M; Gauthier, V J; Stapleton, S A; Agodoa, L Y

1987-06-15

In previously published studies, highly cationized antibodies alone and in immune complexes bound to glomeruli by charge-charge interaction, but only immune complexes persisted in glomeruli. Because normal IgG does not deposit in glomeruli, studies were conducted to determine whether cationized antibodies can be prepared which deposit in glomeruli when bound to antigen but not when free in circulation. A series of cationized rabbit antiHSA was prepared with the number of added amino groups ranging from 13.3 to 60.2 per antibody molecule. Antibodies alone or in preformed soluble immune complexes, prepared at fivefold or 50-fold antigen excess, were administered to mice. With the injection of a fixed dose of 100 micrograms per mouse, antibodies alone did not deposit in glomeruli with less than 29.6 added amino groups by immunofluorescence microscopy. In contrast, 100 micrograms of antibodies with 23.5 added amino groups in immune complexes, made at fivefold antigen excess, formed immune deposits in glomeruli. With selected preparations of cationized, radiolabeled antibodies, deposition in glomeruli was quantified by isolation of mouse glomeruli. These quantitative data were in good agreement with the results of immunofluorescence microscopy. Immune complexes made at 50-fold antigen excess, containing only small-latticed immune complexes with no more than two antibody molecules per complex, deposited in glomeruli similar to antibodies alone. Selected cationized antibodies alone or in immune complexes were administered to mice in varying doses. In these experiments, glomerular deposition of immune complexes, made at fivefold antigen excess, was detected with five- to 10-fold smaller doses than the deposition of the same antibodies alone. These studies demonstrate that antibody molecules in immune complexes are more likely to deposit in glomeruli by charge-charge interactions than antibodies alone.

Cesium Platinide Hydride 4Cs 2 Pt-CsH: An Intermetallic Double Salt Featuring Metal Anions

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

Smetana, Volodymyr; Mudring, Anja-Verena

2016-10-24

With Cs9Pt4H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs 9Pt 4H exhibits a complex crystal structure containing Cs + cations, Pt 2- and H - anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the “alloy” cesium–platinum, or better cesium platinide, Cs2Pt, and the salt cesium hydride CsH according to Cs 9Pt 4H≡4 Cs 2Pt∙CsH.

Laser desorption/ionization mass spectrometry of dye-sensitized solar cells: identification of the dye-electrolyte interaction.

PubMed

Ellis, Hanna; Leandri, Valentina; Hagfeldt, Anders; Boschloo, Gerrit; Bergquist, Jonas; Shevchenko, Denys

2015-05-01

Dye-sensitized solar cells (DSCs) have great potential to provide sustainable electricity from sunlight. The photoanode in DSCs consists of a dye-sensitized metal oxide film deposited on a conductive substrate. This configuration makes the photoanode a perfect sample for laser desorption/ionization mass spectrometry (LDI-MS). We applied LDI-MS for the study of molecular interactions between a dye and electrolyte on the surface of a TiO2 photoanode. We found that a dye containing polyoxyethylene groups forms complexes with alkali metal cations from the electrolyte, while a dye substituted with alkoxy groups does not. Guanidinium ion forms adducts with neither of the two dyes. Copyright © 2015 John Wiley & Sons, Ltd.

Crystal structure of (18-crown-6)potassium(I) [(1,2,3,4,5-η)-cyclo-hepta-dien-yl][(1,2,3-η)-cyclo-hepta-trien-yl]cobalt(I).

PubMed

Brennessel, William W; Ellis, John E

2015-03-01

The reaction of bis-(anthracene)cobaltate(-I) with excess cyclo-hepta-triene, C7H8, resulted in a new 18-electron cobaltate containing two different seven-membered ring ligands, based on single-crystal X-ray diffraction. The asymmetric unit of this structure contains two independent cation-anion pairs of the title complex, [K(18-crown-6)][Co(η(3)-C7H7)(η(5)-C7H9)], where 18-crown-6 stands for 1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane (C12H24O6), in general positions and well separated. Each (18-crown-6)potassium cation is in contact with the η(3)-coordinating ligand of one cobaltate complex. Each η(3)-coordinating ligand behaves as an allylic anion whose exo-diene moiety is bent away from the allylic plane, and thus is not involved directly in the bonding. The metal-coordinating portions of the anionic η(5) ligands are planar and one of these ligands is modeled as disordered over two positions, with occupancy ratio 0.699 (5):0.301 (5), such that one orientation is rotated by one carbon atom with respect to the other. The diffraction intensities were integrated according to non-merohedral twin law [-1 0 0/0 -1 0/0.064 0 1], a 180° rotation about reciprocal lattice axis [001], and the masses of the twin domains refined to equal amounts. As both ligands are formally coordinated as anions, the cobalt atom is best considered to be Co(I). This compound is of inter-est as the first to possess cyclo-hepta-trienyl and cyclo-hepta-dienyl ligands in an anionic metal complex.

Complexes of monocationic Group 13 elements with pentaphospha- and pentaarsaferrocene.

PubMed

Fleischmann, Martin; Welsch, Stefan; Krauss, Hannes; Schmidt, Monika; Bodensteiner, Michael; Peresypkina, Eugenia V; Sierka, Marek; Gröger, Christian; Scheer, Manfred

2014-03-24

Reactions of the sandwich complexes [Cp*Fe(η(5)-E5)] (Cp*=η(5)-C5Me5; E=P (1), As (2)) with the monovalent Group 13 metals Tl(+), In(+), and Ga(+) containing the weakly coordinating anion [TEF] ([TEF]=[Al{OC(CF3)3}4](-)) are described. Here, the one-dimensional coordination polymers [M(μ,η(5):η(1 -E5 FeCp*)3]n [TEF]n (E=P, M=Tl (3 a), In (3 b), Ga (3 c); E=As, M=Tl (4 a), In (4 b)) are obtained as sole products in good yields. All products were analyzed by single-crystal X-ray diffraction, revealing a similar assembly of the products with η(5)-bound E5 ligands and very weak σ-interactions between one P or As atom of the ring to the neighbored Group 13 metal cation. By exchanging the [TEF] anion of 4 a for the larger [FAl] anion ([FAl]=[FAl{OC6F10(C6F5)}3](-)), the coordination compound [Tl{(η(5)-As5)FeCp*}3][FAl] (5) without any σ-interactions of the As5-ring is obtained. All products are readily soluble in CH2 Cl2 and exhibit a dynamic coordination behavior in solution, which is supported by NMR spectroscopy and ESI-MS spectrometry as well as by osmometric molecular-weight determination. For a better understanding of the proceeding equilibrium DFT calculations of the cationic complexes were performed for the gas phase and in solution. Furthermore, the (31)P{(1)H} magic-angle spinning (MAS) NMR spectra of 3 a-c are presented and the first crystal structure of the starting material 2 was determined. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA –); Synthesis and Structure of M IVTTA 4 (M IV = Zr, Hf, Ce, Th, U, Np, Pu) and M III(TTA) 4 – (M III = Ce, Nd, Sm, Yb)

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

Cary, Samantha K.; Livshits, Maksim; Cross, Justin N.

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction—or find alternatives—because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report in this paper advances in fundamental understandingmore » of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV(TTA) 4. Meanwhile, +3 metals formed anionic M III(TTA) 4 – species. Characterization of these M(TTA) 4 x– (x = 0, 1) compounds by UV–vis–NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV(TTA) 4 and Pu IV(TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV(TTA) 4 and M III(TTA) 4 – are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Finally and moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV, Hf IV, and Zr IV.« less

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA –); Synthesis and Structure of M IVTTA 4 (M IV = Zr, Hf, Ce, Th, U, Np, Pu) and M III(TTA) 4 – (M III = Ce, Nd, Sm, Yb)

DOE PAGES

Cary, Samantha K.; Livshits, Maksim; Cross, Justin N.; ...

2018-03-21

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction—or find alternatives—because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report in this paper advances in fundamental understandingmore » of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV(TTA) 4. Meanwhile, +3 metals formed anionic M III(TTA) 4 – species. Characterization of these M(TTA) 4 x– (x = 0, 1) compounds by UV–vis–NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV(TTA) 4 and Pu IV(TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV(TTA) 4 and M III(TTA) 4 – are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Finally and moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV, Hf IV, and Zr IV.« less

Cation-containing lipid membranes – experiment and md simulations

DOE PAGES

Kučerka, Norbert; Dushanov, Ermuhammas; Kholmurodov, Kholmirzo T.; ...

2017-11-27

Here, using small angle neutron diffraction and molecular dynamics simulations we studied the interactions between calcium (Ca 2+) or zinc (Zn 2+) cations, and oriented gel phase dipalmitoyl-phosphatidylcholine (DPPC) bilayers. For both cations studied at ~1:7 divalent metal ion to lipid molar ratio (Me2+:DPPC), bilayer thickness increased. Simulation results helped reveal subtle differences in the effects of the two cations on gel phase membranes.

Divalent cations in tears, and their influence on tear film stability in humans and rabbits.

PubMed

Wei, Xiaojia Eric; Markoulli, Maria; Millar, Thomas J; Willcox, Mark D P; Zhao, Zhenjun

2012-06-05

Reduced tear film stability is reported to contribute to dry eye. Rabbits are known to have a more stable tear film than humans. Thus, we sought to examine the tears of rabbits and humans for metal cations, and to test how they influence tear film stability. Tears were collected from 10 healthy humans and 6 rabbits. Tear osmolality was measured by vapor pressure osmometer, and metals analyzed using inductively coupled plasma (ICP) mass spectrometry or ICP atomic emission spectroscopy. The influence of divalent cations on tears was analyzed by measuring surface tension using the Langmuir trough in vitro, using different concentrations of cations in the subphase, and grading the tear break-up in rabbits in vivo after instillation of chelating agents. Rabbit tears had a higher osmolality compared to humans. Major metals did not differ between species; however, rabbits had higher levels of Mg(2+) (1.13 vs. 0.39 mM) and Ca(2+) (0.75 vs. 0.36 mM). In rabbit tears in vitro, diminishing divalent cations resulted in a decrease in the maximum surface pressure from 37 to 30 mN/m. In vivo, an increase in the amount of tear film that was broken-up was found. In contrast, when changing divalent cation concentrations in human tears, the maximum surface pressure remained at 26 mN/m. The normal osmolality of rabbit tears is significantly higher than that in humans. While divalent cations had little influence on human tears, they appear to have an important role in maintaining tear film stability in rabbits.

Multisite adsorption of cadmium on goethite

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

Venema, P.; Hiemstra, T.; Riemsdijk, W.H. van

1996-11-10

Recently a new general ion adsorption model has been developed for ion binding to mineral surfaces (Hiemstra and van Riemsdijk, 1996). The model uses the Pauling concept of charge distribution (CD) and is an extension of the multi-site complexation (MUSIC) approach. In the CD-MUSIC model the charge of an adsorbing ion that forms an inner sphere complex is distributed over its ligands, which are present in two different electrostatic planes. In this paper the authors have applied the CD-MUSIC model to the adsorption of metal cations, using an extended data set for cadmium adsorbing on goethite. The adsorption of cadmiummore » and the cadmium-proton exchange ratio were measured as function of metal ion concentration, pH, and ionic strength. The data could be described well, taking into account the surface heterogeneity resulting from the presence of two different crystal planes (the dominant 110 face and the minor 021 face). The surface species used in the model are consistent with recent EXAFS data. In accordance with the EXAFS results, high-affinity complexes at the 021 face were used in the model.« less

Citrate, in collaboration with a guanidinium ion, as a generator of cubane-like complexes with a range of metal cations: synthesis, structures, and magnetic properties of [C(NH2)3]8[(M(II))4(cit)4].8H2O (M = Mg, Mn, Fe, Co, Ni, and Zn; cit = Citrate).

PubMed

Hudson, Timothy A; Berry, Kevin J; Moubaraki, Boujemaa; Murray, Keith S; Robson, Richard

2006-05-01

Aqueous reaction mixtures containing citric acid, guanidinium carbonate, and a range of metal cations (Mg2+, Mn2+, Fe2+, Co2+, Ni2+, and Zn2+) at room temperature give crystalline products of composition [C(NH2)3]8[(M(II))4(cit)4].8H2O (cit = citrate). In all cases, the crystals are suitable for single-crystal X-ray diffraction studies, which reveal that the compounds are isostructural (space group P4(2)/n; a approximately 16.2 A, and c approximately 11.5 A). As was intended, cubane-like [M4(cit)4]8- complex anions are present. The individual citrate units are chiral, but each cubane unit contains two of one hand and two of the other, related around an S4 axis. The cubane units are involved in no less than 40 H-bonding interactions with guanidinium cations and lattice water molecules. Detailed susceptibility and magnetization studies show that the intracluster magnetic coupling within the Mn(II), Fe(II), Co(II), and Ni(II) cubanes is very weak in all cases with J values of -0.82, -0.43, and -0.09 cm(-1) for the Mn, Fe, and Co species, respectively. A two-J model gave the best agreement with the susceptibility and high-field magnetization data for the Ni(II) case, over the whole temperature range studied, and the sign of the parameters, J12 = -0.3 cm(-1) and J13 = +2.97 cm(-1), correlated with the two Ni-(mu3-O)-Ni angles observed in the cluster structure. All members of the 3d-block [M4(cit)4]8- family have spin ground states, ST, of zero, with the higher ST levels just a few reciprocal centimeters away in energy.

Thiopyridazine-Based Palladium and Platinum Boratrane Complexes.

PubMed

Holler, Stefan; Tüchler, Michael; Steller, Beate G; Belaj, Ferdinand; Veiros, Luis F; Kirchner, Karl; Mösch-Zanetti, Nadia C

2018-06-07

Palladium and platinum boratrane complexes of the type [M{B(Pn Me, tBu ) 3 }(PPh 3 )] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft scorpionate ligand potassium tris(4-methyl-6- tert-butyl-3-thiopyridazinyl)borate KTn Me, tBu with bis(triphenylphosphine)metal(II) dichloride. While reaction with the Pd precursor allowed direct isolation of a symmetric boratrane complex, the Pt analogue led to the hydrido compound [Pt{B(Pn Me, tBu ) 3 }(PPh 3 )H]Cl (2a), which after reaction with a base gave 2b. Subsequent oxidation with Br 2 and I 2 , respectively, led to the dihalide compounds of the molecular formula [M{B(Pn Me, tBu ) 3 }X 2 ] (3a,b-4a,b). Halide abstraction with Ag(SbF 6 ) further gave interesting cationic compounds of either dimeric [Pd{B(Pn Me, tBu ) 3 }X] 2 (SbF 6 ) 2 (5a,b) or monomeric [Pd{B(Pn Me, tBu ) 3 }(NCMe) 2 ](SbF 6 ) (6) nature. All compounds were spectroscopically and X-ray crystallographically characterized revealing strong metal to boron interactions. DFT calculations of 1, 2a, and 2b confirm the strong M-B interaction and a high positive charge on the metal centers.

Transformation of metals speciation in a combined landfill leachate treatment.

PubMed

Wu, Yanyu; Zhou, Shaoqi; Chen, Dongyu; Zhao, Rong; Li, Huosheng; Lin, Yiming

2011-04-01

Landfill leachate was treated by a combined sequential batch reactor (SBR), coagulation, Fenton oxidation and biological aerated filter (BAF) technology. The metals in treatment process were fractionated into three fractions: particulate and colloidal (size charge filtration), free ion/labile (cation exchange) and non-labile fractions. Fifty percent to 66% Cu, Ni, Zn, Mn, Pb and Cd were present as particulate/colloidal matter in raw leachate, whereas Cr was present 94.9% as non-labile complexes. The free ion/labile fractions of Ni, Zn, Mg, Mn, Pb and Cd increased significantly after treatment except Cr. Fifty-nine percent to 100% of Al was present mainly as particulate/colloidal matter >0.45 μm and the remaining portions were predicted as non-labile complexes except in coagulation effluent. The speciation of Fe varied significantly in various individual processes. Visual MINTEQ simulation showed that 95-100% colloidal species for Cu, Cd and Pb were present as metal-humic complexes even with the lower dissolved organic carbon. Optimum agreements for the free ion/labile species were within acidic solution, whereas under-estimated in alkaline effluents. Overestimated particulate/colloidal fraction consisted with the hypothesis that a portion of colloids in fraction <0.45 μm were considered as dissolved. Copyright © 2011 Elsevier B.V. All rights reserved.

Coordination effect-regulated CO2 capture with an alkali metal onium salts/crown ether system

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

Yang, Zhen-Zhen; Jiang, Deen; Zhu, Xiang

2014-01-01

A coordination effect was employed to realize equimolar CO2 absorption, adopting easily synthesized amino group containing absorbents (alkali metal onium salts). The essence of our strategy was to increase the steric hindrance of cations so as to enhance a carbamic acid pathway for CO2 capture. Our easily synthesized alkali metal amino acid salts or phenolates were coordinated with crown ethers, in which highly sterically hindered cations were obtained through a strong coordination effect of crown ethers with alkali metal cations. For example, a CO2 capacity of 0.99 was attained by potassium prolinate/18-crown-6, being characterized by NMR, FT-IR, and quantum chemistrymore » calculations to go through a carbamic acid formation pathway. The captured CO2 can be stripped under very mild conditions (50 degrees C, N-2). Thus, this protocol offers an alternative for the development of technological innovation towards efficient and low energy processes for carbon capture and sequestration.« less

Roles of cations, electronegativity difference, and anionic interlayer interactions in the metallic versus nonmetallic character of Zintl phases related to arsenic.

PubMed

Alemany, Pere; Llunell, Miquel; Canadell, Enric

2008-10-01

A first-principles Density Functional Theory study of several layered solids structurally related to rhombohedral arsenic has been carried out. The electronic structures of rhombohedral arsenic, CaSi(2), CaAl(2)Si(2), KSnSb, and SrSn(2)As(2) are discussed in detail, emphasizing on the origins of their metallic or nonmetallic behaviours. It is found that all of these systems are metallic except KSnSb. Electronegativity differences between the elements in the anionic sublattice and/or direct interlayer interactions play the main role in controlling the conductivity behavior. CaSi(2) exhibits a peculiar feature since the cation directly influences the conductivity but is not essential for its appearance. Cation-anion interactions are shown to have an important covalent contribution, but despite this fact and the metallic character found for most of these phases, the Zintl approach still provides a valid approximation to their electronic structure. (c) 2008 Wiley Periodicals, Inc.

Impact of Na- and K-C pi-interactions on the structure and binding of M3(sol)n(BINOLate)3Ln catalysts.

PubMed

Wooten, Alfred J; Carroll, Patrick J; Walsh, Patrick J

2007-08-16

Shibasaki's heterobimetallic complexes M3(THF)n(BINOLate)3Ln [M = Li, Na, K; Ln = lanthanide(III)] are among the most successful asymmetric Lewis acid catalysts. Why does M3(THF)n(BINOLate)3Ln readily bind substrates when M = Li but not when M = Na or K? Structural studies herein indicate Na- and K-C cation-pi interactions and alkali metal radius may be more important than even lanthanide radius. Also reported is a novel polymeric [K3(THF)2(BINOLate)3Yb]n structure that provides the first evidence of interactions between M3(THF)n(BINOLate)3Ln complexes.

Impact of Na- and K-C π-Interactions on the Structure and Binding of M3(sol)n(BINOLate)3Ln Catalysts

PubMed Central

Wooten, Alfred J.; Carroll, Patrick J.; Walsh, Patrick J.

2008-01-01

Shibasaki’s heterobimetallic complexes M3(THF)n(BINOLate)3Ln [M = Li, Na, K, Ln = lanthanide(III)] are among the most successful asymmetric Lewis acid catalysts. Why does M3(THF)n(BINOLate)3Ln readily bind substrates when M = Li but not when M = Na or K? Structural studies herein indicate Na- and K-C cation-π interactions and alkali metal radius may be more important than even lanthanide radius. Also reported is a novel polymeric [K3(THF)2(BINOLate)3Yb]n structure that provides the first evidence of interactions between M3(THF)n(BINOLate)3Ln complexes. PMID:17658838

Reduction by monovalent zinc, cadmium, and nickel cations

NASA Technical Reports Server (NTRS)

Meyerstein, D.; Mulac, W. A.

1969-01-01

Understanding of chemical properties of monovalent transition metal cations in aqueous solutions was obtained by a study of kinetics of reduction of different inorganic substrates by zinc, cadmium, and nickel.

Selective enrichment of metal-binding proteins based on magnetic core/shell microspheres functionalized with metal cations.

PubMed

Fang, Caiyun; Zhang, Lei; Zhang, Xiaoqin; Lu, Haojie

2015-06-21

Metal binding proteins play many important roles in a broad range of biological processes. Characterization of metal binding proteins is important for understanding their structure and biological functions, thus leading to a clear understanding of metal associated diseases. The present study is the first to investigate the effectiveness of magnetic microspheres functionalized with metal cations (Ca(2+), Cu(2+), Zn(2+) and Fe(3+)) as the absorbent matrix in IMAC technology to enrich metal containing/binding proteins. The putative metal binding proteins in rat liver were then globally characterized by using this strategy which is very easy to handle and can capture a number of metal binding proteins effectively. In total, 185 putative metal binding proteins were identified from rat liver including some known less abundant and membrane-bound metal binding proteins such as Plcg1, Acsl5, etc. The identified proteins are involved in many important processes including binding, catalytic activity, translation elongation factor activity, electron carrier activity, and so on.

Method for production of ceramic oxide and carbide bodies by polymer inclusion and decomposition

DOEpatents

Quinby, Thomas C.

1985-01-01

A method for the preparation of thin, free-standing metal oxide films which are useful as nuclear accelerator target materials. Cations of any metal except those of Group IA and precious metals, such as, U, Zr, Nd, Ce, Th, pr or Cr, are absorbed on a thin film of polymeric material, such as, carboxymethylcellulose, viscose rayon or cellophane. The cation impregnated polymeric material is dried. Then the impregnated film is heated in an inert atmosphere to form a carbonized membrane. The carbonized membrane is oxidized to yield a thin, self-supporting, metal oxide membrane. Or, the membrane can be heated in an inert atmosphere to yield a thin, self-supporting, metal carbide-containing membrane.

Method for production of ceramic oxide and carbide bodies by polymer inclusion and decomposition

DOEpatents

Quinby, T.C.

1984-08-30

A method for the preparation of thin, free-standing metal oxide films which are useful as nuclear accelerator target materials is described. Cations of any metal except those of Group IA and precious metals, such as, U, Zr, Nd, Ce, Th, Pr or Cr, are absorbed on a thin film of polymeric material, such as carboxymethylcellulose, viscose rayon or cellophane. The cation impregnated polymeric material is dried. Then the impregnated film is heated in an inert atmosphere to form a carbonized membrane. The carbonized membrane is oxidized to yield a thin, self-supporting, metal oxide membrane. Or, the membrane can be heated in an inert atmosphere to yield a thin, self-supporting, metal carbide-containing membrane.

NMR spectroscopy of Group 13 metal ions: biologically relevant aspects.

PubMed

André, J P; Mäcke, H R

2003-12-01

In spite of the fact that Group 13 metal ions (Al(3+), Ga(3+), In(3+) and Tl(+/3+)) show no main biological role, they are NMR-active nuclides which can be used in magnetic resonance spectroscopy of biologically relevant systems. The fact that these metal ions are quadrupolar (with the exception of thallium) means that they are particularly sensitive to ligand type and coordination geometry. The line width of the NMR signals of their complexes shows a strong dependence on the symmetry of coordination, which constitutes an effective tool in the elucidation of structures. Here we report published NMR studies of this family of elements, applied to systems of biological importance. Special emphasis is given to binding studies of these cations to biological molecules, such as proteins, and to chelating agents of radiopharmaceutical interest. The possibility of in vivo NMR studies is also stressed, with extension to (27)Al-based MRI (magnetic resonance imaging) experiments.

Interpretation FTIR spectrum of seawater and sediment in the Ambon Bay (TAD)

NASA Astrophysics Data System (ADS)

Patty, Diana Julaidy; Loupatty, Grace; Sopalauw, Fitria

2017-01-01

Research has done to interpretated FTIR spectrum of seawaters and sediment of the Ambon Bay (TAD). Analysis of samples of sediment and seawater using FTIR spectroscopy. The results showed the sand sediment samples identified Stretch bond OH group (3600-3500 cm-1), N-H Stretch (3400-3300 cm-1), C≡N (2250 cm-1), and NH bending (1640 to 1550 cm-1). And for seawater samples identified bonding group that is N-H Stretch (3400-3350 cm-1), N-H bending (1640 to 1550 cm-1) and C=O (1670-1640 cm-1). The existence of functional groups, carbonyl (C=O), alcohol (OH), carboxyl (COOH) can cause the complexation of metal cations. And the results showed analysis group N-O bond-containing compounds Nitro indicate heavy metal content of Lead (Pb) and group N-H bond-containing compound Amina indicate heavy metal content of Cadmium (Cd).

Electron-Transfer-Enhanced Cation-Cation Interactions in Homo- and Heterobimetallic Actinide Complexes: A Relativistic Density Functional Theory Study.

PubMed

Zheng, Ming; Chen, Fang-Yuan; Tian, Jia-Nan; Pan, Qing-Jiang

2018-04-02

To provide deep insight into cation-cation interactions (CCIs) involving hexavalent actinyl species that are major components in spent nuclear fuel and pose important implications for the effective removal of radiotoxic pollutants in the environment, a series of homo- and heterobimetallic actinide complexes supported by cyclopentadienyl (Cp) and polypyrrolic macrocycle (H 4 L) ligands were systematically investigated using relativistic density functional theory. The metal sort in both parts of (THF)(H 2 L)(OAn VI O) and (An') III Cp 3 from U to Np to Pu, as well as the substituent bonding to Cp from electron-donating Me to H to electron-withdrawing Cl, SiH 3 , and SiMe 3 , was changed. Over 0.70 electrons are unraveled to transfer from the electron-rich U III to the electron-deficient An VI of the actinyl moiety, leading to a more stable An V -U IV isomer; in contrast, uranylneptunium and uranylplutonium complexes behave as electron-resonance structures between VI-III and V-IV. These were further corroborated by geometrical and electronic structures. The energies of CCIs (i.e., O exo -An' bonds) were calculated to be -19.6 to -41.2 kcal/mol, affording those of OUO-Np (-23.9 kcal/mol) and OUO-Pu (-19.6 kcal/mol) with less electron transfer (ET) right at the low limit. Topological analyses of the electron density at the O exo -An' bond critical points demonstrate that the CCIs are ET or dative bonds in nature. A positive correlation has been built between the CCIs' strength and corresponding ET amount. It is concluded that the CCIs of O exo -An' are driven by the electrostatic attraction between the actinyl oxo atom (negative) and the actinide ion (positive) and enhanced by their ET. Finally, experimental syntheses of (THF)(H 2 L)(OU VI O)(An') III Cp 3 (An' = U and Np) were well reproduced by thermodynamic calculations that yielded negative free energies in a tetrahydrofuran solution but a positive one for their uranylplutonium analogue, which was synthetically inaccessible. So, our thermodynamics would provide implications for the synthetic possibility of other theoretically designed bimetallic actinide complexes.

Uncovering the Roles of Oxygen in Cr(III) Photoredox Catalysis.

PubMed

Higgins, Robert F; Fatur, Steven M; Shepard, Samuel G; Stevenson, Susan M; Boston, David J; Ferreira, Eric M; Damrauer, Niels H; Rappé, Anthony K; Shores, Matthew P

2016-04-27

A combined experimental and theoretical investigation aims to elucidate the necessary roles of oxygen in photoredox catalysis of radical cation based Diels-Alder cycloadditions mediated by the first-row transition metal complex [Cr(Ph2phen)3](3+), where Ph2phen = bathophenanthroline. We employ a diverse array of techniques, including catalysis screening, electrochemistry, time-resolved spectroscopy, and computational analyses of reaction thermodynamics. Our key finding is that oxygen acts as a renewable energy and electron shuttle following photoexcitation of the Cr(III) catalyst. First, oxygen quenches the excited Cr(3+)* complex; this energy transfer process protects the catalyst from decomposition while preserving a synthetically useful 13 μs excited state and produces singlet oxygen. Second, singlet oxygen returns the reduced catalyst to the Cr(III) ground state, forming superoxide. Third, the superoxide species reduces the Diels-Alder cycloadduct radical cation to the final product and reforms oxygen. We compare the results of these studies with those from cycloadditions mediated by related Ru(II)-containing complexes and find that the distinct reaction pathways are likely part of a unified mechanistic framework where the photophysical and photochemical properties of the catalyst species lead to oxygen-mediated photocatalysis for the Cr-containing complex but radical chain initiation for the Ru congener. These results provide insight into how oxygen can participate as a sustainable reagent in photocatalysis.

Intermediates in monensin biosynthesis: A late step in biosynthesis of the polyether ionophore monensin is crucial for the integrity of cation binding.

PubMed

Hüttel, Wolfgang; Spencer, Jonathan B; Leadlay, Peter F

2014-01-01

Polyether antibiotics such as monensin are biosynthesised via a cascade of directed ring expansions operating on a putative polyepoxide precursor. The resulting structures containing fused cyclic ethers and a lipophilic backbone can form strong ionophoric complexes with certain metal cations. In this work, we demonstrate for monensin biosynthesis that, as well as ether formation, a late-stage hydroxylation step is crucial for the correct formation of the sodium monensin complex. We have investigated the last two steps in monensin biosynthesis, namely hydroxylation catalysed by the P450 monooxygenase MonD and O-methylation catalysed by the methyl-transferase MonE. The corresponding genes were deleted in-frame in a monensin-overproducing strain of Streptomyces cinnamonensis. The mutants produced the expected monensin derivatives in excellent yields (ΔmonD: 1.13 g L(-1) dehydroxymonensin; ΔmonE: 0.50 g L(-1) demethylmonensin; and double mutant ΔmonDΔmonE: 0.34 g L(-1) dehydroxydemethylmonensin). Single crystals were obtained from purified fractions of dehydroxymonensin and demethylmonensin. X-ray structure analysis revealed that the conformation of sodium dimethylmonensin is very similar to that of sodium monensin. In contrast, the coordination of the sodium ion is significantly different in the sodium dehydroxymonensin complex. This shows that the final constitution of the sodium monensin complex requires this tailoring step as well as polyether formation.

Mutual influence between triel bond and cation-π interactions: an ab initio study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Mousavian, Parisasadat

2017-12-01

Using ab initio calculations, the cooperative and solvent effects on cation-π and B...N interactions are studied in some model ternary complexes, where these interactions coexist. The nature of the interactions and the mechanism of cooperativity are investigated by means of quantum theory of atoms in molecules (QTAIM), noncovalent interaction (NCI) index and natural bond orbital analysis. The results indicate that all cation-π and B...N binding distances in the ternary complexes are shorter than those of corresponding binary systems. The QTAIM analysis reveals that ternary complexes have higher electron density at their bond critical points relative to the corresponding binary complexes. In addition, according to the QTAIM analysis, the formation of cation-π interaction increases covalency of B...N bonds. The NCI analysis indicates that the cooperative effects in the ternary complexes make a shift in the location of the spike associated with each interaction, which can be regarded as an evidence for the reinforcement of both cation-π and B...N interactions in these systems. Solvent effects on the cooperativity of cation-π and B...N interactions are also investigated.

Fascinating interaction of the ammonium cation with [2.2.2]paracyclophane: experimental and theoretical study

NASA Astrophysics Data System (ADS)

Makrlík, Emanuel; Sýkora, David; Böhm, Stanislav; Kvíčalová, Magdalena; Vaňura, Petr

2018-05-01

By means of electrospray ionisation mass spectrometry, it was evidenced experimentally that the ammonium cation (NH4+) reacts with the electroneutral [2.2.2]paracyclophane ligand (C24H24) to form the cationic complex [NH4(C24H24)]+. Moreover, applying quantum chemical calculations, the most probable conformation of the proven [NH4(C24H24)]+ complex was solved. In the complex [NH4(C24H24)]+ having a symmetry very close to C3, the 'central' cation NH4+ is coordinated by three strong bifurcated intramolecular hydrogen bonds to the corresponding six carbon atoms from the three benzene rings of [2.2.2]paracyclophane via cation-π interaction. Finally, the interaction energy, E(int), of the considered complex [NH4(C24H24)]+ was evaluated as -625.8 kJ/mol, confirming the formation of this fascinating complex species as well. It means that the [2.2.2]paracyclophane ligand can be considered as an effective receptor for the ammonium cation in the gas phase.

Pseudosymmetric fac-di-aqua-trichlorido[(di-methyl-phosphor-yl)methanaminium-κO]manganese(II).

PubMed

Reiss, Guido J

2013-05-01

In the title compound, [Mn(C3H11NOP)Cl3(H2O)2], the Mn(II) metal center has a distorted o-cta-hedral geometry, coordinated by the three chloride ligands showing a facial arrangement. Two water mol-ecules and the O-coordinated dpmaH cation [dpmaH = (di-methyl-phosphor-yl)methanaminium] complete the coordination sphere. Each complex mol-ecule is connected to its neighbours by O-H⋯Cl and N-H⋯Cl hydrogen bonds. Two of the chloride ligands and the two water ligands form a hydrogen-bonded polymeric sheet in the ab plane. Furthermore, these planes are connected to adjacent planes by hydrogen bonds from the aminium function of cationic dpmaH ligand. A pseudo-mirror plane perpendicular to the b axis in the chiral space group P21 is observed together with inversion twinning [ratio = 0.864 (5):0.136 (5)].

Double layer effects in electrocatalysis: The oxygen reduction reaction and ethanol oxidation reaction on Au(111), Pt(111) and Ir(111) in alkaline media containing Na and Li cations

DOE PAGES

Lopes, Pietro P.; Strmcnik, Dusan; Jirkovsky, Jakub S.; ...

2015-09-28

Oxygen reduction and ethanol oxidation reactions were studied on Au(111), Pt(111) and Ir(111) in alkaline solutions containing sodium and/or lithium cations. By keeping the same (111) surface orientation and exploring oxophilicity trends and non-covalent interactions between OH ad and alkali metal cations (AMC n+), we were able to gain deep insights into the multiple roles that OH ad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OH ad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OH ad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formationmore » of a “true oxide” layer at higher electrode potentials. Although OH ad is a simple spectator for the ORR, it promotes the ethanol oxidation reaction (EOR) at lower potentials and act as spectator at high OHad coverages. By changing the alkali metal cation at the interface (Li +) on more oxophilic surfaces, it was possible to promote the EOR even more, relative to Na +, without changing the product distribution for the reaction. This cation effect suggests that OH ad—Li +(H 2O) x clusters can stabilize the ethoxide adlayer, thus improving the EOR activity. Finally, our results indicate the importance of the entire electrochemical interface in determining the electrocatalytic activity during reaction.« less

meso-Octamethylcalix[4]pyrrole as an effective macrocyclic receptor for the univalent thallium cation in the gas phase: Experimental and theoretical study

NASA Astrophysics Data System (ADS)

Polášek, Miroslav; Makrlík, Emanuel; Kvíčala, Jaroslav; Křížová, Věra; Vaňura, Petr

2018-02-01

By using electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent thallium cation (Tl+) forms with meso-octamethylcalix[4]pyrrole (1) the cationic complex species 1 Tl+. When this kinetically stable cation-π complex 1 Tl+ is collisionally activated, it decomposes by elimination of the whole ligand 1 or small meso-octamethylcalix[4]pyrrole fragments. Further, applying quantum chemical DFT calculations, four different conformations of the resulting complex 1 Tl+ were derived. It means that under the present experimental conditions, this ligand 1 can be considered as a very effective macrocyclic receptor for the thallium cation.

[Influence of the earthworm Lumbricus terrestris on soil solution complexation capacity].

PubMed

el Gharmali, A; Rada, A; el Meray, M; Nejmeddine, A

2001-04-01

Four soil samples highly contaminated with metals of urban and mine origin (SE1, SE2, SM1, SM2) and having different physico-chemical proprieties were selected to study copper complexation capacity (LT) of soil solution. The effect of Lumbricus terrestris on copper complexation capacity of soil solution was investigated on SE1 and SE2. The complexation capacity was estimated by amperometric titration of soil solution by copper. Free hydrated cation and labile complexes of copper were determined by DPASV. The results show that the copper complexation capacity variation depends on the physico-chemical characteristics of soils, particularly pH. Thus, the values of copper complexation capacity are 0; 0.6 x 10(-7); 1.8 x 10(-7) and 5.5 x 10(-7) mol l-1 respectively for SM2; SM1; SE1 and SE2 which are pH 5; 5.4; 6.5 and 7.4. Based on these results, the bioavailability levels of heavy metals show the following pool ranking: SM2 > SM1 > SE1 > SE2. The copper complexation capacity of soil solution increases with the soil disturbance by Lumbricus terrestris. This is more obvious when the time of disturbance by lumbrics is longer. Indeed, average values determined for 1 month and 3 months are 3.8 x 10(-7) and 7.8 x 10(-7) mol l-1 for SE1; 7.7 x 10(-7) and 15.2 x 10(-7) mol l-1 for SE2 respectively. It seems that the action of earthworm on soil can contribute to the decrease of bioavailability of heavy metals, particularly copper.

Controlling Wafer Contamination Using Automated On-Line Metrology during Wet Chemical Cleaning

NASA Astrophysics Data System (ADS)

Wang, Jason; Kingston, Skip; Han, Ye; Saini, Harmesh; McDonald, Robert; Mui, Rudy

2003-09-01

The capabilities of a trace contamination analyzer are discussed and demonstrated. This analytical tool utilizes an electrospray, time-of-flight mass spectrometer (ES-TOF-MS) for fully automated on-line monitoring of wafer cleaning solutions. The analyzer provides rich information on metallic, anionic, cationic, elemental, and organic species through its ability to provide harsh (elemental) and soft (molecular) ionization under both positive and negative modes. It is designed to meet semiconductor process control and yield management needs for the ever increasing complex new chemistries present in wafer fabrication.

Combined distribution functions: A powerful tool to identify cation coordination geometries in liquid systems

NASA Astrophysics Data System (ADS)

Sessa, Francesco; D'Angelo, Paola; Migliorati, Valentina

2018-01-01

In this work we have developed an analytical procedure to identify metal ion coordination geometries in liquid media based on the calculation of Combined Distribution Functions (CDFs) starting from Molecular Dynamics (MD) simulations. CDFs provide a fingerprint which can be easily and unambiguously assigned to a reference polyhedron. The CDF analysis has been tested on five systems and has proven to reliably identify the correct geometries of several ion coordination complexes. This tool is simple and general and can be efficiently applied to different MD simulations of liquid systems.

Study of intermediates from transition metal excited-state electron-transfer reactions

NASA Astrophysics Data System (ADS)

Hoffman, M. Z.

1984-03-01

Attention during the past year focused on MV(+)., the reduced methyl viologen radical cation, which is a precursor to the formation of H2 in the photosensitized reduction of water. Through the use of photochemical and radiation chemical techniques, the efficiency of interaction of MV(+). with colloidal Pt, the stability of MV(+). as a function of pH, the quantum yield of formation of MV(+). in the Ru(bpy)3(2+)/MV(2+)/EDTA system, and the formation of photoactive charge-transfer complexes between MV(2+) and sacrificial electron donors were studied.

Potassium bis(carbonato-O,O')(ethylenediamine-N,N')cobaltate(III) monohydrate at 173 K.

PubMed

Belai, N; Dickman, M H; Pope, M T

2001-07-01

The title salt, K[Co(C2H8N2)(CO3)2].H2O, consists of a distorted octahedral cobalt complex anion and a seven-coordinate potassium cation. Both metal atoms have crystallographic twofold symmetry, one C2 axis passing through the Co atom and C--C bond, and another along a short K--O (water) bond of 2.600 A (corrected for libration). The carbonate is bidentate to both cobalt and potassium and the water forms a hydrogen bond to a carbonate O atom.

Cation distribution in NiZn-ferrite films via extended x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Koon, N. C.; Williams, C. M.; Zhang, Q.; Abe, M.; Kirkland, J. P.

1996-04-01

We have applied extended x-ray absorption fine structure (EXAFS) spectroscopy to study the cation distribution in a series of spin-sprayed NiZn-ferrite films. A least-squares fitting of experimental EXAFS data with theoretical, multiple-scattering, EXAFS data allowed the quantitative determination of site distributions for all transition metal cations.

Selective time-resolved binding of copper(II) by pyropheophorbide-a methyl ester.

PubMed

Ghosh, Indrajit; Saleh, Na'il; Nau, Werner M

2010-05-01

The complexation behavior of pyropheophorbide-a methyl ester (PPME) with transition metal ions as well as other biologically relevant metal ions has been investigated in water-DMF (2 : 1 v/v) solution. PPME was found to selectively complex Cu(2+) ions, which leads to a distinct change in its absorption spectrum as well as efficient fluorescence quenching. The degree of fluorescence quenching by Cu(2+) depended on concentration and time. Upon addition of Cu(2+), the fluorescence showed a time-resolved decay on the time scale of minutes to hours, with the decay rate being dependent on the cation concentration. Fitting according to a bimolecular reaction rate law provided a rate constant of 650 +/- 90 M(-1) s(-1) at 298 K for metallochlorin formation. The potential implications of Cu(2+) binding for the use of PPME in photodynamic therapy are discussed, along with its use as a fluorescent sensor for detection of micromolar concentrations of Cu(2+).

Toxic effect of metal cation binary mixtures to the seaweed Gracilaria domingensis (Gracilariales, Rhodophyta).

PubMed

Mendes, Luiz Fernando; Stevani, Cassius Vinicius; Zambotti-Villela, Leonardo; Yokoya, Nair Sumie; Colepicolo, Pio

2014-01-01

The macroalga Gracilaria domingensis is an important resource for the food, pharmaceutical, cosmetic, and biotechnology industries. G. domingensis is at a part of the food web foundation, providing nutrients and microelements to upper levels. As seaweed storage metals in the vacuoles, they are considered the main vectors to magnify these toxic elements. This work describes the evaluation of the toxicity of binary mixtures of available metal cations based on the growth rates of G. domingensis over a 48-h exposure. The interactive effects of each binary mixture were determined using a toxic unit (TU) concept that was the sum of the relative contribution of each toxicant and calculated using the ratio between the toxicant concentration and its endpoint. Mixtures of Cd(II)/Cu(II) and Zn(II)/Ca(II) demonstrated to be additive; Cu(II)/Zn(II), Cu(II)/Mg(II), Cu(II)/Ca(II), Zn(II)/Mg(II), and Ca(II)/Mg(II) mixtures were synergistic, and all interactions studied with Cd(II) were antagonistic. Hypotheses that explain the toxicity of binary mixtures at the molecular level are also suggested. These results represent the first effort to characterize the combined effect of available metal cations, based on the TU concept on seaweed in a total controlled medium. The results presented here are invaluable to the understanding of seaweed metal cation toxicity in the marine environment, the mechanism of toxicity action and how the tolerance of the organism.

Cluster-Continuum Calculations of Hydration Free Energies of Anions and Group 12 Divalent Cations.

PubMed

Riccardi, Demian; Guo, Hao-Bo; Parks, Jerry M; Gu, Baohua; Liang, Liyuan; Smith, Jeremy C

2013-01-08

Understanding aqueous phase processes involving group 12 metal cations is relevant to both environmental and biological sciences. Here, quantum chemical methods and polarizable continuum models are used to compute the hydration free energies of a series of divalent group 12 metal cations (Zn(2+), Cd(2+), and Hg(2+)) together with Cu(2+) and the anions OH(-), SH(-), Cl(-), and F(-). A cluster-continuum method is employed, in which gas-phase clusters of the ion and explicit solvent molecules are immersed in a dielectric continuum. Two approaches to define the size of the solute-water cluster are compared, in which the number of explicit waters used is either held constant or determined variationally as that of the most favorable hydration free energy. Results obtained with various polarizable continuum models are also presented. Each leg of the relevant thermodynamic cycle is analyzed in detail to determine how different terms contribute to the observed mean signed error (MSE) and the standard deviation of the error (STDEV) between theory and experiment. The use of a constant number of water molecules for each set of ions is found to lead to predicted relative trends that benefit from error cancellation. Overall, the best results are obtained with MP2 and the Solvent Model D polarizable continuum model (SMD), with eight explicit water molecules for anions and 10 for the metal cations, yielding a STDEV of 2.3 kcal mol(-1) and MSE of 0.9 kcal mol(-1) between theoretical and experimental hydration free energies, which range from -72.4 kcal mol(-1) for SH(-) to -505.9 kcal mol(-1) for Cu(2+). Using B3PW91 with DFT-D3 dispersion corrections (B3PW91-D) and SMD yields a STDEV of 3.3 kcal mol(-1) and MSE of 1.6 kcal mol(-1), to which adding MP2 corrections from smaller divalent metal cation water molecule clusters yields very good agreement with the full MP2 results. Using B3PW91-D and SMD, with two explicit water molecules for anions and six for divalent metal cations, also yields reasonable agreement with experimental values, due in part to fortuitous error cancellation associated with the metal cations. Overall, the results indicate that the careful application of quantum chemical cluster-continuum methods provides valuable insight into aqueous ionic processes that depend on both local and long-range electrostatic interactions with the solvent.

[Ag2M(Te2O5)2]SO4 (M = CeIV or ThIV): A New Purely Inorganic d/f-Heterometallic Cationic Material.

PubMed

Poe, Todd N; White, Frankie D; Proust, Vanessa; Villa, Eric M; Polinski, Matthew J

2018-05-07

Two new isotypic d/f-heterometallic purely inorganic cationic materials, [Ag 2 M(Te 2 O 5 ) 2 ]SO 4 (M = Ce IV or Th IV ), were synthesized using the metal oxides (MO 2 and TeO 2 ), silver nitrate, and sulfuric acid under mild hydrothermal conditions. The prepared materials were characterized via single-crystal X-ray diffraction, which revealed that the materials possess a 3D framework of corner-sharing Te 2 O 5 2- units. The tellurite framework creates four unique pores, three of which are occupied by the M IV and Ag I metal centers. The tellurite network, metal coordination, and total charge yield a cationic framework, which is charge-balanced by electrostatically bound sulfate anions residing in the largest of the four framework pores. These materials also possess Ag I in a ligand-imposed linear geometry.

Human NKCC2 cation–Cl– co-transporter complements lack of Vhc1 transporter in yeast vacuolar membranes.

PubMed

Petrezselyova, Silvia; Dominguez, Angel; Herynkova, Pavla; Macias, Juan F; Sychrova, Hana

2013-10-01

Cation–chloride co-transporters serve to transport Cl– and alkali metal cations. Whereas a large family of these exists in higher eukaryotes, yeasts only possess one cation–chloride co-transporter, Vhc1, localized to the vacuolar membrane. In this study, the human cation–chloride co-transporter NKCC2 complemented the phenotype of VHC1 deletion in Saccharomyces cerevisiae and its activity controlled the growth of salt-sensitive yeast cells in the presence of high KCl, NaCl and LiCl. A S. cerevisiae mutant lacking plasma-membrane alkali–metal cation exporters Nha1 and Ena1-5 and the vacuolar cation–chloride co-transporter Vhc1 is highly sensitive to increased concentrations of alkali–metal cations, and it proved to be a suitable model for characterizing the substrate specificity and transport activity of human wild-type and mutated cation–chloride co-transporters. Copyright © 2013 John Wiley & Sons, Ltd.

Ion exchanger from chemically modified banana leaves.

PubMed

El-Gendy, Ahmed A; Mohamed, Samar H; Abd-Elkader, Amal H

2013-07-25

Cation exchangers from chemically modified banana leaves have been prepared. Banana leaves were treated with different molarities of KMnO4 and cross linked with epichlorohydrin and their effect on metal ion adsorption was investigated. Phosphorylation of chemically modified banana leaves was also studied. The metal ion uptake by these modified banana leaves was clarified. Effect of different varieties, e.g. activation of produced cation exchanger, concentration of metal ions was also investigated. Characterization of the prepared ion exchangers by using infrared and thermal analysis was also taken in consideration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Quantum Chemical Simulation of the Interaction of Functional Groups in Polyurethanes with 3 d-Metal Ions During Their Extraction from Aqueous Solutions

NASA Astrophysics Data System (ADS)

Ksenofontov, M. A.; Bobkova, E. Yu.; Shundalau, M. B.; Ostrovskaya, L. E.; Vasil'eva, V. S.

2017-11-01

The interaction of the functional groups in the polyurethane foam adsorbent Penopurm® with the cations of some 3d-metals upon their extraction from aqueous solutions has been studied by atomic emission spectroscopy, UV/Vis and vibrational IR spectroscopy, and quantum chemical simulation using density functional theory. Penopurm® absorbs 3d-metal cations from aqueous solutions in the pH range 5-7. Some spectral criteria have been found indicating a predominant interaction of Ni2+ ions with various fragments of the polyurethane foam structure.

Examination of the effect of the annealing cation on higher order structures containing guanine or isoguanine repeats

PubMed Central

Pierce, Sarah E.; Wang, Junmei; Jayawickramarajah, Janarthanan; Hamilton, Andrew D.; Brodbelt, Jennifer S.

2010-01-01

Isoguanine (2-oxo-6-amino-guanine), a natural but non-standard base, exhibits unique self-association properties compared to its isomer, guanine, and results in formation of different higher order DNA structures. In this work, the higher order structures formed by oligonucleotides containing guanine repeats or isoguanine repeats after annealing in solutions containing various cations are evaluated by electrospray ionization mass spectrometry (ESI-MS) and circular dichroism (CD) spectroscopy. The guanine-containing strand (G9) consistently formed quadruplexes upon annealing, whereas the isoguanine strand (Ig9) formed both pentaplexes and quadruplexes depending on the annealing cation. Quadruplex formation with G9 showed some dependence on the identity of the cation present during annealing with high relative quadruplex formation detected with six of ten cations. Analogous annealing experiments with Ig9 resulted in complex formation with all ten cations, and the majority of the resulting complexes were pentaplexes. CD results indicated most of the original complexes survived the desalting process necessary for ESI-MS analysis. In addition, several complexes, especially the pentaplexes, were found to be capable of cation exchange with ammonium ions. Ab initio calculations were conducted for isoguanine tetrads and pentads coordinated with all ten cations to predict the most energetically stable structures of the complexes in the gas phase. The observed preference of forming quadruplexes versus pentaplexes as a function of the coordinated cation can be interpreted by the calculated reaction energies of both the tetrads and pentads in combination with the distortion energies of tetrads. PMID:19746468

Integrating bioavailability approaches into waste rock evaluations

USGS Publications Warehouse

Ranville, James F.; Blumenstein, E. P.; Adams, Michael J.; Choate, LaDonna M.; Smith, Kathleen S.; Wildeman, Thomas R.

2006-01-01

The presence of toxic metals in soils affected by mining, industry, agriculture and urbanization, presents problems to human health, the establishment and maintenance of plant and animal habitats, and the rehabilitation of affected areas. A key to managing these problems is predicting the fraction of metal in a given soil that will be biologically labile, and potentially harmful ('bioavailable'). The molecular form of metals and metalloids, particularly the uncomplexed (free) form, controls their bioavailability and toxicity in solution. One computational approach for determining bioavailability, the biotic ligand model (BLM), takes into account not only metal complexation by ligands in solution, but also competitive binding of hardness cations (Ca 2+,Mg 2+,) and metal ions to biological receptor sites. The more direct approach to assess bioavailability is to explicitly measure the response of an organism to a contaminant. A number of microbial enzyme tests have been developed to assess the impact of pollution in a rapid and procedurally simple way. These different approaches in making bioavailability predictions may have value in setting landuse priorities, remediation goals, and habitat reclamation strategies.

Method for the chromatographic separation of cations from aqueous samples

DOEpatents

Horwitz, E.P.; Chiarizia, R.; Dietz, M.L.

1997-07-29

An extraction chromatographic material is described for extracting metal cations from a liquid stream. The extraction chromatographic material is prepared by adsorbing a diesterified methanediphosphonic acid on an inert particulate support. 7 figs.

Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

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

Tatarenko, V.A.; Tsysman, C.L.; Oltarzhevskaya, Y.T.

1994-12-31

The calculations in a majority of previous works for the fulleride (AqC{sub 60}) crystals were performed within the framework of the rigid-lattice model, neglecting the distoration relaxation of the host fullerene (C{sub 60}) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distoration field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. This paper seeks to find a functional relationmore » between the amplitudes of the doping-induced structure-distortion waves and of statistic concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method. In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the statistic inherent reorientation and/or displacements of the solvent molecules from the average-lattice sites as well as on the lattice parameter a of the elastically-anysotropic cubic C{sub 60} crystal are taken into account.« less

Macroscopic and bulk-controlled elastic modes in an interaction of interstitial alcali metal cations within a face-centered cubic crystalline fullerine

NASA Technical Reports Server (NTRS)

Tatarenko, Valentine A.; Tsysman, Constantin L.; Oltarzhevskaya, Yelena T.

1995-01-01

The calculations in a majority of previous works for the fulleride (AqC-60) crystals were performed within the framework of the rigid-lattice model, neglecting the distortion relaxation of the host fullerene (C-60) crystal caused by the interstitial alkali-metal (A) cations. However, an each cation is a source of a static distortion field, and the resulting field is a superposition of such fields generated by all cations. This is a reason why the host-crystal distortions depend on the A-cations configurations, i.e. on a type of a spatial bulk distribution of interstitial cations. The given paper seeks to find a functional relation between the amplitudes of the doping-induced structure-distortion waves and of static concentration ones. A semiphenomenological model is constructed here within the scope of statistical-thermodynamic treatment and using the lattice-statistics simulation method(*). In this model the effects due to the presence of q solute A cations over available interstices (per unit cell) on the static inherent reorientation and/or displacements of the solvent molecules from the 'average-lattice' sites' as well as on the lattice parameter a of a elastically-anysotropic 'cubic' C-60 crystal are taken into account.

Understanding the self-assembly process and behavior of metal-seamed pyrogallol[4]arene nanocapsules

NASA Astrophysics Data System (ADS)

Mossine, Andrew V.

C-alkylpyrogallol[4]arenes (PgCs) are bowl-shaped compounds that are commonly used as supramolecular building blocks in the construction of larger entities such as capsules, nanotubes, and layered networks. Many of these assemblies are constructed using non-covalent means and, as such, are inherently unstable in polar media. Although metal coordination with the hydroxyl-rich PgC upper rim can be exploited to synthesize assemblies with enhanced stability, few reports of this can be found in the literature. Thus, a thorough investigation of these metal-seamed assemblies and their manipulation is of importance. Prior work in the Atwood lab has produced three examples of metal-organic nanocapsules (MONCs) based on PgCs. These include two hexameric MONCs (based on Cu2+ and Ga3+) as well as a single example of a dimeric MONC (based on Zn2+). As it was unknown whether other metal cations could lead to the formation of similar entities, PgC complexation experiments were conducted with other first series transition metal cations, notably Ni2+, Co2+ and Mn2+. All of these led to nanocapsular materials, which were identified and studied using single crystal X-ray diffraction (scXRD). Once the foundational studies were complete, syntheses were also performed under varied conditions, specifically with Ni2+ and Cu2+. This led to the characterization of both dimeric and hexameric MONCs with these two metals, as well as the characterization of many other capsular materials. The information collected from these experiments also led to an intriguing question: which specific conditions lead to the formation of dimeric vs. hexameric MONCs? To answer this question, solid-state analysis using scXRD was coupled to in situ analysis utilizing small angle neutron scattering (SANS). This work showed that the formation of the dimer is typically favored at higher temperatures while the formation of the hexamer is favored at lower temperatures for both of the metals tested. Studies that varied time of measurement as well as the solvent system during synthesis were also performed. Furthermore, SANS was also used to study Fe3+-PgC complexes. These complexes are difficult if not impossible to crystallize, and therefore cannot be studied using scXRD. SANS was used in conjunction with elemental analysis to deduce a structure for these materials. In addition to understanding the synthesis of MONCs, another goal was to also use them for other (possibly practical) purposes. To this end, PgC-based MONCs were used as building blocks in metal-organic frameworks (MOFs). This involved the use of divergent ligands to "link" capsular monomers together, resulting in one and two dimensional frameworks. This work not only produced functional materials that may be useful in future research efforts, but also showed that exo-ligand exchange can be used to derivatize MONCs into potentially useful and functional materials. The introduction of radioisotopes into the nanocapsule was another method by which functionality could theoretically be imparted into MONCs. It was envisioned that MONCs could potentially be used as carrier systems for radioisotopes, and thereby function as agents for therapy or medical imaging. Copper hexamers constructed from 64Cu2+ were therefore prepared and studied in a living system. However, these studies were unsuccessful at showing that the copper-seamed MONCs differed in behavior from 64Cu in vivo, either due to poor labeling efficiency or metabolism. Nevertheless, radiolabeling of hexameric nanocapsules was helpful in broadening our understanding of these materials. Some of the studies that were conducted include those that gauge the solubility and stability of nanocapsules, as well as others that explore the conditions required for cationic uptake and exchange.

Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

DOE PAGES

Berg, John M.; Gaunt, Andrew J.; May, Iain; ...

2015-04-22

A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW 9O 34] 9-, [AsW 9O 34] 9-, [SiW 9O 34] 10- and [GeW 9O 34] 10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO 2} 2+, {NpO 2} +, {NpO 2} 2+ & {PuO 2} 2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na +, K + or NH 4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinylmore » cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH 4) 13 [Na(NpO 2) 2(A-α- PW 9O 34) 2]·12H 2O. The anion in this complex, [Na(NpO 2) 2(PW 9O 34) 2] 13-, contains one Na + cation and two {NpO 2} 2+ cations held between two [PW 9O 34] 9- anions – with an additional partial occupancy NH 4 + or {NpO 2} 2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH 4Cl in the parent solution, it was previously shown that [(NH 4) 2(U VIO 2) 2(A-PW 9O 34) 2] 12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO 2} 2+/[PW 9O 34] 9- and {UO 2} 2+/[PW 9O 34] 9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.« less

Stabilization of battery electrodes using polymer coatings

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

Wessells, Colin Deane; Huggins, Robert Alan

An electrochemical device (e.g., a battery (cell)) including: an aqueous electrolyte and one or two electrodes (e.g., an anode and/or a cathode), one or both of which is a Prussian Blue analogue material of the general chemical formula A.sub.xP[R(CN).sub.6-jL.sub.j].sub.z.nH.sub.2O, where: A is a cation; P is a metal cation; R is a transition metal cation; L is a ligand that may be substituted in the place of a CN.sup.- ligand; 0.ltoreq.x.ltoreq.2; 0.ltoreq.z.ltoreq.1; and 0.ltoreq.n.ltoreq.5, the electrode including a polymer coating to reduce capacity loss.

Force Spectroscopy Reveals the Effect of Different Ions in the Nanomechanical Behavior of Phospholipid Model Membranes: The Case of Potassium Cation

PubMed Central

Redondo-Morata, Lorena; Oncins, Gerard; Sanz, Fausto

2012-01-01

How do metal cations affect the stability and structure of phospholipid bilayers? What role does ion binding play in the insertion of proteins and the overall mechanical stability of biological membranes? Investigators have used different theoretical and microscopic approaches to study the mechanical properties of lipid bilayers. Although they are crucial for such studies, molecular-dynamics simulations cannot yet span the complexity of biological membranes. In addition, there are still some experimental difficulties when it comes to testing the ion binding to lipid bilayers in an accurate way. Hence, there is a need to establish a new approach from the perspective of the nanometric scale, where most of the specific molecular phenomena take place. Atomic force microscopy has become an essential tool for examining the structure and behavior of lipid bilayers. In this work, we used force spectroscopy to quantitatively characterize nanomechanical resistance as a function of the electrolyte composition by means of a reliable molecular fingerprint that reveals itself as a repetitive jump in the approaching force curve. By systematically probing a set of bilayers of different composition immersed in electrolytes composed of a variety of monovalent and divalent metal cations, we were able to obtain a wealth of information showing that each ion makes an independent and important contribution to the gross mechanical resistance and its plastic properties. This work addresses the need to assess the effects of different ions on the structure of phospholipid membranes, and opens new avenues for characterizing the (nano)mechanical stability of membranes. PMID:22225799

Amylose-Based Cationic Star Polymers for siRNA Delivery.

PubMed

Nishimura, Tomoki; Umezaki, Kaori; Mukai, Sada-atsu; Sawada, Shin-ichi; Akiyoshi, Kazunari

2015-01-01

A new siRNA delivery system using a cationic glyco-star polymer is described. Spermine-modified 8-arm amylose star polymer (with a degree of polymerization of approximately 60 per arm) was synthesized by chemoenzymatic methods. The cationic star polymer effectively bound to siRNA and formed spherical complexes with an average hydrodynamic diameter of 230 nm. The cationic 8-arm star polymer complexes showed superior cellular uptake characteristics and higher gene silencing effects than a cationic 1-arm polymer. These results suggest that amylose-based star polymers are a promising nanoplatform for glycobiomaterials.

Mononuclear bromide complexes of Sb(V): crystal structures and thermal behaviour

NASA Astrophysics Data System (ADS)

Adonin, Sergey A.; Bondarenko, Mikhail A.; Samsonenko, Denis G.; Semitut, Evgeniy Yu; Sokolov, Maxim N.; Fedin, Vladimir P.

2018-05-01

Reactions of Sb2O3 dissolved in HBr/Br2 and bromides of pyridinium-derived cations result in mononuclear complexes of Sb(V) - (cation)[SbBr6] (cation = 2-chloropyridinium (1), 2-bromopyridinium (2)). Thermal behaviour of 1 and 2, as well as similar previously reported complexes Et4N [SbBr6] (3) and (N-EtPy)[SbBr6] (4), was studied and discussed.

Enhancing glycan isomer separations with metal ions and positive and negative polarity ion mobility spectrometry-mass spectrometry analyses

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

Zheng, Xueyun; Zhang, Xing; Schocker, Nathaniel S.

Glycomics has become an increasingly important field of research since glycans play critical roles in biology processes ranging from molecular recognition and signaling to cellular communication. Glycans often conjugate with other biomolecules such as proteins and lipids, and alter their properties and functions, so understanding the effect glycans have on cellular systems is essential. However the analysis of glycans is extremely difficult due to their complexity and structural diversity (i.e., the number and identity of monomer units, and configuration of their glycosidic linkages and connectivities). In this work, we coupled ion mobility spectrometry with mass spectrometry (IMS-MS) to characterize glycanmore » standards and biologically important isomers of synthetic αGal-containing O-glycans including glycotopes of the protozoan parasite Trypanosoma cruzi, which is the causative agent of Chagas disease. IMS-MS results showed significant differences for the glycan structural isomers when analyzed in positive and negative polarity and complexed with different metal cations. These results suggest specific metal ions or ion polarities could be used to target and baseline separate glycan isomers of interest with IMS-MS.« less

Flow microcapillary plasma mass spectrometry-based investigation of new Al-Cr-Fe complex metallic alloy passivation.

PubMed

Ott, N; Beni, A; Ulrich, A; Ludwig, C; Schmutz, P

2014-03-01

Al-Cr-Fe complex metallic alloys are new intermetallic phases with low surface energy, low friction, and high corrosion resistance down to very low pH values (0-2). Flow microcapillary plasma mass spectrometry under potentiostatic control was used to characterize the dynamic aspect of passivation of an Al-Cr-Fe gamma phase in acidic electrolytes, allowing a better insight on the parameters inducing chemical stability at the oxyhydroxide-solution interface. In sulfuric acid pH 0, low element dissolution rates (in the µg cm(-2) range after 60 min) evidenced the passive state of the Al-Cr-Fe gamma phase with a preferential over-stoichiometric dissolution of Al and Fe cations. Longer air-aging was found to be beneficial for stabilizing the passive film. In chloride-containing electrolytes, ten times higher Al dissolution rates were detected at open-circuit potential (OCP), indicating that the spontaneously formed passive film becomes unstable. However, electrochemical polarization at low passive potentials induces electrical field generated oxide film modification, increasing chemical stability at the oxyhydroxide-solution interface. In the high potential passive region, localized attack is initiated with subsequent active metal dissolution. © 2013 Published by Elsevier B.V.

Reaction of 1H-1-oxo-2,4,6,8-tetrakis(tert-butyl)phenoxazine with certain group II-IV metals

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

Karsanov, I.V.; Ivakhnenko, E.P.; Khandkarova, V.S.

1987-07-10

It has already been shown that 2-amino-4,6-di(tert-butyl)phenol reacts with 3,5-di(tert-butyl)-o-benzoquinone to form 1H-1-oxo-2,4,6,8-tetrakis(tert-butyl)phenoxazine (I), which is readily reduced by alkali metals to the corresponding semiquinone anion-radical (II), and further to the diamagnetic dianion (IIA). They made use of this ability of (I) to undergo reduction to prepare anion-radical salts with different group II-IV metals in the form of their amalgams. In the EPR spectrum of the anion-radical complex (III) formed in the reduction of (I) by a thallium amalgam, the HFI constants of the unpaired electron with magnetic nuclei of the organic ligand are close to those of the K-saltmore » (II), and a substantial HFI is observed with the /sup 203,205/Tl nuclei. This unequivocally proves that the complex has a semiquinone structure, since an HFI on the /sup 203,205/Tl nuclei of such an order of magnitude is characteristic of o-benzoquinone salts with a thallium cation.« less

Evidence for percolation diffusion of cations and reordering in disordered pyrochlore from accelerated molecular dynamics

DOE PAGES

Perriot, Romain; Uberuaga, Blas P.; Zamora, Richard J.; ...

2017-09-20

Diffusion in complex oxides is critical to ionic transport, radiation damage evolution, sintering, and aging. In complex oxides such as pyrochlores, anionic diffusion is dramatically affected by cation disorder. However, little is known about how disorder influences cation transport. Here, we report results from classical and accelerated molecular dynamics simulations of vacancy-mediated cation diffusion in Gd 2Ti 2O 7 pyrochlore, on the microsecond timescale. We find that diffusion is slow at low levels of disorder, while higher disorder allows for fast diffusion, which is then accompanied by antisite annihilation and reordering, and thus a slowing of cation transport. Cation diffusivitymore » is therefore not constant, but decreases as the material reorders. We also show that fast cation diffusion is triggered by the formation of a percolation network of antisites. This is in contrast with observations from other complex oxides and disordered media models, suggesting a fundamentally different relation between disorder and mass transport.« less