Na+ Interactions with the Neutral Amino Acid Transporter ASCT1*

PubMed Central

Scopelliti, Amanda J.; Heinzelmann, Germano; Kuyucak, Serdar; Ryan, Renae M.; Vandenberg, Robert J.

2014-01-01

The alanine, serine, cysteine transporters (ASCTs) belong to the solute carrier family 1A (SLC1A), which also includes the excitatory amino acid transporters (EAATs) and the prokaryotic aspartate transporter GltPh. Acidic amino acid transport by the EAATs is coupled to the co-transport of three Na+ ions and one proton, and the counter-transport of one K+ ion. In contrast, neutral amino acid exchange by the ASCTs does not require protons or the counter-transport of K+ ions and the number of Na+ ions required is not well established. One property common to SLC1A family members is a substrate-activated anion conductance. We have investigated the number and location of Na+ ions required by ASCT1 by mutating residues in ASCT1 that correspond to residues in the EAATs and GltPh that are involved in Na+ binding. Mutations to all three proposed Na+ sites influence the binding of substrate and/or Na+, or the rate of substrate exchange. A G422S mutation near the Na2 site reduced Na+ affinity, without affecting the rate of exchange. D467T and D467A mutations in the Na1 site reduce Na+ and substrate affinity and also the rate of substrate exchange. T124A and D380A mutations in the Na3 site selectively reduce the affinity for Na+ and the rate of substrate exchange without affecting substrate affinity. In many of the mutants that reduce the rate of substrate transport the amplitudes of the substrate-activated anion conductances are not substantially affected indicating altered ion dependence for channel activation compared with substrate exchange. PMID:24808181

Transient chloride binding as a contributory factor to corneal stromal swelling in the ox.

PubMed Central

Hodson, S; Kaila, D; Hammond, S; Rebello, G; al-Omari, Y

1992-01-01

1. Investigations were made of the cation exchange capacity of fresh isolated ox corneal stroma (Q, units: mequiv fixed stromal charge/kg stromal fluid) at pH 7.4 over a variety of stomal hydrations (H, units: kg stromal fluid/kg dry tissue) both above and below the physiological hydration of 3.2, whilst the stromas were immersed in a variety of sodium chloride solutions (range 5-1000 mM). 2. At any particular salt concentration, the product QH (dry tissue exchange capacity, units: mequiv/kg dry tissue) appeared constant, over all the hydrations investigated. 3. Dry tissue exchange capacity (QH) varied, however, when the bathing salt concentration was altered. It varied between 55 mequiv/kg dry tissue (e.g. Q = 17 mequiv at H = 3.2) in 5 mM-NaCl to 240 mequiv/kg dry tissue (e.g. Q = 75 mequiv/l at H = 3.2) in 1000 mM-NaCl. 4. The variation of stromal exchange capacity in NaCl solutions of different concentrations was similar when detected by three independent procedures: stromal gel pressure measurements, intrastromal sodium ion distributions, and intrastromal electrical potentials. 5. Intrastromal chloride ion distributions were anomalous. Total chloride (measured by radio-isotopes) was consistently higher than that predicted by Donnan theory. 6. The data were consistent with Elliott's hypothesis that a fraction of intrastromal chloride ions bind to the corneal stromal matrix and in so doing contribute to the fixed negative charge of the stroma. 7. Our observations may be explained by a model of the cation exchange capacity of ox cornea which has two types of components. On is (at constant pH) invariant, and has a dry tissue exchange capacity of about 50 mequiv/kg dry tissue, and is probably generated by the sulphonic and carboxylic acid groups of the glycosaminoglycans. The other is explained by supposing it to consist of a chloride binding ligand which exhibits first order binding, is half occupied at ambient chloride concentrations of 300 mM, and has a total capacity of 240 mequiv/kg dry tissue. 8. Partial stromal extraction with 4 M-guanidine HCl indicated that the chloride binding ligand is not associated with the collagen molecules in the corneal stromal fibrils. 9. It is suggested that such a stromal chloride ion binding ligand would help to stabilize the hydration and transparency of the living cornea when it is exposed to environments of varying tonicity (such as in river or sea bathing). PMID:1432722

Fractionation of whey proteins with high-capacity superparamagnetic ion-exchangers.

PubMed

Heebøll-Nielsen, Anders; Justesen, Sune F L; Thomas, Owen R T

2004-09-30

In this study we describe the design, preparation and testing of superparamagnetic anion-exchangers, and their use together with cation-exchangers in the fractionation of bovine whey proteins as a model study for high-gradient magnetic fishing. Adsorbents prepared by attachment of trimethyl amine to particles activated in sequential reactions with allyl bromide and N-bromosuccinimide yielded a maximum bovine serum albumin binding capacity of 156 mg g(-1) combined with a dissociation constant of 0.60 microM, whereas ion-exchangers created by linking polyethylene imine through superficial aldehydes bound up to 337 mg g(-1) with a dissociation constant of 0.042 microM. The latter anion-exchanger was selected for studies of whey protein fractionation. In these, crude bovine whey was treated with a superparamagnetic cation-exchanger to adsorb basic protein species, and the supernatant arising from this treatment was then contacted with the anion-exchanger. For both adsorbent classes of ion-exchanger, desorption selectivity was subsequently studied by sequentially increasing the concentration of NaCl in the elution buffer. In the initial cation-exchange step quantitative removal of lactoferrin (LF) and lactoperoxidase (LPO) was achieved with some simultaneous binding of immunoglobulins (Ig). The immunoglobulins were separated from the other two proteins by desorbing with a low concentration of NaCl (< or = 0.4 M), whereas lactoferrin and lactoperoxidase were co-eluted in significantly purer form, e.g. lactoperoxidase was purified 28-fold over the starting material, when the NaCl concentration was increased to 0.4-1 M. The anion-exchanger adsorbed beta-lactoglobulin (beta-LG) selectively allowing separation from the remaining protein.

Calculation of Free Energy Landscape in Multi-Dimensions with Hamiltonian-Exchange Umbrella Sampling on Petascale Supercomputer.

PubMed

Jiang, Wei; Luo, Yun; Maragliano, Luca; Roux, Benoît

2012-11-13

An extremely scalable computational strategy is described for calculations of the potential of mean force (PMF) in multidimensions on massively distributed supercomputers. The approach involves coupling thousands of umbrella sampling (US) simulation windows distributed to cover the space of order parameters with a Hamiltonian molecular dynamics replica-exchange (H-REMD) algorithm to enhance the sampling of each simulation. In the present application, US/H-REMD is carried out in a two-dimensional (2D) space and exchanges are attempted alternatively along the two axes corresponding to the two order parameters. The US/H-REMD strategy is implemented on the basis of parallel/parallel multiple copy protocol at the MPI level, and therefore can fully exploit computing power of large-scale supercomputers. Here the novel technique is illustrated using the leadership supercomputer IBM Blue Gene/P with an application to a typical biomolecular calculation of general interest, namely the binding of calcium ions to the small protein Calbindin D9k. The free energy landscape associated with two order parameters, the distance between the ion and its binding pocket and the root-mean-square deviation (rmsd) of the binding pocket relative the crystal structure, was calculated using the US/H-REMD method. The results are then used to estimate the absolute binding free energy of calcium ion to Calbindin D9k. The tests demonstrate that the 2D US/H-REMD scheme greatly accelerates the configurational sampling of the binding pocket, thereby improving the convergence of the potential of mean force calculation.

Dispersion- and Exchange-Corrected Density Functional Theory for Sodium Ion Hydration.

PubMed

Soniat, Marielle; Rogers, David M; Rempe, Susan B

2015-07-14

A challenge in density functional theory is developing functionals that simultaneously describe intermolecular electron correlation and electron delocalization. Recent exchange-correlation functionals address those two issues by adding corrections important at long ranges: an atom-centered pairwise dispersion term to account for correlation and a modified long-range component of the electron exchange term to correct for delocalization. Here we investigate how those corrections influence the accuracy of binding free energy predictions for sodium-water clusters. We find that the dual-corrected ωB97X-D functional gives cluster binding energies closest to high-level ab initio methods (CCSD(T)). Binding energy decomposition shows that the ωB97X-D functional predicts the smallest ion-water (pairwise) interaction energy and larger multibody contributions for a four-water cluster than most other functionals - a trend consistent with CCSD(T) results. Also, ωB97X-D produces the smallest amounts of charge transfer and the least polarizable waters of the density functionals studied, which mimics the lower polarizability of CCSD. When compared with experimental binding free energies, however, the exchange-corrected CAM-B3LYP functional performs best (error <1 kcal/mol), possibly because of its parametrization to experimental formation enthalpies. For clusters containing more than four waters, "split-shell" coordination must be considered to obtain accurate free energies in comparison with experiment.

Microbial biofilms for the removal of Cu²⁺ from CMP wastewater.

PubMed

Mosier, Aaron P; Behnke, Jason; Jin, Eileen T; Cady, Nathaniel C

2015-09-01

The modern semiconductor industry relies heavily on a process known as chemical mechanical planarization, which uses physical and chemical processes to remove excess material from the surface of silicon wafers during microchip fabrication. This process results in large volumes of wastewater containing dissolved metals including copper (Cu(2+)), which must then be filtered and treated before release into municipal waste systems. We have investigated the potential use of bacterial and fungal biomass as an alternative to the currently used ion-exchange resins for the adsorption of dissolved Cu(2+) from high-throughput industrial waste streams. A library of candidate microorganisms, including Lactobacillus casei and Pichia pastoris, was screened for ability to bind Cu(2+) from solution and to form static biofilm communities within packed-bed adsorption columns. The binding efficiency of these biomass-based adsorption columns was assessed under various flow conditions and compared to that of industrially used ion-exchange resins. We demonstrated the potential to regenerate the biomass within the adsorption columns through the use of a hydrochloric acid wash, and subsequently reuse the columns for additional copper binding. While the binding efficiency and capacity of the developed L. casei/P. pastoris biomass filters was inferior to ion-exchange resin, the potential for repeated reuse of these filters, coupled with the advantages of a more sustainable "green" adsorption process, make this technique an attractive candidate for use in industrial-scale CMP wastewater treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Location and ion-binding of membrane-associated valinomycin, a proton nuclear magnetic resonance study.

PubMed

Meers, P; Feigenson, G W

1988-03-03

Valinomycin, incorporated in small unilamellar vesicles of perdeuterated dimyristoylphosphatidylcholine, reveals several well-resolved 1H-NMR resonances. These resonances were used to examine the location, orientation and ion-binding of membrane-bound valinomycin. The order of affinity of membrane-bound valinomycin for cations is Rb+ greater than K+ greater than Cs+ greater than Ba2+, and binding is sensitive to surface change. The exchange between bound and free forms is fast on the NMR time scale. The intrinsic binding constants, extrapolated to zero anion concentration, are similar to those determined in aqueous solution. Rb+ and K+ show 1:1 binding to valinomycin, whereas the stoichiometry of Cs+ and Ba2+ is not certain. Paramagnetic chemical shift reagents and nitroxide spin label relaxation probes were used to study the location and orientation of valinomycin in the membrane. Despite relatively fast exchange of bound cations, the time average location of the cation-free form of valinomycin is deep within the bilayer under the conditions of these experiments. Upon complexation to K+, valinomycin moves closer to the interfacial region.

Role of Microbial Exopolymeric Substances (EPS) on Chromium Sorption and Transport in Heterogeneous Subsurface Soils: I. Cr(III) Complexation with EPS in Aqueous Solution

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

C Kantar; H Demiray; N Dogan

2011-12-31

Chromium (III) binding by exopolymeric substances (EPS) isolated from Pseudomonas putida P18, Pseudomonas aeruginosa P16 and Pseudomonas stutzeri P40 strains were investigated by the determination of conditional stability constants and the concentration of functional groups using the ion-exchange experiments and potentiometric titrations. Spectroscopic (EXAFS) analysis was also used to obtain information on the nature of Cr(III) binding with EPS functional groups. The data from ion-exchange experiments and potentiometric titrations were evaluated using a non-electrostatic discrete ligand approach. The modeling results show that the acid/base properties of EPSs can be best characterized by invoking four different types of acid functional groupsmore » with arbitrarily assigned pK{sub a} values of 4, 6, 8 and 10. The analysis of ion-exchange data using the discrete ligand approach suggests that while the Cr binding by EPS from P. aeruginosa can be successfully described based on a reaction stoichiometry of 1:2 between Cr(III) and HL{sub 2} monoprotic ligands, the accurate description of Cr binding by EPSs extracted from P. putida and P. stutzeri requires postulation of 1:1 Cr(III)-ligand complexes with HL{sub 2} and HL{sub 3} monoprotic ligands, respectively. These results indicate that the carboxyl and/or phosphoric acid sites contribute to Cr(III) binding by microbial EPS, as also confirmed by EXAFS analysis performed in the current study. Overall, this study highlights the need for incorporation of Cr-EPS interactions into transport and speciation models to more accurately assess microbial Cr(VI) reduction and chromium transport in subsurface systems, including microbial reactive treatment barriers.« less

Role of microbial exopolymeric substances (EPS) on chromium sorption and transport in heterogeneous subsurface soils: I. Cr(III) complexation with EPS in aqueous solution

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

Kantar, C.; Dodge, C.; Demiray, H.

2011-01-26

Chromium (III) binding by exopolymeric substances (EPS) isolated from Pseudomonas putida P18, Pseudomonas aeruginosa P16 and Pseudomonas stutzeri P40 strains were investigated by the determination of conditional stability constants and the concentration of functional groups using the ion-exchange experiments and potentiometric titrations. Spectroscopic (EXAFS) analysis was also used to obtain information on the nature of Cr(III) binding with EPS functional groups. The data from ion-exchange experiments and potentiometric titrations were evaluated using a non-electrostatic discrete ligand approach. The modeling results show that the acid/base properties of EPSs can be best characterized by invoking four different types of acid functional groupsmore » with arbitrarily assigned pK{sub a} values of 4, 6, 8 and 10. The analysis of ion-exchange data using the discrete ligand approach suggests that while the Cr binding by EPS from P. aeruginosa can be successfully described based on a reaction stoichiometry of 1:2 between Cr(III) and HL{sub 2} monoprotic ligands, the accurate description of Cr binding by EPSs extracted from P. putida and P. stutzeri requires postulation of 1:1 Cr(III)-ligand complexes with HL{sub 2} and HL{sub 3} monoprotic ligands, respectively. These results indicate that the carboxyl and/or phosphoric acid sites contribute to Cr(III) binding by microbial EPS, as also confirmed by EXAFS analysis performed in the current study. Overall, this study highlights the need for incorporation of Cr-EPS interactions into transport and speciation models to more accurately assess microbial Cr(VI) reduction and chromium transport in subsurface systems, including microbial reactive treatment barriers.« less

Soil-modified carbon paste electrode: a useful tool in environmental assessment of heavy metal ion binding interactions.

PubMed

Svegl, I G; Ogorevc, B

2000-08-01

Carbon paste electrodes (CPEs) modified with different soils in their native form were prepared to create a soil-like solid phase suitable for application in studies of heavy metal ion uptake and binding interactions. The preparation of CPEs modified with five different soils was examined and their heavy metal ion uptake behavior investigated using a model Cu(II) aqueous solution. Metal ions were accumulated under open circuit conditions and were determined after a medium exchange using differential pulse anodic stripping voltammetry, applying preelectrolysis at -0.7 V. The soil-modified CPE accumulation behavior, including the linearity of the current response versus Cu(II) concentration, the influence of the pH on the solution, and the uptake kinetics, was thoroughly investigated. The correlation between the soil-modified CPE uptake capability and the standard soil parameters, such as ion exchange capacity, soil pH, organic matter and clay content, were evaluated for all five examined soils. The influence of selected endogenous cations (K(I), Ca(II), Fe(III)) on the transfer of Cu(II) ions from a solution to the simulated soil solid phase was examined and is discussed. Preliminary examinations of the soil-modified CPE uptake behavior with some exogenous heavy metal ions of strong environmental interest (Pb(II), Hg(II), Cd(II) and Ag(I)) are also presented. This work demonstrates some attractive possibilities for the application of a soil-modified CPE in studying soil-heavy metal ion binding interactions, with a further potential use as a new environmental sensor appropriate for fist on-site testing of polluted soils.

Nanofiber Ion-Exchange Membranes for the Rapid Uptake and Recovery of Heavy Metals from Water

PubMed Central

Chitpong, Nithinart; Husson, Scott M.

2016-01-01

An evaluation of the performance of polyelectrolyte-modified nanofiber membranes was undertaken to determine their efficacy in the rapid uptake and recovery of heavy metals from impaired waters. The membranes were prepared by grafting poly(acrylic acid) (PAA) and poly(itaconic acid) (PIA) to cellulose nanofiber mats. Performance measurements quantified the dynamic ion-exchange capacity for cadmium (Cd), productivity, and recovery of Cd(II) from the membranes by regeneration. The dynamic binding capacities of Cd(II) on both types of nanofiber membrane were independent of the linear flow velocity, with a residence time of as low as 2 s. Analysis of breakthrough curves indicated that the mass flow rate increased rapidly at constant applied pressure after membranes approached equilibrium load capacity for Cd(II), apparently due to a collapse of the polymer chains on the membrane surface, leading to an increased porosity. This mechanism is supported by hydrodynamic radius (Rh) measurements for PAA and PIA obtained from dynamic light scattering, which show that Rh values decrease upon Cd(II) binding. Volumetric productivity was high for the nanofiber membranes, and reached 0.55 mg Cd/g/min. The use of ethylenediaminetetraacetic acid as regeneration reagent was effective in fully recovering Cd(II) from the membranes. Ion-exchange capacities were constant over five cycles of binding-regeneration. PMID:27999394

Nanofiber Ion-Exchange Membranes for the Rapid Uptake and Recovery of Heavy Metals from Water.

PubMed

Chitpong, Nithinart; Husson, Scott M

2016-12-20

An evaluation of the performance of polyelectrolyte-modified nanofiber membranes was undertaken to determine their efficacy in the rapid uptake and recovery of heavy metals from impaired waters. The membranes were prepared by grafting poly(acrylic acid) (PAA) and poly(itaconic acid) (PIA) to cellulose nanofiber mats. Performance measurements quantified the dynamic ion-exchange capacity for cadmium (Cd), productivity, and recovery of Cd(II) from the membranes by regeneration. The dynamic binding capacities of Cd(II) on both types of nanofiber membrane were independent of the linear flow velocity, with a residence time of as low as 2 s. Analysis of breakthrough curves indicated that the mass flow rate increased rapidly at constant applied pressure after membranes approached equilibrium load capacity for Cd(II), apparently due to a collapse of the polymer chains on the membrane surface, leading to an increased porosity. This mechanism is supported by hydrodynamic radius (R h ) measurements for PAA and PIA obtained from dynamic light scattering, which show that R h values decrease upon Cd(II) binding. Volumetric productivity was high for the nanofiber membranes, and reached 0.55 mg Cd/g/min. The use of ethylenediaminetetraacetic acid as regeneration reagent was effective in fully recovering Cd(II) from the membranes. Ion-exchange capacities were constant over five cycles of binding-regeneration.

Cation exchange assisted binding-elution strategy for enzymatic synthesis of human milk oligosaccharides (HMOs).

PubMed

Zhu, Hailiang; Wu, Zhigang; Gadi, Madhusudhan Reddy; Wang, Shuaishuai; Guo, Yuxi; Edmunds, Garrett; Guan, Wanyi; Fang, Junqiang

2017-09-15

A cation exchange assisted binding-elution (BE) strategy for enzymatic synthesis of human milk oligosaccharides (HMOs) was developed. An amino linker was used to provide the cation ion under acidic condition which can be readily bound to cation exchange resin and then eluted off by saturated ammonium bicarbonate. Ammonium bicarbonate in the collections was easily removed by vacuum evaporation. This strategy circumvented the incompatible issue between glycosyltransferases and solid support or large polymers, and no purification was needed for intermediate products. With current approach, polyLacNAc backbones of HMOs and fucosylated HMOs were synthesized smoothly. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of synthetic macroporous ion-exchange resins in low-pressure cartridges and columns. Evaluation of the performance of Macro-Prep 50 S resin in the purification of anti-Klenow antibodies from goat serum.

PubMed

Dunn, L; Abouelezz, M; Cummings, L; Navvab, M; Ordunez, C; Siebert, C J; Talmadge, K W

1991-07-12

Three ion-exchange materials and one hydrophobic-interaction chromatography packing, based on a rigid macroporous polymer with large, relatively uniform pores, have been evaluated for low-pressure liquid chromatography of antibodies. These sorbents have high capacities for both small and large proteins and are mechanically, chemically, and thermally stable. Macro-Prep 50 S. CM and Q ion-exchange materials are strongly acidic, weakly acidic, and strongly basic, respectively. Protein binding and recovery, pressure-flow properties, and chemical and thermal stability were determined for each sorbent. A rapid, two-step method for the purification of anti-Klenow antibodies from goat serum was developed, based on the Macro-Prep 50 S strong-acid cation-exchange material and the Econo-Pac HIC prepacked hydrophobic-interaction cartridge.

Pyruvate and ketone-body transport across the mitochondrial membrane. Exchange properties, pH-dependence and mechanism of the carrier.

PubMed

Halestrap, A P

1978-06-15

The effects of exchangeable ions and pH on the efflux of pyruvate from preloaded mitochondria are reported. Efflux obeys first-order kinetics, and the stimulation of efflux by exchangeable ions such as acetoacetate and lactate obeys Michaelis--Menten kinetics. The apparent Km value +/- S.E. for acetoacetate was 0.56 +/- 0.14 mM (n = 5) and that for lactate 12.3 +/- 2.3 mM (n = 6). The Vmax. values +/- S.E. at 0 degrees C were 16.2 +/- 2.0 and 21.9 +/- 2.7 nmol/min per mg of protein. The exchange of a variety of other substituted monocarboxylates was also studied. Efflux was also stimulated by increasing the external pH. The data gave a pK for the transport process of 8.35 and a Vmax. of 3.31 +/- 0.14 nmol/min per mg. The similarity of the Vmax. values for various exchangeable ions but the difference of this from the Vmax. in the absence of exchangeable ions may indicate that transport of pyruvate occurs with H+ and not in exchange for an OH- ion. The inhibition of transport by alpha-cyano-4-hydroxycinnamate took several seconds to reach completion at 0 degrees C. It is proposed that inhibition occurs by binding to the substrate site and subsequent reaction with an -SH group on the inside of the membrane. The inhibitor can be displaced by substrates that can also enter the mitochondria independently of the carrier and so compete with the inhibitor for the substrate-binding site on the inside of the membrane. A mechanism for transport is proposed that invokes a transition state of pyruvate involving addition of an -SH group to the 2-carbon of pyruvate. Evidence is presented that suggests that ketone bodies may cross the mitochondrial membrane either on the carrier or by free diffusion. The physiological involvement of the carrier in ketone-body metabolism is discussed. The role of ketone bodies and pH in the physiological regulation of pyruvate transport is considered.

Separating the Role of Protein Restraints and Local Metal-Site Interaction Chemistry in the Thermodynamics of a Zinc Finger Protein

PubMed Central

Dixit, Purushottam D.; Asthagiri, D.

2011-01-01

We express the effective Hamiltonian of an ion-binding site in a protein as a combination of the Hamiltonian of the ion-bound site in vacuum and the restraints of the protein on the site. The protein restraints are described by the quadratic elastic network model. The Hamiltonian of the ion-bound site in vacuum is approximated as a generalized Hessian around the minimum energy configuration. The resultant of the two quadratic Hamiltonians is cast into a pure quadratic form. In the canonical ensemble, the quadratic nature of the resultant Hamiltonian allows us to express analytically the excess free energy, enthalpy, and entropy of ion binding to the protein. The analytical expressions allow us to separate the roles of the dynamic restraints imposed by the protein on the binding site and the temperature-independent chemical effects in metal-ligand coordination. For the consensus zinc-finger peptide, relative to the aqueous phase, the calculated free energy of exchanging Zn2+ with Fe2+, Co2+, Ni2+, and Cd2+ are in agreement with experiments. The predicted excess enthalpy of ion exchange between Zn2+ and Co2+ also agrees with the available experimental estimate. The free energy of applying the protein restraints reveals that relative to Zn2+, the Co2+, and Cd2+-site clusters are more destabilized by the protein restraints. This leads to an experimentally testable hypothesis that a tetrahedral metal binding site with minimal protein restraints will be less selective for Zn2+ over Co2+ and Cd2+ compared to a zinc finger peptide. No appreciable change is expected for Fe2+ and Ni2+. The framework presented here may prove useful in protein engineering to tune metal selectivity. PMID:21943427

Structure-Functional Basis of Ion Transport in Sodium–Calcium Exchanger (NCX) Proteins

PubMed Central

Giladi, Moshe; Shor, Reut; Lisnyansky, Michal; Khananshvili, Daniel

2016-01-01

The membrane-bound sodium–calcium exchanger (NCX) proteins shape Ca2+ homeostasis in many cell types, thus participating in a wide range of physiological and pathological processes. Determination of the crystal structure of an archaeal NCX (NCX_Mj) paved the way for a thorough and systematic investigation of ion transport mechanisms in NCX proteins. Here, we review the data gathered from the X-ray crystallography, molecular dynamics simulations, hydrogen–deuterium exchange mass-spectrometry (HDX-MS), and ion-flux analyses of mutants. Strikingly, the apo NCX_Mj protein exhibits characteristic patterns in the local backbone dynamics at particular helix segments, thereby possessing characteristic HDX profiles, suggesting structure-dynamic preorganization (geometric arrangements of catalytic residues before the transition state) of conserved α1 and α2 repeats at ion-coordinating residues involved in transport activities. Moreover, dynamic preorganization of local structural entities in the apo protein predefines the status of ion-occlusion and transition states, even though Na+ or Ca2+ binding modifies the preceding backbone dynamics nearby functionally important residues. Future challenges include resolving the structural-dynamic determinants governing the ion selectivity, functional asymmetry and ion-induced alternating access. Taking into account the structural similarities of NCX_Mj with the other proteins belonging to the Ca2+/cation exchanger superfamily, the recent findings can significantly improve our understanding of ion transport mechanisms in NCX and similar proteins. PMID:27879668

Structure-Functional Basis of Ion Transport in Sodium-Calcium Exchanger (NCX) Proteins.

PubMed

Giladi, Moshe; Shor, Reut; Lisnyansky, Michal; Khananshvili, Daniel

2016-11-22

The membrane-bound sodium-calcium exchanger (NCX) proteins shape Ca 2+ homeostasis in many cell types, thus participating in a wide range of physiological and pathological processes. Determination of the crystal structure of an archaeal NCX (NCX_Mj) paved the way for a thorough and systematic investigation of ion transport mechanisms in NCX proteins. Here, we review the data gathered from the X-ray crystallography, molecular dynamics simulations, hydrogen-deuterium exchange mass-spectrometry (HDX-MS), and ion-flux analyses of mutants. Strikingly, the apo NCX_Mj protein exhibits characteristic patterns in the local backbone dynamics at particular helix segments, thereby possessing characteristic HDX profiles, suggesting structure-dynamic preorganization (geometric arrangements of catalytic residues before the transition state) of conserved α₁ and α₂ repeats at ion-coordinating residues involved in transport activities. Moreover, dynamic preorganization of local structural entities in the apo protein predefines the status of ion-occlusion and transition states, even though Na⁺ or Ca 2+ binding modifies the preceding backbone dynamics nearby functionally important residues. Future challenges include resolving the structural-dynamic determinants governing the ion selectivity, functional asymmetry and ion-induced alternating access. Taking into account the structural similarities of NCX_Mj with the other proteins belonging to the Ca 2+ /cation exchanger superfamily, the recent findings can significantly improve our understanding of ion transport mechanisms in NCX and similar proteins.

Binding of Dissolved Strontium by Micrococcus luteus

PubMed Central

Faison, Brendlyn D.; Cancel, Carmen A.; Lewis, Susan N.; Adler, Howard I.

1990-01-01

Resting cells of Micrococcus luteus have been shown to remove strontium (Sr) from dilute aqueous solutions of SrCl2 at pH 7. Loadings of 25 mg of Sr per g of cell dry weight were achieved by cells exposed to a solution containing 50 ppm (mg/liter) of Sr. Sr binding occurred in the absence of nutrients and did not require metabolic activity. Initial binding was quite rapid (<0.5 h), although a slow, spontaneous release of Sr was observed over time. Sr binding was inhibited in the presence of polyvalent cations but not monovalent cations. Ca and Sr were bound preferentially over all other cations tested. Sr-binding activity was localized on the cell envelope and was sensitive to various chemical and physical pretreatments. Bound Sr was displaced by divalent ions or by H+. Other monovalent ions were less effective. Bound Sr was also removed by various chelating agents. It was concluded that Sr binding by M. luteus is a reversible equilibrium process. Both ion exchange mediated by acidic cell surface components and intracellular uptake may be involved in this activity. PMID:16348370

A versatile method for fabricating ion-exchange hydrogel nanofibrous membranes with superb biomolecule adsorption and separation properties.

PubMed

Lv, Huan; Wang, Xueqin; Fu, Qiuxia; Si, Yang; Yin, Xia; Li, Xiaoran; Sun, Gang; Yu, Jianyong; Ding, Bin

2017-11-15

Construction ion-exchange membranes with superb biomolecules adsorption and purification performance plays a greatly important role in the fields of biotechnological and biopharmaceutical industry, yet still remains an extremely challenging. Herein, we in situ synthesized the cis-butenedioic anhydride grafted poly(vinyl alcohol) hydrogel nanofibrous membranes (CBA-g-PVA HNFM) by combining electrospinning technique with the grafting-copolymerization crosslinking. Taking advantages of the large specific surface area which could provide numerous sites available for functional groups and biomolecules binding, highly tortuous and interconnected porous channel for biomolecules transfer, and enhanced mechanical strength, the resultant CBA-g-PVA HNFM exhibited relatively high binding amount of 170mgg -1 , rapid equilibrium time of 8h towards the biomolecule template of lysozyme, and the performance could be tailored by regulating the buffer properties and protein concentrations. Additionally, the resultant functional HNFM also possessed superior acid resistance property, excellent reversibility and regeneration performance. More importantly, the obtained CBA-g-PVA HNFM could directly extract lysozyme from fresh chicken eggs with capacity of 125mgg -1 , exhibiting excellent practical application properties. The fabrication of proposed CBA-g-PVA HNFM offers a feasible alternative for construction of ion-exchange chromatograph column for bio-separation and purification engineering. Copyright © 2017 Elsevier Inc. All rights reserved.

New Gel-Like Polymers as Selective Weak-Base Anion Exchangers

PubMed Central

Gierczyk, Błażej; Cegłowski, Michał; Zalas, Maciej

2015-01-01

A group of new anion exchangers, based on polyamine podands and of excellent ion-binding capacity, were synthesized. The materials were obtained in reactions between various poly(ethyleneamines) with glycidyl derivatives of cyclotetrasiloxane. The final polymeric, strongly cross-linked materials form gel-like solids. Their structures and interactions with anions adsorbed were studied by spectroscopic methods (CP-MAS NMR, FR-IR, UV-Vis). The sorption isotherms and kinetic parameters were determined for 29 anions. Materials studied show high ion capacity and selectivity towards some important anions, e.g., selenate(VI) or perrhenate. PMID:25946220

Disturbances of Ligand Potency and Enhanced Degradation of the Human Glycine Receptor at Affected Positions G160 and T162 Originally Identified in Patients Suffering from Hyperekplexia

PubMed Central

Atak, Sinem; Langlhofer, Georg; Schaefer, Natascha; Kessler, Denise; Meiselbach, Heike; Delto, Carolyn; Schindelin, Hermann; Villmann, Carmen

2015-01-01

Ligand-binding of Cys-loop receptors is determined by N-terminal extracellular loop structures from the plus as well as from the minus side of two adjacent subunits in the pentameric receptor complex. An aromatic residue in loop B of the glycine receptor (GlyR) undergoes direct interaction with the incoming ligand via a cation-π interaction. Recently, we showed that mutated residues in loop B identified from human patients suffering from hyperekplexia disturb ligand-binding. Here, we exchanged the affected human residues by amino acids found in related members of the Cys-loop receptor family to determine the effects of side chain volume for ion channel properties. GlyR variants were characterized in vitro following transfection into cell lines in order to analyze protein expression, trafficking, degradation and ion channel function. GlyR α1 G160 mutations significantly decrease glycine potency arguing for a positional effect on neighboring aromatic residues and consequently glycine-binding within the ligand-binding pocket. Disturbed glycinergic inhibition due to T162 α1 mutations is an additive effect of affected biogenesis and structural changes within the ligand-binding site. Protein trafficking from the ER toward the ER-Golgi intermediate compartment, the secretory Golgi pathways and finally the cell surface is largely diminished, but still sufficient to deliver ion channels that are functional at least at high glycine concentrations. The majority of T162 mutant protein accumulates in the ER and is delivered to ER-associated proteasomal degradation. Hence, G160 is an important determinant during glycine binding. In contrast, T162 affects primarily receptor biogenesis whereas exchanges in functionality are secondary effects thereof. PMID:26733802

A critical review of three methods used for the measurement of mercury (Hg2+)-dissolved organic matter stability constants

USGS Publications Warehouse

Gasper, J.D.; Aiken, G.R.; Ryan, J.N.

2007-01-01

Three experimental techniques - ion exchange, liquid-liquid extraction with competitive ligand exchange, and solid-phase extraction with competitive ligand exchange (CLE-SPE) - were evaluated as methods for determining conditional stability constants (K) for the binding of mercury (Hg2+) to dissolved organic matter (DOM). To determine the utility of a given method to measure stability constants at environmentally relevant experimental conditions, experimental results should meet three criteria: (1) the data must be experimentally valid, in that they were acquired under conditions that meet all the requirements of the experimental method, (2) the Hg:DOM ratio should be determined and it should fall within levels that are consistent with environmental conditions, and (3) the stability constants must fall within the detection window of the method. The ion exchange method was found to be limited by its detection window, which constrains the method to stability constants with log K values less than about 14. The liquid-liquid extraction method was found to be complicated by the ability of Hg-DOM complexes to partition into the organic phase. The CLE-SPE method was found to be the most suitable of these methods for the measurement of Hg-DOM stability constants. Stability constants for DOM isolates measured using the CLE-SPE method at environmentally relevant Hg:DOM ratios were log K = 25-30 (M-1). These values are consistent with the strong Hg2+ binding expected for reduced S-containing binding sites. ?? 2007 Elsevier Ltd. All rights reserved.

Solution and Gas-Phase H/D Exchange of Protein-Small-Molecule Complexes: Cex and Its Inhibitors

NASA Astrophysics Data System (ADS)

Kang, Yang; Terrier, Peran; Ding, Chuanfan; Douglas, D. J.

2012-01-01

The properties of noncovalent complexes of the enzyme exo-1,4-β-D-glycanase ("Cex") with three aza-sugar inhibitors, deoxynojirimycin (X2DNJ), isofagomine lactam (X2IL), and isofagomine (X2IF), have been studied with solution and gas-phase hydrogen deuterium exchange (H/Dx) and measurements of collision cross sections of gas-phase ions. In solution, complexes have lower H/Dx levels than free Cex because binding the inhibitors blocks some sites from H/Dx and reduces fluctuations of the protein. In mass spectra of complexes, abundant Cex ions are seen, which mostly are formed by dissociation of complexes in the ion sampling interface. Both complex ions and Cex ions formed from a solution containing complexes have lower cross sections than Cex ions from a solution of Cex alone. This suggests the Cex ions formed by dissociation "remember" their solution conformations. For a given charge, ions of the complexes have greater gas-phase H/Dx levels than ions of Cex. Unlike cross sections, H/Dx levels of the complexes do not correlate with the relative gas-phase binding strengths measured by MS/MS. Cex ions from solutions with or without inhibitors, which have different cross sections, show the same H/Dx level after 15 s, indicating the ions may fold or unfold on the seconds time scale of the H/Dx experiment. Thus, cross sections show that complexes have more compact conformations than free protein ions on the time scale of ca. 1 ms. The gas-phase H/Dx measurements show that at least some complexes retain different conformations from the Cex ions on a time scale of seconds.

Combined computational and biochemical study reveals the importance of electrostatic interactions between the "pH sensor" and the cation binding site of the sodium/proton antiporter NhaA of Escherichia coli.

PubMed

Olkhova, Elena; Kozachkov, Lena; Padan, Etana; Michel, Hartmut

2009-08-15

Sodium proton antiporters are essential enzymes that catalyze the exchange of sodium ions for protons across biological membranes. The crystal structure of NhaA has provided a basis to explore the mechanism of ion exchange and its unique regulation by pH. Here, the mechanism of the pH activation of the antiporter is investigated through functional and computational studies of several variants with mutations in the ion-binding site (D163, D164). The most significant difference found computationally between the wild type antiporter and the active site variants, D163E and D164N, are low pK(a) values of Glu78 making them insensitive to pH. Although in the variant D163N the pK(a) of Glu78 is comparable to the physiological one, this variant cannot demonstrate the long-range electrostatic effect of Glu78 on the pH-dependent structural reorganization of trans-membrane helix X and, hence, is proposed to be inactive. In marked contrast, variant D164E remains sensitive to pH and can be activated by alkaline pH shift. Remarkably, as expected computationally and discovered here biochemically, D164E is viable and active in Na(+)/H(+) exchange albeit with increased apparent K(M). Our results unravel the unique electrostatic network of NhaA that connect the coupled clusters of the "pH sensor" with the binding site, which is crucial for pH activation of NhaA. 2009 Wiley-Liss, Inc.

Studies on the application of temperature-responsive ion exchange polymers with whey proteins.

PubMed

Maharjan, Pankaj; Campi, Eva M; De Silva, Kirthi; Woonton, Brad W; Jackson, W Roy; Hearn, Milton T W

2016-03-18

Several new types of temperature-responsive ion exchange resins of different polymer composition have been prepared by grafting the products from the co-polymerisation of N-phenylacrylamide, N-iso-propylacrylamide and acrylic acid derivatives onto cross-linked agarose. Analysis of the binding isotherms for these different resins obtained under batch adsorption conditions indicated that the resin based on N-iso-propylacrylamide containing 5% (w/w) N-phenylacrylamide and 5% (w/w) acrylic acid resulted in the highest adsorption capacity, Bmax, for the whey protein, bovine lactoferrin, e.g. 14 mg bovine lactoferrin/mL resin at 4 °C and 62 mg bovine lactoferrin/mL resin at 40 °C, respectively. Under dynamic loading conditions at 40 °C, 94% of the loaded bovine lactoferrin on a normalised mg protein per mL resin basis was adsorbed by this new temperature-responsive ion-exchanger, and 76% was eluted by a single cycle temperature shift to 4 °C without varying the composition of the 10mM sodium dihydrogen phosphate buffer, pH 6.5, or the flow rate. The binding characteristics of these different ion exchange resins with bovine lactoferrin were also compared to results obtained using other resins based on N-isopropylacrylamide but contained N-tert-butylacrylamide rather than N-phenylacrylamide, where the corresponding dynamic capture and release properties for bovine lactoferrin required different temperature conditions of 20 °C and 50 °C, respectively for optimal desorption/adsorption. The cationic protein, bovine lactoperoxidase, was also adsorbed and desorbed with these temperature-responsive resins under similar conditions of changing temperature, whereas the anionic protein, bovine β-lactoglobulin, was not adsorbed under this regime of temperature conditions but instead eluted in the flow-through. Copyright © 2016 Elsevier B.V. All rights reserved.

A structural coarse-grained model for clays using simple iterative Boltzmann inversion

NASA Astrophysics Data System (ADS)

Schaettle, Karl; Ruiz Pestana, Luis; Head-Gordon, Teresa; Lammers, Laura Nielsen

2018-06-01

Cesium-137 is a major byproduct of nuclear energy generation and is environmentally threatening due to its long half-life and affinity for naturally occurring micaceous clays. Recent experimental observations of illite and phlogopite mica indicate that Cs+ is capable of exchanging with K+ bound in the anhydrous interlayers of layered silicates, forming sharp exchange fronts, leading to interstratification of Cs- and K-illite. We present here a coarse-grained (CG) model of the anhydrous illite interlayer developed using iterative Boltzmann inversion that qualitatively and quantitatively reproduces features of a previously proposed feedback mechanism of ion exchange. The CG model represents a 70-fold speedup over all-atom models of clay systems and predicts interlayer expansion for K-illite near ion exchange fronts. Contrary to the longstanding theory that ion exchange in a neighboring layer increases the binding of K in lattice counterion sites leading to interstratification, we find that the presence of neighboring exchanged layers leads to short-range structural relaxations that increase basal spacing and decrease cohesion of the neighboring K-illite layers. We also provide evidence that the formation of alternating Cs- and K-illite interlayers (i.e., ordered interstratification) is both thermodynamically and mechanically favorable compared to exchange in adjacent interlayers.

Unified superresolution experiments and stochastic theory provide mechanistic insight into protein ion-exchange adsorptive separations

PubMed Central

Kisley, Lydia; Chen, Jixin; Mansur, Andrea P.; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Chen, Wen-Hsiang; Dhamane, Sagar; Willson, Richard C.; Landes, Christy F.

2014-01-01

Chromatographic protein separations, immunoassays, and biosensing all typically involve the adsorption of proteins to surfaces decorated with charged, hydrophobic, or affinity ligands. Despite increasingly widespread use throughout the pharmaceutical industry, mechanistic detail about the interactions of proteins with individual chromatographic adsorbent sites is available only via inference from ensemble measurements such as binding isotherms, calorimetry, and chromatography. In this work, we present the direct superresolution mapping and kinetic characterization of functional sites on ion-exchange ligands based on agarose, a support matrix routinely used in protein chromatography. By quantifying the interactions of single proteins with individual charged ligands, we demonstrate that clusters of charges are necessary to create detectable adsorption sites and that even chemically identical ligands create adsorption sites of varying kinetic properties that depend on steric availability at the interface. Additionally, we relate experimental results to the stochastic theory of chromatography. Simulated elution profiles calculated from the molecular-scale data suggest that, if it were possible to engineer uniform optimal interactions into ion-exchange systems, separation efficiencies could be improved by as much as a factor of five by deliberately exploiting clustered interactions that currently dominate the ion-exchange process only accidentally. PMID:24459184

Unified superresolution experiments and stochastic theory provide mechanistic insight into protein ion-exchange adsorptive separations.

PubMed

Kisley, Lydia; Chen, Jixin; Mansur, Andrea P; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Chen, Wen-Hsiang; Dhamane, Sagar; Willson, Richard C; Landes, Christy F

2014-02-11

Chromatographic protein separations, immunoassays, and biosensing all typically involve the adsorption of proteins to surfaces decorated with charged, hydrophobic, or affinity ligands. Despite increasingly widespread use throughout the pharmaceutical industry, mechanistic detail about the interactions of proteins with individual chromatographic adsorbent sites is available only via inference from ensemble measurements such as binding isotherms, calorimetry, and chromatography. In this work, we present the direct superresolution mapping and kinetic characterization of functional sites on ion-exchange ligands based on agarose, a support matrix routinely used in protein chromatography. By quantifying the interactions of single proteins with individual charged ligands, we demonstrate that clusters of charges are necessary to create detectable adsorption sites and that even chemically identical ligands create adsorption sites of varying kinetic properties that depend on steric availability at the interface. Additionally, we relate experimental results to the stochastic theory of chromatography. Simulated elution profiles calculated from the molecular-scale data suggest that, if it were possible to engineer uniform optimal interactions into ion-exchange systems, separation efficiencies could be improved by as much as a factor of five by deliberately exploiting clustered interactions that currently dominate the ion-exchange process only accidentally.

Binding patterns of vanadium ions with different valence states to human serum transferrin studied by HPLC/high-resolution ICP-MS.

PubMed

Nagaoka, Megumi Hamano; Yamazaki, Takeshi; Maitani, Tamio

2002-09-06

Vanadium (V) is an essential metal for mammals and has different valence states. In blood, V is bound to serum transferrin (Tf), a glycoprotein which has two metal-binding sites, and carbonate is generally required for the binding. In this study, the binding patterns of V(III), V(IV), and V(V) to human serum Tf (hTf) were analyzed using an HPLC system equipped with an anion-exchange column and directly connected to a high-resolution inductively coupled plasma-mass spectrometer for metal detection (51V). In affinity to hTf, the three ions were ranked V(III)>V(IV)>V(V) in the presence of bicarbonate and V(III) reverse congruent V(IV)>V(V) in the absence. Intermediates in the "open forms" binding to the respective sites were detected at the initial stage. V(IV) and V(V) were bound to the N-lobe site in the "closed form" and "open form," respectively. In the absence of bicarbonate, V ions with respective valence states were bound to hTf in the "open form." In terms of binding to hTf, tri-valent V was most favorable in the presence of bicarbonate.

The tight binding model study of the role of anisotropic AFM spin ordering in the charge ordered CMR manganites

NASA Astrophysics Data System (ADS)

Kar, J. K.; Panda, Saswati; Rout, G. C.

2017-05-01

We propose here a tight binding model study of the interplay between charge and spin orderings in the CMR manganites taking anisotropic effect due to electron hoppings and spin exchanges. The Hamiltonian consists of the kinetic energies of eg and t2g electrons of manganese ion. It further includes double exchange and Heisenberg interactions. The charge density wave interaction (CDW) describes an extra mechanism for the insulating character of the system. The CDW gap and spin parameters are calculated using Zubarev's Green's function technique and computed self-consistently. The results are reported in this communication.

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

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

Probing the conformation of a conserved glutamic acid within the Cl− pathway of a CLC H+/Cl− exchanger

PubMed Central

Vien, Malvin

2017-01-01

The CLC proteins form a broad family of anion-selective transport proteins that includes both channels and exchangers. Despite extensive structural, functional, and computational studies, the transport mechanism of the CLC exchangers remains poorly understood. Several transport models have been proposed but have failed to capture all the key features of these transporters. Multiple CLC crystal structures have suggested that a conserved glutamic acid, Gluex, can adopt three conformations and that the interconversion of its side chain between these states underlies H+/Cl− exchange. One of these states, in which Gluex occupies the central binding site (Scen) while Cl− ions fill the internal and external sites (Sint and Sext), has only been observed in one homologue, the eukaryotic cmCLC. The existence of such a state in other CLCs has not been demonstrated. In this study, we find that during transport, the prototypical prokaryotic CLC exchanger, CLC-ec1, adopts a conformation with functional characteristics that match those predicted for a cmCLC-like state, with Gluex trapped in Scen between two Cl− ions. Transport by CLC-ec1 is reduced when [Cl−] is symmetrically increased on both sides of the membrane and mutations that disrupt the hydrogen bonds stabilizing Gluex in Scen destabilize this trapped state. Furthermore, inhibition of transport by high [Cl−] is abolished in the E148A mutant, in which the Gluex side chain is removed. Collectively, our results suggest that, during the CLC transport cycle, Gluex can occupy Scen as well as the Sext position in which it has been captured crystallographically and that hydrogen bonds with the side chains of residues that coordinate ion binding to Scen play a role in determining the equilibrium between these two conformations. PMID:28246117

Route, mechanism, and implications of proton import during Na+/K+ exchange by native Na+/K+-ATPase pumps

PubMed Central

Vedovato, Natascia

2014-01-01

A single Na+/K+-ATPase pumps three Na+ outwards and two K+ inwards by alternately exposing ion-binding sites to opposite sides of the membrane in a conformational sequence coupled to pump autophosphorylation from ATP and auto-dephosphorylation. The larger flow of Na+ than K+ generates outward current across the cell membrane. Less well understood is the ability of Na+/K+ pumps to generate an inward current of protons. Originally noted in pumps deprived of external K+ and Na+ ions, as inward current at negative membrane potentials that becomes amplified when external pH is lowered, this proton current is generally viewed as an artifact of those unnatural conditions. We demonstrate here that this inward current also flows at physiological K+ and Na+ concentrations. We show that protons exploit ready reversibility of conformational changes associated with extracellular Na+ release from phosphorylated Na+/K+ pumps. Reversal of a subset of these transitions allows an extracellular proton to bind an acidic side chain and to be subsequently released to the cytoplasm. This back-step of phosphorylated Na+/K+ pumps that enables proton import is not required for completion of the 3 Na+/2 K+ transport cycle. However, the back-step occurs readily during Na+/K+ transport when external K+ ion binding and occlusion are delayed, and it occurs more frequently when lowered extracellular pH raises the probability of protonation of the externally accessible carboxylate side chain. The proton route passes through the Na+-selective binding site III and is distinct from the principal pathway traversed by the majority of transported Na+ and K+ ions that passes through binding site II. The inferred occurrence of Na+/K+ exchange and H+ import during the same conformational cycle of a single molecule identifies the Na+/K+ pump as a hybrid transporter. Whether Na+/K+ pump–mediated proton inflow may have any physiological or pathophysiological significance remains to be clarified. PMID:24688018

Study of the mechanisms of cadmium biosorption by dealginated seaweed waste.

PubMed

Romero-Gonzalez, M E; Williams, C J; Gardiner, P H

2001-07-15

The ability of dealginated seaweed waste, a waste material derived from the commercial processing of seaweed for alginate production, to remove cadmium from solution was determined. Cadmium sorption was found to be rapid (91% removal within 5 min), achieving a residual concentration of 0.8 mg L-1 after 1-h contact time from an initial solution concentration of 10 mg L-1. The binding of cadmium by dealginate was found to be pH dependent, optimal sorption occurring at around pH 6-8. The mechanism of cadmium ion binding by dealginate was investigated by a number of techniques. Potentiometric titration of the dealginate revealed two distinct pKa values, the first having a value similar to carboxyl groups and the second comparable with that of saturated thiols and amines. Esterification of the dealginate resulted in the subsequent reduction in cadmium sorption (95% to 17%), indicating that carboxyl groups are largely responsible for sorption. Evidence from FT-IR spectra confirmed the presence of carboxyl groups in untreated dealginate, while the number of carboxyl groups was markedly reduced in the esterified sample. Furthermore, the FT-IR spectrum for dealginate was found to be similar to that previously reported for mannuronic acid-rich calcium alginate. Determination of a molar ratio in the displacement of calcium by cadmium on dealginate further supported the presence of an ion-exchange relationship. The ion-exchange constant was calculated to be 0.329 x 10(-6). The speciation of cadmium in solution both before and after sorption was determined by an ion-selective electrode (ISE) technique. The findings of this study suggest that the sorption of cadmium by dealginate is mainly due to an ion-exchange mechanism.

Investigation of Anion-Exchange and Immunoaffinity Particle-Loaded Membranes for the Isolation of Charged Organic Analytes from Water

USGS Publications Warehouse

Dombrowski, T.R.; Wilson, G.S.; Thurman, E.M.

1998-01-01

Anion-exchange and immunoaffinity particle loaded membranes (PLMs) were investigated as a mechanism for the isolation of charged organic analytes from water. Kinetic properties determined theoretically included dynamic capacity, pressure drop (??P), residence and diffusion times (Tr, Td), and total membrane porosity (???T). These properties were confirmed through experimental evaluation, and the PLM method showed significant improvement over conventional solid-phase extraction (SPE) and ion-exchange formats. Recoveries of more than 90% were observed for a variety of test compounds at flow rates up to 70 mL/min (equipment-limited maximum flow rate). A fast-flow immunoaffinity column was developed using antibodies (Abs) attached to the PLMs. Reproducible recoveries (88% ?? 4%) were observed at flow rates up to 70 mL/min for the antibody (Ab)-loaded PLMs. Findings indicate increased selectivity over anion-exchange PLMs and conventional SPE or ion-exchange methods and rapid Ab-antigen binding rates given the excellent mass-transfer characteristics of the PLMs.

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

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

Chouyyok, Wilaiwan; Yantasee, Wassana; Shin, Yongsoon

2009-11-01

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

Sample displacement chromatography as a method for purification of proteins and peptides from complex mixtures

PubMed Central

Gajdosik, Martina Srajer; Clifton, James; Josic, Djuro

2012-01-01

Sample displacement chromatography (SDC) in reversed-phase and ion-exchange modes was introduced approximately twenty years ago. This method takes advantage of relative binding affinities of components in a sample mixture. During loading, there is a competition among different sample components for the sorption on the surface of the stationary phase. SDC was first used for the preparative purification of proteins. Later, it was demonstrated that this kind of chromatography can also be performed in ion-exchange, affinity and hydrophobic-interaction mode. It has also been shown that SDC can be performed on monoliths and membrane-based supports in both analytical and preparative scale. Recently, SDC in ion-exchange and hydrophobic interaction mode was also employed successfully for the removal of trace proteins from monoclonal antibody preparations and for the enrichment of low abundance proteins from human plasma. In this review, the principals of SDC are introduced, and the potential for separation of proteins and peptides in micro-analytical, analytical and preparative scale is discussed. PMID:22520159

Interpretation with a Donnan-based concept of the influence of simple salt concentration on the apparent binding of divalent ions to the polyelectrolytes polystyrenesulfonate and dextran sulfate

USGS Publications Warehouse

Marinsky, J.A.; Baldwin, Robert F.; Reddy, M.M.

1985-01-01

It has been shown that the apparent enhancement of divalent metal ion binding to polyions such as polystyrenesulfonate (PSS) and dextran sulfate (DS) by decreasing the ionic strength of these mixed counterion systems (M2+, M+, X-, polyion) can be anticipated with the Donnan-based model developed by one of us (J.A.M.). Ion-exchange distribution methods have been employed to measure the removal by the polyion of trace divalent metal ion from simple salt (NaClO4)-polyion (NaPSS) mixtures. These data and polyion interaction data published earlier by Mattai and Kwak for the mixed counterion systems MgCl2-LiCl-DS and MgCl2-CsCl-DS have been shown to be amenable to rather precise analysis by this model. ?? 1985 American Chemical Society.

Adhesion of a bimetallic interface. Ph.D. Thesis - Case Western Reserve Univ.; [for Al, Mg, and Zn

NASA Technical Reports Server (NTRS)

Ferrante, J.

1978-01-01

The Hohenberg-Kohn and Kohn-Sham formalisms are used to examine binding (binding energy as a function of separation) for combinations of the simple metals Al(111), Zn(0001), Mg(0001), and Na(110) in contact. Similar metal contacts between Al, Zn, Mg, and Na are examined self-consistently in an ab initio calculation using the Kohn-Sham formalism. Crystallinity is included using the Aschroft pseudopotential via first order perturbation theory for the electron-ion interaction; and the ion-ion interaction is included exactly via a lattice sum. Binding energy was determined both in the local-density approximation and including gradient corrections to the exchange and correlation energy. Binding was found in all cases. In dissimilar metal contacts, interfacial bonding was greater than that in the weaker material predicting the possibility of metallic transfer. The nonzero position of the energy minimum in like metal contacts is explained in terms of consistency between the Ashcroft pseudopotential and the bulk charge density. Good agreement with experimental surface energies is obtained in the self-consistent calculation when nonlocal terms are included.

Application of the Nernst-Planck approach to lead ion exchange in Ca-loaded Pelvetia canaliculata.

PubMed

Costa, Joana F de Sá S; Vilar, Vítor J P; Botelho, Cidália M S; da Silva, Eduardo A B; Boaventura, Rui A R

2010-07-01

Ca-loaded Pelvetia canaliculata biomass was used to remove Pb(2+) in aqueous solution from batch and continuous systems. The physicochemical characterization of algae Pelvetia particles by potentiometric titration and FTIR analysis has shown a gel structure with two major binding groups - carboxylic (2.8 mmol g(-1)) and hydroxyl (0.8 mmol g(-1)), with an affinity constant distribution for hydrogen ions well described by a Quasi-Gaussian distribution. Equilibrium adsorption (pH 3 and 5) and desorption (eluents: HNO(3) and CaCl(2)) experiments were performed, showing that the biosorption mechanism was attributed to ion exchange among calcium, lead and hydrogen ions with stoichiometry 1:1 (Ca:Pb) and 1:2 (Ca:H and Pb:H). The uptake capacity of lead ions decreased with pH, suggesting that there is a competition between H(+) and Pb(2+) for the same binding sites. A mass action law for the ternary mixture was able to predict the equilibrium data, with the selectivity constants alpha(Ca)(H)=9+/-1 and alpha(Ca)(Pb)=44+/-5, revealing a higher affinity of the biomass towards lead ions. Adsorption (initial solution pH 4.5 and 2.5) and desorption (0.3M HNO(3)) kinetics were performed in batch and continuous systems. A mass transfer model using the Nernst-Planck approximation for the ionic flux of each counter-ion was used for the prediction of the ions profiles in batch systems and packed bed columns. The intraparticle effective diffusion constants were determined as 3.73x10(-7)cm(2)s(-1) for H(+), 7.56x10(-8)cm(2)s(-1) for Pb(2+) and 6.37x10(-8)cm(2)s(-1) for Ca(2+). Copyright 2010 Elsevier Ltd. All rights reserved.

Calcium Sensing by Recoverin: Effect of Protein Conformation on Ion Affinity.

PubMed

Timr, Štěpán; Kadlec, Jan; Srb, Pavel; Ollila, O H Samuli; Jungwirth, Pavel

2018-04-05

The detailed functional mechanism of recoverin, which acts as a myristoyl switch at the rod outer-segment disk membrane, is elucidated by direct and replica-exchange molecular dynamics. In accord with NMR structural evidence and calcium binding assays, simulations point to the key role of enhanced calcium binding to the EF3 loop of the semiopen state of recoverin as compared to the closed state. This 2-4-order decrease in calcium dissociation constant stabilizes the semiopen state in response to the increase of cytosolic calcium concentration in the vicinity of recoverin. A second calcium ion then binds to the EF2 loop and, consequently, the structure of the protein changes from the semiopen to the open state. The latter has the myristoyl chain extruded to the cytosol, ready to act as a membrane anchor of recoverin.

Potassium and the K+/H+ Exchanger Kha1p Promote Binding of Copper to ApoFet3p Multi-copper Ferroxidase*

PubMed Central

Wu, Xiaobin; Kim, Heejeong; Seravalli, Javier; Barycki, Joseph J.; Hart, P. John; Gohara, David W.; Di Cera, Enrico; Jung, Won Hee; Kosman, Daniel J.; Lee, Jaekwon

2016-01-01

Acquisition and distribution of metal ions support a number of biological processes. Here we show that respiratory growth of and iron acquisition by the yeast Saccharomyces cerevisiae relies on potassium (K+) compartmentalization to the trans-Golgi network via Kha1p, a K+/H+ exchanger. K+ in the trans-Golgi network facilitates binding of copper to the Fet3p multi-copper ferroxidase. The effect of K+ is not dependent on stable binding with Fet3p or alteration of the characteristics of the secretory pathway. The data suggest that K+ acts as a chemical factor in Fet3p maturation, a role similar to that of cations in folding of nucleic acids. Up-regulation of KHA1 gene in response to iron limitation via iron-specific transcription factors indicates that K+ compartmentalization is linked to cellular iron homeostasis. Our study reveals a novel functional role of K+ in the binding of copper to apoFet3p and identifies a K+/H+ exchanger at the secretory pathway as a new molecular factor associated with iron uptake in yeast. PMID:26966178

Role of urea on recombinant Apo A-I stability and its utilization in anion exchange chromatography.

PubMed

Angarita, Monica; Arosio, Paolo; Müller-Späth, Thomas; Baur, Daniel; Falkenstein, Roberto; Kuhne, Wolfgang; Morbidelli, Massimo

2014-08-08

Apolipoprotein A-I (Apo A-I) is an important lipid-binding protein involved in the transport and metabolism of cholesterol. High protein purity, in particular with respect to endotoxins is required for therapeutic applications. The use of urea during the purification process of recombinant Apo A-I produced in Escherichia coli has been suggested so as to provide high endotoxin clearance. In this work, we show that urea can be used as a sole modifier during the ion exchange chromatographic purification of Apo A-I and we investigate the molecular mechanism of elution by correlating the effect of urea on self-association, conformation and adsorption equilibrium properties of a modified model Apo A-I. In the absence of urea the protein was found to be present as a population of oligomers represented mainly by trimers, hexamers and nonamers. The addition of urea induced oligomer dissociation and protein structure unfolding. We correlated the changes in protein association and conformation with variations of the adsorption equilibrium of the protein on a strong anion exchanger. It was confirmed that the adsorption isotherms, described by a Langmuir model, were dependent on both protein and urea concentrations. Monomers, observed at low urea concentration (0.5M), were characterized by larger binding affinity and adsorption capacity compared to both protein oligomers (0M) and unfolded monomers (2-8M). The reduction of both the binding strength and maximum adsorption capacity at urea concentrations larger than 0.5M explains the ability of urea of inducing elution of the protein from the ion exchange resin. The dissociation of the protein complexes occurring during the elution could likely be the origin of the effective clearance of endotoxins originally trapped inside the oligomers. Copyright © 2014 Elsevier B.V. All rights reserved.

Engineering of a calcium-ion binding site into the RC-LH1-PufX complex of Rhodobacter sphaeroides to enable ion-dependent spectral red-shifting.

PubMed

Swainsbury, David J K; Martin, Elizabeth C; Vasilev, Cvetelin; Parkes-Loach, Pamela S; Loach, Paul A; Neil Hunter, C

2017-11-01

The reaction centre-light harvesting 1 (RC-LH1) complex of Thermochromatium (Tch.) tepidum has a unique calcium-ion binding site that enhances thermal stability and red-shifts the absorption of LH1 from 880nm to 915nm in the presence of calcium-ions. The LH1 antenna of mesophilic species of phototrophic bacteria such as Rhodobacter (Rba.) sphaeroides does not possess such properties. We have engineered calcium-ion binding into the LH1 antenna of Rba. sphaeroides by progressively modifying the native LH1 polypeptides with sequences from Tch. tepidum. We show that acquisition of the C-terminal domains from LH1 α and β of Tch. tepidum is sufficient to activate calcium-ion binding and the extent of red-shifting increases with the proportion of Tch. tepidum sequence incorporated. However, full exchange of the LH1 polypeptides with those of Tch. tepidum results in misassembled core complexes. Isolated α and β polypeptides from our most successful mutant were reconstituted in vitro with BChl a to form an LH1-type complex, which was stabilised 3-fold by calcium-ions. Additionally, carotenoid specificity was changed from spheroidene found in Rba. sphaeroides to spirilloxanthin found in Tch. tepidum, with the latter enhancing in vitro formation of LH1. These data show that the C-terminal LH1 α/β domains of Tch. tepidum behave autonomously, and are able to transmit calcium-ion induced conformational changes to BChls bound to the rest of a foreign antenna complex. Thus, elements of foreign antenna complexes, such as calcium-ion binding and blue/red switching of absorption, can be ported into Rhodobacter sphaeroides using careful design processes. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Ceramic Spheres From Cation Exchange Beads

NASA Technical Reports Server (NTRS)

Dynys, F. W.

2003-01-01

Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

NMR resolved multiple anesthetic binding sites in the TM domains of the α4β2 nAChR

PubMed Central

Bondarenko, Vasyl; Mowrey, David; Liu, Lu Tian; Xu, Yan; Tang, Pei

2012-01-01

The α4β2 nicotinic acetylcholine receptor (nAChR) has significant roles in nervous system function and disease. It is also a molecular target of general anesthetics. Anesthetics inhibit the α4β2 nAChR at clinically relevant concentrations, but their binding sites in α4β2 remain unclear. The recently determined NMR structures of the α4β2 nAChR transmembrane (TM) domains provide valuable frameworks for identifying the binding sites. In this study, we performed solution NMR experiments on the α4β2 TM domains in the absence and presence of halothane and ketamine. Both anesthetics were found in an intra-subunit cavity near the extracellular end of the 2 transmembrane helices, homologous to a common anesthetic binding site observed in X-ray structures of anesthetic-bound GLIC (Nury, et. al. 2011). Halothane, but not ketamine, was also found in cavities adjacent to the common anesthetic site at the interface of α4 and β2. In addition, both anesthetics bound to cavities near the ion selectivity filter at the intracellular end of the TM domains. Anesthetic binding induced profound changes in protein conformational exchanges. A number of residues, close to or remote from the binding sites, showed resonance signal splitting from single to double peaks, signifying that anesthetics decreased conformation exchange rates. It was also evident that anesthetics shifted population of two conformations. Altogether, the study comprehensively resolved anesthetic binding sites in the α4β2 nAChR. Furthermore, the study provided compelling experimental evidence of anesthetic-induced changes in protein dynamics, especially near regions of the hydrophobic gate and ion selectivity filter that directly regulate channel functions. PMID:23000369

NMR resolved multiple anesthetic binding sites in the TM domains of the α4β2 nAChR.

PubMed

Bondarenko, Vasyl; Mowrey, David; Liu, Lu Tian; Xu, Yan; Tang, Pei

2013-02-01

The α4β2 nicotinic acetylcholine receptor (nAChR) has significant roles in nervous system function and disease. It is also a molecular target of general anesthetics. Anesthetics inhibit the α4β2 nAChR at clinically relevant concentrations, but their binding sites in α4β2 remain unclear. The recently determined NMR structures of the α4β2 nAChR transmembrane (TM) domains provide valuable frameworks for identifying the binding sites. In this study, we performed solution NMR experiments on the α4β2 TM domains in the absence and presence of halothane and ketamine. Both anesthetics were found in an intra-subunit cavity near the extracellular end of the β2 transmembrane helices, homologous to a common anesthetic binding site observed in X-ray structures of anesthetic-bound GLIC (Nury et al., [32]). Halothane, but not ketamine, was also found in cavities adjacent to the common anesthetic site at the interface of α4 and β2. In addition, both anesthetics bound to cavities near the ion selectivity filter at the intracellular end of the TM domains. Anesthetic binding induced profound changes in protein conformational exchanges. A number of residues, close to or remote from the binding sites, showed resonance signal splitting from single to double peaks, signifying that anesthetics decreased conformation exchange rates. It was also evident that anesthetics shifted population of two conformations. Altogether, the study comprehensively resolved anesthetic binding sites in the α4β2 nAChR. Furthermore, the study provided compelling experimental evidence of anesthetic-induced changes in protein dynamics, especially near regions of the hydrophobic gate and ion selectivity filter that directly regulate channel functions. Copyright © 2012 Elsevier B.V. All rights reserved.

The second Cu(II)-binding site in a proton-rich environment interferes with the aggregation of amyloid-beta(1-40) into amyloid fibrils.

PubMed

Jun, Sangmi; Gillespie, Joel R; Shin, Byong-kyu; Saxena, Sunil

2009-11-17

The overall morphology and Cu(II) ion coordination for the aggregated amyloid-beta(1-40) [Abeta(1-40)] in N-ethylmorpholine (NEM) buffer are affected by Cu(II) ion concentration. This effect is investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and electron spin echo envelope modulation (ESEEM) spectroscopy. At lower than equimolar concentrations of Cu(II) ions, fibrillar aggregates of Abeta(1-40) are observed. At these concentrations of Cu(II), the monomeric and fibrillar Abeta(1-40) ESEEM data indicate that the Cu(II) ion is coordinated by histidine residues. For aggregated Abeta(1-40) at a Cu(II):Abeta molar ratio of 2:1, TEM and AFM images show both linear fibrils and granular amorphous aggregates. The ESEEM spectra show that the multi-histidine coordination for Cu(II) ion partially breaks up and becomes exposed to water or exchangeable protons of the peptide at a higher Cu(II) concentration. Since the continuous-wave electron spin resonance results also suggest two copper-binding sites in Abeta(1-40), the proton ESEEM peak may arise from the second copper-binding site, which may be significantly involved in the formation of granular amorphous aggregates. Thioflavin T fluorescence and circular dichroism experiments also show that Cu(II) inhibits the formation of fibrils and induces a nonfibrillar beta-sheet conformation. Therefore, we propose that Abeta(1-40) has a second copper-binding site in a proton-rich environment and the second binding Cu(II) ion interferes with a conformational transition into amyloid fibrils, inducing the formation of granular amorphous aggregates.

Probing the conformation of a conserved glutamic acid within the Cl- pathway of a CLC H+/Cl- exchanger.

PubMed

Vien, Malvin; Basilio, Daniel; Leisle, Lilia; Accardi, Alessio

2017-04-03

The CLC proteins form a broad family of anion-selective transport proteins that includes both channels and exchangers. Despite extensive structural, functional, and computational studies, the transport mechanism of the CLC exchangers remains poorly understood. Several transport models have been proposed but have failed to capture all the key features of these transporters. Multiple CLC crystal structures have suggested that a conserved glutamic acid, Glu ex , can adopt three conformations and that the interconversion of its side chain between these states underlies H + /Cl - exchange. One of these states, in which Glu ex occupies the central binding site (S cen ) while Cl - ions fill the internal and external sites (S int and S ext ), has only been observed in one homologue, the eukaryotic cmCLC. The existence of such a state in other CLCs has not been demonstrated. In this study, we find that during transport, the prototypical prokaryotic CLC exchanger, CLC-ec1, adopts a conformation with functional characteristics that match those predicted for a cmCLC-like state, with Glu ex trapped in S cen between two Cl - ions. Transport by CLC-ec1 is reduced when [Cl - ] is symmetrically increased on both sides of the membrane and mutations that disrupt the hydrogen bonds stabilizing Glu ex in S cen destabilize this trapped state. Furthermore, inhibition of transport by high [Cl - ] is abolished in the E148A mutant, in which the Glu ex side chain is removed. Collectively, our results suggest that, during the CLC transport cycle, Glu ex can occupy S cen as well as the S ext position in which it has been captured crystallographically and that hydrogen bonds with the side chains of residues that coordinate ion binding to S cen play a role in determining the equilibrium between these two conformations. © 2017 Vien et al.

Insights on Na(+) binding and conformational dynamics in multidrug and toxic compound extrusion transporter NorM.

PubMed

Song, Jianing; Ji, Changge; Zhang, John Z H

2014-02-01

MATE (multidrug and toxic compound extrusion) transporter proteins mediate metabolite transport in plants and multidrug resistance in bacteria and mammals. MATE transporter NorM from Vibrio cholerae is an antiporter that is driven by Na+ gradient to extrude the substrates. To understand the molecular mechanism of Na+-substrate exchange, molecular dynamics simulation was performed to study conformational changes of both wild-type and mutant NorM with and without cation bindings. Our results show that NorM is able to bind two Na(+) ions simultaneously, one to each of the carboxylic groups of E255 and D371 in the binding pocket. Furthermore, this di-Na(+) binding state is likely more efficient for conformational changes of NorM_VC toward the inward-facing conformation than single-Na(+) binding state. The observation of two Na(+) binding sites of NorM_VC is consistent with the previous study that two sites for ion binding (denoted as Na1/Na2 sites) are found in the transporter LeuT and BetP, another two secondary transporters. Taken together, our findings shed light on the structure rearrangements of NorM on Na(+) binding and enrich our knowledge of the transport mechanism of secondary transporters. Copyright © 2013 Wiley Periodicals, Inc.

Solving the Mechanism of Na+/H+ Antiporters Using Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Dotson, David L.

Na+/H+ antiporters are vital membrane proteins for cell homeostasis, transporting Na+ ions in exchange for H+ across the lipid bilayer. In humans, dysfunction of these transporters are implicated in hypertension, heart failure, epilepsy, and autism, making them well-established drug targets. Although experimental structures for bacterial homologs of the human Na+/H+ have been obtained, the detailed mechanism for ion transport is still not well-understood. The most well-studied of these transporters, Escherichia coli NhaA, known to transport 2 H+ for every Na+ extruded, was recently shown to bind H+ and Na+ at the same binding site, for which the two ion species compete. Using molecular dynamics simulations, the work presented in this dissertation shows that Na+ binding disrupts a previously-unidentified salt bridge between two conserved residues, suggesting that one of these residues, Lys300, may participate directly in transport of H+. This work also demonstrates that the conformational change required for ion translocation in a homolog of NhaA, Thermus thermophilus NapA, thought by some to involve only small helical movements at the ion binding site, is a large-scale, rigid-body movement of the core domain relative to the dimerization domain. This elevator-like transport mechanism translates a bound Na+ up to 10 A across the membrane. These findings constitute a major shift in the prevailing thought on the mechanism of these transporters, and serve as an exciting launchpad for new developments toward understanding that mechanism in detail.

Sodium recognition by the Na+/Ca2+ exchanger in the outward-facing conformation

PubMed Central

Marinelli, Fabrizio; Almagor, Lior; Hiller, Reuben; Giladi, Moshe; Khananshvili, Daniel; Faraldo-Gómez, José D.

2014-01-01

Na+/Ca2+ exchangers (NCXs) are ubiquitous membrane transporters with a key role in Ca2+ homeostasis and signaling. NCXs mediate the bidirectional translocation of either Na+ or Ca2+, and thus can catalyze uphill Ca2+ transport driven by a Na+ gradient, or vice versa. In a major breakthrough, a prokaryotic NCX homolog (NCX_Mj) was recently isolated and its crystal structure determined at atomic resolution. The structure revealed an intriguing architecture consisting of two inverted-topology repeats, each comprising five transmembrane helices. These repeats adopt asymmetric conformations, yielding an outward-facing occluded state. The crystal structure also revealed four putative ion-binding sites, but the occupancy and specificity thereof could not be conclusively established. Here, we use molecular-dynamics simulations and free-energy calculations to identify the ion configuration that best corresponds to the crystallographic data and that is also thermodynamically optimal. In this most probable configuration, three Na+ ions occupy the so-called Sext, SCa, and Sint sites, whereas the Smid site is occupied by one water molecule and one H+, which protonates an adjacent aspartate side chain (D240). Experimental measurements of Na+/Ca2+ and Ca2+/Ca2+ exchange by wild-type and mutagenized NCX_Mj confirm that transport of both Na+ and Ca2+ requires protonation of D240, and that this side chain does not coordinate either ion at Smid. These results imply that the ion exchange stoichiometry of NCX_Mj is 3:1 and that translocation of Na+ across the membrane is electrogenic, whereas transport of Ca2+ is not. Altogether, these findings provide the basis for further experimental and computational studies of the conformational mechanism of this exchanger. PMID:25468964

Sodium recognition by the Na+/Ca2+ exchanger in the outward-facing conformation.

PubMed

Marinelli, Fabrizio; Almagor, Lior; Hiller, Reuben; Giladi, Moshe; Khananshvili, Daniel; Faraldo-Gómez, José D

2014-12-16

Na(+)/Ca(2+) exchangers (NCXs) are ubiquitous membrane transporters with a key role in Ca(2+) homeostasis and signaling. NCXs mediate the bidirectional translocation of either Na(+) or Ca(2+), and thus can catalyze uphill Ca(2+) transport driven by a Na(+) gradient, or vice versa. In a major breakthrough, a prokaryotic NCX homolog (NCX_Mj) was recently isolated and its crystal structure determined at atomic resolution. The structure revealed an intriguing architecture consisting of two inverted-topology repeats, each comprising five transmembrane helices. These repeats adopt asymmetric conformations, yielding an outward-facing occluded state. The crystal structure also revealed four putative ion-binding sites, but the occupancy and specificity thereof could not be conclusively established. Here, we use molecular-dynamics simulations and free-energy calculations to identify the ion configuration that best corresponds to the crystallographic data and that is also thermodynamically optimal. In this most probable configuration, three Na(+) ions occupy the so-called Sext, SCa, and Sint sites, whereas the Smid site is occupied by one water molecule and one H(+), which protonates an adjacent aspartate side chain (D240). Experimental measurements of Na(+)/Ca(2+) and Ca(2+)/Ca(2+) exchange by wild-type and mutagenized NCX_Mj confirm that transport of both Na(+) and Ca(2+) requires protonation of D240, and that this side chain does not coordinate either ion at Smid. These results imply that the ion exchange stoichiometry of NCX_Mj is 3:1 and that translocation of Na(+) across the membrane is electrogenic, whereas transport of Ca(2+) is not. Altogether, these findings provide the basis for further experimental and computational studies of the conformational mechanism of this exchanger.

Catalytic asymmetric dihydroxylation of olefins with reusable OsO(4)(2-) on ion-exchangers: the scope and reactivity using various cooxidants.

PubMed

Choudary, Boyapati M; Chowdari, Naidu S; Jyothi, Karangula; Kantam, Mannepalli L

2002-05-15

Exchanger-OsO(4) catalysts are prepared by an ion-exchange technique using layered double hydroxides and quaternary ammonium salts covalently bound to resin and silica as ion-exchangers. The ion-exchangers with different characteristics and opposite ion selectivities are specially chosen to produce the best heterogeneous catalyst that can operate using the various cooxidants in the asymmetric dihydroxylation reaction. LDH-OsO(4) catalysts composed of different compositions are evaluated for the asymmetric dihydroxylation of trans-stilbene. Resin-OsO(4) and SiO(2)-OsO(4) designed to overcome the problems associated with LDH-OsO(4) indeed show consistent activity and enantioselectivity in asymmetric dihydroxylation of olefins using K(3)Fe(CN)(6) and molecular oxygen as cooxidants. Compared to the Kobayashi heterogeneous systems, resin-OsO(4) is a very efficient catalyst for the dihydroxylation of a wide variety of aromatic, aliphatic, acyclic, cyclic, mono-, di-, and trisubstituted olefins to afford chiral vicinal diols with high yields and enantioselectivities irrespective of the cooxidant used. Resin-OsO(4) is recovered quantitatively by a simple filtration and reused for a number of cycles with consistent activity. The high binding ability of the heterogeneous osmium catalyst enables the use of an equimolar ratio of ligand to osmium to give excellent enantioselectives in asymmetric dihydroxylation in contrast to the homogeneous osmium system in which excess molar quantities of the expensive chiral ligand to osmium are invariably used. The complexation of the chiral ligand (DHQD)(2)PHAL, having very large dimension, a prerequisite to obtain higher ee, is possible only with the OsO(4)(2-) located on the surface of the supports.

Human cytoplasmic copper chaperones Atox1 and CCS exchange copper ions in vitro.

PubMed

Petzoldt, Svenja; Kahra, Dana; Kovermann, Michael; Dingeldein, Artur P G; Niemiec, Moritz S; Ådén, Jörgen; Wittung-Stafshede, Pernilla

2015-06-01

After Ctr1-mediated copper ion (Cu) entry into the human cytoplasm, chaperones Atox1 and CCS deliver Cu to P1B-type ATPases and to superoxide dismutase, respectively, via direct protein-protein interactions. Although the two Cu chaperones are presumed to work along independent pathways, we here assessed cross-reactivity between Atox1 and the first domain of CCS (CCS1) using biochemical and biophysical methods in vitro. By NMR we show that CCS1 is monomeric although it elutes differently from Atox1 in size exclusion chromatography (SEC). This property allows separation of Atox1 and CCS1 by SEC and, combined with the 254/280 nm ratio as an indicator of Cu loading, we demonstrate that Cu can be transferred from one protein to the other. Cu exchange also occurs with full-length CCS and, as expected, the interaction involves the metal binding sites since mutation of Cu-binding cysteine in Atox1 eliminates Cu transfer from CCS1. Cross-reactivity between CCS and Atox1 may aid in regulation of Cu distribution in the cytoplasm.

Intravenous iron-dextran: studies on unsaturated iron-binding capacity

PubMed Central

Cox, J. S. G.; Moss, G. F.; Bremner, I.; Reason, Janet

1968-01-01

A method is described for measuring the plasma unsaturated iron-binding capacity in the presence of very high concentrations of iron as iron-dextran. The procedure utilizes 59Fe to label the apotransferrin with subsequent separation of ionic iron from transferrin-bound iron on an ion exchange or Sephadex G.25 column. The unsaturated iron-binding capacity has been measured in rabbits and dogs after intravenous injection of iron-dextran and in human subjects after total dose infusion of iron-dextran. No evidence of saturation of the unsaturated iron-binding capacity was found even when the plasma iron values were greater than 40,000 μg Fe/100 ml. PMID:5697365

Theory and applications of a novel ion exchange chromatographic technology using controlled pH gradients for separating proteins on anionic and cationic stationary phases.

PubMed

Tsonev, Latchezar I; Hirsh, Allen G

2008-07-25

pISep is a major new advance in low ionic strength ion exchange chromatography. It enables the formation of externally controlled pH gradients over the very broad pH range from 2 to 12. The gradients can be generated on either cationic or anionic exchangers over arbitrary pH ranges wherein the stationary phases remain totally charged. Associated pISep software makes possible the calculation of either linear, nonlinear or combined, multi-step, multi-slope pH gradients. These highly reproducible pH gradients, while separating proteins and glycoproteins in the order of their electrophoretic pIs, provide superior chromatographic resolution compared to salt. This paper also presents a statistical mechanical model for protein binding to ion exchange stationary phases enhancing the electrostatic interaction theory for the general dependence of retention factor k, on both salt and pH simultaneously. It is shown that the retention factors computed from short time isocratic salt elution data of a model protein can be used to accurately predict its salt elution concentration in varying slope salt elution gradients formed at varying isocratic pH as well as the pH at which it will be eluted from an anionic exchange column by a pISep pH gradient in the absence of salt.

Structural Features of Ion Transport and Allosteric Regulation in Sodium-Calcium Exchanger (NCX) Proteins

PubMed Central

Giladi, Moshe; Tal, Inbal; Khananshvili, Daniel

2016-01-01

Na+/Ca2+ exchanger (NCX) proteins extrude Ca2+ from the cell to maintain cellular homeostasis. Since NCX proteins contribute to numerous physiological and pathophysiological events, their pharmacological targeting has been desired for a long time. This intervention remains challenging owing to our poor understanding of the underlying structure-dynamic mechanisms. Recent structural studies have shed light on the structure-function relationships underlying the ion-transport and allosteric regulation of NCX. The crystal structure of an archaeal NCX (NCX_Mj) along with molecular dynamics simulations and ion flux analyses, have assigned the ion binding sites for 3Na+ and 1Ca2+, which are being transported in separate steps. In contrast with NCX_Mj, eukaryotic NCXs contain the regulatory Ca2+-binding domains, CBD1 and CBD2, which affect the membrane embedded ion-transport domains over a distance of ~80 Å. The Ca2+-dependent regulation is ortholog, isoform, and splice-variant dependent to meet physiological requirements, exhibiting either a positive, negative, or no response to regulatory Ca2+. The crystal structures of the two-domain (CBD12) tandem have revealed a common mechanism involving a Ca2+-driven tethering of CBDs in diverse NCX variants. However, dissociation kinetics of occluded Ca2+ (entrapped at the two-domain interface) depends on the alternative-splicing segment (at CBD2), thereby representing splicing-dependent dynamic coupling of CBDs. The HDX-MS, SAXS, NMR, FRET, equilibrium 45Ca2+ binding and stopped-flow techniques provided insights into the dynamic mechanisms of CBDs. Ca2+ binding to CBD1 results in a population shift, where more constraint conformational states become highly populated without global conformational changes in the alignment of CBDs. This mechanism is common among NCXs. Recent HDX-MS studies have demonstrated that the apo CBD1 and CBD2 are stabilized by interacting with each other, while Ca2+ binding to CBD1 rigidifies local backbone segments of CBD2, but not of CBD1. The extent and strength of Ca2+-dependent rigidification at CBD2 is splice-variant dependent, showing clear correlations with phenotypes of matching NCX variants. Therefore, diverse NCX variants share a common mechanism for the initial decoding of the regulatory signal upon Ca2+ binding at the interface of CBDs, whereas the allosteric message is shaped by CBD2, the dynamic features of which are dictated by the splicing segment. PMID:26903880

Spontaneous nucleotide exchange in low molecular weight GTPases by fluorescently labeled γ-phosphate-linked GTP analogs

PubMed Central

Korlach, Jonas; Baird, Daniel W.; Heikal, Ahmed A.; Gee, Kyle R.; Hoffman, Gregory R.; Webb, Watt W.

2004-01-01

Regulated guanosine nucleotide exchange and hydrolysis constitute the fundamental activities of low molecular weight GTPases. We show that three guanosine 5′-triphosphate analogs with BODIPY fluorophores coupled via the gamma phosphate bind to the GTPases Cdc42, Rac1, RhoA, and Ras and displace guanosine 5′-diphosphate with high intrinsic exchange rates in the presence of Mg2+ ions, thereby acting as synthetic, low molecular weight guanine nucleotide exchange factors. The accompanying large fluorescence enhancements (as high as 12-fold), caused by a reduction in guanine quenching of the environmentally sensitive BODIPY dye fluorescence on protein binding, allow for real-time monitoring of this spontaneous nucleotide exchange in the visible spectrum with high signal-to-noise ratios. Binding affinities increased with longer aliphatic linkers connecting the nucleotide and BODIPY fluorophore and were in the 10–100 nM range. Steady-state and time-resolved fluorescence spectroscopy showed an inverse relationship between linker length and fluorescence enhancement factors and differences in protein-bound fluorophore mobilities, providing optimization criteria for future applications of such compounds as efficient elicitors and reporters of nucleotide exchange. EDTA markedly enhanced nucleotide exchange, enabling rapid loading of GTPases with these probes. Differences in active site geometries, in the absence of Mg2+, caused qualitatively different reporting of the bound state by the different analogs. The BODIPY analogs also prevented the interaction of Cdc42 with p21 activated kinase. Together, these results validate the use of these analogs as valuable tools for studying GTPase functions and for developing potent synthetic nucleotide exchange factors for this important class of signaling molecules. PMID:14973186

Simultaneous determination of Ca, Cu, Ni, Zn and Cd binding strengths with fulvic acid fractions by Schubert's method

USGS Publications Warehouse

Brown, G.K.; MacCarthy, P.; Leenheer, J.A.

1999-01-01

The equilibrium binding of Ca2+, Ni2+, Cd2+, Cu2+ and Zn2+ with unfractionated Suwannee river fulvic acid (SRFA) and an enhanced metal binding subfraction of SRFA was measured using Schubert's ion-exchange method at pH 6.0 and at an ionic strength (??) of 0.1 (NaNO3). The fractionation and subfractionation were directed towards obtaining an isolate with an elevated metal binding capacity or binding strength as estimated by Cu2+ potentiometry (ISE). Fractions were obtained by stepwise eluting an XAD-8 column loaded with SRFA with water eluents of pH 1.0 to pH 12.0. Subfractions were obtained by loading the fraction eluted from XAD-8 at pH 5.0 onto a silica gel column and eluting with solvents of increasing polarity. Schuberts ion exchange method was rigorously tested by measuring simultaneously the conditional stability constants (K) of citric acid complexed with the five metals at pH 3.5 and 6.0. The logK of SRFA with Ca2+, Ni2+, Cd2+, Cu2+ and Zn2+ determined simultaneously at pH 6.0 follow the sequence of Cu2+>Cd2+>Ni2+>Zn2+>Ca2+ while all logK values increased for the enhanced metal binding subfraction and followed a different sequence of Cu2+>Cd2+>Ca2+>Ni2+>Zn2+. Both fulvic acid samples and citric acid exhibited a 1:1 metal to ligand stochiometry under the relatively low metal loading conditions used here. Quantitative 13C nuclear magnetic resonance spectroscopy showed increases in aromaticity and ketone content and decreases in aliphatic carbon for the elevated metal binding fraction while the carboxyl carbon, and elemental nitrogen, phosphorus, and sulfur content did not change. The more polar, elevated metal binding fraction did show a significant increase in molecular weight over the unfractionated SRFA. Copyright (C) 1999 Elsevier Science B.V.

Multiscale Kinetic Modeling Reveals an Ensemble of Cl–/H+ Exchange Pathways in ClC-ec1 Antiporter

PubMed Central

2018-01-01

Despite several years of research, the ion exchange mechanisms in chloride/proton antiporters and many other coupled transporters are not yet understood at the molecular level. Here, we present a novel approach to kinetic modeling and apply it to ion exchange in ClC-ec1. Our multiscale kinetic model is developed by (1) calculating the state-to-state rate coefficients with reactive and polarizable molecular dynamics simulations, (2) optimizing these rates in a global kinetic network, and (3) predicting new electrophysiological results. The model shows that the robust Cl:H exchange ratio (2.2:1) can indeed arise from kinetic coupling without large protein conformational changes, indicating a possible facile evolutionary connection to chloride channels. The E148 amino acid residue is shown to couple chloride and proton transport through protonation-dependent blockage of the central anion binding site and an anion-dependent pKa value, which influences proton transport. The results demonstrate how an ensemble of different exchange pathways, as opposed to a single series of transitions, culminates in the macroscopic observables of the antiporter, such as transport rates, chloride/proton stoichiometry, and pH dependence. PMID:29332400

Strontium and barium in aqueous solution and a potassium channel binding site

NASA Astrophysics Data System (ADS)

Chaudhari, Mangesh I.; Rempe, Susan B.

2018-06-01

Ion hydration structure and free energy establish criteria for understanding selective ion binding in potassium (K+) ion channels and may be significant to understanding blocking mechanisms as well. Recently, we investigated the hydration properties of Ba2+, the most potent blocker of K+ channels among the simple metal ions. Here, we use a similar method of combining ab initio molecular dynamics simulations, statistical mechanical theory, and electronic structure calculations to probe the fundamental hydration properties of Sr2+, which does not block bacterial K+ channels. The radial distribution of water around Sr2+ suggests a stable 8-fold geometry in the local hydration environment, similar to Ba2+. While the predicted hydration free energy of -331.8 kcal/mol is comparable with the experimental result of -334 kcal/mol, the value is significantly more favorable than the -305 kcal/mol hydration free energy of Ba2+. When placed in the innermost K+ channel blocking site, the solvation free energies and lowest energy structures of both Sr2+ and Ba2+ are nearly unchanged compared with their respective hydration properties. This result suggests that the block is not attributable to ion trapping due to +2 charge, and differences in blocking behavior arise due to free energies associated with the exchange of water ligands for channel ligands instead of free energies of transfer from water to the binding site.

Sodium and Potassium Ions in Proteins and Enzyme Catalysis.

PubMed

Vašák, Milan; Schnabl, Joachim

2016-01-01

The group I alkali metal ions Na(+) and K(+) are ubiquitous components of biological fluids that surround biological macromolecules. They play important roles other than being nonspecific ionic buffering agents or mediators of solute exchange and transport. Molecular evolution and regulated high intracellular and extracellular M(+) concentrations led to incorporation of selective Na(+) and K(+) binding sites into enzymes to stabilize catalytic intermediates or to provide optimal positioning of substrates. The mechanism of M(+) activation, as derived from kinetic studies along with structural analysis, has led to the classification of cofactor-like (type I) or allosteric effector (type II) activated enzymes. In the type I mechanism substrate anchoring to the enzyme active site is mediated by M(+), often acting in tandem with a divalent cation like Mg(2+), Mn(2+) or Zn(2+). In the allosteric type II mechanism, M(+) binding enhances enzyme activity through conformational transitions triggered upon binding to a distant site. In this chapter, following the discussion of the coordination chemistry of Na(+) and K(+) ions and the structural features responsible for the metal binding site selectivity in M(+)-activated enzymes, well-defined examples of M(+)-activated enzymes are used to illustrate the structural basis for type I and type II activation by Na(+) and K(+).

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.

Probing Long-Range Neutrino-Mediated Forces with Atomic and Nuclear Spectroscopy.

PubMed

Stadnik, Yevgeny V

2018-06-01

The exchange of a pair of low-mass neutrinos between electrons, protons, and neutrons produces a "long-range" 1/r^{5} potential, which can be sought for in phenomena originating on the atomic and subatomic length scales. We calculate the effects of neutrino-pair exchange on transition and binding energies in atoms and nuclei. In the case of atomic s-wave states, there is a large enhancement of the induced energy shifts due to the lack of a centrifugal barrier and the highly singular nature of the neutrino-mediated potential. We derive limits on neutrino-mediated forces from measurements of the deuteron binding energy and transition energies in positronium, muonium, hydrogen, and deuterium, as well as isotope-shift measurements in calcium ions. Our limits improve on existing constraints on neutrino-mediated forces from experiments that search for new macroscopic forces by 18 orders of magnitude. Future spectroscopy experiments have the potential to probe long-range forces mediated by the exchange of pairs of standard-model neutrinos and other weakly charged particles.

Probing Long-Range Neutrino-Mediated Forces with Atomic and Nuclear Spectroscopy

NASA Astrophysics Data System (ADS)

Stadnik, Yevgeny V.

2018-06-01

The exchange of a pair of low-mass neutrinos between electrons, protons, and neutrons produces a "long-range" 1 /r5 potential, which can be sought for in phenomena originating on the atomic and subatomic length scales. We calculate the effects of neutrino-pair exchange on transition and binding energies in atoms and nuclei. In the case of atomic s -wave states, there is a large enhancement of the induced energy shifts due to the lack of a centrifugal barrier and the highly singular nature of the neutrino-mediated potential. We derive limits on neutrino-mediated forces from measurements of the deuteron binding energy and transition energies in positronium, muonium, hydrogen, and deuterium, as well as isotope-shift measurements in calcium ions. Our limits improve on existing constraints on neutrino-mediated forces from experiments that search for new macroscopic forces by 18 orders of magnitude. Future spectroscopy experiments have the potential to probe long-range forces mediated by the exchange of pairs of standard-model neutrinos and other weakly charged particles.

Cr(3+) Binding to DNA Backbone Phosphate and Bases: Slow Ligand Exchange Rates and Metal Hydrolysis.

PubMed

Zhou, Wenhu; Yu, Tianmeng; Vazin, Mahsa; Ding, Jinsong; Liu, Juewen

2016-08-15

The interaction between chromium ions and DNA is of great interest in inorganic chemistry, toxicology, and analytical chemistry. Most previous studies focused on in situ reduction of Cr(VI), producing Cr(3+) for DNA binding. Recently, Cr(3+) was reported to activate the Ce13d DNAzyme for RNA cleavage. Herein, the Ce13d is used to study two types of Cr(3+) and DNA interactions. First, Cr(3+) binds to the DNA phosphate backbone weakly through reversible electrostatic interactions, which is weakened by adding competing inorganic phosphate. However, Cr(3+) coordinates with DNA nucleobases forming stable cross-links that can survive denaturing gel electrophoresis condition. The binding of Cr(3+) to different nucleobases was further studied in terms of binding kinetics and affinity by exploiting carboxyfluorescein-labeled DNA homopolymers. Once binding takes place, the stable Cr(3+)/DNA complex cannot be dissociated by EDTA, attributable to the ultraslow ligand exchange rate of Cr(3+). The binding rate follows the order of G > C > T ≈ A. Finally, Cr(3+) gradually loses its DNA binding ability after being stored at neutral or high pH, attributable to hydrolysis. This hydrolysis can be reversed by lowering the pH. This work provides a deeper insight into the bioinorganic chemistry of Cr(3+) coordination with DNA, clarifies some inconsistency in the previous literature, and offers practically useful information for generating reproducible results.

Thermodynamic evidence of flexibility in H2O and CO2 absorption of transition metal ion exchanged zeolite LTA.

PubMed

Guo, Xin; Wu, Lili; Navrotsky, Alexandra

2018-02-07

Gas absorption calorimetry has been employed to probe the intercation of water and carbon dioxide with transition metal ion (TM = Mn 2+ , Fe 2+ , Co 2+ , Cu 2+ , and Zn 2+ ) exchanged zeolite A samples. There appears to be a two-phase region, indicative of a guest-induced flexibility transition, separating hydrated zeolite A and its dehydrated form, both of which have variable water content in the single phase region. The differential enthalpy of absorption as a function of water loading directly identifies different strengths of multiple interactions along with possible binding mechanisms of Zn-A and Mn-A exhibiting the highest water absorption with most exothermic initial enthalpies of -125.28 ± 4.82 and -115.30 ± 2.56 kJ mol -1 . Zn-A and Mn-A also show moderately good capture ability for CO 2 with zero-coverage negative enthalpies of -55.59 ± 2.48 and -44.07 ± 1.53 kJ mol -1 . The thermodynamic information derived from differential enthalpy, chemical potential and differential entropy elucidated the multistage interactive behavior of small guest molecules (H 2 O/CO 2 ) and ion-exchanged frameworks.

Ion exchange selectivity for cross-linked polyacrylic acid

NASA Technical Reports Server (NTRS)

May, C. E.; Philipp, W. H.

1983-01-01

The ion separation factors for 21 common metal ions with cross-linked polyacrylic acid were determined as a function of pH and the percent of the cross-linked polyacrylic acid neutralized. The calcium ion was used as a reference. At a pH of 5 the decreasing order of affinity of the ions for the cross-linked polyacrylic acid was found to be: Hg++, Fe+++, Pb++, Cr+++, Cu++, Cd++, Al+++, Ag+, Zn++, Ni++, Mn++, Co++, Ca++, Sr++, Ba++, Mg++, K+, Rb+, Cs+, Na+, and Li+. Members of a chemical family exhibited similar selectivities. The Hg++ ion appeared to be about a million times more strongly bound than the alkali metal ions. The relative binding of most of the metal ions varied with pH; the very tightly and very weakly bound ions showed the largest variations with pH. The calcium ion-hydrogen ion equilibrium was perturbed very little by the presence of the other ions. The separation factors and selectivity coefficients are discussed in terms of equilibrium and thermodynamic significance.

CryoEM structure of the human SLC4A4 sodium-coupled acid-base transporter NBCe1.

PubMed

Huynh, Kevin W; Jiang, Jiansen; Abuladze, Natalia; Tsirulnikov, Kirill; Kao, Liyo; Shao, Xuesi; Newman, Debra; Azimov, Rustam; Pushkin, Alexander; Zhou, Z Hong; Kurtz, Ira

2018-03-02

Na + -coupled acid-base transporters play essential roles in human biology. Their dysfunction has been linked to cancer, heart, and brain disease. High-resolution structures of mammalian Na + -coupled acid-base transporters are not available. The sodium-bicarbonate cotransporter NBCe1 functions in multiple organs and its mutations cause blindness, abnormal growth and blood chemistry, migraines, and impaired cognitive function. Here, we have determined the structure of the membrane domain dimer of human NBCe1 at 3.9 Å resolution by cryo electron microscopy. Our atomic model and functional mutagenesis revealed the ion accessibility pathway and the ion coordination site, the latter containing residues involved in human disease-causing mutations. We identified a small number of residues within the ion coordination site whose modification transformed NBCe1 into an anion exchanger. Our data suggest that symporters and exchangers utilize comparable transport machinery and that subtle differences in their substrate-binding regions have very significant effects on their transport mode.

Comparative study of glycated hemoglobin by ion exchange chromatography and affinity binding nycocard reader in type 2 diabetes mellitus.

PubMed

Gautam, N; Dubey, R K; Jayan, A; Nepaune, Y; Padmavathi, P; Chaudhary, S; Jha, S K; Sinha, A K

2014-12-01

The aim of this study was to compare the level of glycated hemoglobin (HbA1c) in type 2 Diabetes Mellitus (DM) patients by two different methods namely Ion Exchange Chromatography and Affinity Binding Nycocard Reader. This is a cross-sectional study conducted on confirmed type 2 diabetes mellitus patients (n = 100) who visited Out Patients Department of the Universal College of Medical Sciences Teaching hospital, Bhairahawa, Nepal from November 2012 to March 2013. The diagnosis of diabetes mellitus was done on the basis of their fasting (164.46 ± 45.33 mg/dl) and random (187.93 ± 78.02 mg/dl) serum glucose level along with clinical history highly suggestive of type 2 DM. The HbA1c values of (7.8 ± 1.9%) and (8.0 ± 2.2%) were found in DM patients as estimated by those two different methods respectively. The highest frequency was observed in HbA1c > 8.0% indicating maximum cases were under very poor glycemic control. However, there were no significant differences observed in HbA1c value showing both methods are comparable in nature and can be used in lab for ease of estimation. The significant raised in HbA1c indicates complications associated with DM and monitoring of therapy become hard for those patients. Despite having standard reference method for HbA1c determination, the availability of report at the time of the patient visit can be made easy by using Nycocard Reader and Ion Exchange Chromatography techniques without any delay in communicating glycemic control, clinical decision-making and changes in treatment regimen.

Determination of Histamine in Silages Using Nanomaghemite Core (γ-Fe2O3)-Titanium Dioxide Shell Nanoparticles Off-Line Coupled with Ion Exchange Chromatography

PubMed Central

Cernei, Natalia; Lackova, Zuzana; Guran, Roman; Hynek, David; Skladanka, Jiri; Horky, Pavel; Zitka, Ondrej; Adam, Vojtech

2016-01-01

The presence of biogenic amines is a hallmark of degraded food and its products. Herein, we focused on the utilization of magnetic nanoparticles off-line coupled with ion exchange chromatography with post-column ninhydrin derivatization and Vis detection for histamine (Him) separation and detection. Primarily, we described the synthesis of magnetic nanoparticles with nanomaghemite core (γ-Fe2O3) functionalized with titanium dioxide and, then, applied these particles to specific isolation of Him. To obtain further insight into interactions between paramagnetic particles’ (PMP) surface and Him, a scanning electron microscope was employed. It was shown that binding of histamine causes an increase of relative current response of deprotonated PMPs, which confirmed formation of Him-PMPs clusters. The recovery of the isolation showed that titanium dioxide-based particles were able to bind and preconcentrate Him with recovery exceeding 90%. Finally, we successfully carried out the analyses of real samples obtained from silage. We can conclude that our modified particles are suitable for Him isolation, and thus may serve as the first isolation step of Him from biological samples, as it is demonstrated on alfalfa seed variety Tereza silage. PMID:27626434

Lateral cis-1,3,5,7-tetraazadecalin podands and their complexes: synthesis, structure, and strong binding with Pb(II) and other heavy metal ions.

PubMed

Reany, Ofer; Fuchs, Benzion

2013-02-18

The chemistry and complexation behavior of diaminal podands based on cis-1,3,5,7-tetraazadecalin (cis-TAD) were elaborated, reassessed, and extended. The synthesis of 2,6-bis(hydroxymethylene)-cis-TAD (9) and 2,6-bis(α,α'-dimethyl-β- hydroxyethyl)-cis-TAD (10) as well as of suitably substituted 2,6-diaryl-cis-TAD podands is laid out. For the latter, the effect of electron donating or withdrawing substituents on the benzaldehyde reagents was examined while 9 and 10 were probed and showed considerable propensity for heavy metal-ion chelation. The [Cd(II)·(9)] and [Pb(II)·(9)] complexes stood out indeed, and their structure and properties show a particularly interesting 5-amino-1,3-diazane chelation type and strong ligand-ion binding mode, with intramolecular donor exchange in solution, all strongly influenced by the anomeric effect in the ligand.

Adsorption of Ag (I) from aqueous solution by waste yeast: kinetic, equilibrium and mechanism studies.

PubMed

Zhao, Yufeng; Wang, Dongfang; Xie, Hezhen; Won, Sung Wook; Cui, Longzhe; Wu, Guiping

2015-01-01

One type of biosorbents, brewer fermentation industry waste yeast, was developed to adsorb the Ag (I) in aqueous solution. The result of FTIR analysis of waste yeast indicated that the ion exchange, chelating and reduction were the main binding mechanisms between the silver ions and the binding sites on the surface of the biomass. Furthermore, TEM, XRD and XPS results suggested that Ag(0) nanoparticles were deposited on the surface of yeast. The kinetic experiments revealed that sorption equilibrium could reach within 60 min, and the removal efficiency of Ag (I) could be still over 93 % when the initial concentration of Ag (I) was below 100 mg/L. Thermodynamic parameters of the adsorption process (ΔG, ΔH and ΔS) identified that the adsorption was a spontaneous and exothermic process. The waste yeast, playing a significant role in the adsorption of the silver ions, is useful to fast adsorb Ag (I) from low concentration.

Optical measurements of Na-Ca-K exchange currents in intact outer segments isolated from bovine retinal rods

PubMed Central

1991-01-01

The properties of Na-Ca-K exchange current through the plasma membrane of intact rod outer segments (ROS) isolated from bovine retinas were studied with the optical probe neutral red. Small cellular organelles such as bovine ROS do not offer an adequate collecting area to measure Na-Ca-K exchange currents with electrophysiological techniques. This study demonstrates that Na-Ca-K exchange current in bovine ROS can be measured with the dye neutral red and dual-wavelength spectrophotometry. The binding of neutral red is sensitive to transport of cations across the plasma membrane of ROS by the effect of the translocated cations on the surface potential of the intracellular disk membranes (1985. J. Membr. Biol. 88: 249-262). Electrogenic Na+ fluxes through the ROS plasma membrane were measured with a resolution of 10(5) Na+ ions/ROS per s, equivalent to a current of approximately 0.01 pA; maximal electrogenic Na-Ca-K exchange flux in bovine ROS was equivalent to a maximal exchange current of 1-2 pA. Electrogenic Na+ fluxes were identified as Na-Ca-K exchange current based on a comparison between electrogenic Na+ flux and Na(+)-stimulated Ca2+ release with respect to flux rate, Na+ dependence, and ion selectivity. Neutral red monitored the net entry of a single positive charge carried by Na+ for each Ca2+ ion released (i.e., monitored the Na-Ca-K exchange current). Na-Ca-K exchange in the plasma membrane of bovine ROS had the following properties: (a) Inward Na-Ca-K exchange current required internal Ca2+ (half-maximal stimulation at a free Ca2+ concentration of 0.9 microM), whereas outward Na-Ca-K exchange current required both external Ca2+ (half-maximal stimulation at a free Ca2+ concentration of 1.1 microM) and external K+. (b) Inward Na-Ca-K exchange current depended in a sigmoidal manner on the external Na+ concentration, identical to Na(+)-stimulated Ca2+ release measured with Ca(2+)- indicating dyes. (c) The neutral red method was modified to measure Ca(2+)-activated K+ fluxes (half-maximal stimulation at 2.7 microM free Ca2+) via the Na-Ca-K exchanger in support of the notion that the rod Na-Ca exchanger is in effect a Na-Ca-K exchanger. (d) Competitive interactions between Ca2+ and Na+ ions on the exchanger protein are described. PMID:1722239

Noncovalent Complexation of Monoamine Neurotransmitters and Related Ammonium Ions by Tetramethoxy Tetraglucosylcalix[4]arene

NASA Astrophysics Data System (ADS)

Torvinen, Mika; Kalenius, Elina; Sansone, Francesco; Casnati, Alessandro; Jänis, Janne

2012-02-01

The noncovalent complexation of monoamine neurotransmitters and related ammonium and quaternary ammonium ions by a conformationally flexible tetramethoxy glucosylcalix[4]arene was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. The glucosylcalixarene exhibited highest binding affinity towards serotonin, norepinephrine, epinephrine, and dopamine. Structural properties of the guests, such as the number, location, and type of hydrogen bonding groups, length of the alkyl spacer between the ammonium head-group and the aromatic ring structure, and the degree of nitrogen substitution affected the complexation. Competition experiments and guest-exchange reactions indicated that the hydroxyl groups of guests participate in intermolecular hydrogen bonding with the glucocalixarene.

Development of novel catalytically active polymer-metal-nanocomposites based on activated foams and textile fibers.

PubMed

Domènech, Berta; Ziegler, Kharla K; Carrillo, Fernando; Muñoz, Maria; Muraviev, Dimitri N; Macanás, Jorge

2013-05-16

In this paper, we report the intermatrix synthesis of Ag nanoparticles in different polymeric matrices such as polyurethane foams and polyacrylonitrile or polyamide fibers. To apply this technique, the polymer must bear functional groups able to bind and retain the nanoparticle ion precursors while ions should diffuse through the matrix. Taking into account the nature of some of the chosen matrices, it was essential to try to activate the support material to obtain an acceptable value of ion exchange capacity. To evaluate the catalytic activity of the developed nanocomposites, a model catalytic reaction was carried out in batch experiments: the reduction of p-nitrophenol by sodium borohydride.

Investigation of metal ions sorption of brown peat moss powder

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Al K x-ray production for incident /sup 16/O ions: The influence of target thickness effects on observed target x-ray yields

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

Gray, T.J.; Richard, P.; Gealy, G.

1979-04-01

Thin solid Al targets ranging in thickness from approx. 1 to 30 ..mu..g/cm/sup 2/ were bombarded by /sup 16/O ions wih incident energies from 0.25 to 2.25 MeV/amu. The effects of target thickness on the measured Al K x-ray yield for ions incident without an initial K-shell vacancy were determined. Comparisons of the data for Al K x-ray production in vanishingly thin targets (and 29-..mu..g/cm/sup 2/ targets) were made to perturbed-stationary-state calculations (PSS) for O ions on Al targets. The PSS calculations contained corrections for Coulomb deflection and binding energy (PSS(CB)) and for Coulomb deflection, binding energy, and polarization (PSS(CBP)).more » Further, two different PSS calculation procedures were employed: calculations without radial cutoffs employed in the binding-energy contribution (PSS), and calculations with radial cutoffs employed in the binding-energy correction (NPSS). The PSS(CBP) calculations agree with the measured Al K x-ray production cross section for data taken in the limit of a vanishingly thin target. The NPSS(CBP) calculations agree with the data taken for a 29-..mu..g/cm/sup 2/ Al target. The latter agreement is fortuitous, as the increase observed in the measured target x-ray yield for the 29-..mu..g/cm/sup 2/ target, in comparison to the yield extracted as rhox ..-->.. 0 at each bombarding energy, is due to K-shell--to--K-shell charge exchange. Comparisons are made with previously published data for /sup 16/O ions incident on finite-thickness Al targets.« less

Nanosecond Dynamics at Protein Metal Sites: An Application of Perturbed Angular Correlation (PAC) of γ-Rays Spectroscopy.

PubMed

Chakraborty, Saumen; Pallada, Stavroula; Pedersen, Jeppe T; Jancso, Attila; Correia, Joao G; Hemmingsen, Lars

2017-09-19

Metalloproteins are essential to numerous reactions in nature, and constitute approximately one-third of all known proteins. Molecular dynamics of proteins has been elucidated with great success both by experimental and theoretical methods, revealing atomic level details of function involving the organic constituents on a broad spectrum of time scales. However, the characterization of dynamics at biomolecular metal sites on nanosecond time scales is scarce in the literature. The aqua ions of many biologically relevant metal ions exhibit exchange of water molecules on the nanosecond time scale or faster, often defining their reactivity in aqueous solution, and this is presumably also a relevant time scale for the making and breaking of coordination bonds between metal ions and ligands at protein metal sites. Ligand exchange dynamics is critical for a variety of elementary steps of reactions in metallobiochemistry, for example, association and dissociation of metal bound water, association of substrate and dissociation of product in the catalytic cycle of metalloenzymes, at regulatory metal sites which require binding and dissociation of metal ions, as well as in the transport of metal ions across cell membranes or between proteins involved in metal ion homeostasis. In Perturbed Angular Correlation of γ-rays (PAC) spectroscopy, the correlation in time and space of two γ-rays emitted successively in a nuclear decay is recorded, reflecting the hyperfine interactions of the PAC probe nucleus with the surroundings. This allows for characterization of molecular and electronic structure as well as nanosecond dynamics at the PAC probe binding site. Herein, selected examples describing the application of PAC spectroscopy in probing the dynamics at protein metal sites are presented, including (1) exchange of Cd 2+ bound water in de novo designed synthetic proteins, and the effect of remote mutations on metal site dynamics; (2) dynamics at the β-lactamase active site, where the metal ion appears to jump between the two adjacent sites; (3) structural relaxation in small blue copper proteins upon 111 Ag + to 111 Cd 2+ transformation in radioactive nuclear decay; (4) metal ion transfer between two HAH1 proteins with change in coordination number; and (5) metal ion sensor proteins with two coexisting metal site structures. With this Account, we hope to make our modest contribution to the field and perhaps spur additional interest in dynamics at protein metal sites, which we consider to be severely underexplored. Relatively little is known about detailed atomic motions at metal sites, for example, how ligand exchange processes affect protein function, and how the amino acid composition of the protein may control this facet of metal site characteristics. We also aim to provide the reader with a qualitative impression of the possibilities offered by PAC spectroscopy in bioinorganic chemistry, especially when elucidating dynamics at protein metal sites, and finally present data that may serve as benchmarks on a relevant time scale for development and tests of theoretical molecular dynamics methods applied to biomolecular metal sites.

Characterization of poly(allylamine) as a polymeric ligand for ion-exchange protein chromatography.

PubMed

Li, Ming; Li, Yanying; Yu, Linling; Sun, Yan

2017-02-24

This work reports poly(allylamine) (PAA), as a polymeric ion-exchange ligand for protein chromatography. Sepharose FF was modified with PAA, and six anion exchangers with ionic capacities (ICs) from 165 to 618mmol/L were prepared. Inverse size exclusion chromatography, adsorption equilibrium, uptake kinetics and column elution were performed. It was found that both the adsorption capacity and effective diffusivity maintained low values in the IC range of 165-373mmol/L, but they started to increase beyond 373mmol/L, and increased by 80% and 23 times, respectively, when the IC reached 618mmol/L. Interestingly, a drastic decrease of pore size was observed around the IC of 373mmol/L. The results suggest that the PAA chains played an important role in protein adsorption by altering the inner pore structure of the gels. It is considered that, PAA chains turn from inextensible states with multipoint-grafting on the pore surface at low coupling densities (IC<373mmol/L) to closer, extended and flexible grafting states with less coupling points at higher coupling densities (IC>373mmol/L). These characters of the grafted chains at higher IC values benefit in protein adsorption by three-dimensional binding and encouraged the happening of "chain delivery" of bound proteins on the chains. Besides, the ion exchangers showed favorable adsorption and uptake properties in a wide ionic strength range, 0-500mmol/L NaCl, indicating much better salt tolerance feature than the so-far reported ion exchangers. Moreover, a mild condition of pH 5.0 offered effective recovery of bound proteins in elution chromatography. The results indicate that the PAA-based anion exchanger of a high IC value is promising for high-capacity protein chromatography dealing with feedstock of a wide range of ionic strengths. Copyright © 2016 Elsevier B.V. All rights reserved.

Integrated-optical directional coupler biosensor

NASA Astrophysics Data System (ADS)

Luff, B. J.; Harris, R. D.; Wilkinson, J. S.; Wilson, R.; Schiffrin, D. J.

1996-04-01

We present measurements of biomolecular binding reactions, using a new type of integrated-optical biosensor based on a planar directional coupler structure. The device is fabricated by Ag+ - Na+ ion exchange in glass, and definition of the sensing region is achieved by use of transparent fluoropolymer isolation layers formed by thermal evaporation. The suitability of the sensor for application to the detection of environmental pollutants is considered.

Sorption of strontium-90 from fresh waters during sulfate modification of barium manganite

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

Ryzhen`kov, A.P.; Egorov, Yu.V.

1995-11-01

Recovery of strontium-90 with barium manganite from fresh waters (natural fresh waters of open basins) can be increased by adding agents that contain sulfate ions and thus modify the sorbent and chemically bind the sorbate. The treatment results in a heterogeneous anion-exchange transformation of barium manganite into barium sulfate-manganese dioxide and in simultaneous absorptive coprecipitation of strontium sulfate (microcomponent).

The Vibrio cholerae Mrp system: cation/proton antiport properties and enhancement of bile salt resistance in a heterologous host.

PubMed

Dzioba-Winogrodzki, Judith; Winogrodzki, Olga; Krulwich, Terry A; Boin, Markus A; Häse, Claudia C; Dibrov, Pavel

2009-01-01

The mrp operon from Vibrio cholerae encoding a putative multisubunit Na(+)/H(+) antiporter was cloned and functionally expressed in the antiporter-deficient strain of Escherichia coli EP432. Cells of EP432 expressing Vc-Mrp exhibited resistance to Na(+) and Li(+) as well as to natural bile salts such as sodium cholate and taurocholate. When assayed in everted membrane vesicles of the E. coli EP432 host, Vc-Mrp had sufficiently high antiport activity to facilitate the first extensive analysis of Mrp system from a Gram-negative bacterium encoded by a group 2 mrp operon. Vc-Mrp was found to exchange protons for Li(+), Na(+), and K(+) ions in pH-dependent manner with maximal activity at pH 9.0-9.5. Exchange was electrogenic (more than one H(+) translocated per cation moved in opposite direction). The apparent K(m) at pH 9.0 was 1.08, 1.30, and 68.5 mM for Li(+), Na(+), and K(+), respectively. Kinetic analyses suggested that Vc-Mrp operates in a binding exchange mode with all cations and protons competing for binding to the antiporter. The robust ion antiport activity of Vc-Mrp in sub-bacterial vesicles and its effect on bile resistance of the heterologous host make Vc-Mrp an attractive experimental model for the further studies of biochemistry and physiology of Mrp systems. Copyright 2008 S. Karger AG, Basel.

The mechanism of water/ion exchange at a protein surface: a weakly bound chloride in Helicobacter pylori apoflavodoxin.

PubMed

Galano-Frutos, Juan J; Morón, M Carmen; Sancho, Javier

2015-11-21

Binding/unbinding of small ligands, such as ions, to/from proteins influences biochemical processes such as protein folding, enzyme catalysis or protein/ligand recognition. We have investigated the mechanism of chloride/water exchange at a protein surface (that of the apoflavodoxin from Helicobacter pylori) using classical all-atom molecular dynamics simulations. They reveal a variety of chloride exit routes and residence times; the latter is related to specific coordination modes of the anion. The role of solvent molecules in the mechanism of chloride unbinding has been studied in detail. We see no temporary increase in chloride coordination along the release process. Instead, the coordination of new water molecules takes place in most cases after the chloride/protein atom release event has begun. Moreover, the distribution function of water entrance events into the first chloride solvation shell peaks after chloride protein atom dissociation events. All these observations together seem to indicate that water molecules simply fill the vacancies left by the previously coordinating protein residues. We thus propose a step-by-step dissociation pathway in which protein/chloride interactions gradually break down before new water molecules progressively fill the vacant positions left by protein atoms. As observed for other systems, water molecules associated with bound chloride or with protein atoms have longer residence times than those bound to the free anion. The implications of the exchange mechanism proposed for the binding of the FMN (Flavin Mononucleotide) protein cofactor are discussed.

Quantification of Transthyretin Kinetic Stability in Human Plasma Using Subunit Exchange

PubMed Central

2015-01-01

The transthyretin (TTR) amyloidoses are a group of degenerative diseases caused by TTR aggregation, requiring rate-limiting tetramer dissociation. Kinetic stabilization of TTR, by preferential binding of a drug to the native tetramer over the dissociative transition state, dramatically slows the progression of familial amyloid polyneuropathy. An established method for quantifying the kinetic stability of recombinant TTR tetramers in buffer is subunit exchange, in which tagged TTR homotetramers are added to untagged homotetramers at equal concentrations to measure the rate at which the subunits exchange. Herein, we report a subunit exchange method for quantifying the kinetic stability of endogenous TTR in human plasma. The subunit exchange reaction is initiated by the addition of a substoichiometric quantity of FLAG-tagged TTR homotetramers to endogenous TTR in plasma. Aliquots of the subunit exchange reaction, taken as a function of time, are then added to an excess of a fluorogenic small molecule, which immediately arrests further subunit exchange. After binding, the small molecule reacts with the TTR tetramers, rendering them fluorescent and detectable in human plasma after subsequent ion exchange chromatography. The ability to report on the extent of TTR kinetic stabilization resulting from treatment with oral tafamidis is important, especially for selection of the appropriate dose for patients carrying rare mutations. This method could also serve as a surrogate biomarker for the prediction of the clinical outcome. Subunit exchange was used to quantify the stabilization of WT TTR from senile systemic amyloidosis patients currently being treated with tafamidis (20 mg orally, once daily). TTR kinetic stability correlated with the tafamidis plasma concentration. PMID:24661308

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

NASA Astrophysics Data System (ADS)

Serrano, Susana; O'Day, Peggy A.; Vlassopoulos, Dimitri; García-González, Maria Teresa; Garrido, Fernando

2009-02-01

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X - and Y -), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions. Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.

Phase Changes of Monosulfoaluminate in NaCl Aqueous Solution

DOE PAGES

Yoon, Seyoon; Ha, Juyoung; Chae, Sejung Rosie; ...

2016-05-21

Monosulfoaluminate (Ca 4Al 2(SO 4)(OH) 12∙6H 2O) plays an important role in anion binding in Portland cement by exchanging its original interlayer ions (SO 4 2- and OH -) with chloride ions. In this study, scanning transmission X-ray microscope (STXM), X-ray absorption near edge structure (XANES) spectroscopy, and X-ray diffraction (XRD) were used to investigate the phase change of monosulfoaluminate due to its interaction with chloride ions. Pure monosulfoaluminate was synthesized and its powder samples were suspended in 0, 0.1, 1, 3, and 5 M NaCl solutions for seven days. At low chloride concentrations, a partial dissolution of monosulfoaluminate formedmore » ettringite, while, with increasing chloride content, the dissolution process was suppressed. As the NaCl concentration increased, the dominant mechanism of the phase change became ion exchange, resulting in direct phase transformation from monosulfoaluminate to Kuzel’s salt or Friedel’s salt. The phase assemblages of the NaCl-reacted samples were explored using thermodynamic calculations and least-square linear combination (LC) fitting of measured XANES spectra. A comprehensive description of the phase change and its dominant mechanism are discussed.« less

Semi-empirical spectrophotometric (SESp) method for the indirect determination of the ratio of cationic micellar binding constants of counterions X⁻ and Br⁻(K(X)/K(Br)).

PubMed

Khan, Mohammad Niyaz; Yusof, Nor Saadah Mohd; Razak, Norazizah Abdul

2013-01-01

The semi-empirical spectrophotometric (SESp) method, for the indirect determination of ion exchange constants (K(X)(Br)) of ion exchange processes occurring between counterions (X⁻ and Br⁻) at the cationic micellar surface, is described in this article. The method uses an anionic spectrophotometric probe molecule, N-(2-methoxyphenyl)phthalamate ion (1⁻), which measures the effects of varying concentrations of inert inorganic or organic salt (Na(v)X, v = 1, 2) on absorbance, (A(ob)) at 310 nm, of samples containing constant concentrations of 1⁻, NaOH and cationic micelles. The observed data fit satisfactorily to an empirical equation which gives the values of two empirical constants. These empirical constants lead to the determination of K(X)(Br) (= K(X)/K(Br) with K(X) and K(Br) representing cationic micellar binding constants of counterions X and Br⁻). This method gives values of K(X)(Br) for both moderately hydrophobic and hydrophilic X⁻. The values of K(X)(Br), obtained by using this method, are comparable with the corresponding values of K(X)(Br), obtained by the use of semi-empirical kinetic (SEK) method, for different moderately hydrophobic X. The values of K(X)(Br) for X = Cl⁻ and 2,6-Cl₂C6H₃CO₂⁻, obtained by the use of SESp and SEK methods, are similar to those obtained by the use of other different conventional methods.

Ion transport controlled by nanoparticle-functionalized membranes.

PubMed

Barry, Edward; McBride, Sean P; Jaeger, Heinrich M; Lin, Xiao-Min

2014-12-17

From proton exchange membranes in fuel cells to ion channels in biological membranes, the well-specified control of ionic interactions in confined geometries profoundly influences the transport and selectivity of porous materials. Here we outline a versatile new approach to control a membrane's electrostatic interactions with ions by depositing ligand-coated nanoparticles around the pore entrances. Leveraging the flexibility and control by which ligated nanoparticles can be synthesized, we demonstrate how ligand terminal groups such as methyl, carboxyl and amine can be used to tune the membrane charge density and control ion transport. Further functionality, exploiting the ligands as binding sites, is demonstrated for sulfonate groups resulting in an enhancement of the membrane charge density. We then extend these results to smaller dimensions by systematically varying the underlying pore diameter. As a whole, these results outline a previously unexplored method for the nanoparticle functionalization of membranes using ligated nanoparticles to control ion transport.

Ion transport controlled by nanoparticle-functionalized membranes

NASA Astrophysics Data System (ADS)

Barry, Edward; McBride, Sean P.; Jaeger, Heinrich M.; Lin, Xiao-Min

2014-12-01

From proton exchange membranes in fuel cells to ion channels in biological membranes, the well-specified control of ionic interactions in confined geometries profoundly influences the transport and selectivity of porous materials. Here we outline a versatile new approach to control a membrane’s electrostatic interactions with ions by depositing ligand-coated nanoparticles around the pore entrances. Leveraging the flexibility and control by which ligated nanoparticles can be synthesized, we demonstrate how ligand terminal groups such as methyl, carboxyl and amine can be used to tune the membrane charge density and control ion transport. Further functionality, exploiting the ligands as binding sites, is demonstrated for sulfonate groups resulting in an enhancement of the membrane charge density. We then extend these results to smaller dimensions by systematically varying the underlying pore diameter. As a whole, these results outline a previously unexplored method for the nanoparticle functionalization of membranes using ligated nanoparticles to control ion transport.

Repair of Nerve Cell Membrane Damage by Calcium-Dependent, Membrane-Binding Proteins (Revised)

DTIC Science & Technology

2012-09-01

protein, in model systems can promote a stable repair of broken membranes that could preserve cell viability. Preliminary data obtained using a novel...multilamellar liposomes prepared from bovine brain Folch Fraction I lipids (Sigma-Aldrich) and ion exchange chromatography on Poros Q medium using a Pharmacia...FPLC system [5]. Strategy for establishing the membrane leakage model The strategy employed in these studies was to encapsulate

Heavy metals binding properties of esterified lemon.

PubMed

Arslanoglu, Hasan; Altundogan, Hamdi Soner; Tumen, Fikret

2009-05-30

Sorption of Cd(2+), Cr(3+), Cu(2+), Ni(2+), Pb(2+) and Zn(2+) onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni(2+)>Cd(2+)>Cu(2+)>Pb(2+)>Zn(2+)>Cr(3+). The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb(2+)>Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Cr(3+). The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol(-1) for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The DeltaG degrees and DeltaH degrees values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low DeltaH degrees values revealed that physical adsorption significantly contributed to the mechanism.

The fundamental nature of life as a chemical system: the part played by inorganic elements.

PubMed

Williams, Robert J P

2002-02-01

In this article we show why inorganic metal elements from the environment were an essential part of the origin of living aqueous systems of chemicals in flow. Unavoidably such systems have many closely fixed parameters, related to thermodynamic binding constants, for the interaction of the essential exchangeable inorganic metal elements with both inorganic and organic non-metal materials. The binding constants give rise to fixed free metal ion concentration profiles for different metal ions and ligands in the cytoplasm of all cells closely related to the Irving-Williams series. The amounts of bound elements depend on the organic molecules present as well as these free ion concentrations. This system must have predated coding which is probably only essential for reproductive life. Later evolution in changing chemical environments became based on the development of extra cytoplasmic compartments containing quite different energised free (and bound) element contents but in feed-back communication with the central primitive cytoplasm which changed little. Hence species multiplied late in evolution in large part due to the coupling with the altered inorganic environment.

Rapid Screening for Potential Epitopes Reactive with a Polycolonal Antibody by Solution-Phase H/D Exchange Monitored by FT-ICR Mass Spectrometry

NASA Astrophysics Data System (ADS)

Zhang, Qian; Noble, Kyle A.; Mao, Yuan; Young, Nicolas L.; Sathe, Shridhar K.; Roux, Kenneth H.; Marshall, Alan G.

2013-07-01

The potential epitopes of a recombinant food allergen protein, cashew Ana o 2, reactive to polyclonal antibodies, were mapped by solution-phase amide backbone H/D exchange (HDX) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Ana o 2 polyclonal antibodies were purified in the serum from a goat immunized with cashew nut extract. Antibodies were incubated with recombinant Ana o 2 (rAna o 2) to form antigen:polyclonal antibody (Ag:pAb) complexes. Complexed and uncomplexed (free) rAna o 2 were then subjected to HDX-MS analysis. Four regions protected from H/D exchange upon pAb binding are identified as potential epitopes and mapped onto a homologous model.

Conformational heterogeneity of the calmodulin binding interface

NASA Astrophysics Data System (ADS)

Shukla, Diwakar; Peck, Ariana; Pande, Vijay S.

2016-04-01

Calmodulin (CaM) is a ubiquitous Ca2+ sensor and a crucial signalling hub in many pathways aberrantly activated in disease. However, the mechanistic basis of its ability to bind diverse signalling molecules including G-protein-coupled receptors, ion channels and kinases remains poorly understood. Here we harness the high resolution of molecular dynamics simulations and the analytical power of Markov state models to dissect the molecular underpinnings of CaM binding diversity. Our computational model indicates that in the absence of Ca2+, sub-states in the folded ensemble of CaM's C-terminal domain present chemically and sterically distinct topologies that may facilitate conformational selection. Furthermore, we find that local unfolding is off-pathway for the exchange process relevant for peptide binding, in contrast to prior hypotheses that unfolding might account for binding diversity. Finally, our model predicts a novel binding interface that is well-populated in the Ca2+-bound regime and, thus, a candidate for pharmacological intervention.

Interpenetrating polymer network ion exchange membranes and method for preparing same

DOEpatents

Alexandratos, Spiro D.; Danesi, Pier R.; Horwitz, E. Philip

1989-01-01

Interpenetrating polymer network ion exchange membranes include a microporous polymeric support film interpenetrated by an ion exchange polymer and are produced by absorbing and polymerizing monomers within the support film. The ion exchange polymer provides ion exchange ligands at the surface of and throughout the support film which have sufficient ligand mobility to extract and transport ions across the membrane.

Liquid membrane coated ion-exchange column solids

DOEpatents

Barkey, Dale P.

1988-01-01

This invention relates to a method for improving the performance of liquid membrane separations by coating a liquid membrane onto solid ion-exchange resin beads in a fixed bed. Ion-exchange beads fabricated from an ion-exchange resin are swelled with water and are coated with a liquid membrane material that forms a film over the beads. The beads constitute a fixed bed ion-exchange column. Fluid being treated that contains the desired ion to be trapped by the ion-exchange particle is passed through the column. A carrier molecule, contained in the liquid membrane ion-exchange material, is selective for the desired ion in the fluid. The carrier molecule forms a complex with the desired ion, transporting it through the membrane and thus separating it from the other ions. The solution is fed continuously until breakthrough occurs at which time the ion is recovered, and the bed is regenerated.

Liquid membrane coated ion-exchange column solids

DOEpatents

Barkey, Dale P.

1989-01-01

This invention relates to a method for improving the performance of liquid embrane separations by coating a liquid membrane onto solid ion-exchange resin beads in a fixed bed. Ion-exchange beads fabricated from an ion-exchange resin are swelled with water and are coated with a liquid membrane material that forms a film over the beads. The beads constitute a fixed bed ion-exchange column. Fluid being treated that contains the desired ion to be trapped by the ion-exchange particle is passed through the column. A carrier molecule, contained in the liquid membrane ion-exchange material, is selected for the desired ion in the fluid. The carrier molecule forms a complex with the desired ion, transporting it through the membrane and thus separating it from the other ions. The solution is fed continuously until breakthrough occurs at which time the ion is recovered, and the bed is regenerated.

Energy landscape of the reactions governing the Na+ deeply occluded state of the Na+/K+-ATPase in the giant axon of the Humboldt squid

PubMed Central

Castillo, Juan P.; De Giorgis, Daniela; Basilio, Daniel; Gadsby, David C.; Rosenthal, Joshua J. C.; Latorre, Ramon; Holmgren, Miguel; Bezanilla, Francisco

2011-01-01

The Na+/K+ pump is a nearly ubiquitous membrane protein in animal cells that uses the free energy of ATP hydrolysis to alternatively export 3Na+ from the cell and import 2K+ per cycle. This exchange of ions produces a steady-state outwardly directed current, which is proportional in magnitude to the turnover rate. Under certain ionic conditions, a sudden voltage jump generates temporally distinct transient currents mediated by the Na+/K+ pump that represent the kinetics of extracellular Na+ binding/release and Na+ occlusion/deocclusion transitions. For many years, these events have escaped a proper thermodynamic treatment due to the relatively small electrical signal. Here, taking the advantages offered by the large diameter of the axons from the squid Dosidicus gigas, we have been able to separate the kinetic components of the transient currents in an extended temperature range and thus characterize the energetic landscape of the pump cycle and those transitions associated with the extracellular release of the first Na+ from the deeply occluded state. Occlusion/deocclusion transition involves large changes in enthalpy and entropy as the ion is exposed to the external milieu for release. Binding/unbinding is substantially less costly, yet larger than predicted for the energetic cost of an ion diffusing through a permeation pathway, which suggests that ion binding/unbinding must involve amino acid side-chain rearrangements at the site. PMID:22143771

Energy landscape of the reactions governing the Na+ deeply occluded state of the Na+/K+-ATPase in the giant axon of the Humboldt squid.

PubMed

Castillo, Juan P; De Giorgis, Daniela; Basilio, Daniel; Gadsby, David C; Rosenthal, Joshua J C; Latorre, Ramon; Holmgren, Miguel; Bezanilla, Francisco

2011-12-20

The Na(+)/K(+) pump is a nearly ubiquitous membrane protein in animal cells that uses the free energy of ATP hydrolysis to alternatively export 3Na(+) from the cell and import 2K(+) per cycle. This exchange of ions produces a steady-state outwardly directed current, which is proportional in magnitude to the turnover rate. Under certain ionic conditions, a sudden voltage jump generates temporally distinct transient currents mediated by the Na(+)/K(+) pump that represent the kinetics of extracellular Na(+) binding/release and Na(+) occlusion/deocclusion transitions. For many years, these events have escaped a proper thermodynamic treatment due to the relatively small electrical signal. Here, taking the advantages offered by the large diameter of the axons from the squid Dosidicus gigas, we have been able to separate the kinetic components of the transient currents in an extended temperature range and thus characterize the energetic landscape of the pump cycle and those transitions associated with the extracellular release of the first Na(+) from the deeply occluded state. Occlusion/deocclusion transition involves large changes in enthalpy and entropy as the ion is exposed to the external milieu for release. Binding/unbinding is substantially less costly, yet larger than predicted for the energetic cost of an ion diffusing through a permeation pathway, which suggests that ion binding/unbinding must involve amino acid side-chain rearrangements at the site.

"In situ" observation of the role of chloride ion binding to monkey green sensitive visual pigment by ATR-FTIR spectroscopy.

PubMed

Katayama, Kota; Furutani, Yuji; Iwaki, Masayo; Fukuda, Tetsuya; Imai, Hiroo; Kandori, Hideki

2018-01-31

Long-wavelength-sensitive (LWS) pigment possesses a chloride binding site in its protein moiety. The binding of chloride alters the absorption spectra of LWS; this is known as the chloride effect. Although the two amino acid substitutions of His197 and Lys200 influence the chloride effect, the molecular mechanism of chloride binding, which underlies the spectral tuning, has yet to be clarified. In this study, we applied ATR-FTIR spectroscopy to monkey green (MG) pigment to gain structural information of the chloride binding site. The results suggest that chloride binding stabilizes the β-sheet structure on the extracellular side loop with perturbation of the retinal polyene chain, promotes a hydrogen bonding exchange with the hydroxyl group of Tyr, and alters the protonation state of carboxylate. Combining with the results of the binding analyses of various anions (Br - , I - and NO 3 - ), our findings suggest that the anion binding pocket is organized for only Cl - (or Br - ) to stabilize conformation around the retinal chromophore, which is functionally relevant with absorbing long wavelength light.

Effects of urea on selectivity and protein-ligand interactions in multimodal cation exchange chromatography.

PubMed

Holstein, Melissa A; Parimal, Siddharth; McCallum, Scott A; Cramer, Steven M

2013-01-08

Nuclear magnetic resonance (NMR) and molecular dynamics (MD) simulations were employed in concert with chromatography to provide insight into the effect of urea on protein-ligand interactions in multimodal (MM) chromatography. Chromatographic experiments with a protein library in ion exchange (IEX) and MM systems indicated that, while urea had a significant effect on protein retention and selectivity for a range of proteins in MM systems, the effects were much less pronounced in IEX. NMR titration experiments carried out with a multimodal ligand, and isotopically enriched human ubiquitin indicated that, while the ligand binding face of ubiquitin remained largely intact in the presence of urea, the strength of binding was decreased. MD simulations were carried out to provide further insight into the effect of urea on MM ligand binding. These results indicated that, while the overall ligand binding face of ubiquitin remained the same, there was a reduction in the occupancy of the MM ligand interaction region along with subtle changes in the residues involved in these interactions. This work demonstrates the effectiveness of urea in enhancing selectivity in MM chromatographic systems and also provides an in-depth analysis of how MM ligand-protein interactions are altered in the presence of this fluid phase modifier.

DNA Interactions Probed by Hydrogen-Deuterium Exchange (HDX) Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Confirm External Binding Sites on the Minichromosomal Maintenance (MCM) Helicase*

PubMed Central

Graham, Brian W.; Tao, Yeqing; Dodge, Katie L.; Thaxton, Carly T.; Olaso, Danae; Young, Nicolas L.; Marshall, Alan G.

2016-01-01

The archaeal minichromosomal maintenance (MCM) helicase from Sulfolobus solfataricus (SsoMCM) is a model for understanding structural and mechanistic aspects of DNA unwinding. Although interactions of the encircled DNA strand within the central channel provide an accepted mode for translocation, interactions with the excluded strand on the exterior surface have mostly been ignored with regard to DNA unwinding. We have previously proposed an extension of the traditional steric exclusion model of unwinding to also include significant contributions with the excluded strand during unwinding, termed steric exclusion and wrapping (SEW). The SEW model hypothesizes that the displaced single strand tracks along paths on the exterior surface of hexameric helicases to protect single-stranded DNA (ssDNA) and stabilize the complex in a forward unwinding mode. Using hydrogen/deuterium exchange monitored by Fourier transform ion cyclotron resonance MS, we have probed the binding sites for ssDNA, using multiple substrates targeting both the encircled and excluded strand interactions. In each experiment, we have obtained >98.7% sequence coverage of SsoMCM from >650 peptides (5–30 residues in length) and are able to identify interacting residues on both the interior and exterior of SsoMCM. Based on identified contacts, positively charged residues within the external waist region were mutated and shown to generally lower DNA unwinding without negatively affecting the ATP hydrolysis. The combined data globally identify binding sites for ssDNA during SsoMCM unwinding as well as validating the importance of the SEW model for hexameric helicase unwinding. PMID:27044751

Comparison of structural, thermodynamic, kinetic and mass transport properties of Mg(2+) ion models commonly used in biomolecular simulations.

PubMed

Panteva, Maria T; Giambaşu, George M; York, Darrin M

2015-05-15

The prevalence of Mg(2+) ions in biology and their essential role in nucleic acid structure and function has motivated the development of various Mg(2+) ion models for use in molecular simulations. Currently, the most widely used models in biomolecular simulations represent a nonbonded metal ion as an ion-centered point charge surrounded by a nonelectrostatic pairwise potential that takes into account dispersion interactions and exchange effects that give rise to the ion's excluded volume. One strategy toward developing improved models for biomolecular simulations is to first identify a Mg(2+) model that is consistent with the simulation force fields that closely reproduces a range of properties in aqueous solution, and then, in a second step, balance the ion-water and ion-solute interactions by tuning parameters in a pairwise fashion where necessary. The present work addresses the first step in which we compare 17 different nonbonded single-site Mg(2+) ion models with respect to their ability to simultaneously reproduce structural, thermodynamic, kinetic and mass transport properties in aqueous solution. None of the models based on a 12-6 nonelectrostatic nonbonded potential was able to reproduce the experimental radial distribution function, solvation free energy, exchange barrier and diffusion constant. The models based on a 12-6-4 potential offered improvement, and one model in particular, in conjunction with the SPC/E water model, performed exceptionally well for all properties. The results reported here establish useful benchmark calculations for Mg(2+) ion models that provide insight into the origin of the behavior in aqueous solution, and may aid in the development of next-generation models that target specific binding sites in biomolecules. © 2015 Wiley Periodicals, Inc.

Advanced purification strategy for CueR, a cysteine containing copper(I) and DNA binding protein.

PubMed

Balogh, Ria K; Gyurcsik, Béla; Hunyadi-Gulyás, Éva; Christensen, Hans E M; Jancsó, Attila

2016-07-01

Metal ion regulation is essential for living organisms. In prokaryotes metal ion dependent transcriptional factors, the so-called metalloregulatory proteins play a fundamental role in controlling the concentration of metal ions. These proteins recognize metal ions with an outstanding selectivity. A detailed understanding of their function may be exploited in potential health, environmental and analytical applications. Members of the MerR protein family sense a broad range of mostly late transition and heavy metal ions through their cysteine thiolates. The air sensitivity of latter groups makes the expression and purification of such proteins challenging. Here we describe a method for the purification of the copper-regulatory CueR protein under optimized conditions. In order to avoid protein precipitation and/or eventual aggregation and to get rid of the co-purifying Escherichia coli elongation factor, our procedure consisted of four steps supplemented by DNA digestion. Subsequent anion exchange on Sepharose FF Q 16/10, affinity chromatography on Heparin FF 16/10, second anion exchange on Source 30 Q 16/13 and gel filtration on Superdex 75 26/60 resulted in large amounts of pure CueR protein without any affinity tag. Structure and functionality tests performed with mass spectrometry, circular dichroism spectroscopy and electrophoretic gel mobility shift assays approved the success of the purification procedure. Copyright © 2016 Elsevier Inc. All rights reserved.

PEROXOTITANATE- AND MONOSODIUM METAL-TITANATE COMPOUNDS AS INHIBITORS OF BACTERIAL GROWTH

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

Hobbs, D.

2011-01-19

Sodium titanates are ion-exchange materials that effectively bind a variety of metal ions over a wide pH range. Sodium titanates alone have no known adverse biological effects but metal-exchanged titanates (or metal titanates) can deliver metal ions to mammalian cells to alter cell processes in vitro. In this work, we test a hypothesis that metal-titanate compounds inhibit bacterial growth; demonstration of this principle is one prerequisite to developing metal-based, titanate-delivered antibacterial agents. Focusing initially on oral diseases, we exposed five species of oral bacteria to titanates for 24 h, with or without loading of Au(III), Pd(II), Pt(II), and Pt(IV), andmore » measuring bacterial growth in planktonic assays through increases in optical density. In each experiment, bacterial growth was compared with control cultures of titanates or bacteria alone. We observed no suppression of bacterial growth by the sodium titanates alone, but significant (p < 0.05, two-sided t-tests) suppression was observed with metal-titanate compounds, particularly Au(III)-titanates, but with other metal titanates as well. Growth inhibition ranged from 15 to 100% depending on the metal ion and bacterial species involved. Furthermore, in specific cases, the titanates inhibited bacterial growth 5- to 375-fold versus metal ions alone, suggesting that titanates enhanced metal-bacteria interactions. This work supports further development of metal titanates as a novel class of antibacterials.« less

Production of sodium-22 from proton irradiated aluminum

DOEpatents

Taylor, Wayne A.; Heaton, Richard C.; Jamriska, David J.

1996-01-01

A process for selective separation of sodium-22 from a proton irradiated minum target including dissolving a proton irradiated aluminum target in hydrochloric acid to form a first solution including aluminum ions and sodium ions, separating a portion of the aluminum ions from the first solution by crystallization of an aluminum salt, contacting the remaining first solution with an anion exchange resin whereby ions selected from the group consisting of iron and copper are selectively absorbed by the anion exchange resin while aluminum ions and sodium ions remain in solution, contacting the solution with an cation exchange resin whereby aluminum ions and sodium ions are adsorbed by the cation exchange resin, and, contacting the cation exchange resin with an acid solution capable of selectively separating the adsorbed sodium ions from the cation exchange resin while aluminum ions remain adsorbed on the cation exchange resin is disclosed.

Biochemical characterization of P-type copper ATPases

PubMed Central

Inesi, Giuseppe; Pilankatta, Rajendra; Tadini-Buoninsegni, Francesco

2014-01-01

Copper ATPases, in analogy with other members of the P-ATPase superfamily, contain a catalytic headpiece including an aspartate residue reacting with ATP to form a phosphoenzyme intermediate, and transmembrane helices containing cation-binding sites [TMBS (transmembrane metal-binding sites)] for catalytic activation and cation translocation. Following phosphoenzyme formation by utilization of ATP, bound copper undergoes displacement from the TMBS to the lumenal membrane surface, with no H+ exchange. Although PII-type ATPases sustain active transport of alkali/alkali-earth ions (i.e. Na+, Ca2+) against electrochemical gradients across defined membranes, PIB-type ATPases transfer transition metal ions (i.e. Cu+) from delivery to acceptor proteins and, prominently in mammalian cells, undergo trafficking from/to various membrane compartments. A specific component of copper ATPases is the NMBD (N-terminal metal-binding domain), containing up to six copper-binding sites in mammalian (ATP7A and ATP7B) enzymes. Copper occupancy of NMBD sites and interaction with the ATPase headpiece are required for catalytic activation. Furthermore, in the presence of copper, the NMBD allows interaction with protein kinase D, yielding phosphorylation of serine residues, ATP7B trafficking and protection from proteasome degradation. A specific feature of ATP7A is glycosylation and stabilization on plasma membranes. Cisplatin, a platinum-containing anti-cancer drug, binds to copper sites of ATP7A and ATP7B, and undergoes vectorial displacement in analogy with copper. PMID:25242165

HD Exchange and PLIMSTEX Determine the Affinities and Order of Binding of Ca2+ with Troponin C

PubMed Central

Huang, Richard Y-C.; Rempel, Don L.; Gross, Michael L.

2011-01-01

Troponin C (TnC), present in all striated muscle, is the Ca2+-activated trigger that initiates myocyte contraction. The binding of Ca2+ to TnC initiates a cascade of conformational changes involving the constituent proteins of the thin filament. The functional properties of TnC and its ability to bind Ca2+ have significant regulatory influence on the contractile reaction of muscle. Changes in TnC may also correlate with cardiac and various other muscle-related diseases. We report here the implementation of the PLIMSTEX strategy (Protein Ligand Interaction by Mass Spectrometry, Titration and H/D Exchange) to elucidate the binding affinity of TnC with Ca2+ and, more importantly, to determine the order of Ca2+ binding of the four EF hands of the protein. The four equilibrium constants, K1 = (5 ± 5) × 10 M-1, K2 = (1.8 ± 0.8) × 107 M-1, K3 = (4.2 ± 0.9) × 106 M-1, and K4 = (1.6 ± 0.6) × 106 M-1, agree well with determinations by other methods and serve to increase our confidence in the PLIMSTEX approach. We determined the order of binding to the four EF hands to be III, IV, II, and I by extracting from the H/DX results the deuterium patterns for each EF hand for each state of the protein (apo through fully Ca2+ bound). This approach, demonstrated for the first time, may be general for determining binding orders of metal ions and other ligands to proteins. PMID:21574565

Development of a high-throughput crystal structure-determination platform for JAK1 using a novel metal-chelator soaking system

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

Caspers, Nicole L.; Han, Seungil; Rajamohan, Francis

2016-10-27

Crystals of phosphorylated JAK1 kinase domain were initially generated in complex with nucleotide (ADP) and magnesium. The tightly bound Mg 2+-ADP at the ATP-binding site proved recalcitrant to ligand displacement. Addition of a molar excess of EDTA helped to dislodge the divalent metal ion, promoting the release of ADP and allowing facile exchange with ATP-competitive small-molecule ligands. Many kinases require the presence of a stabilizing ligand in the ATP site for crystallization. This procedure could be useful for developing co-crystallization systems with an exchangeable ligand to enable structure-based drug design of other protein kinases.

Ion exchange of Group I metals by hydrous crystalline silicotitanates

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

Zheng, Z.; Philip, C.V.; Anthony, R.G.

1996-11-01

A new hydrous crystalline silicotitanate, labeled TAM-5 or CST, was developed for removing radioactive Cs{sup +} from aqueous nuclear waste. This material is stable to radiation, highly selective for cesium relative to sodium, potassium, rubidium, and protons, and performs well in acidic, neutral, and basic solutions. Various experiments were conducted to determine the ion exchange properties of TAM-5. Two kinds of ion exchange sites exist in the solid, and cation exchange in one site affects the ion exchange properties of the other site. These two types of sites have different thermal effects: with increasing temperature the pH of one increasesmore » and the pH of the other one decreases. The total ion exchange capacity is 4.6 mequiv/g, but the cesium ion exchange capacity was less, which shows that not all of the ion exchange sites are available for cesium exchange. Step changes were observed in the ion exchange isotherms. The solid phase behaved ideally prior to the step changes. The apparent capacities within the ideal solid region were 0.57 mequiv/g for Cs{sup +}, 1.18 mequiv/g for Rb{sup +}, and 1.2 mequiv/g for K{sup +}. Both direct competition by rubidium and protons and indirect competition by protons and potassium were observed. The rational selectivities, which were measured from binary ion exchange data, can be used in different solutions including the multicomponent ion exchange systems, because they are constant for an ideal solid. Binary ion exchange isotherms were also developed using the rational selectivity as the parameter for the isotherms of cesium, rubidinium, and potassium.« less

Synthesis and Ion-Exchange Properties of Graphene Th(IV) Phosphate Composite Cation Exchanger: Its Applications in the Selective Separation of Lead Metal Ions

PubMed Central

Rangreez, Tauseef Ahmad; Alhogbi, Basma G.; Naushad, Mu.

2017-01-01

In this study, graphene Th(IV) phosphate was prepared by sol–gel precipitation method. The ion-exchange behavior of this cation-exchanger was studied by investigating properties like ion-exchange capacity for various metal ions, the effect of eluent concentration, elution behavior, and thermal effect on ion-exchange capacity (IEC). Several physicochemical properties as Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) study, thermal studies, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies were also carried out. The material possessed an IEC of 1.56 meq·dry·g−1 of the exchanger and was found to be nano-composite. The selectivity studies showed that the material is selective towards Pb(II) ions. The selectivity of this cation-exchanger was demonstrated in the binary separation of Pb(II) ions from mixture with other metal ions. The recovery was found to be both quantitative and reproducible. PMID:28737717

Microsomal epoxide hydrolase of rat liver. Purification and characterization of enzyme fractions with different chromatographic characteristics.

PubMed Central

Bulleid, N J; Graham, A B; Craft, J A

1986-01-01

Microsomal epoxide hydrolase was purified from rat liver, and different fractions of the purified enzyme, which varied in their contents of phospholipid, were obtained by ion-exchange chromatography. One fraction (A), which did not bind to CM-cellulose, had a high phospholipid content, and a second fraction (B), which was eluted from CM-cellulose at high ionic strength, had a low phospholipid content. Removal of most of the phospholipid from fraction A altered its chromatographic behaviour. When the delipidated material was re-applied to CM-cellulose, most of the enzyme bound to the cation-exchanger. The specific activities of all the fractions described (with styrene epoxide [(1,2-epoxyethyl)benzene] as substrate) were altered by adding the non-ionic detergent Lubrol PX or phospholipid. Lubrol PX inhibited enzyme activity, and phospholipid reversed this inhibition. The various enzyme fractions isolated appeared to be different forms of the same protein, as judged by their minimum Mr values and immunochemical properties. These results indicate that different fractions of epoxide hydrolase isolated by ion-exchange chromatography probably are not different isoenzyme forms. Images Fig. 2. Fig. 3. PMID:3082328

Fixation of radioactive ions in porous media with ion exchange gels

DOEpatents

Mercer, Jr., Basil W.; Godfrey, Wesley L.

1979-01-01

A method is provided for fixing radioactive ions in porous media by injecting into the porous media water-soluble organic monomers which are polymerizable to gel structures with ion exchange sites and polymerizing the monomers to form ion exchange gels. The ions and the particles of the porous media are thereby physically fixed in place by the gel structure and, in addition, the ions are chemically fixed by the ion exchange properties of the resulting gel.

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

PubMed

Sökmen, Ilkay; Sevin, Fatma

2003-08-01

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

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

PubMed

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

2011-10-01

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

Charge exchange molecular ion source

DOEpatents

Vella, Michael C.

2003-06-03

Ions, particularly molecular ions with multiple dopant nucleons per ion, are produced by charge exchange. An ion source contains a minimum of two regions separated by a physical barrier and utilizes charge exchange to enhance production of a desired ion species. The essential elements are a plasma chamber for production of ions of a first species, a physical separator, and a charge transfer chamber where ions of the first species from the plasma chamber undergo charge exchange or transfer with the reactant atom or molecules to produce ions of a second species. Molecular ions may be produced which are useful for ion implantation.

Method for lake restoration

DOEpatents

Dawson, Gaynor W.; Mercer, Basil W.

1979-01-01

A process for removing pollutants or minerals from lake, river or ocean sediments or from mine tailings is disclosed. Magnetically attractable collection units containing an ion exchange or sorbent media with an affinity for a chosen target substance are distributed in the sediments or tailings. After a period of time has passed sufficient for the particles to bind up the target substances, a magnet drawn through the sediments or across the tailings retrieves the units along with the target substance.

Closed cycle ion exchange method for regenerating acids, bases and salts

DOEpatents

Dreyfuss, Robert M.

1976-01-01

A method for conducting a chemical reaction in acidic, basic, or neutral solution as required and then regenerating the acid, base, or salt by means of ion exchange in a closed cycle reaction sequence which comprises contacting the spent acid, base, or salt with an ion exchanger, preferably a synthetic organic ion-exchange resin, so selected that the counter ions thereof are ions also produced as a by-product in the closed reaction cycle, and then regenerating the spent ion exchanger by contact with the by-product counter ions. The method is particularly applicable to closed cycle processes for the thermochemical production of hydrogen.

Porous solid ion exchange wafer for immobilizing biomolecules

DOEpatents

Arora, Michelle B.; Hestekin, Jamie A.; Lin, YuPo J.; St. Martin, Edward J.; Snyder, Seth W.

2007-12-11

A porous solid ion exchange wafer having a combination of a biomolecule capture-resin and an ion-exchange resin forming a charged capture resin within said wafer. Also disclosed is a porous solid ion exchange wafer having a combination of a biomolecule capture-resin and an ion-exchange resin forming a charged capture resin within said wafer containing a biomolecule with a tag. A separate bioreactor is also disclosed incorporating the wafer described above.

Friedel's salt formation in sulfoaluminate cements: A combined XRD and {sup 27}Al MAS NMR study

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

Paul, G.; Boccaleri, E., E-mail: enrico.boccaleri@mfn.unipmn.it; Buzzi, L.

Four different binders based on calcium sulfoaluminate cements have been submitted to accelerated chlorination through ionic exchange on hydrated pastes, in order to investigate their ability to chemically bind chloride ions that might reduce chloride penetration. The composition of hydrated cements before and after the treatment was evaluated by means of an X-Ray Diffraction–{sup 27}Al Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy combined study, allowing to take into account even partially amorphous phases and to make quantitative assumption on the relative abundance of the different aluminium-containing phases. It was found that low SO{sub 3} Sulfoaluminate–Portland ternary systems are the mostmore » effective in binding chloride ions and the active role played by different members of the AFm family in chloride uptake was confirmed. Moreover, a peculiar behavior related to the formation of Friedel's salt in different pH conditions was also established for the different cements.« less

Phosphonic acid based ion exchange resins

DOEpatents

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

1994-01-01

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

Phosphonic acid based ion exchange resins

DOEpatents

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

1996-01-01

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

Dual Mechanism of Ion Permeation through VDAC Revealed with Inorganic Phosphate Ions and Phosphate Metabolites

PubMed Central

Krammer, Eva-Maria; Vu, Giang Thi; Homblé, Fabrice; Prévost, Martine

2015-01-01

In the exchange of metabolites and ions between the mitochondrion and the cytosol, the voltage-dependent anion channel (VDAC) is a key element, as it forms the major transport pathway for these compounds through the mitochondrial outer membrane. Numerous experimental studies have promoted the idea that VDAC acts as a regulator of essential mitochondrial functions. In this study, using a combination of molecular dynamics simulations, free-energy calculations, and electrophysiological measurements, we investigated the transport of ions through VDAC, with a focus on phosphate ions and metabolites. We showed that selectivity of VDAC towards small anions including monovalent phosphates arises from short-lived interactions with positively charged residues scattered throughout the pore. In dramatic contrast, permeation of divalent phosphate ions and phosphate metabolites (AMP and ATP) involves binding sites along a specific translocation pathway. This permeation mechanism offers an explanation for the decrease in VDAC conductance measured in the presence of ATP or AMP at physiological salt concentration. The binding sites occur at similar locations for the divalent phosphate ions, AMP and ATP, and contain identical basic residues. ATP features a marked affinity for a central region of the pore lined by two lysines and one arginine of the N-terminal helix. This cluster of residues together with a few other basic amino acids forms a “charged brush” which facilitates the passage of the anionic metabolites through the pore. All of this reveals that VDAC controls the transport of the inorganic phosphates and phosphate metabolites studied here through two different mechanisms. PMID:25860993

Coupled acoustic-gravity field for dynamic evaluation of ion exchange with a single resin bead.

PubMed

Kanazaki, Takahiro; Hirawa, Shungo; Harada, Makoto; Okada, Tetsuo

2010-06-01

A coupled acoustic-gravity field is efficient for entrapping a particle at the position determined by its acoustic properties rather than its size. This field has been applied to the dynamic observation of ion-exchange reactions occurring in a single resin bead. The replacement of counterions in an ion-exchange resin induces changes in its acoustic properties, such as density and compressibility. Therefore, we can visually trace the advancement of an ion-exchange reaction as a time change in the levitation position of a resin bead entrapped in the field. Cation-exchange reactions occurring in resin beads with diameters of 40-120 microm are typically completed within 100-200 s. Ion-exchange equilibrium or kinetics is often evaluated with off-line chemical analyses, which require a batch amount of ion exchangers. Measurements with a single resin particle allow us to evaluate ion-exchange dynamics and kinetics of ions including those that are difficult to measure by usual off-line analyses. The diffusion properties of ions in resins have been successfully evaluated from the time change in the levitation positions of resin beads.

Intracellular pH recovery from alkalinization. Characterization of chloride and bicarbonate transport by the anion exchange system of human neutrophils

PubMed Central

1990-01-01

The nature of the intracellular pH-regulatory mechanism after imposition of an alkaline load was investigated in isolated human peripheral blood neutrophils. Cells were alkalinized by removal of a DMO prepulse. The major part of the recovery could be ascribed to a Cl- /HCO3- counter-transport system: specifically, a one-for-one exchange of external Cl- for internal HCO3-. This exchange mechanism was sensitive to competitive inhibition by the cinnamate derivative UK-5099 (Ki approximately 1 microM). The half-saturation constants for binding of HCO3- and Cl- to the external translocation site of the carrier were approximately 2.5 and approximately 5.0 mM. In addition, other halides and lyotropic anions could substitute for external Cl-. These ions interacted with the exchanger in a sequence of decreasing affinities: HCO3- greater than Cl approximately NO3- approximately Br greater than I- approximately SCN- greater than PAH-. Glucuronate and SO4(2-) lacked any appreciable affinity. This rank order is reminiscent of the selectivity sequence for the principal anion exchanger in resting cells. Cl- and HCO3- displayed competition kinetics at both the internal and external binding sites of the carrier. Finally, evidence compatible with the existence of an approximately fourfold asymmetry (Michaelis constants inside greater than outside) between inward- and outward-facing states is presented. These results imply that a Cl-/HCO3- exchange mechanism, which displays several properties in common with the classical inorganic anion exchanger of erythrocytes, is primarily responsible for restoring the pHi of human neutrophils to its normal resting value after alkalinization. PMID:2280252

Ion Exchange and Its Relation with Industry. I. Chemistry of Ion Exchangers. Methods of Use; EL CAMBIO DE ION Y SU RELACION CON LA INDUSTRIA. I. QUIMICA DE LOS CAMBIADORES DE ION METODOS DE EMPLEO

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

Perez, B.L.; Hueda, A.H.; Jodra, L.G.

1958-01-01

The lateest trends in the preparation of modern synthetic ion exchangers obtained by the treatment of polymerization and polycondensation products are reviewed. The physical and chemical characteristics, especially the stability, of exchangers are discussed. The utilization of ion exchangers in basic operations is described and illustrated with the results obtained in its application to the hydrometallurgy of uranium. The life of such materials are also considered. The most important synthetic commercial exchangers and their uses and properties are tabulated. (tr-auth)

RECENT ADVANCES IN ION EXCHANGE MATERIALS AND PROCESSES FOR POLLUTION PREVENTION

EPA Science Inventory

The goal of this article was to summarize the recent advances in ion exchange technology for the metal finishing industry. Even though the ion exchange technology is mature and is widely employed in the industry, new applications, approaches and ion exchange materials are emergi...

Pharmaceutical Applications of Ion-Exchange Resins

ERIC Educational Resources Information Center

Elder, David

2005-01-01

The historical uses of ion-exchanged resins and a summary of the basic chemical principles involved in the ion-exchanged process are discussed. Specific applications of ion-exchange are provided that include drug stabilization, pharmaceutical excipients, taste-masking agents, oral sustained-release products, topical products for local application…

A comparative study of chelating and cationic ion exchange resins for the removal of palladium(II) complexes from acidic chloride media.

PubMed

Hubicki, Zbigniew; Wołowicz, Anna

2009-05-30

The increasing demand for palladium for technological application requires the development of ion exchange chromatography. Recently ion exchange chromatography has developed largely as a result of new types of ion exchangers available on the market of which two types are widely applied. One of them are selective (chelating) and modified ion exchangers and the other one are liquid exchangers. Two types of ion exchange resins such as chelating (Lewatit TP 214, Purolite S 920) and cationic (Chelite S, Duolite GT 73) ion exchangers are used for the recovery of palladium(II) complexes from chloride media (0.1-2.0M HCl-1.0M NaCl-0.0011 M Pd(II); 0.1-2.0M HCl-2.0M NaCl-0.0011M Pd(II)). The influence of concentration of hydrochloric acid, sodium chloride as well as the phase contact time on the degree of recovery of palladium(II) complexes was studied. Moreover, the amount of palladium(II) chlorocomplexes sorbed onto ion exchangers, the working ion exchange capacities and the weight and bed distribution coefficients were calculated in order to judge which of two types of resins possesses the best performance towards palladium(II) complexes.

Intercalation of gaseous thiols and sulfides into Ag+ ion-exchanged aluminum dihydrogen triphosphate.

PubMed

Hayashi, Aki; Saimen, Hiroki; Watanabe, Nobuaki; Kimura, Hitomi; Kobayashi, Ayumi; Nakayama, Hirokazu; Tsuhako, Mitsutomo

2005-08-02

Ag(+) ion-exchanged layered aluminum dihydrogen triphosphate (AlP) with the interlayer distance of 0.85 nm was synthesized by the ion-exchange of proton in triphosphate with Ag(+) ion. The amount of exchanged Ag(+) ion depended on the concentration of AgNO(3) aqueous solution. Ag(+) ion-exchanged AlP adsorbed gaseous thiols and sulfides into the interlayer region. The adsorption amounts of thiols were more than those of sulfides, thiols with one mercapto group > thiol with two mercapto groups > sulfides, and depended on the amount of exchanged Ag(+) ion in the interlayer region. The thiols with one mercapto group were intercalated to expand the interlayer distance of Ag(+) ion-exchanged AlP, whereas there was no expansion in the adsorption of sulfide. In the case of thiol with two mercapto groups, there was observed contraction of the interlayer distance through the bridging with Ag(+) ions of the upper and lower sides of the interlayer region.

Pharmaceutical Applications of Ion-Exchange Resins

NASA Astrophysics Data System (ADS)

Elder, David P.

2005-04-01

The historical uses of ion-exchange resins and a summary of the basic chemical principles involved in the ion-exchange process are discussed. Specific applications of ion-exchange resins are provided. The utility of these agents to stabilize drugs are evaluated. Commonly occurring chemical and physical incompatibilities are reviewed. Ion-exchange resins have found applicability as inactive pharmaceutical constituents, particularly as disintegrants (inactive tablet ingredient whose function is to rapidly disrupt the tablet matrix on contact with gastric fluid). One of the more elegant approaches to improving palatability of ionizable drugs is the use of ion-exchange resins as taste-masking agents. The selection, optimization of drug:resin ratio and particle size, together with a review of scaleup of typical manufacturing processes for taste-masked products are provided. Ion-exchange resins have been extensively utilized in oral sustained-release products. The selection, optimization of drug:resin ratio and particle size, together with a summary of commonly occurring commercial sustained-release products are discussed. Ion-exchange resins have also been used in topical products for local application to the skin, including those where drug flux is controlled by a differential electrical current (ionotophoretic delivery). General applicability of ion-exchange resins, including ophthalmic delivery, nasal delivery, use as drugs in their own right (e.g., colestyramine, formerly referred to as cholestyramine), as well as measuring gastrointestinal transit times, are discussed. Finally, pharmaceutical monographs for ion-exchange resins are reviewed.

Carbon dioxide capture using resin-wafer electrodeionization

DOEpatents

Lin, YuPo J.; Snyder, Seth W.; Trachtenberg, Michael S.; Cowan, Robert M.; Datta, Saurav

2015-09-08

The present invention provides a resin-wafer electrodeionization (RW-EDI) apparatus including cathode and anode electrodes separated by a plurality of porous solid ion exchange resin wafers, which when in use are filled with an aqueous fluid. The apparatus includes one or more wafers comprising a basic ion exchange medium, and preferably includes one or more wafers comprising an acidic ion exchange medium. The wafers are separated from one another by ion exchange membranes. The fluid within the acidic and/or basic ion exchange wafers preferably includes, or is in contact with, a carbonic anhydrase (CA) enzyme to facilitate conversion of bicarbonate ion to carbon dioxide within the acidic medium. A pH suitable for exchange of CO.sub.2 is electrochemically maintained within the basic and acidic ion exchange wafers by applying an electric potential across the cathode and anode.

Calcium distribution in Amoeba proteus

PubMed Central

1979-01-01

A preliminary investigation of the distribution of cellular calcium in Amoeba proteus was undertaken. Total cellular calcium under control conditions was found to be 4.59 mmol/kg of cells. When the external Ca++ concentration is increased from the control level of 0.03 to 20 mM, a net Ca++ influx results with a new steady-state cellular calcium level being achieved in integral of 3 h. At steady state the amount of calcium per unit weight of cells is higher than the amount of calcium per unit weight of external solution when the external concentration of Ca++ is below 10 mM. At external Ca++ concentrations above this level, total cellular calcium approaches the medium level of Ca++. Steady- state calcium exchange in Amoeba proteus was determined with 45Ca. There is an immediate and rapid exchange of integral of 0.84 mmol/kg of cells or 18% of the total cellular calcium with the labelled Ca++. Following this initial exchange, there was very little if any further exchange observed. Most of this exchanged calcium could be eliminated from the cell with 1 mM La+++, suggesting that the exchanged calcium is associated with the surface of the cell. Increase in either the external Ca++ concentration of pH raise the amount of exchangeable calcium associated with the cell. Calcium may be associated with the cell surface as a co-ion in the diffuse double layer or bound to fixed negative sites on the surface of the cell. If Ca++-binding sites do exist on the cell surface, there may be more than one type and they may have different dissociation constants. The cytoplasmic Ca++ ion activity is probably maintained at very low levels. PMID:512628

Biosorption of copper and lead ions by waste beer yeast.

PubMed

Han, Runping; Li, Hongkui; Li, Yanhu; Zhang, Jinghua; Xiao, Huijun; Shi, Jie

2006-10-11

Locally available waste beer yeast, a byproduct of brewing industry, was found to be a low cost and promising adsorbent for adsorbing copper and lead ions from wastewater. In this work, biosorption of copper and lead ions on waste beer yeast was investigated in batch mode. The equilibrium adsorptive quantity was determined to be a function of the solution pH, contact time, beer yeast concentration, salt concentration and initial concentration of copper and lead ions. The experimental results were fitted well to the Langmuir and Freundlich model isotherms. According to the parameters of Langmuir isotherm, the maximum biosorption capacities of copper and lead ions onto beer yeast were 0.0228 and 0.0277 mmol g(-1) at 293 K, respectively. The negative values of the standard free energy change (DeltaG degrees ) indicate spontaneous nature of the process. Competitive biosorption of two metal ions was investigated in terms of sorption quantity. The amount of one metal ion adsorbed onto unit weight of biosorbent (q(e)) decreased with increasing the competing metal ion concentration. The binding capacity for lead is more than for copper. Ion exchange is probably one of the main mechanism during adsorptive process.

Polyelectrolyte-coated ion exchangers for cell-resistant expanded bed adsorption.

PubMed

Dainiak, Maria B; Galaev, Igor Yu; Mattiasson, Bo

2002-01-01

Adsorption chromatography in expanded beds is a widely used technology for direct capture of target proteins from fermentation broths. However, in many cases this method cannot be applied as a result of the strong tendency of cells or cell debris to interact with the adsorbent beads. To prevent contamination of the expanded bed with the biomass, STREAMLINE DEAE, anion exchanger designed for expanded bed adsorption, was modified with a layer of poly(acrylic acid) (PAA). The shielding layer of polyelectrolyte was attached to the surface of the matrix beads via electrostatic interactions. PAA with a high degree of polymerization was chosen to prevent diffusion of large polymer molecules into the pores of adsorbent. Thus, the shielding layer of PAA was adsorbed only at the mouth of the pores of STREAMLINE DEAE beads and only marginally decreased the binding capacity of the ion exchanger for bovine serum albumin, the model protein in this study. PAA-coated STREAMLINE DEAE practically did not interact with yeast cells, which otherwise bound strongly to the native adsorbent at neutral conditions. Cell-resistant PAA-coated anion exchanger was successfully used for isolation of BSA from the model protein mixture containing BSA, lysozyme (positively charged at applied conditions), and yeast cells. The layer of PAA was stable under mild elution conditions, and the modified adsorbent could be used in the repeated purification cycles.

DNA Interactions Probed by Hydrogen-Deuterium Exchange (HDX) Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Confirm External Binding Sites on the Minichromosomal Maintenance (MCM) Helicase.

PubMed

Graham, Brian W; Tao, Yeqing; Dodge, Katie L; Thaxton, Carly T; Olaso, Danae; Young, Nicolas L; Marshall, Alan G; Trakselis, Michael A

2016-06-10

The archaeal minichromosomal maintenance (MCM) helicase from Sulfolobus solfataricus (SsoMCM) is a model for understanding structural and mechanistic aspects of DNA unwinding. Although interactions of the encircled DNA strand within the central channel provide an accepted mode for translocation, interactions with the excluded strand on the exterior surface have mostly been ignored with regard to DNA unwinding. We have previously proposed an extension of the traditional steric exclusion model of unwinding to also include significant contributions with the excluded strand during unwinding, termed steric exclusion and wrapping (SEW). The SEW model hypothesizes that the displaced single strand tracks along paths on the exterior surface of hexameric helicases to protect single-stranded DNA (ssDNA) and stabilize the complex in a forward unwinding mode. Using hydrogen/deuterium exchange monitored by Fourier transform ion cyclotron resonance MS, we have probed the binding sites for ssDNA, using multiple substrates targeting both the encircled and excluded strand interactions. In each experiment, we have obtained >98.7% sequence coverage of SsoMCM from >650 peptides (5-30 residues in length) and are able to identify interacting residues on both the interior and exterior of SsoMCM. Based on identified contacts, positively charged residues within the external waist region were mutated and shown to generally lower DNA unwinding without negatively affecting the ATP hydrolysis. The combined data globally identify binding sites for ssDNA during SsoMCM unwinding as well as validating the importance of the SEW model for hexameric helicase unwinding. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

A novel core 1 O-linked glycan-specific binding lectin from the fruiting body of Hericium erinaceus.

PubMed

Kim, Seonghun

2018-02-01

Mucin-type O-glycans are involved in biological functions on the cell surface as well as the glycoproteins and can also be used as specific carbohydrate biomarkers of many diseases. In this study, I purified a novel core 1 O-linked glycan specific lectin, Hericium erinaceus lecin (HeL), from the fruiting body of the mushroom Hericium erinaceus, which is known as the natural source for a sialic acid-binding lectin. Upon optimization of the purification conditions, a sequence of ion exchange, affinity, ion exchange, and size-exclusion chromatography resulted in the highest yield and best quality of lectin without protease activity. The resulting purified HeL is an apparent hexameric protein with a subunit molecular weight of 15kDa, and a pI of 4.3. In hemagglutination inhibition assay, the purified lectin was only inhibited by glycoproteins containing mucin-type O-glycans and reacted weakly with Galβ(1,3)GalNAc. Glycan array analyses showed that HeL specifically interacts with core 1 O-linked glycans as well as extended O-glycan structures containing sialylation or fucosylation. The glycan binding specificity of HeL is comparable to that of peanut agglutinin for detection of a broader range of extended core 1 O-glycan structures. Taken together, these results provide an efficient and optimized procedure for the purification of HeL from the fruiting body of the mushroom Hericium erinaceus. Moreover, HeL represents a powerful tool for analyzing core 1 and extended core 1 O- glycan structures in diagnosis assays. Copyright © 2017 Elsevier B.V. All rights reserved.

Phosphonic acid based ion exchange resins

DOEpatents

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

1996-07-23

An ion exchange resin is described for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene. 10 figs.

Phosphonic acid based ion exchange resins

DOEpatents

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

1994-01-25

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

Effect of the type of ion exchange membrane on performance, ion transport, and pH in biocatalyzed electrolysis of wastewater.

PubMed

Rozendal, R A; Sleutels, T H J A; Hamelers, H V M; Buisman, C J N

2008-01-01

Previous studies have shown that the application of cation exchange membranes (CEMs) in bioelectrochemical systems running on wastewater can cause operational problems. In this paper the effect of alternative types of ion exchange membrane is studied in biocatalyzed electrolysis cells. Four types of ion exchange membranes are used: (i) a CEM, (ii) an anion exchange membrane (AEM), (iii) a bipolar membrane (BPM), and (iv) a charge mosaic membrane (CMM). With respect to the electrochemical performance of the four biocatalyzed electrolysis configurations, the ion exchange membranes are rated in the order AEM > CEM > CMM > BPM. However, with respect to the transport numbers for protons and/or hydroxyl ions (t(H/OH)) and the ability to prevent pH increase in the cathode chamber, the ion exchange membranes are rated in the order BPM > AEM > CMM > CEM.

Gadolinium-hydrogen ion exchange of zirconium phosphate

NASA Technical Reports Server (NTRS)

Liu, D. C.; Power, J. L.

1972-01-01

The Gd(+3)/H(+) ion exchange on a commercial zirconium phosphate ion exchanger was investigated in chloride, sulfate, and phosphate solutions of Gd(+3) at gadolinium concentrations of 0.001 to 1 millimole per cc and in the pH range of 0 to 3.5. Relatively low Gd(+3) capacities, in the range of 0.01 to 0.1 millimole per g of ion exchanger were found at room temperature. A significant difference in Gd(+3) sorption was observed, depending on whether the ion exchanger was converted from initial conditions of greater or lesser Gd(+3) sorption than the specific final conditions. Correlations were found between decrease in Gd(+3) capacity and loss of exchanger phosphate groups due to hydrolysis during washing and between increase in capacity and treatment with H3PO4. Fitting of the experimental data to ideal ion exchange equilibrium expressions indicated that each Gd(+3) ion is sorbed on only one site of the ion exchanger. The selectivity quotient was determined to be 2.5 + or - 0.4 at room temperature on gadolinium desorption in chloride solutions.

Ion-ion charge exchange processes. Final technical report, June 1, 1977-May 31, 1978

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

Poe, R.T.; Choi, B.H.

Under the auspices of ERDA, we have undertaken a vigorous study of ion-ion charge exchange process pertinent to the storage-ring configurations in the heavy-ion fusion program. One particular reaction, singly charged helium charge exchange, was investigated in detail. General trend of the singly charged heavy-ion charge exchange reaction can be inferred from the present study. Some of our results were presented at Proceedings of the Heavy-Ion Fusion Workshop, Argonne National Laboratory (September 1978) as a paper entitled Charge Exchange Between Singly Ionized Helium Ions, by B.H. Choi, R.T. Poe and K.T. Tang. Here, we briefly describe our method and reportmore » the results.« less

On the influence of ion exchange on the local structure of the titanosilicate ETS-10.

PubMed

Pavel, Claudiu C; Zibrowius, Bodo; Löffler, Elke; Schmidt, Wolfgang

2007-07-14

The effect of ion exchange with different monovalent cations (NH(4)(+), K(+), Na(+) and Cs(+)) on the local structure of the titanosilicate ETS-10 has been studied by (29)Si MAS NMR and Raman spectroscopy. Although X-ray diffraction shows no significant influence of ion exchange on the long range order, ammonium exchange is found to result in substantial damage to the local structure. Ion exchange experiments with alkali cations under significantly more acidic conditions clearly show that the structural damage brought about by ammonium exchange is not caused by the low pH of the exchange solution. The exchange with potassium and caesium ions also leads to significant changes in the (29)Si NMR and Raman spectra. However, these changes can largely be reversed by sodium back-exchange.

Membrane consisting of polyquaternary amine ion exchange polymer network interpenetrating the chains of thermoplastic matrix polymer

NASA Technical Reports Server (NTRS)

Rembaum, A.; Wallace, C. J. (Inventor)

1978-01-01

An ion exchange membrane was formed from a solution containing dissolved matrix polymer and a set of monomers which are capable of reacting to form a polyquaternary ion exchange material; for example vinyl pyride and a dihalo hydrocarbon. After casting solution and evaporation of the volatile component's, a relatively strong ion exchange membrane was obtained which is capable of removing anions, such as nitrate or chromate from water. The ion exchange polymer forms an interpenetrating network with the chains of the matrix polymer.

Uncoupling metallonuclease metal ion binding sites via nudge mutagenesis.

PubMed

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

2007-05-01

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

Using Ion Exchange Chromatography to Separate and Quantify Complex Ions

ERIC Educational Resources Information Center

Johnson, Brian J.

2014-01-01

Ion exchange chromatography is an important technique in the separation of charged species, particularly in biological, inorganic, and environmental samples. In this experiment, students are supplied with a mixture of two substitution-inert complex ions. They separate the complexes by ion exchange chromatography using a "flash"…

Molecular Dynamics Investigation of Cl− and Water Transport through a Eukaryotic CLC Transporter

PubMed Central

Cheng, Mary Hongying; Coalson, Rob D.

2012-01-01

Early crystal structures of prokaryotic CLC proteins identified three Cl– binding sites: internal (Sint), central (Scen), and external (Sext). A conserved external GLU (GLUex) residue acts as a gate competing for Sext. Recently, the first crystal structure of a eukaryotic transporter, CmCLC, revealed that in this transporter GLUex competes instead for Scen. Here, we use molecular dynamics simulations to investigate Cl– transport through CmCLC. The gating and Cl–/H+ transport cycle are inferred through comparative molecular dynamics simulations with protonated and deprotonated GLUex in the presence/absence of external potentials. Adaptive biasing force calculations are employed to estimate the potential of mean force profiles associated with transport of a Cl– ion from Sext to Sint, depending on the Cl– occupancy of other sites. Our simulations demonstrate that protonation of GLUex is essential for Cl– transport from Sext to Scen. The Scen site may be occupied by two Cl– ions simultaneously due to a high energy barrier (∼8 Kcal/mol) for a single Cl– ion to translocate from Scen to Sint. Binding two Cl– ions to Scen induces a continuous water wire from Scen to the extracellular solution through the side chain of the GLUex gate. This may initiate deprotonation of GLUex, which then drives the two Cl– ions out of Scen toward the intracellular side via two putative Cl– transport paths. Finally, a conformational cycle is proposed that would account for the exchange stoichiometry. PMID:22455919

Synthesis, characterization and applications of a new cation exchanger tamarind sulphonic acid (TSA) resin.

PubMed

Singh, A V; Sharma, Naresh Kumar; Rathore, Abhay S

2012-01-01

A new composite cation exchanger, tamarind sulphonic acid (TSA) resin has been synthesized. The chemically modified TSA ion exchange resin has been used for the removal and preconcentration of Zn2+, Cd2+, Fe2+, Co2+ and Cu2+ ions in aqueous solution and effluent from the Laxmi steel plant in Jodhpur, India. This type of composite represents a new class of hybrid ion exchangers with good ion exchange capacity, stability, reproducibility and selectivity for toxic metal ions found in effluent from the steel industry. The characterization of the resin was carried out by determining the ion-exchange capacity, elemental analysis, pH titration, Fourier transform infrared spectra and thermal analysis. The distribution coefficients (K(d)) of toxic metal ions were determined in a reference aqueous solution and the steel plant effluent at different pH values; the absorbency of different metal ions on the TSA resin was studied for up to 10 cycles. The adsorption of different metal ions on TSA resin follows the order: Co2+ > Cu2+ > Zn2+ > Fe2+ > Cd2+. The ion exchange capacity of TSA resin is 2.87%.

Ion Exchange Formation via Sulfonated Bicomponent Nonwovens

NASA Astrophysics Data System (ADS)

Stoughton, Hannah L.

For many years ion exchange resins were used to: remove heavy metals from water, recover materials from wastewater, and eliminate harmful gases from the air. While use of these resin beads dominates the ion exchange industry, the beads have limitations that should be considered when decisions are made to employ them. For instance, officials must balance the inherent zero sum surface area and porosity of the materials. This series of studies investigates the use of bicomponent nonwovens as a base substrate for producing high surface area ion exchange materials for the removal of heavy metal ions. Functionalized materials were produced in a two-step process: (1) PET/PE spunbond bicomponent fibers were fractured completely, producing the high surface area nonwoven to be used as the base ion exchange material, and (2) the conditions for functionalizing the PET fibers of the nonwoven webs were investigated where an epoxy containing monomer was grafted to the surface followed by sulfonation of the monomer. The functionalization reactions of the PET fibers were monitored based on: weight gain, FTIR, TOF-SIMS, and SEM. Ion exchange properties were evaluated using titration and copper ion removal capacity from test solutions. The relationship between web structure and removal efficiency of the metal ions was defined through a comparison of the bicomponent and homocomponent nonwovens for copper ion removal efficiency. The investigation revealed that utilizing the high surface area, fractured bicomponent nonwoven ion exchange materials with capacities comparable to commercially available ion exchange resins could be produced.

Pseudo-indicator behaviour of platinum electrode explored for the potentiometric estimation of non-redox systems.

PubMed

Raashid, Syed; Chat, Oyais Ahmad; Rizvi, Masood A; Bhat, Mohsin Ahmad; Khan, Badruddin

2012-11-15

A pseudo-indicator electrode based potentiometric method for estimation of non-redox metal ions is presented. In the proposed method, nature and concentration specific impact of analyte over the redox potential of ideally polarisable Pt/pregenerated-redox-couple interface forms the basis of quantification. Utility of the method in estimation of six non-redox metal ions viz. Zn(2+), Cu(2+), Ni(2+), Cd(2+), Pb(2+), Al(3+) in the concentration range of 10(-1)-10(-3) moldm(-3), individually and as binary mixtures is also presented. Three types of potentiometric behaviours, which we ascribe to the nature specific thermodynamic and kinetic aspects of metal-EDTA binding, were observed. While Cu(2+), Ni(2+), Pb(2+) and Al(3+) were found to bind EDTA efficiently, without exchanging Fe(3+); Zn(2+) and Cd(2+) were observed to replace Fe(3+) from EDTA. In contrast, Ca(2+) and Mg(2+) were found to show no binding affinity to EDTA in the pH range employed in the present work. The proposed method was also used to explore the reversibility and the Nernestian behaviour of ferricyanide/ferrocyanide redox couple through spectroelectrochemical titration of Zn(2+) with ferrocyanide. The presented method is presaged to be a reliable and low cost future replacement for costly and delicate ion selective electrodes (ISE) in the estimation of non-redox species like Zn(2+), Cu(2+), etc. Copyright © 2012 Elsevier B.V. All rights reserved.

Phosphonic acid based exchange resins

DOEpatents

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

1995-01-01

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

Comparison between methods using copper, lanthanum, and colorimetry for the determination of the cation exchange capacity of plant cell walls.

PubMed

Wehr, J Bernhard; Blamey, F Pax C; Menzies, Neal W

2010-04-28

The determination of the cation exchange capacity (CEC) of plant cell walls is important for many physiological studies. We describe the determination of cell wall CEC by cation binding, using either copper (Cu) or lanthanum (La) ions, and by colorimetry. Both cations are strongly bound by cell walls, permitting fast and reproducible determinations of the CEC of small samples. However, the dye binding methods using two cationic dyes, Methylene Blue and Toluidine Blue, overestimated the CEC several-fold. Column and centrifugation methods are proposed for CEC determination by Cu or La binding; both provide similar results. The column method involves packing plant material (2-10 mg dry mass) in a chromatography column (10 mL) and percolating with 20 bed volumes of 1 mM La or Cu solution, followed by washing with deionized water. The centrifugation method uses a suspension of plant material (1-2 mL) that is centrifuged, and the pellet is mixed three times with 10 pellet volumes of 1 mM La or Cu solution followed by centrifugation and final washing with deionized water. In both methods the amount of La or Cu bound to the material was determined by spectroscopic methods.

Modeling metal binding to soils: the role of natural organic matter.

PubMed

Gustafsson, Jon Petter; Pechová, Pavlina; Berggren, Dan

2003-06-15

The use of mechanistically based models to simulate the solution concentrations of heavy metals in soils is complicated by the presence of different sorbents that may bind metals. In this study, the binding of Zn, Pb, Cu, and Cd by 14 different Swedish soil samples was investigated. For 10 of the soils, it was found that the Stockholm Humic Model (SHM) was able to describe the acid-base characteristics, when using the concentrations of "active" humic substances and Al as fitting parameters. Two additional soils could be modeled when ion exchange to clay was also considered, using a component additivity approach. For dissolved Zn, Cd, Ca, and Mg reasonable model fits were produced when the metal-humic complexation parameters were identical for the 12 soils modeled. However, poor fits were obtained for Pb and Cu in Aquept B horizons. In two of the soil suspensions, the Lund A and Romfartuna Bhs, the calculated speciation agreed well with results obtained by using cation-exchange membranes. The results suggest that organic matter is an important sorbent for metals in many surface horizons of soils in temperate and boreal climates, and the necessity of properly accounting for the competition from Al in simulations of dissolved metal concentrations is stressed.

Human granulocyte/pollen-binding protein. Recognition and identification as transferrin.

PubMed Central

Sass-Kuhn, S P; Moqbel, R; Mackay, J A; Cromwell, O; Kay, A B

1984-01-01

Normal human serum was found to contain a heat-stable protein which promoted the binding of granulocytes to timothy grass pollen (granulocyte/pollen-binding protein [GPBP]). GPBP was purified by gel filtration, anion exchange, and affinity chromatography. Virtually all of the granulocyte/pollen-binding activity was associated with a beta-1-protein having a molecular mass of approximately 77,000 D and an isoelectric point of between 5.5 and 6.1. By immunoelectrophoresis and sodium dodecyl sulfate-polyacrylamide gel electrophoresis, the protein was identified as transferrin. Monospecific antisera raised against either GPBP or transferrin removed biological activity from GPBP preparations, and GPBP and transferrin gave lines of identity with these two antisera. The apparent heterogeneity in the molecular size and charge of GPBP observed during progressive purification was minimal when GPBP was saturated with ferric ions before the separation procedures. These experiments indicate that granulocyte/pollen binding is a hitherto unrecognized property of transferrin which appears to be unrelated to iron transport and raises the possibility that transferrin might have a physiological role in the removal of certain organic matter. Images PMID:6690479

Ion-exchange hollow fibers

NASA Technical Reports Server (NTRS)

Rembaum, A.; Yen, S. P. S.; Klein, E. (Inventor)

1976-01-01

An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, crosslinked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

Flow-through lipid nanotube arrays for structure-function studies of membrane proteins by solid-state NMR spectroscopy.

PubMed

Chekmenev, Eduard Y; Gor'kov, Peter L; Cross, Timothy A; Alaouie, Ali M; Smirnov, Alex I

2006-10-15

A novel method for studying membrane proteins in a native lipid bilayer environment by solid-state NMR spectroscopy is described and tested. Anodic aluminum oxide (AAO) substrates with flow-through 175 nm wide and 60-mum-long nanopores were employed to form macroscopically aligned peptide-containing lipid bilayers that are fluid and highly hydrated. We demonstrate that the surfaces of both leaflets of such bilayers are fully accessible to aqueous solutes. Thus, high hydration levels as well as pH and desirable ion and/or drug concentrations could be easily maintained and modified as desired in a series of experiments with the same sample. The method allows for membrane protein NMR experiments in a broad pH range that could be extended to as low as 1 and as high as 12 units for a period of up to a few hours and temperatures as high as 70 degrees C without losing the lipid alignment or bilayers from the nanopores. We demonstrate the utility of this method by a solid-state 19.6 T (17)O NMR study of reversible binding effects of mono- and divalent ions on the chemical shift properties of the Leu(10) carbonyl oxygen of transmembrane pore-forming peptide gramicidin A (gA). We further compare the (17)O shifts induced by binding metal ions to the binding of protons in the pH range from 1 to 12 and find a significant difference. This unexpected result points to a difference in mechanisms for ion and proton conduction by the gA pore. We believe that a large number of solid-state NMR-based studies, including structure-function, drug screening, proton exchange, pH, and other titration experiments, will benefit significantly from the method described here.

A bacterial view of the periodic table: genes and proteins for toxic inorganic ions.

PubMed

Silver, Simon; Phung, Le T

2005-12-01

Essentially all bacteria have genes for toxic metal ion resistances and these include those for Ag+, AsO2-, AsO4(3-), Cd2+ Co2+, CrO4(2-), Cu2+, Hg2+, Ni2+, Pb2+, TeO3(2-), Tl+ and Zn2+. The largest group of resistance systems functions by energy-dependent efflux of toxic ions. Fewer involve enzymatic transformations (oxidation, reduction, methylation, and demethylation) or metal-binding proteins (for example, metallothionein SmtA, chaperone CopZ and periplasmic silver binding protein SilE). Some of the efflux resistance systems are ATPases and others are chemiosmotic ion/proton exchangers. For example, Cd2+-efflux pumps of bacteria are either inner membrane P-type ATPases or three polypeptide RND chemiosmotic complexes consisting of an inner membrane pump, a periplasmic-bridging protein and an outer membrane channel. In addition to the best studied three-polypeptide chemiosmotic system, Czc (Cd2+, Zn2+, and Co2), others are known that efflux Ag+, Cu+, Ni2+, and Zn2+. Resistance to inorganic mercury, Hg2+ (and to organomercurials, such as CH3Hg+ and phenylmercury) involve a series of metal-binding and membrane transport proteins as well as the enzymes mercuric reductase and organomercurial lyase, which overall convert more toxic to less toxic forms. Arsenic resistance and metabolizing systems occur in three patterns, the widely-found ars operon that is present in most bacterial genomes and many plasmids, the more recently recognized arr genes for the periplasmic arsenate reductase that functions in anaerobic respiration as a terminal electron acceptor, and the aso genes for the periplasmic arsenite oxidase that functions as an initial electron donor in aerobic resistance to arsenite.

Studies on adsorption capacity of clay-Sargassum sp biosorbent for Cr (VI) removal in wastewater from electroplating industry

NASA Astrophysics Data System (ADS)

Aprianti, Tine; Aprilyanti, Selvia; Apriani, Rachmawati; Sisnayati

2017-11-01

Various raw biosorbents have been studied for pollutant treatment of heavy metals contained in wastewater. In this study, clay and brown seaweed, Sargassum sp, are used for hexavalent chromium [Cr (VI)] biosorption. The adsorption capacity is adequately improved by combining clay and Sargassum sp as the adsorbent agent. Ion exchange of metal ions has shown strong coordination cross-linkage due to organic functional hydroxyl groups (OH-) contained in brown seaweed that provide sites to capture and bind the metal ions. Clay is known as an inexpensive adsorbent due to its wide availability besides its large specific surface area. Combining clay and Sargassum sp as biosorbent resulting better adsorption, the adsorption capacity reaches most favorable results of 99.39% at Sargassum: clay ratio of 40:60 on contact time 10 h. This study has proven that composit biosorbent used has succeeded in reducing hexavalent chromium pollutant in wastewater.

The 1.3 A resolution structure of the RNA tridecamer r(GCGUUUGAAACGC): metal ion binding correlates with base unstacking and groove contraction.

PubMed

Timsit, Youri; Bombard, Sophie

2007-12-01

Metal ions play a key role in RNA folding and activity. Elucidating the rules that govern the binding of metal ions is therefore an essential step for better understanding the RNA functions. High-resolution data are a prerequisite for a detailed structural analysis of ion binding on RNA and, in particular, the observation of monovalent cations. Here, the high-resolution crystal structures of the tridecamer duplex r(GCGUUUGAAACGC) crystallized under different conditions provides new structural insights on ion binding on GAAA/UUU sequences that exhibit both unusual structural and functional properties in RNA. The present study extends the repertory of RNA ion binding sites in showing that the two first bases of UUU triplets constitute a specific site for sodium ions. A striking asymmetric pattern of metal ion binding in the two equivalent halves of the palindromic sequence demonstrates that sequence and its environment act together to bind metal ions. A highly ionophilic half that binds six metal ions allows, for the first time, the observation of a disodium cluster in RNA. The comparison of the equivalent halves of the duplex provides experimental evidences that ion binding correlates with structural alterations and groove contraction.

Anisotropic microporous supports impregnated with polymeric ion-exchange materials

DOEpatents

Friesen, Dwayne; Babcock, Walter C.; Tuttle, Mark

1985-05-07

Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets.

A review of studies on ion thruster beam and charge-exchange plasmas

NASA Technical Reports Server (NTRS)

Carruth, M. R., Jr.

1982-01-01

Various experimental and analytical studies of the primary beam and charge-exchange plasmas of ion thrusters are reviewed. The history of plasma beam research is recounted, emphasizing experiments on beam neutralization, expansion of the beam, and determination of beam parameters such as electron temperature, plasma density, and plasma potential. The development of modern electron bombardment ion thrusters is treated, detailing experimental results. Studies on charge-exchange plasma are discussed, showing results such as the relationship between neutralizer emission current and plasma beam potential, ion energies as a function of neutralizer bias, charge-exchange ion current collected by an axially moving Faraday cup-RPA for 8-cm and 30-cm ion thrusters, beam density and potential data from a 15-cm ion thruster, and charge-exchange ion flow around a 30-cm thruster. A 20-cm thruster electrical configuration is depicted and facility effects are discussed. Finally, plasma modeling is covered in detail for plasma beam and charge-exchange plasma.

Lead sorption by waste biomass of hazelnut and almond shell.

PubMed

Pehlivan, Erol; Altun, Türkan; Cetin, Serpil; Iqbal Bhanger, M

2009-08-15

The potential to remove Pb(2+) ion from aqueous solutions using the shells of hazelnut (HNS) (Corylus avellana) and almond (AS) (Prunus dulcis) through biosorption was investigated in batch experiments. The main parameters influencing Pb(2+) ion sorption on HNS and AS were: initial metal ion concentration, amount of adsorbent, contact time and pH value of solution. The influences of initial Pb(2+) ion concentration (0.1-1.0mM), pH (2-9), contact time (10-240 min) and adsorbent amount (0.1-1.0 g) have been investigated. Equilibrium isotherms have been measured and modelled. Adsorption of Pb(2+) ions was in all cases pH-dependent showing a maximum at equilibrium pH values between 6.0 and 7.0, depending on the biomaterial, that corresponded to equilibrium pH values of 6.0 for HNS and 7.0 for AS. The equilibrium sorption capacities of HNS and AS were 28.18 and 8.08 mg/g for lead, respectively after equilibrium time of 2h. The adsorption data fit well with the Langmuir isotherm model and the experimental result inferred that adsorption, chelation and ion exchange are major adsorption mechanisms for binding Pb(2+) ion to the sorbents.

Impact of sodium ion on multivalent metal ion content in extracellular polymeric substances of granular sludge from an expanded granular sludge bed.

PubMed

Fang, Peixiang; He, Xinlin; Li, Junfeng; Yang, Guang; Wang, Zhaoyang; Sun, Zhihua; Zhang, Xuan; Zhao, Chun

2018-05-15

The long-term and short-term effects of salinity on the multivalent metal ions within extracellular polymeric substance (EPS) were investigated in this study. The results indicated that the Na + content within the EPS increased significantly from 19.53% to 60.86% under high salinity, and this content in the saline system was 2.2 times higher than that of the control system at the end of the operation. The K + , Ca 2+ and Mg 2+ contents within the EPS decreased from 33.85%, 39.19% and 5.54% to 7.07%, 25.64% and 3.28%, respectively, when the salinity was increased from 0 g/L to 30 g/L. These ions were replaced by Na + through ion exchange and competing ionic binding sites under salt stress. The interaction between divalent metal ions and Na + was reversible with the adaption of anammox to salinity. Salinity exhibited a limited influence on the Fe 3+ within the EPS. Sludge granulation was inhibited under conditions of high salinity due to the replacement of multivalent metal ions by Na + .

Phosphonic acid based exchange resins

DOEpatents

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

1995-09-12

An ion exchange resin is described for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene. 10 figs.

NMR spectroscopy of the ligand binding core of ionotropic glutamate receptor 2 bound to 5-substituted willardiine partial agonists

PubMed Central

Fenwick, Michael K.; Oswald, Robert E.

2008-01-01

Glutamate receptors mediate neuronal intercommunication in the central nervous system by coupling extracellular neurotransmitter-receptor interactions to ion channel conductivity. To gain insight into structural and dynamical factors that underlie this coupling, solution NMR experiments were performed on the bi-lobed ligand-binding core of glutamate receptor 2 in complexes with a set of willardiine partial agonists. These agonists are valuable for studying structure-function relationships because their 5-position substituent size is correlated with ligand efficacy and extent of receptor desensitization whereas the substituent electronegativity is correlated with ligand potency. NMR results show that the protein backbone amide chemical shift deviations correlate mainly with efficacy and extent of desensitization. Pronounced deviations occur at specific residues in the ligand-binding site and in the two helical segments that join the lobes by a disulfide bond. Experiments detecting conformational exchange show that micro- to millisecond timescale motions also occur near the disulfide bond and vary largely with efficacy and extent of desensitization. These results thus identify regions displaying structural and dynamical dissimilarity arising from differences in ligand-protein interactions and lobe closure which may play a critical role in receptor response. Furthermore, measures of line broadening and conformational exchange for a portion of the ligand-binding site correlate with ligand EC50 data. These results do not have any correlate in the currently available crystal structures and thus provide a novel view of ligand-binding events that may be associated with agonist potency differences. PMID:18387631

Evaluation of anion exchange resins Tulsion A-30 and Indion-930A by application of radioanalytical technique

NASA Astrophysics Data System (ADS)

Singare, P. U.

2014-07-01

Radioanalytical technique using 131I and 82Br was employed to evaluate organic based anion exchange resins Tulsion A-30 and Indion-930A. The evaluation was based on performance of these resins during iodide and bromide ion-isotopic exchange reactions. It was observed that for iodide ion-isotopic exchange reaction by using Tulsion A-30 resin, the values of specific reaction rate (min-1), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and log K d were 0.238, 0.477, 0.114, and 11.0, respectively, which was higher than 0.155, 0.360, 0.056, and 7.3, respectively as that obtained by using Indion-930A resins under identical experimental conditions of 40.0°C, 1.000 g of ion exchange resins and 0.003 M labeled iodide ion solution. Also at a constant temperature of 40.0°C, as the concentration of labeled iodide ion solution increases 0.001 to 0.004 M, for Tulsion A-30 resins the percentage of iodide ions exchanged increases from 59.0 to 65.1%, and from 46.4 to 48.8% for Indion-930A resins under identical experimental conditions. The identical trend was observed for both the resins during bromide ion-isotopic exchange reactions. The overall results indicate that under identical experimental conditions, Tulsion A-30 show superior performance over Indion-930A resins. The results of present experimental work have demonstrated that the radioanalytical technique used here can be successfully applied for characterization of different ion exchange resins so as to evaluate their performance under various process parameters.

Anisotropic microporous supports impregnated with polymeric ion-exchange materials

DOEpatents

Friesen, D.; Babcock, W.C.; Tuttle, M.

1985-05-07

Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets. 5 figs.

Ion Exchange Chromatography and Spectrophotometry: An Introductory Undergraduate Laboratory Experiment.

ERIC Educational Resources Information Center

Foster, N.; And Others

1985-01-01

Describes an experiment in which students use ion exchange chromatography to separate a mixture of chloro complexes of transition metal ions and then use spectrophotometry to define qualitatively the efficiency of the ion exchange columns. Background information, materials needed, and procedures used are included. (JN)

Ca2+ improves organization of single-stranded DNA bases in human Rad51 filament, explaining stimulatory effect on gene recombination.

PubMed

Fornander, Louise H; Frykholm, Karolin; Reymer, Anna; Renodon-Cornière, Axelle; Takahashi, Masayuki; Nordén, Bengt

2012-06-01

Human RAD51 protein (HsRad51) catalyses the DNA strand exchange reaction for homologous recombination. To clarify the molecular mechanism of the reaction in vitro being more effective in the presence of Ca(2+) than of Mg(2+), we have investigated the effect of these ions on the structure of HsRad51 filament complexes with single- and double-stranded DNA, the reaction intermediates. Flow linear dichroism spectroscopy shows that the two ionic conditions induce significantly different structures in the HsRad51/single-stranded DNA complex, while the HsRad51/double-stranded DNA complex does not demonstrate this ionic dependence. In the HsRad51/single-stranded DNA filament, the primary intermediate of the strand exchange reaction, ATP/Ca(2+) induces an ordered conformation of DNA, with preferentially perpendicular orientation of nucleobases relative to the filament axis, while the presence of ATP/Mg(2+), ADP/Mg(2+) or ADP/Ca(2+) does not. A high strand exchange activity is observed for the filament formed with ATP/Ca(2+), whereas the other filaments exhibit lower activity. Molecular modelling suggests that the structural variation is caused by the divalent cation interfering with the L2 loop close to the DNA-binding site. It is proposed that the larger Ca(2+) stabilizes the loop conformation and thereby the protein-DNA interaction. A tight binding of DNA, with bases perpendicularly oriented, could facilitate strand exchange.

Process for disposing of radioactive wastes

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

Grantham, L.F.; Gray, R.L.; McCoy, L.R.

1988-05-03

A process for removing water from the pores of spent, contaminated radioactive ion exchange resins and encasing radionuclides entrapped within the pores of the resins, the process is described consisting essentially of the sequential steps of: (a) heating the spent ion exchange resins at a temperature of from about 100/sup 0/C to about 150/sup 0/C to remove water from within and fill the pores of the ion exchange resins by heating the ion exchange resins for from about 46 to about 610 hours at a temperature at which the pores of the resins are sealed while avoiding any fusing ormore » melting of the ion exchange resins to encase radionuclides contained within the resins; and (b) cooling the resins to obtain dry, flowable ion exchange resins having radionuclides encased within sealed polymeric spheres.« less

Citropin 1.1 Trifluoroacetate to Chloride Counter-Ion Exchange in HCl-Saturated Organic Solutions: An Alternative Approach.

PubMed

Sikora, Karol; Neubauer, Damian; Jaśkiewicz, Maciej; Kamysz, Wojciech

2018-01-01

In view of the increasing interest in peptides in various market sectors, a stronger emphasis on topics related to their production has been seen. Fmoc-based solid phase peptide synthesis, although being fast and efficient, provides final products with significant amounts of trifluoroacetate ions in the form of either a counter-ion or an unbound impurity. Because of the proven toxicity towards cells and peptide activity inhibition, ion exchange to more biocompatible one is purposeful. Additionally, as most of the currently used counter-ion exchange techniques are time-consuming and burdened by peptide yield reduction risk, development of a new approach is still a sensible solution. In this study, we examined the potential of peptide counter-ion exchange using non-aqueous organic solvents saturated with HCl. Counter-ion exchange of a model peptide, citropin 1.1 (GLFDVIKKVASVIGGL-NH 2 ), for each solvent was conducted through incubation with subsequent evaporation under reduced pressure, dissolution in water and lyophilization. Each exchange was performed four times and compared to a reference method-lyophilization of the peptide from an 0.1 M HCl solution. The results showed superior counter-ion exchange efficiency for most of the organic solutions in relation to the reference method. Moreover, HCl-saturated acetonitrile and tert -butanol provided a satisfying exchange level after just one repetition. Thus, those two organic solvents can be potentially introduced into routine peptide counter-ion exchange.

Comparison of monomode KTiOPO4 waveguide formed by C3+ ion implantation and Rb+ ion exchange

NASA Astrophysics Data System (ADS)

Cui, Xiao-Jun; Wang, Liang-Ling

2017-02-01

In this work, we report on the formation and characterization of monomode KTiOPO4 waveguide at 1539 nm by 6.0 MeV C3+ ion implantation with the dose of 2×1015 ions/cm2 and Rb+-K+ ion exchange, respectively. The relative intensity of light as a function of effective refractive index of TM modes at 633 nm and 1539 nm for KTiOPO4 waveguide formed by two different methods were compared with the prism coupling technique. The refractive index (nz) profile for the ion implanted waveguide was reconstructed by reflectivity calculation method, and one for the ion exchanged waveguide was by inverse Wentzel-Kramers-Brillouin. The nuclear energy loss versus penetration depth of the C3+ ions implantation into KTiOPO4 was simulated using the Stopping Range of Ions in Matter software. The Rutherford Backscattering Spectrometry spectrum of KTiOPO4 waveguide was analyzed after ions exchanged. The results showed that monomode waveguide at 1539 nm can be formed by ion implantation and Rb+ -K+ ion exchange, respectively.

Beam efflux measurements

NASA Technical Reports Server (NTRS)

Komatsu, G. K.; Stellen, J. M., Jr.

1976-01-01

Measurements have been made of the high energy thrust ions, (Group I), high angle/high energy ions (Group II), and high angle/low energy ions (Group IV) of a mercury electron bombardment thruster in the angular divergence range from 0 deg to greater than 90 deg. The measurements have been made as a function of thrust ion current, propellant utilization efficiency, bombardment discharge voltage, screen and accelerator grid potential (accel-decel ratio) and neutralizer keeper potential. The shape of the Group IV (charge exchange) ion plume has remained essentially fixed within the range of variation of the engine operation parameters. The magnitude of the charge exchange ion flux scales with thrust ion current, for good propellant utilization conditions. For fixed thrust ion current, charge exchange ion flux increases for diminishing propellant utilization efficiency. Facility effects influence experimental accuracies within the range of propellant utilization efficiency used in the experiments. The flux of high angle/high energy Group II ions is significantly diminished by the use of minimum decel voltages on the accelerator grid. A computer model of charge exchange ion production and motion has been developed. The program allows computation of charge exchange ion volume production rate, total production rate, and charge exchange ion trajectories for "genuine" and "facilities effects" particles. In the computed flux deposition patterns, the Group I and Group IV ion plumes exhibit a counter motion.

Modeling multicomponent ion exchange equilibrium utilizing hydrous crystalline silicotitanates by a multiple interactive ion exchange site model

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

Zheng, Z.; Anthony, R.G.; Miller, J.E.

1997-06-01

An equilibrium multicomponent ion exchange model is presented for the ion exchange of group I metals by TAM-5, a hydrous crystalline silicotitanate. On the basis of the data from ion exchange and structure studies, the solid phase is represented as Na{sub 3}X instead of the usual form of NaX. By using this solid phase representation, the solid can be considered as an ideal phase. A set of model ion exchange reactions is proposed for ion exchange between H{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, and Cs{sup +}. The equilibrium constants for these reactions were estimated from experiments with simplemore » ion exchange systems. Bromley`s model for activity coefficients of electrolytic solutions was used to account for liquid phase nonideality. Bromley`s model parameters for CsOH at high ionic strength and for NO{sub 2}{sup {minus}} and Al(OH){sub 4}{sup {minus}} were estimated in order to apply the model for complex waste simulants. The equilibrium compositions and distribution coefficients of counterions were calculated for complex simulants typical of DOE wastes by solving the equilibrium equations for the model reactions and material balance equations. The predictions match the experimental results within 10% for all of these solutions.« less

Ion-exchange hollow fibers

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Klein, Elias (Inventor)

1980-01-01

An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

Ion-exchange hollow fibers

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Klein, Elias (Inventor)

1977-01-01

An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

Mechanism of pyridine-ligand exchanges at the different labile sites of 3d heterometallic and mixed valence mu3-oxo trinuclear clusters.

PubMed

Novitchi, Ghenadie; Riblet, Fabrice; Scopelliti, Rosario; Helm, Lothar; Gulea, Aurelian; Merbach, André E

2008-11-17

The syntheses and single crystal X-ray structural analysis of five novel hetero- and homometallic mu 3-oxo trinuclear cluster with the formula [Fe (III) 2M (II)(mu 3-O)(mu-O 2CCH 3) 6(4-Rpy) 3]. x(4-Rpy). y(CH 3CN) where R = Ph for 1(Fe 2Mn), 2(Fe 2Fe), 3(Fe 2Co), 4(Fe 2Ni) and R = CF 3 for 5(Fe 2Co), are reported. The persistence of the structure for compounds 2- 5 in dichloromethane solution in the temperature range 190-320 K is demonstrated by (1)H and (19)F NMR spectroscopy. Even at the lowest temperature, the electron exchange in the homometallic mixed-valence compound 2(Fe 2Fe) is in the fast regime at the NMR time scale. Variable temperature and pressure NMR line broadening allowed quantifying the fast coordinated/free 4-Rpy exchanges at the two labile metal centers in these clusters: 2: Fe (III)( k (298)/10 (3) s (-1) = 16.6; Delta H (++) = 60.32 kJ mol (-1); Delta S (++) = + 34.8 J K (-1) mol (-1); Delta V (++) = + 12.5 cm (3) mol (-1)); 3: Fe (11.9; 58.92; +30.7; +10.6) and Co (2.8; 68.24; +49.8; +13.9); 4: Fe(12.2; 67.91; +61.0; -) and Ni (0.37; 78.62; +67.8; +12.3); 5: Fe (46; 58.21; +39.3; +14.2) and Co (4.7; 55.37; +11.2; +10.9). A limiting D mechanism is assigned to these exchange reactions. This assignment is based on a first-order rate law, the detection of intermediates, the positive and large entropies and volumes of activation. The order of reactivity k (Co) > k (Ni) is expected for a D mechanism at these metal centers: their low exchange rates are due to their strong binding with the 4-Rpy donor. Surrounded by oxygen donors the d (5) iron(III) usually reacts associatively; however, here due to low affinity of this ion for nitrogen the mechanism is D and the rate of exchange is very fast, even faster than on the divalent ions. There is no significant effect of the divalent ion in cluster 2, 3, and 5 on the exchange rates of 4-Phpy at the iron center, which seems to indicate that the specific electronic interactions between the three ions making the clusters do not influence the Fe (III)-N bond strength.

Binding of perlecan to transthyretin in vitro.

PubMed Central

Smeland, S; Kolset, S O; Lyon, M; Norum, K R; Blomhoff, R

1997-01-01

Transthyretin is one of two specific proteins involved in the transport of thyroid hormones in plasma; it possesses two binding sites for serum retinol-binding protein. In the present study we demonstrate that transthyretin also interacts in vitro with [35S]sulphate-labelled material from the medium of HepG2 cells. By using the same strategy as for purifying serum retinol-binding protein, [35S]sulphate-labelled medium was specifically eluted from a transthyretin-affinity column. Ion-exchange chromatography showed that the material was highly polyanionic, and its size and alkali susceptibility suggested that it was a proteoglycan. Structural analyses with chondroitinase ABC lyase and nitrous acid revealed that approx. 20% was chondroitin sulphate and 80% heparan sulphate. Immunoprecipitation showed that the [35S]sulphate-labelled material contained perlecan. Further analysis by binding studies revealed specific and saturable binding of 125I-transthyretin to perlecan-enriched Matrigel. Because inhibition of sulphation by treating HepG2 cells with sodium chlorate increased the affinity of the perlecan for transthyretin, and [3H]heparin was not retained by the transthyretin affinity column, the binding is probably mediated by the core protein and is not a protein-glycosaminoglycan interaction. Because perlecan is released from transthyretin in water, the binding might be due to hydrophobic interactions. PMID:9307034

Enhanced capacity and stability for the separation of cesium in electrically switched ion exchange

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

Tawfic, A.F.; Dickson, S.E.; Kim, Y.

2015-03-15

Electrically switched ion exchange (ESIX) can be used to separate ionic contaminants from industrial wastewater, including that generated by the nuclear industry. The ESIX method involves sequential application of reduction and oxidation potentials to an ion exchange film to induce the respective loading and unloading of cesium. This technology is superior to conventional methods (e.g electrodialysis reversal or reverse osmosis) as it requires very little energy for ionic separation. In previous studies, ESIX films have demonstrated relatively low ion exchange capacities and limited film stabilities over repeated potential applications. In this study, the methodology for the deposition of electro-active filmsmore » (nickel hexacyanoferrate) on nickel electrodes was modified to improve the ion exchange capacity for cesium removal using ESIX. Cyclic voltammetry was used to investigate the ion exchange capacity and stability. Scanning electron microscopy (SEM) was used to characterize the modified film surfaces. Additionally, the films were examined for the separation of cesium ions. This modified film preparation technique enhanced the ion exchange capacity and improves the film stability compared to previous methods for the deposition of ESIX films. (authors)« less

A protein with anion exchange properties found in the kidney proximal tubule.

PubMed

Soleimani, M; Bizal, G L; Anderson, C C

1993-09-01

One important mechanism for reabsorption of chloride in the kidney proximal tubule involves anion exchange of chloride for a base. Anion exchange transport systems in general demonstrate sensitivity to inhibition by disulfonic stilbenes, probenecid, furosemide, and the arginyl amino group modifier phenylglyoxal. Using disulfonic stilbene affinity chromatography, we have identified and partially purified a protein with anion exchanger properties in luminal membrane vesicles isolated from rabbit kidney cortex. This protein has a molecular weight of 162 kD. The binding of the 162 kD protein to the stilbene affinity matrix is inhibited by disulfonic stilbenes, probenecid, furosemide, and phenylglyoxal. Reconstitution of the proteins eluted from the affinity matrix into liposomes demonstrates anion exchange activity as assayed by radiolabeled chloride influx. Deletion of the 162 kD protein from the eluted mixture by probenecid diminishes the anion exchanger activity in the reconstituted liposomes. Further purification of the disulfonic stilbene column eluant by Econo-Pac Q ion exchange chromatography resulted in significant enrichment in 162 kD protein abundance and also anion exchange activity in reconstituted liposomes. The results of the above experiments strongly suggest that the 162 kD protein is an anion exchanger. Insight into the functional and molecular characteristics of this protein should provide important information about the mechanism(s) of chloride reabsorption in the kidney proximal tubule.

Recognizing metal and acid radical ion-binding sites by integrating ab initio modeling with template-based transferals.

PubMed

Hu, Xiuzhen; Dong, Qiwen; Yang, Jianyi; Zhang, Yang

2016-11-01

More than half of proteins require binding of metal and acid radical ions for their structure and function. Identification of the ion-binding locations is important for understanding the biological functions of proteins. Due to the small size and high versatility of the metal and acid radical ions, however, computational prediction of their binding sites remains difficult. We proposed a new ligand-specific approach devoted to the binding site prediction of 13 metal ions (Zn 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Ca 2+ , Mg 2+ , Mn 2+ , Na + , K + ) and acid radical ion ligands (CO3 2- , NO2 - , SO4 2- , PO4 3- ) that are most frequently seen in protein databases. A sequence-based ab initio model is first trained on sequence profiles, where a modified AdaBoost algorithm is extended to balance binding and non-binding residue samples. A composite method IonCom is then developed to combine the ab initio model with multiple threading alignments for further improving the robustness of the binding site predictions. The pipeline was tested using 5-fold cross validations on a comprehensive set of 2,100 non-redundant proteins bound with 3,075 small ion ligands. Significant advantage was demonstrated compared with the state of the art ligand-binding methods including COACH and TargetS for high-accuracy ion-binding site identification. Detailed data analyses show that the major advantage of IonCom lies at the integration of complementary ab initio and template-based components. Ion-specific feature design and binding library selection also contribute to the improvement of small ion ligand binding predictions. http://zhanglab.ccmb.med.umich.edu/IonCom CONTACT: hxz@imut.edu.cn or zhng@umich.eduSupplementary information: Supplementary data are available at Bioinformatics online. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Metal Binding Studies and EPR Spectroscopy of the Manganese Transport Regulator MntR†

PubMed Central

Golynskiy, Misha V.; Gunderson, William A.; Hendrich, Michael P.; Cohen, Seth M.

2007-01-01

Manganese transport regulator (MntR) is a member of the diphtheria toxin repressor (DtxR) family of transcription factors that is responsible for manganese homeostasis in Bacillus subtilis. Prior biophysical studies have focused on the metal-mediated DNA binding of MntR [Lieser, S. A., Davis, T. C., Helmann, J. D., and Cohen, S. M. (2003) Biochemistry 42, 12634-12642], as well as metal stabilization of the MntR structure [Golynskiy, M. V., Davis, T. C., Helmann, J. D., and Cohen, S. M. (2005) Biochemistry 44, 3380-3389], but only limited data on the metal-binding affinities for MntR are available. Herein, the metal-binding affinities of MntR were determined by using electron paramagnetic resonance (EPR) spectroscopy, as well as competition experiments with the fluorimetric dyes Fura-2 and Mag-fura-2. MntR was not capable of competing with Fura-2 for the binding of transition metal ions. Therefore, the metal-binding affinities and stoichiometries of Mag-fura-2 for Mn2+, Co2+, Ni2+, Zn2+, and Cd2+ were determined and utilized in MntR/Mag-fura-2 competition experiments. The measured Kd values for MntR metal binding are comparable to those reported for DtxR metal binding [Kd from 10-7 to 10-4 M; D’Aquino, J. A., et al. (2005) Proc. Natl. Acad. Sci. U.S.A. 102, 18408-18413], AntR [a homologue from Bacillus anthracis; Sen, K. I. et al. (2006) Biochemistry 45, 4295-4303], and generally follow the Irving-Williams series. Direct detection of the dinuclear Mn2+ site in MntR with EPR spectroscopy is presented, and the exchange interaction was determined, J = -0.2 cm-1. This value is lower in magnitude than most known dinuclear Mn2+ sites in proteins and synthetic complexes and is consistent with a dinuclear Mn2+ site with a longer Mn···Mn distance (4.4 Å) observed in some of the available crystal structures. MntR is found to have a surprisingly low binding affinity (∼160 μM) for its cognate metal ion Mn2+. Moreover, the results of DNA binding studies in the presence of limiting metal ion concentrations were found to be consistent with the measured metal-binding constants. The metal-binding affinities of MntR reported here help to elucidate the regulatory mechanism of this metal-dependent transcription factor. PMID:17176058

A new configuration of membrane stack for retrieval of nickel absorbed in resins*

PubMed Central

Chen, Xue-fen; Wu, Zu-cheng

2005-01-01

A new configuration integrated ion exchange effect with both electro-migration and electrochemical reaction in a single cell was developed to effectively retrieve metal ions from simulated wastewater using ion exchange resins without additive chemicals. By simply assembling cation exchange resins and anion exchange resins separated by homogeneous membranes, we found that the system will always be acidic in the concentrate compartment so that ion exchange resins could be in-situ regenerated without hydroxide precipitation. Such a realizable design will be really suitable for wastewater purification. PMID:15909341

Charged particle measurements on a 30-CM diameter mercury ion engine thrust beam

NASA Technical Reports Server (NTRS)

Sellen, J. M., Jr.; Komatsu, G. K.; Hoffmaster, D. K.; Kemp, R. F.

1974-01-01

Measurements of both thrust ions and charge exchange ions were made in the beam of a 30 centimeter diameter electron bombardment mercury ion thruster. A qualitative model is presented which describes magnitudes of charge exchange ion formation and motions of these ions in the weak electric field structure of the neutralized thrust beam plasma. Areas of agreement and discrepancy between observed and modeled charge exchange properties are discussed.

Silver-Ion-Exchanged Nanostructured Zeolite X as Antibacterial Agent with Superior Ion Release Kinetics and Efficacy against Methicillin-Resistant Staphylococcus aureus.

PubMed

Chen, Shaojiang; Popovich, John; Iannuzo, Natalie; Haydel, Shelley E; Seo, Dong-Kyun

2017-11-15

As antibiotic resistance continues to be a major public health problem, antimicrobial alternatives have become critically important. Nanostructured zeolites have been considered as an ideal host for improving popular antimicrobial silver-ion-exchanged zeolites, because with very short diffusion path lengths they offer advantages in ion diffusion and release over their conventional microsized zeolite counterparts. Herein, comprehensive studies are reported on materials characteristics, silver-ion release kinetics, and antibacterial properties of silver-ion-exchanged nanostructured zeolite X with comparisons to conventional microsized silver-ion-exchanged zeolite (∼2 μm) as a reference. The nanostructured zeolites are submicrometer-sized aggregates (100-700 nm) made up of primary zeolite particles with an average primary particle size of 24 nm. The silver-ion-exchanged nanostructured zeolite released twice the concentration of silver ions at a rate approximately three times faster than the reference. The material exhibited rapid antimicrobial activity against methicillin-resistant Staphylococcus aureus (MRSA) with minimum inhibitory concentration (MIC) values ranging from 4 to 16 μg/mL after 24 h exposure in various growth media and a minimum bactericidal concentration (MBC; >99.9% population reduction) of 1 μg/mL after 2 h in water. While high concentrations of silver-ion-exchanged nanostructured zeolite X were ineffective at reducing MRSA biofilm cell viability, efficacy increased at lower concentrations. In consideration of potential medical applications, cytotoxicity of the silver-ion-exchanged nanostructured zeolite X was also investigated. After 4 days of incubation, significant reduction in eukaryotic cell viability was observed only at concentrations 4-16-fold greater than the 24 h MIC, indicating low cytotoxicity of the material. Our results establish silver-ion-exchanged nanostructured zeolites as an effective antibacterial material against dangerous antibiotic-resistant bacteria.

The Role of Ion Exchange Membranes in Membrane Capacitive Deionisation.

PubMed

Hassanvand, Armineh; Wei, Kajia; Talebi, Sahar; Chen, George Q; Kentish, Sandra E

2017-09-14

Ion-exchange membranes (IEMs) are unique in combining the electrochemical properties of ion exchange resins and the permeability of a membrane. They are being used widely to treat industrial effluents, and in seawater and brackish water desalination. Membrane Capacitive Deionisation (MCDI) is an emerging, energy efficient technology for brackish water desalination in which these ion-exchange membranes act as selective gates allowing the transport of counter-ions toward carbon electrodes. This article provides a summary of recent developments in the preparation, characterization, and performance of ion exchange membranes in the MCDI field. In some parts of this review, the most relevant literature in the area of electrodialysis (ED) is also discussed to better elucidate the role of the ion exchange membranes. We conclude that more work is required to better define the desalination performance of the proposed novel materials and cell designs for MCDI in treating a wide range of feed waters. The extent of fouling, the development of cleaning strategies, and further techno-economic studies, will add value to this emerging technique.

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.

Free Energy Simulations of Ligand Binding to the Aspartate Transporter GltPh

PubMed Central

Heinzelmann, Germano; Baştuğ, Turgut; Kuyucak, Serdar

2011-01-01

Glutamate/Aspartate transporters cotransport three Na+ and one H+ ions with the substrate and countertransport one K+ ion. The binding sites for the substrate and two Na+ ions have been observed in the crystal structure of the archeal homolog GltPh, while the binding site for the third Na+ ion has been proposed from computational studies and confirmed by experiments. Here we perform detailed free energy simulations of GltPh, giving a comprehensive characterization of the substrate and ion binding sites, and calculating their binding free energies in various configurations. Our results show unequivocally that the substrate binds after the binding of two Na+ ions. They also shed light into Asp/Glu selectivity of GltPh, which is not observed in eukaryotic glutamate transporters. PMID:22098736

Ion-exchange chromatography separates activities synthesizing and degrading fructose 2,6-bisphosphate from C3 and C4 leaves but not from rat liver

NASA Technical Reports Server (NTRS)

Macdonald, F. D.; Chou, Q.; Buchanan, B. B.

1987-01-01

Fructose-6-phosphate,2-kinase and fructose-2,6-bisphosphatase were separated on the basis of charge from leaves of C3 (spinach, lettuce, and pea) and C4 (sorghum and amaranthus) plants but not from rat liver--a tissue known to contain a bifunctional enzyme with both activities. [2-32P]Fructose 2,6-bisphosphate binding experiments also suggest that the major forms of these activities reside on different proteins in leaves.

The Urtica dioica Agglutinin Is a Complex Mixture of Isolectins 1

PubMed Central

Van Damme, Els J. M.; Broekaert, Willem F.; Peumans, Willy J.

1988-01-01

Rhizomes of stinging nettle (Urtica dioica) contain a complex mixture of isolectins. Ion exchange chromatography with a high resolution fast protein liquid chromatography system revealed six isoforms which exhibit identical agglutination properties and carbohydrate-binding specificity and in addition have the same molecular structure and virtually identical biochemical properties. However, since the U. dioica agglutinin isolectins differ definitely with respect to their amino acid composition, it is likely that at least some of them are different polypeptides coded for by different genes. Images Fig. 3 PMID:16665952

An Empirical Formula From Ion Exchange Chromatography and Colorimetry.

ERIC Educational Resources Information Center

Johnson, Steven D.

1996-01-01

Presents a detailed procedure for finding an empirical formula from ion exchange chromatography and colorimetry. Introduces students to more varied techniques including volumetric manipulation, titration, ion-exchange, preparation of a calibration curve, and the use of colorimetry. (JRH)

Effect of silver ions and clusters on the luminescence properties of Eu-doped borate glasses

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

Jiao, Qing, E-mail: jiaoqing@nbu.edu.cn; Wang, Xi; Qiu, Jianbei

2015-12-15

Highlights: • Ag{sup +} and Ag clusters are investigated in the borate glasses via ion exchange method. • The aggregation of silver ions to the clusters was controlled by the ion exchange concentration. • Eu{sup 3+}/Eu{sup 2+} ions emission was enhanced with the sensitization of the silver species. • Energy transfer process from Ag ions and Ag clusters to Eu ions is identified by the lifetime measurements. - Abstract: Silver ions and clusters were applied to Eu{sup 3+}-doped borate glasses via the Ag{sup +}–Na{sup +} ion exchange method. Eu{sup 3+}/Eu{sup 2+} ion luminescence enhancement was achieved after silver ion exchange.more » Absorption spectra showed no band at 420 nm, which indicates that silver nanoparticles can be excluded as a silver state in the glass. Silver ion aggregation into clusters during the ion exchange process may be inferred. The effect of silver ions and clusters on rare earth emissions was investigated using spectral information and lifetime measurements. Significant luminescence enhancements were observed from the energy transfer of Ag{sup +} ions and clusters to Eu{sup 3+}/Eu{sup 2+} ions, companied with the silver ions aggregated into the clusters state. The results of this research may extend the current understanding of interactions between rare-earth ions and Ag species.« less

Synergistic integration of ion-exchange and catalytic reduction for complete decomposition of perchlorate in waste water.

PubMed

Kim, You-Na; Choi, Minkee

2014-07-01

Ion-exchange has been frequently used for the treatment of perchlorate (ClO4(-)), but disposal or regeneration of the spent resins has been the major hurdle for field application. Here we demonstrate a synergistic integration of ion-exchange and catalytic decomposition by using Pd-supported ion-exchange resin as an adsorption/catalysis bifunctional material. The ion-exchange capability of the resin did not change after generation of the Pd clusters via mild ethanol reduction, and thus showed very high ion-exchange selectivity and capacity toward ClO4(-). After the resin was saturated with ClO4(-) in an adsorption mode, it was possible to fully decompose the adsorbed ClO4(-) into nontoxic Cl(-) by the catalytic function of the Pd catalysts under H2 atmosphere. It was demonstrated that prewetting the ion-exchange resin with ethanol significantly accelerate the decomposition of ClO4(-) due to the weaker association of ClO4(-) with the ion-exchange sites of the resin, which allows more facile access of ClO4(-) to the catalytically active Pd-resin interface. In the presence of ethanol, >90% of the adsorbed ClO4(-) could be decomposed within 24 h at 10 bar H2 and 373 K. The ClO4(-) adsorption-catalytic decomposition cycle could be repeated up to five times without loss of ClO4(-) adsorption capacity and selectivity.

Processes for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil, and apparatuses for treating biomass-derived pyrolysis oil

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

Baird, Lance Awender; Brandvold, Timothy A.

Processes and apparatuses for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil are provided herein. An exemplary process for washing a spent ion exchange bed employed in purification of biomass-derived pyrolysis oil includes the step of providing a ion-depleted pyrolysis oil stream having an original oxygen content. The ion-depleted pyrolysis oil stream is partially hydrotreated to reduce the oxygen content thereof, thereby producing a partially hydrotreated pyrolysis oil stream having a residual oxygen content that is less than the original oxygen content. At least a portion of the partially hydrotreated pyrolysis oil stream is passed throughmore » the spent ion exchange bed. Water is passed through the spent ion exchange bed after passing at least the portion of the partially hydrotreated pyrolysis oil stream therethrough.« less

Ion Exchange and Adsorption of Inorganic Contaminants

EPA Science Inventory

In the first part of the chapter, the fundamentals of ion exchange and adsorption processes are explained, with the goal of demonstrating how these principles influence process design for inorganic contaminant removal. In the second part, ion exchange and adsorption processes th...

Predicting Nonspecific Ion Binding Using DelPhi

PubMed Central

Petukh, Marharyta; Zhenirovskyy, Maxim; Li, Chuan; Li, Lin; Wang, Lin; Alexov, Emil

2012-01-01

Ions are an important component of the cell and affect the corresponding biological macromolecules either via direct binding or as a screening ion cloud. Although some ion binding is highly specific and frequently associated with the function of the macromolecule, other ions bind to the protein surface nonspecifically, presumably because the electrostatic attraction is strong enough to immobilize them. Here, we test such a scenario and demonstrate that experimentally identified surface-bound ions are located at a potential that facilitates binding, which indicates that the major driving force is the electrostatics. Without taking into consideration geometrical factors and structural fluctuations, we show that ions tend to be bound onto the protein surface at positions with strong potential but with polarity opposite to that of the ion. This observation is used to develop a method that uses a DelPhi-calculated potential map in conjunction with an in-house-developed clustering algorithm to predict nonspecific ion-binding sites. Although this approach distinguishes only the polarity of the ions, and not their chemical nature, it can predict nonspecific binding of positively or negatively charged ions with acceptable accuracy. One can use the predictions in the Poisson-Boltzmann approach by placing explicit ions in the predicted positions, which in turn will reduce the magnitude of the local potential and extend the limits of the Poisson-Boltzmann equation. In addition, one can use this approach to place the desired number of ions before conducting molecular-dynamics simulations to neutralize the net charge of the protein, because it was shown to perform better than standard screened Coulomb canned routines, or to predict ion-binding sites in proteins. This latter is especially true for proteins that are involved in ion transport, because such ions are loosely bound and very difficult to detect experimentally. PMID:22735539

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.

Programmatic Re-Evaluation of Ion Exchange as a 1st Generation ITP Replacement

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

Scott, A.B.

This re-evaluation differs from previous work in that (1) the Ion Exchange option was evaluated from a standpoint assuming that ITP would never start up, thus Ion Exchange was the only viable option, (2) the DOE prescribed balanced assumptions were quite different than the WSRC Assumptions used previously, and (3) other Site events and changes within HLWM have tended to reduce the disadvantages of Ion Exchange relative to ITP as the first generation salt decontamination process.

Simultaneous Isolation of Lactoferrin and Lactoperoxidase from Bovine Colostrum by SPEC 70 SLS Cation Exchange Resin

PubMed Central

Liang, Yafei; Wang, Xuewan; Wu, Mianbin; Zhu, Wanping

2011-01-01

In this work, simultaneous isolation of lactoferrin (Lf) and lactoperoxidase (Lp) from defatted bovine colostrum by one-step cation exchange chromatography with SPEC 70 SLS ion-exchange resin was investigated. A RP-HPLC method for Lf and Lp determination was developed and optimized as the following conditions: detection wavelength of 220 nm, flow rate of 1 mL/min and acetonitrile concentration from 25% to 75% within 20 min. The adsorption process of Lf on SPEC 70 SLS resin was optimized using Lf standard as substrate. The maximum static binding capacity of SPEC 70 SLS resin was of 22.0 mg/g resin at 15 °C, pH 7.0 and adsorption time 3 h. The Lf adsorption process could be well described by the Langmuir adsorption isotherm model, with a maximum adsorption capacity of 21.73 mg/g resin at 15 °C. In batch fractionation of defatted colostrum, the binding capacities of SPEC 70 SLS resin for adsorbing Lf and Lp simultaneously under the abovementioned conditions were 7.60 and 6.89 mg/g resin, respectively, both of which were superior to those of CM Sepharose F.F. or SP Sepharose F.F. resins under the same conditions. As a result, SPEC 70 SLS resin was considered as a successful candidate for direct and economic purification of Lf and Lp from defatted colostrum. PMID:22016715

A heteronuclear zero quantum coherence Nz-exchange experiment that resolves resonance overlap and its application to measure the rates of heme binding to the IsdC protein.

PubMed

Robson, Scott A; Peterson, Robert; Bouchard, Louis-S; Villareal, Valerie A; Clubb, Robert T

2010-07-21

Chemical exchange phenomena in NMR spectra can be quantitatively interpreted to measure the rates of ligand binding, as well as conformational and chemical rearrangements. In macromolecules, processes that occur slowly on the chemical shift time scale are frequently studied using 2D heteronuclear ZZ or N(z)-exchange spectroscopy. However, to successfully apply this method, peaks arising from each exchanging species must have unique chemical shifts in both dimensions, a condition that is often not satisfied in protein-ligand binding equilibria for (15)N nuclei. To overcome the problem of (15)N chemical shift degeneracy we developed a heteronuclear zero-quantum (and double-quantum) coherence N(z)-exchange experiment that resolves (15)N chemical shift degeneracy in the indirect dimension. We demonstrate the utility of this new experiment by measuring the heme binding kinetics of the IsdC protein from Staphylococcus aureus. Because of peak overlap, we could not reliably analyze binding kinetics using conventional methods. However, our new experiment resulted in six well-resolved systems that yielded interpretable data. We measured a relatively slow k(off) rate of heme from IsdC (<10 s(-1)), which we interpret as necessary so heme loaded IsdC has time to encounter downstream binding partners to which it passes the heme. The utility of using this new exchange experiment can be easily expanded to (13)C nuclei. We expect our heteronuclear zero-quantum coherence N(z)-exchange experiment will expand the usefulness of exchange spectroscopy to slow chemical exchange events that involve ligand binding.

Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 1. Peptides to Proteins

NASA Astrophysics Data System (ADS)

Donohoe, Gregory C.; Khakinejad, Mahdiar; Valentine, Stephen J.

2015-04-01

Ion mobility spectrometry (IMS) coupled with hydrogen deuterium exchange (HDX)-mass spectrometry (MS) has been used to study the conformations of negatively-charged peptide and protein ions. Results are presented for ion conformers of angiotensin 1, a synthetic peptide (SP), bovine insulin, ubiquitin, and equine cytochrome c. In general, the SP ion conformers demonstrate a greater level of HDX efficiency as a greater proportion of the sites undergo HDX. Additionally, these ions exhibit the fastest rates of exchange. Comparatively, the angiotensin 1 ions exhibit a lower rate of exchange and HDX level presumably because of decreased accessibility of exchange sites by charge sites. The latter are likely confined to the peptide termini. Insulin ions show dramatically reduced HDX levels and exchange rates, which can be attributed to decreased conformational flexibility resulting from the disulfide bonds. For the larger ubiquitin and protein ions, increased HDX is observed for larger ions of higher charge state. For ubiquitin, a conformational transition from compact to more elongated species (from lower to higher charge states) is reflected by an increase in HDX levels. These results can be explained by a combination of interior site protection by compact conformers as well as decreased access by charge sites. The elongated cytochrome c ions provide the largest HDX levels where higher values correlate with charge state. These results are consistent with increased exchange site accessibility by additional charge sites. The data from these enhanced IMS-HDX experiments are described in terms of charge site location, conformer rigidity, and interior site protection.

Method of detecting defects in ion exchange membranes of electrochemical cells by chemochromic sensors

DOEpatents

Brooker, Robert Paul; Mohajeri, Nahid

2016-01-05

A method of detecting defects in membranes such as ion exchange membranes of electrochemical cells. The electrochemical cell includes an assembly having an anode side and a cathode side with the ion exchange membrane in between. In a configuration step a chemochromic sensor is placed above the cathode and flow isolation hardware lateral to the ion exchange membrane which prevents a flow of hydrogen (H.sub.2) between the cathode and anode side. The anode side is exposed to a first reactant fluid including hydrogen. The chemochromic sensor is examined after the exposing for a color change. A color change evidences the ion exchange membrane has at least one defect that permits H.sub.2 transmission therethrough.

The Role of Ion Exchange Membranes in Membrane Capacitive Deionisation

PubMed Central

Hassanvand, Armineh; Wei, Kajia; Talebi, Sahar

2017-01-01

Ion-exchange membranes (IEMs) are unique in combining the electrochemical properties of ion exchange resins and the permeability of a membrane. They are being used widely to treat industrial effluents, and in seawater and brackish water desalination. Membrane Capacitive Deionisation (MCDI) is an emerging, energy efficient technology for brackish water desalination in which these ion-exchange membranes act as selective gates allowing the transport of counter-ions toward carbon electrodes. This article provides a summary of recent developments in the preparation, characterization, and performance of ion exchange membranes in the MCDI field. In some parts of this review, the most relevant literature in the area of electrodialysis (ED) is also discussed to better elucidate the role of the ion exchange membranes. We conclude that more work is required to better define the desalination performance of the proposed novel materials and cell designs for MCDI in treating a wide range of feed waters. The extent of fouling, the development of cleaning strategies, and further techno-economic studies, will add value to this emerging technique. PMID:28906442

High-capacity cation-exchange column for enhanced resolution of adjacent peaks of cations in ion chromatography.

PubMed

Rey, M A

2001-06-22

One of the advantages of ion chromatography [Anal Chem. 47 (1975) 1801] as compared to other analytical techniques is that several ions may be analyzed simultaneously. One of the most important contributions of cation-exchange chromatography is its sensitivity to ammonium ion, which is difficult to analyze by other techniques [J. Weiss, in: E.L. Johnson (Ed.), Handbook of Ion Chromatography, Dionex, Sunnyvale, CA, USA]. The determination of low concentrations of ammonium ion in the presence of high concentrations of sodium poses a challenge in cation-exchange chromatography [J. Weiss, Ion Chromatography, VCH, 2nd Edition, Weinheim, 1995], as both cations have similar selectivities for the common stationary phases containing either sulfonate or carboxylate functional groups. The task was to develop a new cation-exchange stationary phase (for diverse concentration ratios of adjacent peaks) to overcome limitations experienced in previous trails. Various cation-exchange capacities and column body formats were investigated to optimize this application and others. The advantages and disadvantages of two carboxylic acid columns of different cation-exchange capacities and different column formats will be discussed.

Properties of a Novel Ion-Exchange Film

NASA Technical Reports Server (NTRS)

Street, Kenneth W.; Hill, Carol M.; Philipp, Warren H.; Tanner, Stephen P.; Gorse, Joseph; Lusk, Amy; Taylor, Jason; Dickens, Jason

2002-01-01

A new ion-exchange material (based on polyacrylic acid) and some of its analytical applications have been reported. This paper contains data on the ion-exchange properties of the film form of the material and its potential application to the decontamination of waste water and drinking water. The film has a high exchange capacity of 5 to 6 meq/g and a pK(sub a) of 5.7. The calcium form is the most effective for removing metal ions from solution, and the optimum pH range is between 5 and 7. The exchange rates are slower for the film than for bead and powder forms of the ion-exchange material; otherwise, the properties are similar. The film is effective when hard water solutions are employed and also when metal ions are in the complex matrix of waste water from electroplating. The film can be used in flow systems having a flow channel large enough to allow passage of turbid solutions.

Ion Exchange Equilibrium and Kinetic Properties of Polyacrylate Films and Applications to Chemical Analysis and Environmental Decontamination

NASA Technical Reports Server (NTRS)

Tanner, Stephen P.

1997-01-01

One of the goals of the original proposal was to study how cross-linking affects the properties of an ion exchange material(IEM) developed at Lewis Research Center. However, prior to the start of this work, other workers at LERC investigated the effect of cross-linking on the properties of this material. Other than variation in the ion exchange capacity, the chemical characteristics were shown to be independent of the cross-linking agent, and the degree of cross-linking. New physical forms of the film were developed (film, supported film, various sizes of beads, and powder). All showed similar properties with respect to ion exchange equilibria but the kinetics of ion exchange depended on the surface area per unit mass; the powder form of the IEM exchanging much more rapidly than the other forms. The research performed under this grant was directed towards the application of the IEM to the analysis of metal ions at environmental concentrations.

Properties of a Novel Ion-Exchange Film

NASA Technical Reports Server (NTRS)

Street, Kenneth W.; Hill, Carol M.; Philipp, Warren H.; Tanner, Stephen P.; Gorse, Joseph; Lusk, Amy; Taylor, Jason; Dickens, Jason

2004-01-01

A new ion-exchange material (based on polyacrylic acid) and some of its analytical applications have been reported. This paper contains data on the ion-exchange properties of the film form of the material and its potential application to the decontamination of waste water and drinking water. The film has a high exchange capacity of 5 to 6 meq/g and a pK(sub a) of 5.7. The calcium form is the most effective for removing metal ions from solution, and the optimum pH range is between 5 and 7. The exchange rates are slower for the film than for bead and powder forms of the ion-exchange material; otherwise, the properties are similar. The film is effective when hard water solutions are employed and also when metal ions are in the complex matrix of waste water from electroplating. The film can be used in flow systems having a flow channel large enough to allow passage of turbid solutions.

Proton and metal ion binding to natural organic polyelectrolytes-II. Preliminary investigation with a peat and a humic acid

USGS Publications Warehouse

Marinsky, J.A.; Reddy, M.M.

1984-01-01

We summarize here experimental studies of proton and metal ion binding to a peat and a humic acid. Data analysis is based on a unified physico-chemical model for reaction of simple ions with polyelectrolytes employing a modified Henderson-Hasselbalch equation. Peat exhibited an apparent intrinsic acid dissociation constant of 10-4.05, and an apparent intrinsic metal ion binding constant of: 400 for cadmium ion; 600 for zinc ion; 4000 for copper ion; 20000 for lead ion. A humic acid was found to have an apparent intrinsic proton binding constant of 10-2.6. Copper ion binding to this humic acid sample occurred at two types of sites. The first site exhibited reaction characteristics which were independent of solution pH and required the interaction of two ligands on the humic acid matrix to simultaneously complex with each copper ion. The second complex species is assumed to be a simple monodentate copper ion-carboxylate species with a stability constant of 18. ?? 1984.

Novel Functional Properties of Drosophila CNS Glutamate Receptors

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

Li, Yan; Dharkar, Poorva; Han, Tae-Hee

Phylogenetic analysis reveals AMPA, kainate, and NMDA receptor families in insect genomes, suggesting conserved functional properties corresponding to their vertebrate counterparts. However, heterologous expression of the Drosophila kainate receptor DKaiR1D and the AMPA receptor DGluR1A revealed novel ligand selectivity at odds with the classification used for vertebrate glutamate receptor ion channels (iGluRs). DKaiR1D forms a rapidly activating and desensitizing receptor that is inhibited by both NMDA and the NMDA receptor antagonist AP5; crystallization of the KaiR1D ligand-binding domain reveals that these ligands stabilize open cleft conformations, explaining their action as antagonists. Surprisingly, the AMPA receptor DGluR1A shows weak activation bymore » its namesake agonist AMPA and also by quisqualate. Crystallization of the DGluR1A ligand-binding domain reveals amino acid exchanges that interfere with binding of these ligands. The unexpected ligand-binding profiles of insect iGluRs allows classical tools to be used in novel approaches for the study of synaptic regulation.« less

Novel Functional Properties of Drosophila CNS Glutamate Receptors.

PubMed

Li, Yan; Dharkar, Poorva; Han, Tae-Hee; Serpe, Mihaela; Lee, Chi-Hon; Mayer, Mark L

2016-12-07

Phylogenetic analysis reveals AMPA, kainate, and NMDA receptor families in insect genomes, suggesting conserved functional properties corresponding to their vertebrate counterparts. However, heterologous expression of the Drosophila kainate receptor DKaiR1D and the AMPA receptor DGluR1A revealed novel ligand selectivity at odds with the classification used for vertebrate glutamate receptor ion channels (iGluRs). DKaiR1D forms a rapidly activating and desensitizing receptor that is inhibited by both NMDA and the NMDA receptor antagonist AP5; crystallization of the KaiR1D ligand-binding domain reveals that these ligands stabilize open cleft conformations, explaining their action as antagonists. Surprisingly, the AMPA receptor DGluR1A shows weak activation by its namesake agonist AMPA and also by quisqualate. Crystallization of the DGluR1A ligand-binding domain reveals amino acid exchanges that interfere with binding of these ligands. The unexpected ligand-binding profiles of insect iGluRs allows classical tools to be used in novel approaches for the study of synaptic regulation. VIDEO ABSTRACT. Published by Elsevier Inc.

Donor states in a semimagnetic Cd1 -xinMnxin Te /Cd1 -xoutMnxout Te Double Quantum Well

NASA Astrophysics Data System (ADS)

Kalpana, Panneer Selvam; Nithiananthi, Perumal; Jayakumar, Kalyanasundaram

2017-02-01

The theoretical investigation has been carried out on the binding energy of donor associated with the electrons confined in a Cd1 -xinMnxin Te /Cd1 -xoutMnxout Te Double Quantum Well (DQW) as a function of central barrier width for various well dimensions and impurity locations in the barrier and the well. The magnetic field can act as a tool to continuously change the interwell coupling inside this DQW systems and its effect on donor binding has also been studied. Moreover, the polaronic corrections, which is due to the strong exchange interaction between the magnetic moment of Mn2+ ion and the spin of the confined carrier, to the binding energy of the hydrogenic donor impurity has also been estimated with and without the application of magnetic field. The binding energy of the donor impurity is determined by solving the Schrodinger equation variationally in the effective mass approximation and the effect due to Bound Magnetic Polaron (BMP) is included using mean field theory with the modified Brillouin function. The results are reported and discussed.

Structurally colored biopolymer thin films for detection of dissolved metal ions in aqueous solution

NASA Astrophysics Data System (ADS)

Cathell, Matthew David

Natural polymers, such as the polysaccharides alginate and chitosan, are noted sorbents of heavy metals. Their polymer backbone structures are rich in ligands that can interact with metal ions through chelation, electrostatics, ion exchange and nonspecific mechanisms. These water-soluble biopolymer materials can be processed into hydrogel thin films, creating high surface area interfaces ideal for binding and sequestering metal ions from solution. By virtue of their uniform nanoscale dimensions (with thicknesses smaller than wavelengths of visible light) polymer thin films exhibit structure-based coloration. This phenomenon, frequently observed in nature, causes the transparent and essentially colorless films to reflect light in a wide array of colors. The lamellar film structures act as one-dimensional photonic crystals, allowing selective reflection of certain wavelengths of light while minimizing other wavelengths by out-of-phase interference. The combination of metal-binding and reflective properties make alginate and chitosan thin films attractive candidates for analyte sensing. Interactions with metal ions can induce changes in film thicknesses and refractive indices, thus altering the path of light reflected through the film. Small changes in dimensional or optical properties can lead to shifts in film color that are perceivable by the unaided eye. These thin films offer the potential for optical sensing of toxic dissolved materials without the need for instrumentation, external power or scientific expertise. With the use of a spectroscopic ellipsometer and a fiber optic reflectance spectrometer, the physical and optical characteristics of biopolymer thin films have been characterized in response to 50 ppm metal ion solutions. It has been determined that metal interactions can lead to measurable changes in both film thicknesses and effective refractive indices. The intrinsic response behaviors of alginate and chitosan, as well as the responses of modified derivatives of these materials, have been investigated. It has been found that the natural metal selectivity of biopolymer films can be tuned and refined by adjusting the ligand environment through backbone modification. Other investigations have also been undertaken, including in situ monitoring of biopolymer---metal interactions and quantification of thin film metal-binding capacities.

Ion Binding Energies Determining Functional Transport of ClC Proteins

NASA Astrophysics Data System (ADS)

Yu, Tao; Guo, Xu; Zou, Xian-Wu; Sang, Jian-Ping

2014-06-01

The ClC-type proteins, a large family of chloride transport proteins ubiquitously expressed in biological organisms, have been extensively studied for decades. Biological function of ClC proteins can be reflected by analyzing the binding situation of Cl- ions. We investigate ion binding properties of ClC-ec1 protein with the atomic molecular dynamics simulation approach. The calculated electrostatic binding energy results indicate that Cl- at the central binding site Scen has more binding stability than the internal binding site Sint. Quantitative comparison between the latest experimental heat release data isothermal titration calorimetry (ITC) and our calculated results demonstrates that chloride ions prefer to bind at Scen than Sint in the wild-type ClC-ec1 structure and prefer to bind at Sext and Scen than Sint in mutant E148A/E148Q structures. Even though the chloride ions make less contribution to heat release when binding to Sint and are relatively unstable in the Cl- pathway, they are still part contributors for the Cl- functional transport. This work provides a guide rule to estimate the importance of Cl- at the binding sites and how chloride ions have influences on the function of ClC proteins.

Nanopore Device for Reversible Ion and Molecule Sensing or Migration

NASA Technical Reports Server (NTRS)

Seger, R. Adam (Inventor); Pourmand, Nader (Inventor); Actis, Paolo (Inventor); Singaram, Bakthan (Inventor); Vilozny, Boaz (Inventor)

2015-01-01

Disclosed are methods and devices for detection of ion migration and binding, utilizing a nanopipette adapted for use in an electrochemical sensing circuit. The nanopipette may be functionalized on its interior bore with metal chelators for binding and sensing metal ions or other specific binding molecules such as boronic acid for binding and sensing glucose. Such a functionalized nanopipette is comprised in an electrical sensor that detects when the nanopipette selectively and reversibly binds ions or small molecules. Also disclosed is a nanoreactor, comprising a nanopipette, for controlling precipitation in aqueous solutions by voltage-directed ion migration, wherein ions may be directed out of the interior bore by a repulsing charge in the bore.

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

USGS Publications Warehouse

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

2001-01-01

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

Experimental study of copper-alkali ion exchange in glass

NASA Astrophysics Data System (ADS)

Gonella, F.; Caccavale, F.; Bogomolova, L. D.; D'Acapito, F.; Quaranta, A.

1998-02-01

Copper-alkali ion exchange was performed by immersing different silicate glasses (soda-lime and BK7) in different molten eutectic salt baths (CuSO4:Na2SO4 and CuSO4:K2SO4). The obtained optical waveguides were characterized by m-lines spectroscopy for the determination of refractive index profiles, and by secondary ion mass spectrometry for the concentration profiles of the ion species involved in the exchange process. The different oxidation states of copper inside the glass structure were studied by electron paramagnetic resonance and x-ray absorption techniques. Interdiffusion copper coefficients were also determined. The Cu-alkali exchange was observed to give rise to local structural rearrangement of the atoms in the glass matrix. The Cu+ ion was found to mainly govern the exchange process, while competition between Cu-Na and K-Na exchanges occurred when a potassium sulfate bath was used. In this case, significant waveguide modal birefringence was observed.

17 CFR 260.7a-3 - Number of copies; filing; signatures; binding.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 17 Commodity and Securities Exchanges 3 2010-04-01 2010-04-01 false Number of copies; filing; signatures; binding. 260.7a-3 Section 260.7a-3 Commodity and Securities Exchanges SECURITIES AND EXCHANGE... § 260.7a-3 Number of copies; filing; signatures; binding. (a) Three copies of the complete application...

17 CFR 260.4c-3 - Number of copies; filing; signatures; binding.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 17 Commodity and Securities Exchanges 3 2010-04-01 2010-04-01 false Number of copies; filing; signatures; binding. 260.4c-3 Section 260.4c-3 Commodity and Securities Exchanges SECURITIES AND EXCHANGE... § 260.4c-3 Number of copies; filing; signatures; binding. (a) Three copies of every application and of...

17 CFR 260.5a-3 - Number of copies; filing; signatures; binding.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 17 Commodity and Securities Exchanges 3 2010-04-01 2010-04-01 false Number of copies; filing; signatures; binding. 260.5a-3 Section 260.5a-3 Commodity and Securities Exchanges SECURITIES AND EXCHANGE... § 260.5a-3 Number of copies; filing; signatures; binding. (a) Three copies of each statement of...

Functional characterization of chitin-binding lectin from Solanum integrifolium containing anti-fungal and insecticidal activities.

PubMed

Chen, Chang-Shan; Chen, Chun-Yi; Ravinath, Divya Malathy; Bungahot, Agustina; Cheng, Chi-Ping; You, Ren-In

2018-01-03

Along with the rapid development of glycomic tools, the study of lectin-carbohydrate interactions has expanded, opening the way for applications in the fields of analytic, diagnostic, and drug delivery. Chitin-binding lectins (CBLs) play roles in immune defense against chitin-containing pathogens. CBLs from species of the Solanaceae family, such as tomato, potato and jimsonweed, display different binding specificities to sugar chains containing poly-N-acetyllactosamine. In this report, CBLs from Solanum integrifolium were isolated by ion exchange chromatography. The fractions showed hemagglutination activity (HA). The recombinant CBL in the 293F cell culture supernatant was able to inhibit the growth of Rhizoctonia solani and Colletotrichum gloeosporioide. Furthermore, the carbohydrate-binding property of CBLs was confirmed with the inhibition of HA. Binding of CBL to Spodoptera frugiperda (sf21) insect cells can partly be inhibited by N-Acetylglucosamine (GlcNAc), which is related to decrease mitochondrial membrane potential of sf21 cells. The results showed that CBL exhibited antifungal properties and inhibited insect cell growth, which is directly correlated to the lectin-carbohydrate interaction. Further identification and characterization of CBLs will help to broaden their scope of application in plant defense and in biomedical applications.

Mechanism of Positive Allosteric Modulators Acting on AMPA Receptors

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

Jin,R.; Clark, S.; Weeks, A.

2005-01-01

Ligand-gated ion channels involved in the modulation of synaptic strength are the AMPA, kainate, and NMDA glutamate receptors. Small molecules that potentiate AMPA receptor currents relieve cognitive deficits caused by neurodegenerative diseases such as Alzheimer's disease and show promise in the treatment of depression. Previously, there has been limited understanding of the molecular mechanism of action for AMPA receptor potentiators. Here we present cocrystal structures of the glutamate receptor GluR2 S1S2 ligand-binding domain in complex with aniracetam [1-(4-methoxybenzoyl)-2-pyrrolidinone] or CX614 (pyrrolidino-1, 3-oxazino benzo-1, 4-dioxan-10-one), two AMPA receptor potentiators that preferentially slow AMPA receptor deactivation. Both potentiators bind within the dimermore » interface of the nondesensitized receptor at a common site located on the twofold axis of molecular symmetry. Importantly, the potentiator binding site is adjacent to the 'hinge' in the ligand-binding core 'clamshell' that undergoes conformational rearrangement after glutamate binding. Using rapid solution exchange, patch-clamp electrophysiology experiments, we show that point mutations of residues that interact with potentiators in the cocrystal disrupt potentiator function. We suggest that the potentiators slow deactivation by stabilizing the clamshell in its closed-cleft, glutamate-bound conformation.« less

Modeling and simulation of anion-exchange membrane chromatography for purification of Sf9 insect cell-derived virus-like particles.

PubMed

Ladd Effio, Christopher; Hahn, Tobias; Seiler, Julia; Oelmeier, Stefan A; Asen, Iris; Silberer, Christine; Villain, Louis; Hubbuch, Jürgen

2016-01-15

Recombinant protein-based virus-like particles (VLPs) are steadily gaining in importance as innovative vaccines against cancer and infectious diseases. Multiple VLPs are currently evaluated in clinical phases requiring a straightforward and rational process design. To date, there is no generic platform process available for the purification of VLPs. In order to accelerate and simplify VLP downstream processing, there is a demand for novel development approaches, technologies, and purification tools. Membrane adsorbers have been identified as promising stationary phases for the processing of bionanoparticles due to their large pore sizes. In this work, we present the potential of two strategies for designing VLP processes following the basic tenet of 'quality by design': High-throughput experimentation and process modeling of an anion-exchange membrane capture step. Automated membrane screenings allowed the identification of optimal VLP binding conditions yielding a dynamic binding capacity of 5.7 mg/mL for human B19 parvovirus-like particles derived from Spodoptera frugiperda Sf9 insect cells. A mechanistic approach was implemented for radial ion-exchange membrane chromatography using the lumped-rate model and stoichiometric displacement model for the in silico optimization of a VLP capture step. For the first time, process modeling enabled the in silico design of a selective, robust and scalable process with minimal experimental effort for a complex VLP feedstock. The optimized anion-exchange membrane chromatography process resulted in a protein purity of 81.5%, a DNA clearance of 99.2%, and a VLP recovery of 59%. Copyright © 2015 Elsevier B.V. All rights reserved.

PARACEST Properties of a Dinuclear Neodymium(III) Complex Bound to DNA or Carbonate

PubMed Central

Nwe, Kido; Andolina, Christopher M.; Huang, Ching-Hui; Morrow, Janet R.

2009-01-01

A dinuclear Nd(III) macrocyclic complex of 1 (1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene) and mononuclear complexes of 1,4,7-tris-1,4,7,10-tetraazacyclododecane 2, and 1,4,7-tris[(N-N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane, 3, are prepared. Complexes of 1 and 2 give rise to a PARACEST (paramagnetic chemical exchange saturation transfer) peak from exchangeable amide protons that resonate approximately 12 ppm downfield from the bulk water proton resonance. The dinuclear Nd(III) complex is promising as a PARACEST contrast agent for MRI applications because it has an optimal pH of 7.5 and the rate constant for amide proton exchange (2700 s−1) is nearly as large as it can be within slow exchange conditions with bulk water. Dinuclear Ln2(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethylphosphate and DNA. The CEST amide peak of Nd2(1) is enhanced by certain DNA sequences that contain hairpin loops, but decreases in the presence of diethyl phosphate or carbonate. Direct excitation luminescence studies of Eu2(1) show that double-stranded and hairpin loop DNA sequences displace one water ligand on each Eu(III) center. DNA displaces carbonate ion despite the low dissociation constant for the Eu2(1) carbonate complex (Kd = 15 µM). Enhancement of the CEST effect of a lanthanide complex by binding to DNA is a promising step toward the preparation of PARACEST agents containing DNA scaffolds. PMID:19555071

PARACEST properties of a dinuclear neodymium(III) complex bound to DNA or carbonate.

PubMed

Nwe, Kido; Andolina, Christopher M; Huang, Ching-Hui; Morrow, Janet R

2009-07-01

A dinuclear Nd(III) macrocyclic complex of 1 (1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene) and mononuclear complexes of 1,4,7-tris-1,4,7,10-tetraazacyclododecane, 2, and 1,4,7-tris[(N-N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane, 3, are prepared. Complexes of 1 and 2 give rise to a PARACEST (paramagnetic chemical exchange saturation transfer) peak from exchangeable amide protons that resonate approximately 12 ppm downfield from the bulk water proton resonance. The dinuclear Nd(III) complex is promising as a PARACEST contrast agent for MRI applications, because it has an optimal pH of 7.5 and the rate constant for amide proton exchange (2700 s(-1)) is nearly as large as it can be within slow exchange conditions with bulk water. Dinuclear Ln(2)(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethyl phosphate, and DNA. The CEST amide peak of Nd(2)(1) is enhanced by certain DNA sequences that contain hairpin loops, but decreases in the presence of diethyl phosphate or carbonate. Direct excitation luminescence studies of Eu(2)(1) show that double-stranded and hairpin-loop DNA sequences displace one water ligand on each Eu(III) center. DNA displaces carbonate ion despite the low dissociation constant for the Eu(2)(1) carbonate complex (K(d) = 15 microM). Enhancement of the CEST effect of a lanthanide complex by binding to DNA is a promising step toward the preparation of PARACEST agents containing DNA scaffolds.

Hydrogeochemical processes controlling changes in fluoride ion concentration within alluvial and hard rock aquifers in a part of a semi-arid region of Northern India

NASA Astrophysics Data System (ADS)

Singh, Priyadarshini; Ashthana, Harshita; Rena, Vikas; Kumar, Pardeep; Mukherjee, Saumitra

2017-04-01

Geochemical signatures from alluvial and hard rock aquifers in a part of Northern India elucidate the chemical processes controlling fluctuations in fluoride ion concentration linked to changes in major ion groundwater chemistry. Majority of samples from the hard rock and the alluvial aquifers for pre-monsoon show both carbonate and silicate weathering, ion exchange, evaporation and rock water interaction as the processes controlling major ion chemistry whereas for post monsoon samples, contribution of silicate weathering and ion exchange process were observed. Evaporative processes causing the increase in Na+ ion concentration in premonsoon enhance the reverse ion exchange processes causing increase in Ca2+ ions which impedes fluorite mineral dissolution in the premonsoon groundwater samples within the study area. Alternately, it is observed that the removal of Ca2+ ion from solution plays a key role in increase in fluorite mineral dissolution despite its saturation in groundwater in the postmonsoon samples. Also, ion exchange process on clay surfaces is more pronounced in the postmonsoon samples leading to the uptake of Ca2+ ion upon release of Na+ and K+ ion in solution. Ca2+ ion concentration is inversely correlated with F- ion concentration in both the aquifers in the postmonsoon season validating the role of calcite precipitation as a major reason for the fluoride ion increase. Moreover, increase in silicate weathering in the postmonsoon samples leads to increase in clay particles acting as suitable sites for ion exchange enhancing Ca2+ removal from groundwater. Cationic dominance of Na+ ion in the post monsoon samples also validates the occurrence of this process. Collectively, these processes set the ideal conditions for increase in the fluoride ion concentration particularly in the alluvium aquifer waters in the postmonsoon season Keywords: geochemistry, ion-exchange, rock-water interaction, mineral dissolution, weathering.

Preparation and characterization of (St-DVB-MAA) ion exchange resins

NASA Astrophysics Data System (ADS)

Jiang, Shanquan; Sun, Xiangwei; Ling, Lixing; Wang, Shumin; Wu, Wufeng; Cheng, Shihong; Hu, Yue; Zhong, Chunyan

2017-08-01

In this paper, used polyvinyl alcohol as dispersing agent, Benzoyl peroxide as initiator of polymerization, Divinyl benzene as cross-linking agent, Styrene and 2-Methylpropenoic acid as monomer, ion exchange resin (copolymer of St-DVB-MAA)were prepared by suspension polymerization on 80°C. The structures, components and properties of the prepared composite micro gels were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA). The experiment of ion exchange was conducted by resin to deal with copper ions in the solution. The result showed that performance of the ion exchange capacity was excellent, which impacted by pH.

Internal gas and liquid distributor for electrodeionization device

DOEpatents

Lin, YuPo J.; Snyder, Seth W.; Henry, Michael P.; Datta, Saurav

2016-05-17

The present invention provides a resin-wafer electrodeionization (RW-EDI) apparatus including cathode and anode electrodes separated by a plurality of porous solid ion exchange resin wafers, which when in use are filled with an aqueous fluid. The apparatus includes one or more wafers comprising a basic ion exchange medium, and preferably includes one or more wafers comprising an acidic ion exchange medium. The wafers are separated from one another by ion exchange membranes. The gas and aqueous fluid are introduced into each basic wafer via a porous gas distributor which disperses the gas as micro-sized bubbles laterally throughout the distributor before entering the wafer. The fluid within the acidic and/or basic ion exchange wafers preferably includes, or is in contact with, a carbonic anhydrase (CA) enzyme or inorganic catalyst to facilitate conversion of bicarbonate ion to carbon dioxide within the acidic medium.

Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.

PubMed

Kumar, Prashant; Lau, Pei Wen; Kale, Sandeep; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet; Lali, Arvind

2014-08-22

Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Mineral Separation in a CELSS by Ion-exchange Chromatography

NASA Technical Reports Server (NTRS)

Ballou, E. V.; Spitze, L. A.; Wong, F. W.; Wydeven, T.; Johnson, C. C.

1982-01-01

Operational parameters pertinent to ion exchange chromatography separation were identified. The experiments were performed with 9 mm diameter ion exchange columns and conventional column accessories. The cation separation beds were packed with AG 50W-X2 strong acid cation exchange resin in H(+) form and 200-400 dry mesh particle size. The stripper beds used in some experiments were packed with AG 1-XB strong base cation exchange resin in OH(-) form and 200-400 dry mesh particle size.

Dynamic Multi-Component Covalent Assembly for the Reversible Binding of Secondary Alcohols and Chirality Sensing

PubMed Central

You, Lei; Berman, Jeffrey S.; Anslyn, Eric V.

2011-01-01

Reversible covalent bonding is often employed for the creation of novel supramolecular structures, multi-component assemblies, and sensing ensembles. In spite of remarkable success of dynamic covalent systems, the reversible binding of a mono-alcohol with high strength is challenging. Here we show that a strategy of carbonyl activation and hemiaminal ether stabilization can be embodied in a four-component reversible assembly that creates a tetradentate ligand and incorporates secondary alcohols with exceptionally high affinity. Evidence is presented that the intermediate leading to binding and exchange of alcohols is an iminium ion. Further, to demonstrate the use of this assembly process we explored chirality sensing and enantiomeric excess determinations. An induced twist in the ligand by a chiral mono-ol results in large Cotton effects in the circular dichroism spectra indicative of the alcohol’s handedness. The strategy revealed in this study should prove broadly applicable for the incorporation of alcohols into supramolecular architecture construction. PMID:22109274

Overexpression, purification and crystallization of a choline-binding protein CbpI from Streptococcus pneumoniae

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

Paterson, Neil G., E-mail: neison@chem.gla.ac.uk; Riboldi-Tunicliffe, Alan; Mitchell, Timothy J.

2006-07-01

The choline-binding protein CbpI from S. pneumoniae has been purified and crystallized and diffraction data have been collected to 3.5 Å resolution. The choline-binding protein CbpI from Streptococcus pneumoniae is a 23.4 kDa protein with no known function. The protein has been successfully purified initially using Ni–NTA chromatography and to homogeneity using Q-Sepharose ion-exchange resin as an affinity column. CbpI was crystallized using PEG 3350 as a precipitant and X-ray crystallographic analysis showed that the crystals belonged to the tetragonal space group P4, with unit-cell parameters a = b = 83.31, c = 80.29 Å, α = β = γmore » = 90°. The crystal contains two molecules in the asymmetric unit with a solvent content of 55.7% (V{sub M} = 2.77 Å{sup 3} Da{sup −1}) and shows a diffraction limit of 3.5 Å.« less

The Award for the Development of Ion Exchange Systems for Food Processing

NASA Astrophysics Data System (ADS)

Yao, Eiya

In the food industry, ion exchange resins have been used not only for water treatment, but also for the purification of foodstuff itself. Here I will introduce some topics in the development and improvement of ion exchange systems for food proccssing that I have worked on.

ION-EXCHANGE METHOD FOR SEPARATING RADIUM FROM RADIUM-BARIUM MIXTURES

DOEpatents

Fuentevilla, M.E.

1959-06-30

An improved process is presented for separating radium from an aqueous feed solution containing radium and barium values and a complexing agent for these metals. In this process a feed solutlon containing radium and barium ions and a complexing agent for said ions ls cycled through an exchange zone in resins. The radiumenriched resin is then stripped of radium values to form a regeneration liquid, a portion of which is collected as an enriched product, the remaining portion being recycled to the exchange zone to further enrich the ion exchange resin in radium.

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf])

NASA Astrophysics Data System (ADS)

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J.; Cisneros, G. Andrés

2018-01-01

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO4]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf]- anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf]).

PubMed

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J; Cisneros, G Andrés

2018-01-14

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17 O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO 4 ]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf] - anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

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

NMR Chemical Exchange as a Probe for Ligand-Binding Kinetics in a Theophylline-Binding RNA Aptamer

PubMed Central

Latham, Michael P.; Zimmermann, Grant R.; Pardi, Arthur

2009-01-01

The apparent on- and off-rate constants for theophylline binding to its RNA aptamer in the absence of Mg2+ were determined here by 2D 1H-1H NMR ZZ-exchange spectroscopy. Analysis of the build-up rate of the exchange cross peaks for several base-paired imino protons in the RNA yielded an apparent kon of 600 M-1 s-1. This small apparent kon results from the free RNA existing as a dynamic equilibrium of inactive states rapidly interconverting with a low population of active species. The data here indicate that the RNA aptamer employs a conformational selection mechanism for binding theophylline in the absence of Mg2+. The kinetic data here also explain a very unusual property of this RNA-theophylline system, slow exchange on the NMR chemical shift timescale for a weak-binding complex. To our knowledge, it is unprecedented to have such a weak binding complex (Kd ≈ 3.0 mM at 15 °C) show slow exchange on the NMR chemical shift timescale, but the results clearly demonstrate that slow exchange and weak binding are readily rationalized by a small kon. Comparisons with other ligand-receptor interactions are presented. PMID:19317486

Enhancing recovery of recombinant hepatitis B surface antigen in lab-scale and large-scale anion-exchange chromatography by optimizing the conductivity of buffers.

PubMed

Mojarrad Moghanloo, Gol Mohammad; Khatami, Maryam; Javidanbardan, Amin; Hosseini, Seyed Nezamedin

2018-01-01

In biopharmaceutical science, ion-exchange chromatography (IEC) is a well-known purification technique to separate the impurities such as host cell proteins from recombinant proteins. However, IEC is one of the limiting steps in the purification process of recombinant hepatitis B surface antigen (rHBsAg), due to its low recovery rate (<50%). In the current study, we hypothesized that ionic strengths of IEC buffers are easy-to-control parameters which can play a major role in optimizing the process and increasing the recovery. Thus, we investigated the effects of ionic strengths of buffers on rHBsAg recovery via adjusting Tris-HCl and NaCl concentrations. Increasing the conductivity of equilibration (Eq.), washing (Wash.) and elution (Elut.) buffers from their initial values of 1.6 mS/cm, 1.6 mS/cm, and 7.0 mS/cm to 1.6 mS/cm, 7 mS/cm and 50 mS/cm, respectively yielded an average recovery rate of 82% in both lab-scale and large-scale weak anion-exchange chromatography without any harsh effect on the purity percentage of rHBsAg. The recovery enhancement via increasing the conductivity of Eq. and Wash. buffers can be explained by their roles in reducing the binding strength and aggregation of retained particles in the column. Moreover, further increase in the salt concentration of Elut. Buffer could substantially promote the ion exchange process and the elution of retained rHBsAg. Copyright © 2017 Elsevier Inc. All rights reserved.

High-throughput screening of chromatographic separations: IV. Ion-exchange.

PubMed

Kelley, Brian D; Switzer, Mary; Bastek, Patrick; Kramarczyk, Jack F; Molnar, Kathleen; Yu, Tianning; Coffman, Jon

2008-08-01

Ion-exchange (IEX) chromatography steps are widely applied in protein purification processes because of their high capacity, selectivity, robust operation, and well-understood principles. Optimization of IEX steps typically involves resin screening and selection of the pH and counterion concentrations of the load, wash, and elution steps. Time and material constraints associated with operating laboratory columns often preclude evaluating more than 20-50 conditions during early stages of process development. To overcome this limitation, a high-throughput screening (HTS) system employing a robotic liquid handling system and 96-well filterplates was used to evaluate various operating conditions for IEX steps for monoclonal antibody (mAb) purification. A screening study for an adsorptive cation-exchange step evaluated eight different resins. Sodium chloride concentrations defining the operating boundaries of product binding and elution were established at four different pH levels for each resin. Adsorption isotherms were measured for 24 different pH and salt combinations for a single resin. An anion-exchange flowthrough step was then examined, generating data on mAb adsorption for 48 different combinations of pH and counterion concentration for three different resins. The mAb partition coefficients were calculated and used to estimate the characteristic charge of the resin-protein interaction. Host cell protein and residual Protein A impurity levels were also measured, providing information on selectivity within this operating window. The HTS system shows promise for accelerating process development of IEX steps, enabling rapid acquisition of large datasets addressing the performance of the chromatography step under many different operating conditions. (c) 2008 Wiley Periodicals, Inc.

Relating saturation capacity to charge density in strong cation exchangers.

PubMed

Steinebach, Fabian; Coquebert de Neuville, Bertrand; Morbidelli, Massimo

2017-07-21

In this work the relation between physical and chemical resin characteristics and the total amount of adsorbed protein (saturation capacity) for ion-exchange resins is discussed. Eleven different packing materials with a sulfo-functionalization and one multimodal resin were analyzed in terms of their porosity, pore size distribution, ligand density and binding capacity. By specifying the ligand density and binding capacity by the total and accessible surface area, two different groups of resins were identified: Below a ligand density of approx. 2.5μmol/m 2 area the ligand density controls the saturation capacity, while above this limit the accessible surface area becomes the limiting factor. This results in a maximum protein uptake of around 2.5mg/m 2 of accessible surface area. The obtained results allow estimating the saturation capacity from independent resin characteristics like the saturation capacity mainly depends on "library data" such as the accessible and total surface area and the charge density. Hence these results give an insight into the fundamentals of protein adsorption and help to find suitable resins, thus limiting the experimental effort in early process development stages. Copyright © 2017 Elsevier B.V. All rights reserved.

Mechanism of Metal Ion Activation of the Diphtheria Toxin Repressor DtxR

NASA Astrophysics Data System (ADS)

D'Aquino, J. Alejandro; Ringe, Dagmar

2006-08-01

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

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

In Situ Tracking Kinetic Pathways of Li+/Na+ Substitution during Ion-Exchange Synthesis of LixNa1.5-xVOPO4F0.5.

PubMed

Park, Young-Uk; Bai, Jianming; Wang, Liping; Yoon, Gabin; Zhang, Wei; Kim, Hyungsub; Lee, Seongsu; Kim, Sung-Wook; Looney, J Patrick; Kang, Kisuk; Wang, Feng

2017-09-13

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li + /Na + substitution during solvothermal ion-exchange synthesis of Li x Na 1.5-x VOPO 4 F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li + , leading to peculiar Na + /Li + /vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.

The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences.

PubMed

Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

2014-01-01

Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug-fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug-fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid.

The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences

PubMed Central

Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

2014-01-01

Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug–fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug–fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid. PMID:25114504

A scale of metal ion binding strengths correlating with ionic charge, Pauling electronegativity, toxicity, and other physiological effects.

PubMed

Kinraide, Thomas B; Yermiyahu, Uri

2007-09-01

Equilibrium constants for binding to plant plasma membranes have been reported for several metal ions, based upon adsorption studies and zeta-potential measurements. LogK values for the ions are these: Al(3+), 4.30; La(3+), 3.34; Cu(2+), 2.60; Ca(2+) and Mg(2+), 1.48; Na(+) and K(+), 0 M(-1). These values correlate well with logK values for ion binding to many organic and inorganic ligands. LogK values for metal ion binding to 12 ligands were normalized and averaged to produce a scale for the binding of 49 ions. The scale correlates well with the values presented above (R(2)=0.998) and with ion binding to cell walls and other biomass. The scale is closely related to the charge (Z) and Pauling electronegativity (PE) of 48 ions (all but Hg(2+)); R(2)=0.969 for the equation (Scale values)=-1.68+Z(1.22+0.444PE). Minimum rhizotoxicity of metal ions appears to be determined by binding strengths: log a(PM,M)=1.60-2.41exp[0.238(Scale values)] determines the value of ion activities at the plasma membrane surface (a(PM,M)) that will ensure inhibition of root elongation. Additional toxicity appears to be related to softness, accounting for the great toxicity of Ag(+), for example. These binding-strength values correlate with additional physiological effects and are suitable for the computation of cell-surface electrical potentials.

Ion-exchange controls the kinetics of deswelling of polyelectrolyte microgels in solutions of oppositely charged surfactant.

PubMed

Nilsson, Peter; Hansson, Per

2005-12-22

The kinetics of deswelling of sodium polyacrylate microgels (radius 30-140 microm) in aqueous solutions of dodecyltrimethylammonium bromide is investigated by means of micropipet-assisted light microscopy. The purpose of the study is to test a recent model (J. Phys. Chem. B 2003, 107, 9203) proposing that the rate of the volume change is controlled by the transport of surfactant from the solution to the gel core (ion exchange) via the surfactant-rich surface phase appearing in the gel during the volume transition. Equilibrium swelling characteristics of the gel network in surfactant-free solutions and with various amounts of surfactant present are presented and discussed with reference to related systems. A relationship between gel volume and degree of surfactant binding is determined and used in theoretical predictions of the deswelling kinetics. Experimental data for single gel beads observed during deswelling under conditions of forced convection are presented and compared with model calculations. It is demonstrated that the dependences of the kinetics on initial gel size, the surfactant concentration in the solution, and the liquid flow rate are well accounted for by the model. It is concluded that the deswelling rates of the studied gels are strongly influenced by the mass transport of surfactant between gel and solution (stagnant layer diffusion), but only to a minor extent by the transport through the surface phase. The results indicate that, during the volume transition, swelling equilibrium (network relaxation/transport of water) is established on a relatively short time scale and, therefore, can be treated as independent of the ion-exchange kinetics. Theoretical aspects of the kinetics and mechanisms of surfactant transport through the surface phase are discussed.

Studying ion exchange in solution and at biological membranes by FCS.

PubMed

Widengren, Jerker

2013-01-01

By FCS, a wide range of processes can be studied, covering time ranges from subnanoseconds to seconds. In principle, any process at equilibrium conditions can be measured, which reflects itself by a change in the detected fluorescence intensity. In this review, it is described how FCS and variants thereof can be used to monitor ion exchange, in solution and along biological membranes. Analyzing fluorescence fluctuations of ion-sensitive fluorophores by FCS offers selective advantages over other techniques for measuring local ion concentrations, and, in particular, for studying exchange kinetics of ions on a very local scale. This opens for several areas of application. The FCS approach was used to investigate fundamental aspects of proton exchange at and along biological membranes. The protonation relaxation rate, as measured by FCS for a pH-sensitive dye, can also provide information about local accessibility/interaction of a particular labeling site and conformational states of biomolecules, in a similar fashion as in a fluorescence quenching experiment. The same FCS concept can also be applied to ion exchange studies using other ion-sensitive fluorophores, and by use of dyes sensitive to other ambient conditions the concept can be extended also beyond ion exchange studies. Copyright © 2013 Elsevier Inc. All rights reserved.

Samarium (III) Selective Membrane Sensor Based on Tin (IV) Boratophosphate

PubMed Central

Mittal, Susheel K.; Sharma, Harish Kumar; Kumar, Ashok S. K.

2004-01-01

A number of Sm (III) selective membranes of varying compositions using tin (IV) boratophosphate as electroactive material were prepared. Polyvinyl chloride, polystyrene and epoxy resin were used as binding materials. Membrane having composition of 40% exchanger and 60% epoxy resin exhibited best performance. This membrane worked well over a wide concentration range of 1×10-5M to 1×10-1 M of samarium ions with a Super-Nernstian slope of 40 mV/decade. It has a fast response time of less than 10 seconds and can be used for at least six months without any considerable divergence in potentials. The proposed sensor revealed good selectivities with respect to alkali, alkaline earth, some transition and rare earth metal ions and can be used in the pH range of 4.0-10.0. It was used as an indicator electrode in the potentiometric titration of Sm (III) ions against EDTA. Effect of internal solution was studied and the electrode was successfully used in non-aqueous media, too.

Effective removal of cadmium ions from a simulated gastrointestinal fluid by Lentinus edodes.

PubMed

Qiao, Xin; Huang, Wen; Bian, Yinbing

2014-12-01

Lentinus edodes, a functional food, was evaluated as a potential antidote for adsorption/removal of cadmium ion from simulated gastrointestinal fluids. An adsorption/removal capacity of 65.12 mg/g was achieved by L. edodes in solutions with a pH ranging from 2.5 to 6.0, while little if any adsorption was observed in solutions with a pH under 2.5. In solutions with pH 6.0, 84% of the cadmium adsorption by L. edodes occurred in the first minute. Scanning electronic microscopic examination showed that the cell wall polysaccharides of L. edodes provided a rough sponge-like surface for effective cadmium adsorption. FTIR indicated that the carboxyl, hydroxyl and -NH groups of the cell wall polysaccharides and proteins were the primary functional groups that chemically bind with cadmium ions. The energy dispersive spectrometry further revealed that cation exchange might be attributed to cadmium biosorption. These results suggested that L. edodes was effective for cadmium detoxication, especially in low concentration.

Ion-exchange and iontophoresis-controlled delivery of apomorphine.

PubMed

Malinovskaja, Kristina; Laaksonen, Timo; Kontturi, Kyösti; Hirvonen, Jouni

2013-04-01

The objective of this study was to test a drug delivery system that combines iontophoresis and cation-exchange fibers as drug matrices for the controlled transdermal delivery of antiparkinsonian drug apomorphine. Positively charged apomorphine was bound to the ion-exchange groups of the cation-exchange fibers until it was released by mobile counter-ions in the external solution. The release of the drug was controlled by modifying either the fiber type or the ionic composition of the external solution. Due to high affinity of apomorphine toward the ion-exchanger, a clear reduction in the in vitro transdermal fluxes from the fibers was observed compared to the respective fluxes from apomorphine solutions. Changes in the ionic composition of the donor formulations affected both the release and iontophoretic flux of the drug. Upon the application of higher co-ion concentrations or co-ions of higher valence in the donor formulation, the release from the fibers was enhanced, but the iontophoretic steady-state flux was decreased. Overall, the present study has demonstrated a promising approach using ion-exchange fibers for controlling the release and iontophoretic transdermal delivery of apomorphine. Copyright © 2012 Elsevier B.V. All rights reserved.

Extraction of mercury from groundwater using immobilized algae.

PubMed

Barkley, N P

1991-10-01

Bio-Recovery Systems, Inc. conducted a project under the Emerging Technology portion of the United States Environmental Protection Agency's (EPAs) Superfund Innovative Technology Evaluation (SITE) Program to evaluate the ability of immobilized algae to adsorb mercury from contaminated groundwater in laboratory studies and pilot-scale field tests. Algal biomass was incorporated in a permeable polymeric matrix. The product, AlgaSORB, packed into adsorption columns, exhibited excellent flow characteristics, and functioned as a "biological" ion exchange resin. A sequence of eleven laboratory tests demonstrated the ability of this product to adsorb mercury from groundwater that contained high levels of total dissolved solids and hard water components. However, use of a single AlgaSORB preparation yielded nonrepeatable results with samples collected at different times of the year. The strategy of sequentially extracting the groundwater through two columns containing different preparations of AlgaSORB was developed and proved successful in laboratory and pilot-scale field tests. Field test results indicate that AlgaSORB could be economically competitive with ion exchange resins for removal of mercury, with the advantage that hardness and other dissolved solids do not appear to compete with heavy metals for binding capacity.

The application and properties of composite sorbents of inorganic ion exchangers and polyacrylonitrile binding matrix.

PubMed

Nilchi, A; Khanchi, A; Atashi, H; Bagheri, A; Nematollahi, L

2006-10-11

A description is given of the preparation and properties of potassium hexacyanocobalt (II) ferrate (II) (KCFC) and the composite, potassium hexacyanocobalt (II) ferrate (II)-polyacrylonitrile (KCFC-PAN). The materials were dried at high temperatures and characterized by chemical analysis, scanning electron microscope, X-ray diffraction, inductively coupled plasma and infrared. The ion exchange of alkaline earth metals and molybdenum on a nonstoichiometric compound K(2)[CoFe(CN)(6)] and its PAN based absorber was examined by batch methods. The adsorption of molybdenum from aqueous solutions on KCFC-PAN was investigated and optimized as a function of equilibration time and pH. The materials which were dried at optimum high temperature of 110 degrees C were found to be stable in water, dilute acids, alkaline solutions and relatively high temperature. The distribution coefficient values K(d) for alkaline earth metals, followed the same trend of increase for both sets of absorbers studied, i.e. Ba(2+)>Sr(2+)>Ca(2+)>Mg(2+), which closely resembles to the order of the size of the hydrated cations. However, the K(d) values show a significant increase for PAN based absorbers in comparison to KCFC absorbers.

Recent developments on ion-exchange membranes and electro-membrane processes.

PubMed

Nagarale, R K; Gohil, G S; Shahi, Vinod K

2006-02-28

Rapid growth of chemical and biotechnology in diversified areas fuels the demand for the need of reliable green technologies for the down stream processes, which include separation, purification and isolation of the molecules. Ion-exchange membrane technologies are non-hazardous in nature and being widely used not only for separation and purification but their application also extended towards energy conversion devices, storage batteries and sensors etc. Now there is a quite demand for the ion-exchange membrane with better selectivities, less electrical resistance, high chemical, mechanical and thermal stability as well as good durability. A lot of work has been done for the development of these types of ion-exchange membranes during the past twenty-five years. Herein we have reviewed the preparation of various types of ion-exchange membranes, their characterization and applications for different electro-membrane processes. Primary attention has been given to the chemical route used for the membrane preparation. Several general reactions used for the preparation of ion-exchange membranes were described. Methodologies used for the characterization of these membranes and their applications were also reviewed for the benefit of readers, so that they can get all information about the ion-exchange membranes at one platform. Although there are large number of reports available regarding preparations and applications of ion-exchange membranes more emphasis were predicted for the usefulness of these membranes or processes for solving certain type of industrial or social problems. More efforts are needed to bring many products or processes to pilot scale and extent their applications.

Groundwater transport of strontium 90 in a glacial outwash environment

USGS Publications Warehouse

Kipp, Kenneth L.; Stollenwerk, Kenneth G.; Grove, David B.

1986-01-01

As part of the investigation of groundwater contamination at a uranium-scrap recovery plant at Wood River Junction, Rhode Island, laboratory experiments led to the development of a model for predicting the transport of strontium 90 in glacial outwash sediments based on an approximate mechanism for ion exchange. The multicomponent system was simplified to two components by regarding all exchangeable cations other than strontium 90 as a single component. The binary ion-exchange parameter was a function of the variable, total ion concentration. A one-dimensional solute transport model was formulated to evaluate the time necessary for natural groundwater flow to remove the strontium 90 contamination plume from the groundwater system to the Pawcatuck River. The finite difference transport equations were solved sequentially for total ion concentrations, then strontium 90 concentrations. Clay-free quartz and feldspar sands at the study site have little potential for strontium 90 sorption, and high calcium, magnesium, and sodium concentrations compete for the few ion exchange sites. As the total ion concentration plume moves out of the system, ion exchange of strontium 90 increases, reducing the strontium 90 concentration in the groundwater. Cleanout times predicted using the binary ion exchange mechanism were about two thirds of those predicted using a constant distribution coefficient. It is suggested that this type of model can simulate solute transport more realistically in many groundwater systems where the total ion concentration is not constant.

The influence of cation exchange treatment on the final characteristics of red wines.

PubMed

Lasanta, Cristina; Caro, Ildefonso; Pérez, Luis

2013-06-01

Ion exchange technology has been applied to adjust the pH of red wine and improve its tartaric and oxidative stability. Ion exchange appears to be a useful technique to achieve these objectives. Regarding the effect of ion exchange on organoleptic characteristics and the quality of the obtained wines, a slight decrease in both anthocyanin and tannin contents was observed along with a small drop in the aromatic content. However, the treated wines had lower hue and higher colour intensity and gave better punctuations in the sensory evaluation. These results confirm that ion exchange is an interesting technique for application in red winemaking. Copyright © 2012 Elsevier Ltd. All rights reserved.

Titania bound sodium titanate ion exchanger

DOEpatents

DeFilippi, Irene C. G.; Yates, Stephen Frederic; Shen, Jian-Kun; Gaita, Romulus; Sedath, Robert Henry; Seminara, Gary Joseph; Straszewski, Michael Peter; Anderson, David Joseph

1999-03-23

This invention is method for preparing a titania bound ion exchange composition comprising admixing crystalline sodium titanate and a hydrolyzable titanium compound and, thereafter drying the titania bound crystalline sodium titanate and subjecting the dried titania bound ion exchange composition to optional compaction and calcination steps to improve the physical strength of the titania bound composition.

Mechanical-structural investigation of chemical strengthening aluminosilicate glass through introducing phosphorus pentoxide

NASA Astrophysics Data System (ADS)

Zeng, Huidan; Wang, Ling; Ye, Feng; Yang, Bin; Chen, Jianding; Chen, Guorong; Sun, Luyi

2016-11-01

Chemical strengthening of aluminosilicate glasses through K+-Na+ ion exchange has attracted tremendous attentions because of the accelerating demand for high strength and damage resistance glasses. However, a paramount challenge still exists to fabricate glasses with a higher strength and greater depth of ion-exchange layer. Herein, aluminosilicate glasses with different contents of P2O5 were prepared and the influence of P2O5 on the increased compressive stress and depth of ion-exchange layer was investigated by micro-Raman technique. It was noticed that the hardness, compressive stress, as well as the depth of ion-exchange layer substantially increased with an increasing concentration of P2O5 varied from 1 to 7 mol%. The obtained micro-Raman spectra confirmed the formation of relatively depolymerized silicate anions that accelerated the ion exchange. Phosphorus containing aluminosilicate glasses with a lower polymerization degree exhibited a higher strength and deeper depth of ion-exchange layer, which suggests that the phosphorus containing aluminosilicate glasses have promising applications in flat panel displays, windshields, and wafer sealing substrates.

Experimental findings on actinide recovery utilizing oxidation by peroxydisulfate followed by ion exchange: Fuel cycle research & development

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

Hobbs, D. T.; Shehee, T. C.

2015-08-31

Our research seeks to determine if inorganic ion-exchange materials can be exploited to provide effective minor actinide (Am, Cm) separation from lanthanides. Previous work has established that a number of inorganic and UMOF ion-exchange materials exhibit varying affinities for actinides and lanthanides, which may be exploited for effective separations. During FY15, experimental work focused on investigating methods to oxidize americium in dilute nitric and perchloric acid with subsequent ion-exchange performance measurements of ion exchangers with the oxidized americium in dilute nitric acid. Ion-exchange materials tested included a variety of alkali titanates. Americium oxidation testing sought to determine the influence thatmore » other redox active components may have on the oxidation of Am III. Experimental findings indicated that Ce III, Np V, and Ru II are oxidized by peroxydisulfate, but there are no indications that the presence of Ce III, Np V, and Ru II affected the rate or extent of americium oxidation at the concentrations of peroxydisulfate being used.« less

Transport, charge exchange and loss of energetic heavy ions in the earth's radiation belts - Applicability and limitations of theory

NASA Technical Reports Server (NTRS)

Spjeldvik, W. N.

1981-01-01

Computer simulations of processes which control the relative abundances of ions in the trapping regions of geospace are compared with observations from discriminating ion detectors. Energy losses due to Coulomb collisions between ions and exospheric neutrals are considered, along with charge exchange losses and internal charge exchanges. The time evolution of energetic ion fluxes of equatorially mirroring ions under radial diffusion is modelled to include geomagnetic and geoelectric fluctutations. Limits to the validity of diffusion transport theory are discussed, and the simulation is noted to contain provisions for six ionic charge states and the source effect on the radiation belt oxygen ion distributions. Comparisons are made with ion flux data gathered on Explorer 45 and ISEE-1 spacecraft and results indicate that internal charge exchanges cause the radiation belt ion charge state to be independent of source charge rate characteristics, and relative charge state distribution is independent of the radially diffusive transport rate below the charge state redistribution zone.

Identification of Mutations in SLC24A4, Encoding a Potassium-Dependent Sodium/Calcium Exchanger, as a Cause of Amelogenesis Imperfecta

PubMed Central

Parry, David A.; Poulter, James A.; Logan, Clare V.; Brookes, Steven J.; Jafri, Hussain; Ferguson, Christopher H.; Anwari, Babra M.; Rashid, Yasmin; Zhao, Haiqing; Johnson, Colin A.; Inglehearn, Chris F.; Mighell, Alan J.

2013-01-01

A combination of autozygosity mapping and exome sequencing identified a null mutation in SLC24A4 in a family with hypomineralized amelogenesis imperfect a (AI), a condition in which tooth enamel formation fails. SLC24A4 encodes a calcium transporter upregulated in ameloblasts during the maturation stage of amelogenesis. Screening of further AI families identified a missense mutation in the ion-binding site of SLC24A4 expected to severely diminish or abolish the ion transport function of the protein. Furthermore, examination of previously generated Slc24a4 null mice identified a severe defect in tooth enamel that reflects impaired amelogenesis. These findings support a key role for SLC24A4 in calcium transport during enamel formation. PMID:23375655

Protein destabilisation in ionic liquids: the role of preferential interactions in denaturation.

PubMed

Figueiredo, Angelo Miguel; Sardinha, Joao; Moore, Geoffrey R; Cabrita, Eurico J

2013-12-07

The preferential binding of anions and cations in aqueous solutions of the ionic liquids (ILs) 1-butyl-3-methylimidazolium ([C4mim](+)) and 1-ethyl-3-methylimidazolium ([C2mim](+)) chloride and dicyanamide (dca(-)) with the small alpha-helical protein Im7 was investigated using a combination of differential scanning calorimetry, NMR spectroscopy and molecular dynamics (MD) simulations. Our results show that direct ion interactions are crucial to understand the effects of ILs on the stability of proteins and that an anion effect is dominant. We show that the binding of weakly hydrated anions to positively charged or polar residues leads to the partial dehydration of the backbone groups, and is critical to control stability, explaining why dca(-) is more denaturing than Cl(-). Direct cation-protein interactions also mediate stability; cation size and hydrophobicity are relevant to account for destabilisation as shown by the effect of [C4mim](+) compared to [C2mim](+). The specificity in the interaction of IL ions with protein residues established by weak favourable interactions is confirmed by NMR chemical shift perturbation, amide hydrogen exchange data and MD simulations. Differences in specificity are due to the balance of interaction established between ion pairs and ion-solvent that determine the type of residues affected. When the interaction of both cation and anion with the protein is strong the net result is similar to a non-specific interaction, leading ultimately to unfolding. Since the nature of the ions is a determinant of the level of interaction with the protein towards denaturation or stabilisation, ILs offer a unique possibility to modulate protein stabilisation or even folding events.

Decontamination of spent ion-exchangers contaminated with cesium radionuclides using resorcinol-formaldehyde resins.

PubMed

Palamarchuk, Marina; Egorin, Andrey; Tokar, Eduard; Tutov, Mikhail; Marinin, Dmitry; Avramenko, Valentin

2017-01-05

The origin of the emergence of radioactive contamination not removable in the process of acid-base regeneration of ion-exchange resins used in treatment of technological media and liquid radioactive waste streams has been determined. It has been shown that a majority of cesium radionuclides not removable by regeneration are bound to inorganic deposits on the surface and inside the ion-exchange resin beads. The nature of the above inorganic inclusions has been investigated by means of the methods of electron microscopy, IR spectrometry and X-ray diffraction. The method of decontamination of spent ion-exchange resins and zeolites contaminated with cesium radionuclides employing selective resorcinol-formaldehyde resins has been suggested. Good prospects of such an approach in deep decontamination of spent ion exchangers have been demonstrated. Copyright © 2016 Elsevier B.V. All rights reserved.

High resolution main-ion charge exchange spectroscopy in the DIII-D H-mode pedestal.

PubMed

Grierson, B A; Burrell, K H; Chrystal, C; Groebner, R J; Haskey, S R; Kaplan, D H

2016-11-01

A new high spatial resolution main-ion (deuterium) charge-exchange spectroscopy system covering the tokamak boundary region has been installed on the DIII-D tokamak. Sixteen new edge main-ion charge-exchange recombination sightlines have been combined with nineteen impurity sightlines in a tangentially viewing geometry on the DIII-D midplane with an interleaving design that achieves 8 mm inter-channel radial resolution for detailed profiles of main-ion temperature, velocity, charge-exchange emission, and neutral beam emission. At the plasma boundary, we find a strong enhancement of the main-ion toroidal velocity that exceeds the impurity velocity by a factor of two. The unique combination of experimentally measured main-ion and impurity profiles provides a powerful quasi-neutrality constraint for reconstruction of tokamak H-mode pedestals.

Humic Acid Isolations from Lignite by Ion Exchange Method

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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.

Sequence-specific binding of counterions to B-DNA

PubMed Central

Denisov, Vladimir P.; Halle, Bertil

2000-01-01

Recent studies by x-ray crystallography, NMR, and molecular simulations have suggested that monovalent counterions can penetrate deeply into the minor groove of B form DNA. Such groove-bound ions potentially could play an important role in AT-tract bending and groove narrowing, thereby modulating DNA function in vivo. To address this issue, we report here 23Na magnetic relaxation dispersion measurements on oligonucleotides, including difference experiments with the groove-binding drug netropsin. The exquisite sensitivity of this method to ions in long-lived and intimate association with DNA allows us to detect sequence-specific sodium ion binding in the minor groove AT tract of three B-DNA dodecamers. The sodium ion occupancy is only a few percent, however, and therefore is not likely to contribute importantly to the ensemble of B-DNA structures. We also report results of ion competition experiments, indicating that potassium, rubidium, and cesium ions bind to the minor groove with similarly weak affinity as sodium ions, whereas ammonium ion binding is somewhat stronger. The present findings are discussed in the light of previous NMR and diffraction studies of sequence-specific counterion binding to DNA. PMID:10639130

Antifungal activities against toxigenic Fusarium specie and deoxynivalenol adsorption capacity of ion-exchanged zeolites.

PubMed

Savi, Geovana D; Cardoso, William A; Furtado, Bianca G; Bortolotto, Tiago; Zanoni, Elton T; Scussel, Rahisa; Rezende, Lucas F; Machado-de-Ávila, Ricardo A; Montedo, Oscar R K; Angioletto, Elidio

2018-03-04

Zeolites are often used as adsorbents materials and their loaded cations can be exchanged with metal ions in order to add antimicrobial properties. The aim of this study was to use the 4A zeolite and its derived ion-exchanged forms with Zn 2+ , Li + , Cu 2+ and Co 2+ in order to evaluate their antifungal properties against Fusarium graminearum, including their capacity in terms of metal ions release, conidia germination and the deoxynivalenol (DON) adsorption. The zeolites ion-exchanged with Li + , Cu 2+ , and Co 2+ showed an excellent antifungal activity against F. graminearum, using an agar diffusion method, with a zone of inhibition observed around the samples of 45.3 ± 0.6 mm, 25.7 ± 1.5 mm, and 24.7 ± 0.6 mm, respectively. Similar results using agar dilution method were found showing significant growth inhibition of F. graminearum for ion-exchanged zeolites with Zn 2+ , Li + , Cu 2+ , and Co 2+ . The fungi growth inhibition decreased as zeolite-Cu 2+ >zeolite-Li + >zeolite-Co 2+ >zeolite-Zn 2+ . In addition, the conidia germination was strongly affected by ion-exchanged zeolites. With regard to adsorption capacity, results indicate that only zeolite-Li + were capable of DON adsorption significantly (P < 0.001) with 37% at 2 mg mL -1 concentration. The antifungal effects of the ion-exchanged zeolites can be ascribed to the interactions of the metal ions released from the zeolite structure, especially for zeolite-Li + , which showed to be a promising agent against F. graminearum and its toxin.

Separation techniques: Chromatography

PubMed Central

Coskun, Ozlem

2016-01-01

Chromatography is an important biophysical technique that enables the separation, identification, and purification of the components of a mixture for qualitative and quantitative analysis. Proteins can be purified based on characteristics such as size and shape, total charge, hydrophobic groups present on the surface, and binding capacity with the stationary phase. Four separation techniques based on molecular characteristics and interaction type use mechanisms of ion exchange, surface adsorption, partition, and size exclusion. Other chromatography techniques are based on the stationary bed, including column, thin layer, and paper chromatography. Column chromatography is one of the most common methods of protein purification. PMID:28058406

Crystal structure and cation exchanging properties of a novel open framework phosphate of Ce (IV)

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

Bevara, Samatha; Achary, S. N., E-mail: sachary@barc.gov.in; Tyagi, A. K.

2016-05-23

Herein we report preparation, crystal structure and ion exchanging properties of a new phosphate of tetravalent cerium, K{sub 2}Ce(PO{sub 4}){sub 2}. A monoclinic structure having framework type arrangement of Ce(PO{sub 4}){sub 6} units formed by C2O{sub 8} square-antiprism and PO{sub 4} tetrahedra is assigned for K{sub C}e(PO{sub 4}){sub 2}. The K{sup +} ions are occupied in the channels formed by the Ce(PO{sub 4})6 and provide overall charge neutrality. The unique channel type arrangements of the K+ make them exchangeable with other cations. The ion exchanging properties of K2Ce(PO4)2 has been investigated by equilibrating with solution of 90Sr followed by radiometricmore » analysis. In optimum conditions, significant exchange of K+ with Sr2+ with Kd ~ 8000 mL/g is observed. The details of crystal structure and ion exchange properties are explained and a plausible mechanism for ion exchange is presented.« less

A Conserved Aspartate Residue Located at the Extracellular End of the Binding Pocket Controls Cation Interactions in Brain Glutamate Transporters*

PubMed Central

Rosental, Noa; Gameiro, Armanda; Grewer, Christof; Kanner, Baruch I.

2011-01-01

In the brain, transporters of the major excitatory neurotransmitter glutamate remove their substrate from the synaptic cleft to allow optimal glutamatergic neurotransmission. Their transport cycle consists of two sequential translocation steps, namely cotransport of glutamic acid with three Na+ ions, followed by countertransport of K+. Recent studies, based on several crystal structures of the archeal homologue GltPh, indicate that glutamate translocation occurs by an elevator-like mechanism. The resolution of these structures was not sufficiently high to unambiguously identify the sites of Na+ binding, but functional and computational studies suggest some candidate sites. In the GltPh structure, a conserved aspartate residue (Asp-390) is located adjacent to a conserved tyrosine residue, previously shown to be a molecular determinant of ion selectivity in the brain glutamate transporter GLT-1. In this study, we characterize mutants of Asp-440 of the neuronal transporter EAAC1, which is the counterpart of Asp-390 of GltPh. Except for substitution by glutamate, this residue is functionally irreplaceable. Using biochemical and electrophysiological approaches, we conclude that although D440E is intrinsically capable of net flux, this mutant behaves as an exchanger under physiological conditions, due to increased and decreased apparent affinities for Na+ and K+, respectively. Our present and previous data are compatible with the idea that the conserved tyrosine and aspartate residues, located at the external end of the binding pocket, may serve as a transient or stable cation binding site in the glutamate transporters. PMID:21984827

A conserved aspartate residue located at the extracellular end of the binding pocket controls cation interactions in brain glutamate transporters.

PubMed

Rosental, Noa; Gameiro, Armanda; Grewer, Christof; Kanner, Baruch I

2011-12-02

In the brain, transporters of the major excitatory neurotransmitter glutamate remove their substrate from the synaptic cleft to allow optimal glutamatergic neurotransmission. Their transport cycle consists of two sequential translocation steps, namely cotransport of glutamic acid with three Na(+) ions, followed by countertransport of K(+). Recent studies, based on several crystal structures of the archeal homologue Glt(Ph), indicate that glutamate translocation occurs by an elevator-like mechanism. The resolution of these structures was not sufficiently high to unambiguously identify the sites of Na(+) binding, but functional and computational studies suggest some candidate sites. In the Glt(Ph) structure, a conserved aspartate residue (Asp-390) is located adjacent to a conserved tyrosine residue, previously shown to be a molecular determinant of ion selectivity in the brain glutamate transporter GLT-1. In this study, we characterize mutants of Asp-440 of the neuronal transporter EAAC1, which is the counterpart of Asp-390 of Glt(Ph). Except for substitution by glutamate, this residue is functionally irreplaceable. Using biochemical and electrophysiological approaches, we conclude that although D440E is intrinsically capable of net flux, this mutant behaves as an exchanger under physiological conditions, due to increased and decreased apparent affinities for Na(+) and K(+), respectively. Our present and previous data are compatible with the idea that the conserved tyrosine and aspartate residues, located at the external end of the binding pocket, may serve as a transient or stable cation binding site in the glutamate transporters.

Binding of the Zn2+ ion to ferric uptake regulation protein from E. coli and the competition with Fe2+ binding: a molecular modeling study of the effect on DNA binding and conformational changes of Fur

NASA Astrophysics Data System (ADS)

Jabour, Salih; Hamed, Mazen Y.

2009-04-01

The three dimensional structure of Ferric uptake regulation protein dimer from E. coli, determined by molecular modeling, was docked on a DNA fragment (iron box) and Zn2+ ions were added in two steps. The first step involved the binding of one Zn2+ ion to what is known as the zinc site which consists of the residues Cys 92, Cys 95, Asp 137, Asp141, Arg139, Glu 140, His 145 and His 143 with an average metal-Nitrogen distance of 2.5 Å and metal-oxygen distance of 3.1-3.2 Å. The second Zn2+ ion is bound to the iron activating site formed from the residues Ile 50, His 71, Asn 72, Gly 97, Asp 105 and Ala 109. The binding of the second Zn2+ ion strengthened the binding of the first ion as indicated by the shortening of the zinc-residue distances. Fe2+, when added to the complex consisting of 2Zn2+/Fur dimer/DNA, replaced the Zn2+ ion in the zinc site and when a second Fe2+ was added, it replaced the second zinc ion in the iron activating site. The binding of both zinc and iron ions induced a similar change in Fur conformations, but shifted residues closer to DNA in a different manner. This is discussed along with a possible role for the Zn2+ ion in the Fur dimer binding of DNA in its repressor activity.

Charge-exchange plasma environment for an ion drive spacecraft. [a model for describing mercury ion engines and its effect on spacecraft subsystems

NASA Technical Reports Server (NTRS)

Kaufman, H. R.; Carruth, M. R., Jr.

1979-01-01

The charge exchange plasma environment around a spacecraft that uses mercury ion thrusters for propulsion is described. The interactions between the plasma environment and the spacecraft are determined and a model which describes the propagation of the mercury charge exchange plasma is discussed. The model is extended to describe the flow of the molybdenum component of the charge exchange plasma. The uncertainties in the models for various conditions are discussed and current drain to the solar array, charge exchange plasma material deposition, and the effects of space plasma on the charge exchange plasma propagation are addressed.

In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of Li xNa 1.5–x VOPO 4 F 0.5

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

Park, Young-Uk; Bai, Jianming; Wang, Liping

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li +/Na + substitution during solvothermal ion-exchange synthesis of Li xNa 1.5-xVOPO 4F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-timemore » observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li +, leading to peculiar Na +/Li +/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.« less

In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of Li xNa 1.5–x VOPO 4 F 0.5

DOE PAGES

Park, Young-Uk; Bai, Jianming; Wang, Liping; ...

2017-08-29

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li +/Na + substitution during solvothermal ion-exchange synthesis of Li xNa 1.5-xVOPO 4F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-timemore » observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li +, leading to peculiar Na +/Li +/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.« less

Rates of nickel(II) capture from complexes with NTA, EDDA, and related tetradentate chelating agents by the hexadentate chelating agents EDTA and CDTA: Evidence of a "semijunctive" ligand exchange pathway

NASA Astrophysics Data System (ADS)

Boland, Nathan E.; Stone, Alan T.

2017-09-01

Many siderophores and metallophores produced by soil organisms, as well as anthropogenic chelating agent soil amendments, rely upon amine and carboxylate Lewis base groups for metal ion binding. UV-visible spectra of metal ion-chelating agent complexes are often similar and, as a consequence, whole-sample absorbance measurements are an unreliable means of monitoring the progress of exchange reactions. In the present work, we employ capillary electrophoresis to physically separate Ni(II)-tetradentate chelating agent complexes (NiL) from Ni(II)-hexadentate chelating agent complexes (NiY) prior to UV detection, such that progress of the reaction NiL + Y → NiY + L can be conveniently monitored. Rates of ligand exchange for Ni(II) are lower than for other +II transition metal ions. Ni(II) speciation in environmental media is often under kinetic rather than equilibrium control. Nitrilotriacetic acid (NTA), with three carboxylate groups all tethered to a central amine Lewis base group, ethylenediamine-N,N‧-diacetic acid (EDDA), with carboxylate-amine-amine-carboxylate groups arranged linearly, plus four structurally related compounds, are used as tetradentate chelating agents. Ethylenediaminetetraacetic acid (EDTA) and the structurally more rigid analog trans-cyclohexaneethylenediaminetetraacetic acid (CDTA) are used as hexadentate chelating agents. Effects of pH and reactant concentration are explored. Ni(II) capture by EDTA was consistently more than an order of magnitude faster than capture by CDTA, and too fast to quantify using our capillary electrophoresis-based technique. Using NiNTA as a reactant, Ni(II) capture by CDTA is independent of CDTA concentration and greatly enhanced by a proton-catalyzed pathway at low pH. Using NiEDDA as reactant, Ni(II) capture by CDTA is first order with respect to CDTA concentration, and the contribution from the proton-catalyzed pathway diminished by CDTA protonation. While the convention is to assign either a disjunctive pathway or adjunctive pathway to multidentate ligand exchange reactions, our results indicate that a third "semijunctive" pathway is necessary to account for slow reactions progressing through Lsbnd Nisbnd Y ternary complexes. Ligand exchange pathways with NTA-type chelating agents are assigned a disjunctive pathway, while pathways with EDDA-type chelating agents are assigned a semijunctive pathway. Based upon operative mechanism(s), magnitudes of exchange rates and effects of ambient geochemical conditions can be predicted.

Structure, Kinetics, and Thermodynamics of the Aqueous Uranyl(VI) Cation

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

Kerisit, Sebastien N.; Liu, Chongxuan

2013-08-20

Molecular simulation techniques are employed to gain insights into the structural, kinetic, and thermodynamic properties of the uranyl(VI) cation (UO22+) in aqueous solution. The simulations make use of an atomistic potential model (force field) derived in this work and based on the model of Guilbaud and Wipff (Guilbaud, P.; Wipff, G. J. Mol. Struct. (THEOCHEM) 1996, 366, 55-63). Reactive flux and thermodynamic integration calculations show that the derived potential model yields predictions for the water exchange rate and free energy of hydration, respectively, that are in agreement with experimental data. The water binding energies, hydration shell structure, and self-diffusion coefficientmore » are also calculated and discussed. Finally, a combination of metadynamics and transition path sampling simulations is employed to probe the mechanisms of water exchange reactions in the first hydration shell of the uranyl ion. These atomistic simulations indicate, based on two-dimensional free energy surfaces, that water exchanges follow an associative interchange mechanism. The nature and structure of the water exchange transition states are also determined. The improved potential model is expected to lead to more accurate predictions of uranyl adsorption energies at mineral surfaces using potential-based molecular dynamics simulations.« less

Ion-binding properties of the ClC chloride selectivity filter

PubMed Central

Lobet, Séverine; Dutzler, Raimund

2006-01-01

The ClC channels are members of a large protein family of chloride (Cl−) channels and secondary active Cl− transporters. Despite their diverse functions, the transmembrane architecture within the family is conserved. Here we present a crystallographic study on the ion-binding properties of the ClC selectivity filter in the close homolog from Escherichia coli (EcClC). The ClC selectivity filter contains three ion-binding sites that bridge the extra- and intracellular solutions. The sites bind Cl− ions with mM affinity. Despite their close proximity within the filter, the three sites can be occupied simultaneously. The ion-binding properties are found conserved from the bacterial transporter EcClC to the human Cl− channel ClC-1, suggesting a close functional link between ion permeation in the channels and active transport in the transporters. In resemblance to K+ channels, ions permeate the ClC channel in a single file, with mutual repulsion between the ions fostering rapid conduction. PMID:16341087

Adsorption and ion exchange: basic principles and their application in food processing.

PubMed

Kammerer, Judith; Carle, Reinhold; Kammerer, Dietmar R

2011-01-12

A comprehensive overview of adsorption and ion exchange technology applied for food and nutraceutical production purposes is given in the present paper. Emanating from these fields of application, the main adsorbent and ion-exchange resin materials, their historical development, industrial production, and the main parameters characterizing these sorbents are covered. Furthermore, adsorption and ion exchange processes are detailed, also providing profound insights into kinetics, thermodynamics, and equilibrium model assumptions. In addition, the most important industrial adsorber and ion exchange processes making use of vessels and columns are summarized. Finally, an extensive overview of selected industrial applications of these technologies is provided, which is divided into general applications, food production applications, and the recovery of valuable bio- and technofunctional compounds from the byproducts of plant food processing, which may be used as natural food additives or for their potential health-beneficial effects in functional or enriched foods and nutraceuticals.

Ion-exchange chromatography separation applied to mineral recycle in closed systems

NASA Technical Reports Server (NTRS)

Ballou, E.; Spitze, L. A.; Wong, F. W.; Wydeven, T.; Johnson, C. C.

1981-01-01

As part of the controlled ecological life support system (CELSS) program, a study is being made of mineral separation on ion-exchange columns. The purpose of the mineral separation step is to allow minerals to be recycled from the oxidized waste products of plants, man, and animals for hydroponic food production. In the CELSS application, relatively large quantities of minerals in a broad concentration range must be recovered by the desired system, rather than the trace quantities and very low concentrations treated in analytical applications of ion-exchange chromatography. Experiments have been carried out to assess the parameters pertinent to the scale-up of ion-exchange chromatography and to determine feasibility. Preliminary conclusions are that the column scale-up is in a reasonable size range for the CELSS application. The recycling of a suitable eluent, however, remains a major challenge to the suitability of using ion exchange chromatography in closed systems.

Lead Removal From Synthetic Leachate Matrices by a Novel Ion-Exchange Material

NASA Technical Reports Server (NTRS)

Street, Kenneth W., Jr.; Hovanitz, Edward S.; Chi, Sulan

2002-01-01

This report discusses the application of a novel polyacrylate-based ion-exchange material (IEM) for the removal of lead (Pb) ions from water. Preliminary testing includes the establishment of the operating pH range, capacity information, and the effect of calcium and anions in the matrix. Batch testing with powder indicates slightly different optimal operational conditions from those used for column testing. The ion exchanger is excellent for removing lead from aqueous solutions.

Synthesis of ion-exchange resin for selective thorium and uranyl ions sorption

NASA Astrophysics Data System (ADS)

Konovalov, Konstantin; Sachkov, Victor

2017-11-01

In this work, the method of ion-exchange resin synthesis selective to radionuclides (uranium and thorium) is presented. The method includes synthesis of polymeric styrene-divinylbenzene macroporous matrix with size of 0.1-0.2 mm, and its subsequent transformation by nitration and then reduction by tin (II) chloride. For passivation of active primary amines partially oxidation by oxygen from air is used. Obtained ion-exchange resin has ratio of sorption sum U+Th to sorption sum of other total rare-earth elements as 1:1.88 at ratio of solid to liquid phase 1:200. The proposed method of ion-exchange resin synthesis is scaled-up for laboratory reactors with volume of 5 and 50 liters.

High resolution main-ion charge exchange spectroscopy in the DIII-D H-mode pedestal

DOE PAGES

Grierson, B. A.; Burrell, K. H.; Chrystal, C.; ...

2016-09-12

A new high spatial resolution main-ion (deuterium) charge-exchange spectroscopy system covering the tokamak boundary region has been installed on the DIII-D tokamak. Sixteen new edge main-ion charge-exchange recombination sightlines have been combined with nineteen impurity sightlines in a tangentially viewing geometry on the DIII-D midplane with an interleaving design that achieves 8 mm inter-channel radial resolution for detailed profiles of main-ion temperature, velocity, charge-exchange emission, and neutral beam emission. At the plasma boundary, we find a strong enhancement of the main-ion toroidal velocity that exceeds the impurity velocity by a factor of two. Furthermore, the unique combination of experimentally measuredmore » main-ion and impurity profiles provides a powerful quasi-neutrality constraint for reconstruction of tokamak H-mode pedestals.« less

Probing peptide fragment ion structures by combining sustained off-resonance collision-induced dissociation and gas-phase H/D exchange (SORI-HDX) in Fourier transform ion-cyclotron resonance (FT-ICR) instruments.

PubMed

Somogyi, Arpád

2008-12-01

The usefulness of gas-phase H/D exchange is demonstrated to probe heterogeneous fragment and parent ion populations. Singly and multiply protonated peptides/proteins were fragmented by using sustained off-resonance irradiation collision-induced dissociation (SORI-CID). The fragments and the surviving precursor ions then all undergo H/D exchange in the gas-phase with either D(2)O or CD(3)OD under the same experimental conditions. Usually, 10 to 60 s of reaction time is adequate to monitor characteristic differences in the H/D exchange kinetic rates. These differences are then correlated to isomeric ion structures. The SORI-HDX method can be used to rapidly test fragment ion structures and provides useful insights into peptide fragmentation mechanisms.

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

PubMed

Rungrodnimitchai, Supitcha

2014-01-01

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

Calcium ion binding to a soil fulvic acid using a donnan potential model

USGS Publications Warehouse

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

1999-01-01

Calcium ion binding to a soil fulvic acid (Armadale Bh Horizon) was evaluated over a range of calcium ion concentrations, from pH 3.8 to 7.3, using potentiometric titrations and calcium ion electrode measurements. Fulvic acid concentration was constant (100 milligrams per liter) and calcium ion concentration varied up to 8 X 10-4 moles per liter. Experiments discussed here included: (1) titrations of fulvic acid-calcium ion containing solutions with sodium hydroxide; and (2) titrations of fully neutralized fulvic acid with calcium chloride solutions. Apparent binding constants (expressed as the logarithm of the value, log ??app) vary with solution pH, calcium ion concentration, degree of acid dissociation, and ionic strength (from log ??app = 2.5 to 3.9) and are similar to those reported by others. Fulvic acid charge, and the associated Donnan Potential, influences calcium ion-fulvic acid ion pair formation. A Donnan Potential corrrection term allowed calculation of intrinsic calcium ion-fulvic acid binding constants. Intrinsic binding constants vary from 1.2 to 2.5 (the average value is about log??= 1.6) and are similar to, but somewhat higher than, stability constants for calcium ion-carboxylic acid monodentate complexes. ?? by Oldenbourg Wissenschaftsverlag, Mu??nchen.

Characterization of xenon ion and neutral interactions in a well-characterized experiment

NASA Astrophysics Data System (ADS)

Patino, Marlene I.; Wirz, Richard E.

2018-06-01

Interactions between fast ions and slow neutral atoms are commonly dominated by charge-exchange and momentum-exchange collisions, which are important to understanding and simulating the performance and behavior of many plasma devices. To investigate these interactions, this work developed a simple, well-characterized experiment that accurately measures the behavior of high energy xenon ions incident on a background of xenon neutral atoms. By using well-defined operating conditions and a simple geometry, these results serve as canonical data for the development and validation of plasma models and models of neutral beam sources that need to ensure accurate treatment of angular scattering distributions of charge-exchange and momentum-exchange ions and neutrals. The energies used in this study are relevant for electric propulsion devices ˜1.5 keV and can be used to improve models of ion-neutral interactions in the plume. By comparing these results to both analytical and computational models of ion-neutral interactions, we discovered the importance of (1) accurately treating the differential cross-sections for momentum-exchange and charge-exchange collisions over a large range of neutral background pressures and (2) properly considering commonly overlooked interactions, such as ion-induced electron emission from nearby surfaces and neutral-neutral ionization collisions.

Binding of corroded ions to human saliva.

PubMed

Mueller, H J

1985-05-01

Employing equilibrium dialysis, the binding abilities of Cu, Al, Co and Cr ions from corroded Cu-Al and Co-Cr dental casting alloys towards human saliva and two of its gel chromatographic fractions were determined. Results indicate that both Cu and Co bind to human saliva i.e. 0.045 and 0.027 mg/mg protein, respectively. Besides possessing the largest binding ability, Cu also possessed the largest binding capacity. The saturation of Cu binding was not reached up to the limit of 0.35 mg protein/ml employed in the tests, while Co reached full saturation at about 0.2 mg protein/ml. Chromium showed absolutely no binding to human saliva while Al ions did not pass through the dialysis membranes. Compared to the binding with solutions that were synthetically made up to contain added salivary-type proteins, it is shown that the binding to human saliva is about 1 order of magnitude larger, at least for Cu ions.

Regeneration of spent powdered activated carbon saturated with inorganic ions by cavitation united with ion exchange method.

PubMed

Li, Gang; Gao, Hong; Li, Yansheng; Yang, Huixin

2011-06-01

Using ion exchange resin as transfer media, regenerate powdered activated carbon (PAC) adsorbed inorganic ions by cavitation to enhance the transfer; we studied how the regeneration time and the mass ratio of resin and PAC influence the regeneration rate respectively through re-adsorption. The result showed that the effective regeneration of PAC saturated with inorganic ions was above 90% using ion exchange resin as media and transfer carrier, the quantity of PAC did not reduced but activated in the process. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Ion-exchange selectivity of diclofenac, ibuprofen, ketoprofen, and naproxen in ureolyzed human urine.

PubMed

Landry, Kelly A; Sun, Peizhe; Huang, Ching-Hua; Boyer, Treavor H

2015-01-01

This research advances the knowledge of ion-exchange of four non-steroidal anti-inflammatory drugs (NSAIDs) - diclofenac (DCF), ibuprofen (IBP), ketoprofen (KTP), and naproxen (NPX) - and one analgesic drug-paracetamol (PCM) - by strong-base anion exchange resin (AER) in synthetic ureolyzed urine. Freundlich, Langmuir, Dubinin-Astakhov, and Dubinin-Radushkevich isotherm models were fit to experimental equilibrium data using nonlinear least squares method. Favorable ion-exchange was observed for DCF, KTP, and NPX, whereas unfavorable ion-exchange was observed for IBP and PCM. The ion-exchange selectivity of the AER was enhanced by van der Waals interactions between the pharmaceutical and AER as well as the hydrophobicity of the pharmaceutical. For instance, the high selectivity of the AER for DCF was due to the combination of Coulombic interactions between quaternary ammonium functional group of resin and carboxylate functional group of DCF, van der Waals interactions between polystyrene resin matrix and benzene rings of DCF, and possibly hydrogen bonding between dimethylethanol amine functional group side chain and carboxylate and amine functional groups of DCF. Based on analysis of covariance, the presence of multiple pharmaceuticals did not have a significant effect on ion-exchange removal when the NSAIDs were combined in solution. The AER reached saturation of the pharmaceuticals in a continuous-flow column at varying bed volumes following a decreasing order of DCF > NPX ≈ KTP > IBP. Complete regeneration of the column was achieved using a 5% (m/m) NaCl, equal-volume water-methanol solution. Results from multiple treatment and regeneration cycles provide insight into the practical application of pharmaceutical ion-exchange in ureolyzed urine using AER.

Effects of bicarbonate on lithium transport in human red cells

PubMed Central

1978-01-01

Lithium influx into human erythrocytes increased 12-fold, when chloride was replaced with bicarbonate in a 150 mM lithium medium (38 degrees C. pH 7.4). The increase was linearly related to both lithium- and bicarbonate concentration, and was completely eliminated by the amino reagent 4, 4'- diisothiocyanostilbene-2,2'-disulfonic acid (DIDS). DIDS binds to an integral membrane protein (mol wt approximately 10(5) dalton) involved in anion exchange. Inhibition of both anion exchange and of bicarbonate-stimulated lithium influx was linearly related to DIDS binding. 1.1 X 10(6) DIDS molecules per cell caused complete inhibition of both processes. Both Cl- and Li+ can apparently be transported by the anion transport mechanism. The results support our previous proposal that bicarbonate-induced lithium permeability is due to transport of lithium-carbonate ion pairs (LiCO-3). DIDS-sensitive lithium influx had a high activation energy (24 kcal/mol), compatible with transport by the anion exchange mechanism. We have examined how variations of passive lithium permeability, induced by bicarbonate, affect the sodium-driven lithium counter-transport in human erythrocytes. The ability of the counter-transport system to establish a lithium gradient across the membrane decrease linearly with bicarbonate concentration in the medium. The counter-transport system was unaffected by DIDS treatement. At a plasma bicarbonate concentration of 24 mM, two-thirds of the lithium influx is mediated by the bicarbonate-stimulated pathway, and the fraction will increase significantly in metabolic alkalosis. PMID:670928

Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

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

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.

Methods are described that include reacting a starting nanocrystal that includes a starting nanocrystal core and a covalently bound surface species to create an ion-exchangeable (IE) nanocrystal that includes a surface charge and a first ion-exchangeable (IE) surface ligand ionically bound to the surface charge, where the starting nanocrystal core includes a group IV element.

Ion-exchange sorption of silver(I) chloride complexes from aqueous HCl solutions

NASA Astrophysics Data System (ADS)

Kononova, O. N.; Duba, E. V.; Medovikov, D. V.; Efimova, A. S.; Ivanov, A. I.; Krylov, A. S.

2017-12-01

The ion-exchange sorption of silver(I) chloride complexes from 1-4 M aqueous solutions of HCl on a series of Purolite anionites with various functional groups was studied. The ion-exchange equilibria in the systems were found to be anomalous according to Raman spectroscopy, which does not significantly affect the sorption properties of the ionites.

Ion exchange of H+, Na+, Mg2+, Ca2+, Mn2+, and Ba2+, on wood pulp

Treesearch

Alan W. Rudie; Alan Ball; Narendra Patel

2006-01-01

Ion exchange selectivity coefficients were measured for the partition of metals between solution and pulp fibers. The method accurately models the ion exchange isotherms for all cation pairs evaluated and is accurate up to approximately 0.05 molar concentrations. Selectivity coefficients were determined for calcium and magnesium with each other and with hydrogen....

The use of fibrous ion exchangers in gold hydrometallurgy

NASA Astrophysics Data System (ADS)

Kautzmann, R. M.; Sampaio, C. H.; Cortina, J. L.; Soldatov, V.; Shunkevich, A.

2002-10-01

This article examines a family of ion-exchange fibers, FIBAN, containing primary and secondary amine groups. These ion exchangers have a fiber diameter of 20 40 Μm, high osmotic and mechanic stability, a high rate of adsorption and regeneration, and excellent dynamic characteristics as filtering media. Inparticular, this article discusses the use of FIBAN fibrous ion exchangers in the recovery of gold cyanide andbase-metal cyanides (copper and mercury) from mineral-leaching solutions. The influence of polymer structure and water content on their extraction ability is described, along with key parameters of gold hydrometallurgy such as extraction efficiency, selectivity, pH dependence, gold cyanide loading, kinetics, and stripping.

Adsorption of three pharmaceuticals on two magnetic ion-exchange resins.

PubMed

Jiang, Miao; Yang, Weiben; Zhang, Ziwei; Yang, Zhen; Wang, Yuping

2015-05-01

The presence of pharmaceuticals in aquatic environments poses potential risks to the ecology and human health. This study investigated the removal of three widely detected and abundant pharmaceuticals, namely, ibuprofen (IBU), diclofenac (DC), and sulfadiazine (SDZ), by two magnetic ion-exchange resins. The adsorption kinetics of the three adsorbates onto both resins was relatively fast and followed pseudo-second-order kinetics. Despite the different pore structures of the two resins, similar adsorption patterns of DC and SDZ were observed, implying the existence of an ion-exchange mechanism. IBU demonstrated a combination of interactions during the adsorption process. These interactions were dependent on the specific surface area and functional groups of the resin. The adsorption isotherm fittings verified the differences in the behavior of the three pharmaceuticals on the two magnetic ion-exchange resins. The presence of Cl- and SO4(2-) suppressed the adsorption amount, but with different inhibition levels for different adsorbates. This work facilitates the understanding of the adsorption behavior and mechanism of pharmaceuticals on magnetic ion-exchange resins. The results will expand the application of magnetic ion-exchange resins to the removal of pharmaceuticals in waters. Copyright © 2015. Published by Elsevier B.V.

Geochemistry of fluoride in the Black Creek aquifer system of Horry and Georgetown Counties, South Carolina--and its physiological implications

USGS Publications Warehouse

Zack, Allen L.

1980-01-01

High concentrations of fluoride in ground-water supplies in certain areas of Horry and Georgetown Counties, S.C., have been the cause of dental fluorosis (tooth mottling) among persons who have lived in these areas and have ingested the water as children. Geochemical evidence and laboratory experiments demonstrate that fluorapatite in the form of fossil shark teeth is the source of fluoride, and that the fluoride ions are liberated to the ground-water system through anion exchange, rather than by dissolution. Calcite-cemented quartz sand in the upper third of the Black Creek Formation of Late Cretaceous age contains the fossil shark teeth. As ground water progresses downdip, the calcite matrix dissolves and hydrolyzes, releasing bicarbonate, hydroxyl, and calcium ions. The calcium ions are immediately exchanged for sodium ions adsorbed on sodium-rich clays, and the bicarbonate ions accumulate. As the shark teeth are exposed, the hydroxyl ions in solution exchange with fluoride ions on fluorapatite surfaces. Experiments using fossil shark teeth show that sodium chloride in solution inhibits the rate of exchange of fluoride ions from tooth surfaces for hydroxyl ions in solution. The amount of fluoride removed from water and exchanged for hydroxyl ions in the presence of pure hydroxylapatite (hog teeth) was greater in saline water than in freshwater.

Comparison of magnetic carboxymethyl chitosan nanoparticles and cation exchange resin for the efficient purification of lysine-tagged small ubiquitin-like modifier protease.

PubMed

Li, Junhua; Zhang, Yang; Shen, Fei; Yang, Yanjun

2012-10-15

A fusion tag that can be purified by the cheap ion-exchanger based on the ionic binding force may provide a cost-effective scheme over other affinity fusion tags. Small ubiquitin-like modifier (SUMO) protease derived from Saccharomyces cerevisiae was fused with a poly lysine tag containing 10 lysine residues at its C-terminus and then expressed in Escherichia coli. The ionic binding force provided by the ploy lysine tag allowed the selective recovery of the small ubiquitin-like modifier protease from recombinant E. coli cell extracts. A preliminary comparative study of the adsorption and elution of poly lysine tagged SUMO protease on Amberlite Cobalamion and magnetite carboxymethyl chitosan nanoparticles was performed. Amberlite Cobalamion and magnetite nanoparticles had the similar elution profile due to the common functional groups - carboxyl groups. The maximum dynamic adsorption capacity of Amberlite Cobalamion and magnetite nanoparticles reached 36.8 and 211.4 mg/g, respectively. The lysine-tagged protease can be simply purified by magnetite nanoparticles from cell extracts with higher purity than that by Amberlite Cobalamion. The superparamagnetic nanoparticles possess the advantages of highly specific, fast and excellent binding of a larger amount of lysine tagged SUMO modifier protease, and it is also easier to separate from the crude biological process liquors compared with the conventional separation techniques of polycationic amino acids fusion proteins. Copyright © 2012 Elsevier B.V. All rights reserved.

ADPase activity of recombinantly expressed thermotolerant ATPases may be caused by copurification of adenylate kinase of Escherichia coli

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

Chen, Baoyu; Sysoeva, Tatyana A.; Chowdhury, Saikat

2009-10-06

Except for apyrases, ATPases generally target only the {gamma}-phosphate of a nucleotide. Some non-apyrase ATPases from thermophilic microorganisms are reported to hydrolyze ADP as well as ATP, which has been described as a novel property of the ATPases from extreme thermophiles. Here, we describe an apparent ADP hydrolysis by highly purified preparations of the AAA+ ATPase NtrC1 from an extremely thermophilic bacterium, Aquifex aeolicus. This activity is actually a combination of the activities of the ATPase and contaminating adenylate kinase (AK) from Escherichia coli, which is present at 1/10 000 of the level of the ATPase. AK catalyzes conversion ofmore » two molecules of ADP into AMP and ATP, the latter being a substrate for the ATPase. We raise concern that the observed thermotolerance of E. coli AK and its copurification with thermostable proteins by commonly used methods may confound studies of enzymes that specifically catalyze hydrolysis of nucleoside diphosphates or triphosphates. For example, contamination with E. coli AK may be responsible for reported ADPase activities of the ATPase chaperonins from Pyrococcus furiosus, Pyrococcus horikoshii, Methanococcus jannaschii and Thermoplasma acidophilum; the ATP/ADP-dependent DNA ligases from Aeropyrum pernix K1 and Staphylothermus marinus; or the reported ATP-dependent activities of ADP-dependent phosphofructokinase of P. furiosus. Purification methods developed to separate NtrC1 ATPase from AK also revealed two distinct forms of the ATPase. One is tightly bound to ADP or GDP and able to bind to Q but not S ion exchange matrixes. The other is nucleotide-free and binds to both Q and S ion exchange matrixes.« less

Adsorptive removal of antibiotics from water using magnetic ion exchange resin.

PubMed

Wang, Tianyue; Pan, Xun; Ben, Weiwei; Wang, Jianbing; Hou, Pin; Qiang, Zhimin

2017-02-01

The occurrence of antibiotics in the environment has recently raised serious concern regarding their potential threat to aquatic ecosystem and human health. In this study, the magnetic ion exchange (MIEX) resin was applied for removing three commonly-used antibiotics, sulfamethoxazole (SMX), tetracycline (TCN) and amoxicillin (AMX) from water. The results of batch experiments show that the maximum adsorption capacities on the MIEX resin for SMX, TCN and AMX were 789.32, 443.18 and 155.15μg/mL at 25°C, respectively, which were 2-7 times that for the powdered activated carbon. The adsorption kinetics of antibiotics on the MIEX resin could be simulated by the pseudo-second-order model (R 2 =0.99), and the adsorption isotherm data were well described by the Langmuir model (R 2 =0.97). Solution pH exhibited a remarkable impact on the adsorption process and the absorbed concentrations of the tested antibiotics were obtained around the neutral pH. The MIEX resin could be easily regenerated by 2mol/L NaCl solution and maintained high adsorption removal for the tested antibiotics after regeneration. Anion exchange mechanism mainly controlled the adsorption of antibiotic and the formation of hydrogen binding between the antibiotic and resin can also result in the increase of adsorption capacity. The high adsorption capacity, fast adsorption rate and prominent reusability make the MIEX resin a potential adsorbent in the application for removing antibiotics from water. Copyright © 2016. Published by Elsevier B.V.

Assessment of the hazard posed by metal forms in water and sediments.

PubMed

Wojtkowska, Małgorzata; Bogacki, Jan; Witeska, Anna

2016-05-01

This study aimed to describe the prevalence heavy metals (Zn, Cu, Pb, and Cd) forms in the ecosystem of the Utrata river in order to determine the mobile forms and bioavailability of metals. To extract the dissolved forms of metals in the water of the Utrata PHREEQC2 geochemical speciation model was used. The river waters show a high percentage of mobile and eco-toxic forms of Zn, Cu and Pb. The percentage of carbonate forms for all the studied metals was low (<1%). The content of carbonates in the water and the prevailing physical and chemical conditions (pH, hardness, alkalinity) reduce the share of toxic metal forms, which precipitate as hardly soluble carbonate salts of Zn, Cu, Cd and Pb. Cu in the water in 90% of cases appeared in the form of hydroxyl compounds. To identify the forms of metal occurrence in the sediments Tessier's sequential extraction was used, allowing to assay bound metals in five fractions (ion exchange, carbonate, adsorption, organic, residual), whose nature and bioavailability varies in aquatic environments. The study has shown a large share of metals in labile and bioavailable forms. The speciation analysis revealed an absolute dominance of the organic fraction in the binding of Cu and Pb. Potent affinity for this fraction was also exhibited by Cd. The rations of exchangeable Zn and Cu forms in the sediments were similar. Both these metals had the lowest share in the most mobile ion exchange fraction. Copyright © 2016. Published by Elsevier B.V.

21 CFR 173.25 - Ion-exchange resins.

Code of Federal Regulations, 2013 CFR

2013-04-01

... the starting quantity of cellulose. (b) Ion-exchange resins are used in the purification of foods, including potable water, to remove undesirable ions or to replace less desirable ions with one or more of...) (12) and (16) of this section are used to treat water for use in the manufacture of distilled...

21 CFR 173.25 - Ion-exchange resins.

Code of Federal Regulations, 2012 CFR

2012-04-01

... the starting quantity of cellulose. (b) Ion-exchange resins are used in the purification of foods, including potable water, to remove undesirable ions or to replace less desirable ions with one or more of...) (12) and (16) of this section are used to treat water for use in the manufacture of distilled...

Intensification of ammonia removal from waste water in biologically active zeolitic ion exchange columns.

PubMed

Almutairi, Azel; Weatherley, Laurence R

2015-09-01

The use of nitrification filters for the removal of ammonium ion from waste-water is an established technology deployed extensively in municipal water treatment, in industrial water treatment and in applications such as fish farming. The process involves the development of immobilized bacterial films on a solid packing support, which is designed to provide a suitable host for the film, and allow supply of oxygen to promote aerobic action. Removal of ammonia and nitrite is increasingly necessary to meet drinking water and discharge standards being applied in the US, Europe and other places. Ion-exchange techniques are also effective for removal of ammonia (as the ammonium ion) from waste water and have the advantage of fast start-up times compared to biological filtration which in some cases may take several weeks to be fully operational. Here we explore the performance of ion exchange columns in which nitrifying bacteria are cultivated, with the goal of a "combined" process involving simultaneous ion-exchange and nitrification, intensified by in-situ aeration with a novel membrane module. There were three experimental goals. Firstly, ion exchange zeolites were characterized and prepared for comparative column breakthrough studies for ammonia removal. Secondly effective in-situ aeration for promotion of nitrifying bacterial growth was studied using a number of different membranes including polyethersulfone (PES), polypropylene (PP), nylon, and polytetra-fluoroethylene (PTFE). Thirdly the breakthrough performance of ion exchange columns filled with zeolite in the presence of aeration and in the presence of nitrifying bacteria was determined to establish the influence of biomass, and aeration upon breakthrough during ammonium ion uptake. The methodology adopted included screening of two types of the naturally occuring zeolite clinoptilolite for effective ammonia removal in continuous ion-exchange columns. Next, the performance of fixed beds of clinoptilolite in the presence of nitrifying bacteria is compared to that in columns in which only ion exchange is occurring. The aeration performance of each of the chosen membranes was compared experimentally using a newly developed membrane support module which is also described. Comparison of ammonia removal in columns equipped with in-situ aeration using each membrane was undertaken and the breakthrough characteristics determined. The results showed that ammonia removal in the presence of the nitrifiers was significantly intensified. Column operation with membrane aeration showed further enhancement of ammonia removal. The greatest enhancement was observed in the case of the polyethersulfone membrane (PES). It is concluded that combined nitrification and ion-exchange is significantly intensified in packed columns by in-situ aeration using a novel membrane module. There is significant potential for extending the ion-exchange cycle time and thus potential cost reduction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Localizing Carbohydrate Binding Sites in Proteins Using Hydrogen/Deuterium Exchange Mass Spectrometry

NASA Astrophysics Data System (ADS)

Zhang, Jingjing; Kitova, Elena N.; Li, Jun; Eugenio, Luiz; Ng, Kenneth; Klassen, John S.

2016-01-01

The application of hydrogen/deuterium exchange mass spectrometry (HDX-MS) to localize ligand binding sites in carbohydrate-binding proteins is described. Proteins from three bacterial toxins, the B subunit homopentamers of Cholera toxin and Shiga toxin type 1 and a fragment of Clostridium difficile toxin A, and their interactions with native carbohydrate receptors, GM1 pentasaccharides (β-Gal-(1→3)-β-GalNAc-(1→4)[α-Neu5Ac-(2→3)]-β-Gal-(1→4)-Glc), Pk trisaccharide (α-Gal-(1→4)-β-Gal-(1→4)-Glc) and CD-grease (α-Gal-(1→3)-β-Gal-(1→4)-β-GlcNAcO(CH2)8CO2CH3), respectively, served as model systems for this study. Comparison of the differences in deuterium uptake for peptic peptides produced in the absence and presence of ligand revealed regions of the proteins that are protected against deuterium exchange upon ligand binding. Notably, protected regions generally coincide with the carbohydrate binding sites identified by X-ray crystallography. However, ligand binding can also result in increased deuterium exchange in other parts of the protein, presumably through allosteric effects. Overall, the results of this study suggest that HDX-MS can serve as a useful tool for localizing the ligand binding sites in carbohydrate-binding proteins. However, a detailed interpretation of the changes in deuterium exchange upon ligand binding can be challenging because of the presence of ligand-induced changes in protein structure and dynamics.

A comparison of experimental and computer model results on the charge-exchange plasma flow from a 30 cm mercury ion thruster

NASA Technical Reports Server (NTRS)

Gabriel, S. B.; Kaufman, H. R.

1982-01-01

Ion thrusters can be used in a variety of primary and auxiliary space-propulsion applications. A thruster produces a charge-exchange plasma which can interact with various systems on the spacecraft. The propagation of the charge-exchange plasma is crucial in determining the interaction of that plasma with the spacecraft. This paper compares experimental measurements with computer model predictions of the propagation of the charge-exchange plasma from a 30 cm mercury ion thruster. The plasma potentials, and ion densities, and directed energies are discussed. Good agreement is found in a region upstream of, and close to, the ion thruster optics. Outside of this region the agreement is reasonable in view of the modeling difficulties.

Electron binding energy of uranium-ligand and uranyl-ligand anions

NASA Astrophysics Data System (ADS)

Wang, Lei; Horowitz, Steven; Marston, Brad

2012-02-01

Electron binding energies of the early actinide element uranium in gas-phase anion complexes are calculated by relativistic density functional theory (DFT) with two different exchange-correlation functions (RPBE and B3LYP) and also in the Hartree-Fock (HF) approximationootnotetextADF2010.02, SCM.com. Scalar and spin-orbit calculations are performed, and the calculated energies are compared to available experimental measurements and shown to disagree by energies of order 1 eV. Strong correlations that are poorly treated in DFT and HF can be included by a hybrid approach in which a generalized Anderson impurity model is numerically diagonalized. Reduction-oxidation (redox) potentials of aqueous actinide ions show improved agreement with measured values in the hybrid approachootnotetextS. E. Horowitz and J. B. Marston, J. Chem. Phys 134 064510 (2011).. We test whether or not similar improvements are found in the gas-phase.

Production of High Energy Ions Near an Ion Thruster Discharge Hollow Cathode

NASA Technical Reports Server (NTRS)

Katz, Ira; Mikellides, I. G.; Goebel, D. M.; Jameson, K. K.; Wirz, R.; Polk, James E.

2006-01-01

Several researchers have measured ions leaving ion thruster discharge chambers with energies far greater than measured discharge chamber potentials. Presented in this paper is a new mechanism for the generation of high energy ions and a comparison with measured ion spectra. The source of high energy ions has been a puzzle because they not only have energies in excess of measured steady state potentials, but as reported by Goebel et. al. [1], their flux is independent of the amplitude of time dependent plasma fluctuations. The mechanism relies on the charge exchange neutralization of xenon ions accelerated radially into the potential trough in front of the discharge cathode. Previous researchers [2] have identified the importance of charge exchange in this region as a mechanism for protecting discharge cathode surfaces from ion bombardment. This paper is the first to identify how charge exchange in this region can lead to ion energy enhancement.

Protein Arginine Deiminase 2 Binds Calcium in an Ordered Fashion: Implications for Inhibitor Design

PubMed Central

2015-01-01

Protein arginine deiminases (PADs) are calcium-dependent histone-modifying enzymes whose activity is dysregulated in inflammatory diseases and cancer. PAD2 functions as an Estrogen Receptor (ER) coactivator in breast cancer cells via the citrullination of histone tail arginine residues at ER binding sites. Although an attractive therapeutic target, the mechanisms that regulate PAD2 activity are largely unknown, especially the detailed role of how calcium facilitates enzyme activation. To gain insights into these regulatory processes, we determined the first structures of PAD2 (27 in total), and through calcium-titrations by X-ray crystallography, determined the order of binding and affinity for the six calcium ions that bind and activate this enzyme. These structures also identified several PAD2 regulatory elements, including a calcium switch that controls proper positioning of the catalytic cysteine residue, and a novel active site shielding mechanism. Additional biochemical and mass-spectrometry-based hydrogen/deuterium exchange studies support these structural findings. The identification of multiple intermediate calcium-bound structures along the PAD2 activation pathway provides critical insights that will aid the development of allosteric inhibitors targeting the PADs. PMID:25621824

Evaluation of protein adsorption and preferred binding regions in multimodal chromatography using NMR

PubMed Central

Chung, Wai Keen; Freed, Alexander S.; Holstein, Melissa A.; McCallum, Scott A.; Cramer, Steven M.

2010-01-01

NMR titration experiments with labeled human ubiquitin were employed in concert with chromatographic data obtained with a library of ubiquitin mutants to study the nature of protein adsorption in multimodal (MM) chromatography. The elution order of the mutants on the MM resin was significantly different from that obtained by ion-exchange chromatography. Further, the chromatographic results with the protein library indicated that mutations in a defined region induced greater changes in protein affinity to the solid support. Chemical shift mapping and determination of dissociation constants from NMR titration experiments with the MM ligand and isotopically enriched ubiquitin were used to determine and rank the relative binding affinities of interaction sites on the protein surface. The results with NMR confirmed that the protein possessed a distinct preferred binding region for the MM ligand in agreement with the chromatographic results. Finally, coarse-grained ligand docking simulations were employed to study the modes of interaction between the MM ligand and ubiquitin. The use of NMR titration experiments in concert with chromatographic data obtained with protein libraries represents a previously undescribed approach for elucidating the structural basis of protein binding affinity in MM chromatographic systems. PMID:20837551

Vitrification of ion exchange resins

DOEpatents

Cicero-Herman, Connie A.; Workman, Rhonda Jackson

2001-01-01

The present invention relates to vitrification of ion exchange resins that have become loaded with hazardous or radioactive wastes, in a way that produces a homogenous and durable waste form and reduces the disposal volume of the resin. The methods of the present invention involve directly adding borosilicate glass formers and an oxidizer to the ion exchange resin and heating the mixture at sufficient temperature to produce homogeneous glass.

Equivalence of two approaches for modeling ion permeation through a transmembrane channel with an internal binding site

NASA Astrophysics Data System (ADS)

Zhou, Huan-Xiang

2011-04-01

Ion permeation through transmembrane channels has traditionally been modeled using two different approaches. In one approach, the translocation of the permeant ion through the channel pore is modeled as continuous diffusion and the rate of ion transport is obtained from solving the steady-state diffusion equation. In the other approach, the translocation of the permeant ion through the pore is modeled as hopping along a discrete set of internal binding sites and the rate of ion transport is obtained from solving a set of steady-state rate equations. In a recent work [Zhou, J. Phys. Chem. Lett. 1, 1973 (2010)], the rate constants for binding to an internal site were further calculated by modeling binding as diffusion-influenced reactions. That work provided the foundation for bridging the two approaches. Here we show that, by representing a binding site as an energy well, the two approaches indeed give the same result for the rate of ion transport.

Strengthening, Crack Arrest And Multiple Cracking In Brittle Materials Using Residual Stresses.

DOEpatents

Green, David J.; Sglavo, Vincenzo M.; Tandon, Rajan

2003-02-11

Embodiments include a method for forming a glass which displays visible cracking prior to failure when subjected to predetermined stress level that is greater than a predetermined minimum stress level and less than a failure stress level. The method includes determining a critical flaw size in the glass and introducing a residual stress profile to the glass so that a plurality of visible cracks are formed prior to failure when the glass is subjected to a stress that is greater than the minimum stress level and lower than the critical stress. One method for forming the residual stress profile includes performing a first ion exchange so that a first plurality of ions of a first element in the glass are exchanged with a second plurality of ions of a second element that have a larger volume than the first ions. A second ion exchange is also performed so that a plurality of the second ions in the glass are exchanged back to ions of the first element.

Synthesis, characterization and analytical application of hybrid; acrylamide zirconium (IV) arsenate a cation exchanger, effect of dielectric constant on distribution coefficient of metal ions.

PubMed

Nabi, Syed A; Shalla, Aabid H

2009-04-30

A new hybrid inorganic-organic cation exchanger acrylamide zirconium (IV) arsenate has been synthesized, characterized and its analytical application explored. The effect of experimental parameters such as mixing ratio of reagents, temperature, and pH on the properties of material has been studied. FTIR, TGA, X-ray, UV-vis spectrophotometry, SEM and elemental analysis were used to determine the physiochemical properties of this hybrid ion exchanger. The material behaves as a monofunctional acid with ion-exchange capacity of 1.65 meq/g for Na(+) ions. The chemical stability data reveals that the exchanger is quite stable in mineral acids, bases and fairly stable in organic solvents, while as thermal analysis shows that the material retain 84% of its ion-exchange capacity up to 600 degrees C. Adsorption behavior of metal ions in solvents with increasing dielectric constant has also been explored. The sorption studies reveal that the material is selective for Pb(2+) ions. The analytical utility of the material has been explored by achieving some binary separations of metal ions on its column. Pb(2+) has been selectively removed from synthetic mixtures containing Mg(2+), Ca(2+), Sr(2+), Zn(2+) and Cu(2+), Al(3+), Ni(2+), Fe(3+). In order to demonstrate practical utility of the material quantitative separation of the Cu(2+) and Zn(2+) in brass sample has been achieved on its columns.

Efficient and selective heavy metal sequestration from water by using layered sulfide K 2x Sn 4-x S 8-x (x = 0.65–1; KTS-3)

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

Sarma, Debajit; Islam, Saiful M.; Subrahmanyam, K. S.

Heavy metal ions (Cd 2+, Hg 2+, As 3+ and Pb 2+) are an important contributor to the contamination of groundwater and other water bodies in and around industrial areas. Herein, we demonstrate the rapid and efficient capacity of a layered metal sulfide material, K2xSn4-xS8-x (x = 0.65-1, KTS-3) for heavy metal ion removal from water. The effect of concentration, pH, kinetics, and competitive ions such as Na +/Ca 2+ on the heavy metal ion removal capacity of KTS-3 was systematically investigated. X-ray photoelectron spectroscopy (XPS), elemental analyses, and powder X-ray diffraction studies revealed that the heavy metal ion-exchange ofmore » KTS-3 is complete (quantitative replacement of all potassium ions) and topotactic. The heavy metal ion-exchange by using KTS-3 follows the Langmuir-Freundlich model with high exchange capacities, q(m) 205(17) mg g -1 for Cd 2+, 372(21) mg g -1 for Hg 2+ and 391(89) mg g -1 for Pb 2+. KTS-3 retains excellent heavy metal ion-exchange capacity even in very high concentration (1 M) of competing ions (Na +/Ca 2+) and also over a broad pH range (2-12). KTS-3 also exhibits very good ion-exchange capacity for precious Ag + and toxic As 3+ ions. The kinetics of heavy metal ion adsorption by KTS-3 are rapid (absorbs all ions within a few minutes). These properties and the environmentally friendly character of KTS-3 make it a promising candidate for sequestration of heavy metal ions from water.« less

Modeling the ion transfer and polarization of ion exchange membranes in bioelectrochemical systems.

PubMed

Harnisch, Falk; Warmbier, Robert; Schneider, Ralf; Schröder, Uwe

2009-06-01

An explicit numerical model for the charge balancing ion transfer across monopolar ion exchange membranes under conditions of bioelectrochemical systems is presented. Diffusion and migration equations have been solved according to the Nernst-Planck Equation and the resulting ion concentrations, pH values and the resistance values of the membrane for different conditions were computed. The modeling results underline the principle limitations of the application of ion exchange membranes in biological fuel cells and electrolyzers, caused by the inherent occurrence of a pH-gradient between anode and cathode compartment, and an increased ohmic membrane resistance at decreasing electrolyte concentrations. Finally, the physical and numerical limitations of the model are discussed.

Characterizing multiple metal ion binding sites within a ribozyme by cadmium-induced EPR silencing

PubMed Central

Kisseleva, Natalia; Kraut, Stefanie; Jäschke, Andres; Schiemann, Olav

2007-01-01

In ribozyme catalysis, metal ions are generally known to make structural and∕or mechanistic contributions. The catalytic activity of a previously described Diels-Alderase ribozyme was found to depend on the concentration of divalent metal ions, and crystallographic data revealed multiple binding sites. Here, we elucidate the interactions of this ribozyme with divalent metal ions in solution using electron paramagnetic resonance (EPR) spectroscopy. Manganese ion titrations revealed five high-affinity Mn2+ binding sites with an upper Kd of 0.6±0.2 μM. In order to characterize each binding site individually, EPR-silent Cd2+ ions were used to saturate the other binding sites. This cadmium-induced EPR silencing showed that the Mn2+ binding sites possess different affinities. In addition, these binding sites could be assigned to three different types, including innersphere, outersphere, and a Mn2+ dimer. Based on simulations, the Mn2+-Mn2+ distance within the dimer was found to be ∼6 Å, which is in good agreement with crystallographic data. The EPR-spectroscopic characterization reveals no structural changes upon addition of a Diels-Alder product, supporting the concept of a preorganized catalytic pocket in the Diels-Alder ribozyme and the structural role of these ions. PMID:19404418

Extraction of steroidal glucosiduronic acids from aqueous solutions by anionic liquid ion-exchangers

PubMed Central

Mattox, Vernon R.; Litwiller, Robert D.; Goodrich, June E.

1972-01-01

A pilot study on the extraction of three steroidal glucosiduronic acids from water into organic solutions of liquid ion-exchangers is reported. A single extraction of a 0.5mm aqueous solution of either 11-deoxycorticosterone 21-glucosiduronic acid or cortisone 21-glucosiduronic acid with 0.1m-tetraheptylammonium chloride in chloroform took more than 99% of the conjugate into the organic phase; under the same conditions, the very polar conjugate, β-cortol 3-glucosiduronic acid, was extracted to the extent of 43%. The presence of a small amount of chloride, acetate, or sulphate ion in the aqueous phase inhibited extraction, but making the aqueous phase 4.0m with ammonium sulphate promoted extraction strongly. An increase in the concentration of ion-exchanger in the organic phase also promoted extraction. The amount of cortisone 21-glucosiduronic acid extracted by tetraheptylammonium chloride over the pH range of 3.9 to 10.7 was essentially constant. Chloroform solutions of a tertiary, a secondary, or a primary amine hydrochloride also will extract cortisone 21-glucosiduronic acid from water. The various liquid ion exchangers will extract steroidal glucosiduronic acid methyl esters from water into chloroform, although less completely than the corresponding free acids. The extraction of the glucosiduronic acids from water by tetraheptylammonium chloride occurs by an ion-exchange process; extraction of the esters does not involve ion exchange. PMID:5075264

21 CFR 173.25 - Ion-exchange resins.

Code of Federal Regulations, 2014 CFR

2014-04-01

... weight of the starting quantity of cellulose. (b) Ion-exchange resins are used in the purification of foods, including potable water, to remove undesirable ions or to replace less desirable ions with one or... paragraphs (a) (12) and (16) of this section are used to treat water for use in the manufacture of distilled...

Nanosilver - does it have only one face?

PubMed

Likus, Wirginia; Bajor, Grzegorz; Siemianowicz, Krzysztof

2013-01-01

Silver nanoparticles (NPs) have at least one dimension of a particle smaller than 100 nm and contain 20-15,000 silver atoms. Due to its antibacterial activity nanosilver (NS) is used for medical purposes. NS particles can be obtained by various methods. Potentially, the best method of the NS synthesis for medical purposes is based on a brief flow of electric current between two silver electrodes placed in deionized water. It is accepted that the major antibacterial effect of silver is its partial oxidation and releasing silver ions, which interact with thiol groups of peptidoglicans of bacterial cell wall, and proteins of the cell membrane causing cell lysis. Silver ions can also bind to bacterial DNA preventing its replication and stopping synthesis of bacterial proteins. The rise in exposure to silver NPs has spurred interest into their toxicology. NS undergoes a set of biochemical transformations including accelerated oxidative dissolution in gastric acid, binding to thiol groups of serum and tissue proteins, exchange between thiol groups, sulfides and selenides, binding to selenoproroteins and photoreduction in skin to zerovalent metallic silver. Animal studies have shown that exposure to NS may lead to liver and spleen damage. NS can also stimulate an increased secretion of proinflammatory cytokines by monocytes. As a spectrum of NS applications is still growing, the complex evaluation of a safety of its use becomes an important task. This requires an elucidation of not only the influence of NS on human cells and organism, but also its biotransformation in organism and in environment.

A novel electrochemical ion exchange system and its application in water treatment.

PubMed

Li, Yansheng; Li, Yongbin; Liu, Zhigang; Wu, Tao; Tian, Ying

2011-06-01

A novel electrochemical ion exchange system with porous cylinder electrodes is proposed for treatment of wastewater. This system can be used for desalination without the costly ion-exchange membrane and extra chemical reagents. Since the electrodes are completely uniform and no ion-exchange membrane was used in this system, it can be operated by switching anodes and cathodes flexibly for eliminating the scaling on the surface of electrodes. The strong base ion-exchange resin grains placed among the anode and cathode have played as supporting electrolyte, which is capable for the treatment of wastewater with low conductivity. The concentrated and neutralized anolyte containing chlorine is effective for disinfection and contaminants removal. Under the experimental conditions, the removal percentage of total dissolved salts was 83% and the removal percentage of chemical oxygen demand was 92% without consumption of extra chemical reagents. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

The transfer behavior of different ions across anion and cation exchange membranes under vanadium flow battery medium

NASA Astrophysics Data System (ADS)

Sun, Jiawei; Li, Xianfeng; Xi, Xiaoli; Lai, Qinzhi; Liu, Tao; Zhang, Huamin

2014-12-01

The transfer behavior of different ions (V2+, V3+, VO2+, VO2+, H+, SO42-) across ion exchange membranes is investigated under vanadium flow battery (VFB) operating condition. VX-20 anion exchange membrane (AEM) and Nafion 115 cation exchange membrane (CEM) are selected to investigate the influence of fixed charged groups on the transfer behavior of different ions. The interaction between different ions and water is discussed in detail aiming to ascertain the variation of different ions in the charge-discharge process. Under the VFB medium, the transfer behavior and function of different ions are very different for the AEM and CEM. V2+ ions at the negative side accumulate when VFB is assembled with Nafion 115, while the VO2+ ions at the positive side accumulate for VX-20. The SO42- ions will transfer across Nafion 115 to balance the charges and the protons can balance the charges of VX-20. Finally the capacity fade mechanism of different membranes is investigated, showing that the capacity decay of VFB assembled with Nafion 115 mainly results from the cross mix of vanadium ions across the membrane, however, for VX-20, the side reactions can be the major reason. This paper provides important information about electrolyte for the application of VFB.

The international water conference proceedings

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

Guseman, J.R.

1984-10-01

This book provides information on computer applications to water chemistry control, groundwater, membrane technology, instrumentation/analytical techniques and ion exchange. Other topics of discussion include cooling water, biocontrol, the hydraulic properties of ion exchange resins, steam electric power plant aqueous discharges and colorimetric determination of trace benzotriazole or tolytriazole. Water chemistry guidelines for large steam generating power plants is discussed, as well as wastewater treatment, boiler water conditioning and ion exchange/computer related topics.

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

PubMed Central

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

2015-01-01

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

Experiments on Anion Exchange with Amberlite Ir-120 Resin; ENSAYOS DE INTERCAMBIO ANIONICO CON RESINA AMBERLITA Ir-120

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

Cellini, R.F.; Palomino, J.V.

1956-01-01

The ion exchange of the uranyl ion on Amberlite Ir-120 resin was studied with different uranyl ion concentrations. Elution with sulfuric acid was investlgated and the elution curve for the experimental conditions was determined. From the concentrations of the ions of Cu/sup 2+/, Ni/sup 2+/, Fe/sup 3+/, Cd/sup 2+/, Mn/sup 2+/, and Cr/sup 3+/ the maximum exchange capacity was tested and elation curves with 4 N sulfuric acid were obtained. (tr-auth)

Differential Cationization of Fatty Acids with Monovalent Cations Studied by ESI-MS/MS and Computational Approach.

PubMed

Sudarshana Reddy, B; Pavankumar, P; Sridhar, L; Saha, Soumen; Narahari Sastry, G; Prabhakar, S

2018-04-24

The intercellular and intracellular transport of charged species (Na + /K + ) entail interaction of the ions with neutral organic molecules and formation of adduct ions. The rate of transport of the ions across the cell membrane(s) may depend on the stability of the adduct ions, which in turn rely on structural aspects of the organic molecules that interact with the ions. Positive ion ESI mass spectra were recorded for the solutions containing fatty acids (FAs) and monovalent cations (X=Li + , Na + , K + , Rb + and Cs + ). Product ion spectra of the [FA+X] + ions were recorded at different collision energies. Theoretical studies were exploited under both gas phase and solvent phase to investigate the structural effects of the fatty acids during cationization. Stability of [FA+X] + adduct ions were further estimated by means of AIM topological analyses and interaction energy (IE) values. Positive ion ESI-MS analyses of the solution of FAs and X + ions showed preferential binding of the K + ions to FAs. The K + ion binding increased with the increase in number of double bonds of FAs, while decreased with increase in the number of carbons of FAs. Dissociation curves of [FA+X] + ions indicated the relative stability order of the [FA+X] + ions and it was in line with the observed trends in ESI-MS. The solvent phase computational studies divulged the mode of binding and the binding efficiencies of different FAs with monovalent cations. Among the studied monovalent cations, the cationization of FAs follow the order K + >Na + >Li + >Rb + >Cs + . The docosahexaenoic acid showed high efficiency in binding with K + ion. The K + ion binding efficiency of FAs depends on the number of double bonds in unsaturated FAs and the carbon chain length in saturated FAs. The cationization trends of FAs obtained from the ESI-MS, ESI-MS/MS analyses were in good agreement with solvent phase computational studies. This article is protected by copyright. All rights reserved.

Mechanism of Metal Ion Activation of the Diphtheria Toxin Repressor DtxR

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

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

2005-01-01

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

Role of the constant region domain in the structural diversity of human antibody light chains.

PubMed

Hifumi, Emi; Taguchi, Hiroaki; Kato, Ryuichi; Uda, Taizo

2017-04-01

Issues regarding the structural diversity (heterogeneity) of an antibody molecule have been the subject of discussion along with the development of antibody drugs. Research on heterogeneity has been extensive in recent years, but no clear solution has been reached. Heterogeneity is also observed in catalytic antibody κ light chains (CLs). In this study, we investigated how the constant region domain of CLs concerns structural diversity because it is a simple and good example for elucidating heterogeneity. By means of cation-exchange chromatography, SDS-PAGE, and 2-dimensional electrophoresis for the CL, multimolecular forms consisting of different electrical charges and molecular sizes coexisted in the solution, resulting in the similar heterogeneity of the full length of CLs. The addition of copper ion could cause the multimolecular forms to change to monomolecular forms. Copper ion contributed greatly to the enrichment of the dimer form of CL and the homogenization of the differently charged CLs. Two molecules of the CL protein bound one copper ion. The binding affinity of the ion was 48.0 μM -1 Several divalent metal ions were examined, but only zinc showed a similar effect.-Hifumi, E., Taguchi, H., Kato, R., Uda, T. Role of the constant region domain in the structural diversity of human antibody light chains. © FASEB.

Effect of grinding and fluoride-gel exposure on strength of ion-exchanged porcelain.

PubMed

Anusavice, K J; Hojjatie, B; Chang, T C

1994-08-01

Strengthening of dental porcelain through a diffusion heat treatment at 450 degrees C of a potassium-enriched, ion-exchange surface coating has been demonstrated in several recent studies. However, little attention has been focused on the potential strength reduction of these materials when the treated surfaces are ground or etched under clinically simulated conditions. The objective of this study was to test the hypothesis that partial removal of the surface layers of ion-exchanged porcelains by grinding or exposure to acidulated fluoride gel will significantly reduce their flexure strength. Nine groups of body porcelain disks were ion-exchanged at 450 degrees C for 30 min. One of these groups was subjected to ion exchange and no further surface treatment. Eight specimen groups were subjected to the following procedures after ion exchange: grinding to depths of 50 microns, 100 microns, 150 microns, 200 microns, and 250 microns, and exposure to acidulated fluoride for 30 min, 60 min, and 300 min. A tenth group (FC) was fired at 960 degrees C and fast-cooled in air, but the disks were not subjected to the ion-exchange treatment. Surface stress was calculated from measured values of cracks induced in the treated surfaces. Fluoride exposure for up to 60 min resulted in a significant decrease in surface compression (P < or = 0.05), although this treatment had no effect on strength. Grinding to a depth of from 100 microns to 250 microns caused a significant decrease in strength, while removal of a 50-microns layer caused no significant change (P > 0.05).

Mapping the contact surfaces in the Lamin A:AIMP3 complex by hydrogen/deuterium exchange FT-ICR mass spectrometry.

PubMed

Tao, Yeqing; Fang, Pengfei; Kim, Sunghoon; Guo, Min; Young, Nicolas L; Marshall, Alan G

2017-01-01

Aminoacyl-tRNA synthetases-interacting multifunctional protein3 (AIMP3/p18) is involved in the macromolecular tRNA synthetase complex via its interaction with several aminoacyl-tRNA synthetases. Recent reports reveal a novel function of AIMP3 as a tumor suppressor by accelerating cellular senescence and causing defects in nuclear morphology. AIMP3 specifically mediates degradation of mature Lamin A (LmnA), a major component of the nuclear envelope matrix; however, the mechanism of how AIMP3 interacts with LmnA is unclear. Here we report solution-phase hydrogen/deuterium exchange (HDX) for AIMP3, LmnA, and AIMP3 in association with the LmnA C-terminus. Reversed-phase LC coupled with LTQ 14.5 T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results in high mass accuracy and resolving power for comparing the D-uptake profiles for AIMP3, LmnA, and their complex. The results show that the AIMP3-LmnA interaction involves one of the two putative binding sites and an adjacent novel interface on AIMP3. LmnA binds AIMP3 via its extreme C-terminus. Together these findings provide a structural insight for understanding the interaction between AIMP3 and LmnA in AIMP3 degradation.

Plasma particle simulation of electrostatic ion thrusters

NASA Technical Reports Server (NTRS)

Peng, Xiaohang; Keefer, Dennis; Ruyten, Wilhelmus

1990-01-01

Charge exchange collisons between beam ions and neutral propellant gas can result in erosion of the accelerator grid surfaces of an ion engine. A particle in cell (PIC) is developed along with a Monte Carlo method to simulate the ion dynamics and charge exchange processes in the grid region of an ion thruster. The simulation is two-dimensional axisymmetric and uses three velocity components (2d3v) to investigate the influence of charge exchange collisions on the ion sputtering of the accelerator grid surfaces. An example calculation has been performed for an ion thruster operated on xenon propellant. The simulation shows that the greatest sputtering occurs on the downstream surface of the grid, but some sputtering can also occur on the upstream surface as well as on the interior of the grid aperture.

Characterization of the internal ion environment of biofilms based on charge density and shape of ion.

PubMed

Kurniawan, Andi; Tsuchiya, Yuki; Eda, Shima; Morisaki, Hisao

2015-12-01

Biofilm polymers contain both electrically positively and negatively charged sites. These charged sites enable the biofilm to trap and retain ions leading to an important role of biofilm such as nutrient recycling and pollutant purification. Much work has focused on the ion-exchange capacity of biofilms, and they are known to adsorb ions through an exchange mechanism between the ions in solution and the ions adsorbed to the charged sites on the biofilm polymer. However, recent studies suggest that the adsorption/desorption behavior of ions in a biofilm cannot be explained solely by this ion exchange mechanism. To examine the possibility that a substantial amount of ions are held in the interstitial region of the biofilm polymer by an electrostatic interaction, intact biofilms formed in a natural environment were immersed in distilled water and ion desorption was investigated. All of the detected ion species were released from the biofilms over a short period of time, and very few ions were subsequently released over more time, indicating that the interstitial region of biofilm polymers is another ion reserve. The extent of ion retention in the interstitial region of biofilms for each ion can be determined largely by charge density, |Z|/r, where |Z| is the ion valence as absolute value and r is the ion radius. The higher |Z|/r value an ion has, the stronger it is retained in the interstitial region of biofilms. Ion shape is also a key determinant of ion retention. Spherical and non-spherical ions have different correlations between the condensation ratio and |Z|/r. The generality of these findings were assured by various biofilm samples. Thus, the internal regions of biofilms exchange ions dynamically with the outside environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Purification and characterization of tomato polygalacturonase converter.

PubMed

Pressey, R

1984-10-15

Extracts of ripe tomatoes contain two forms of polygalacturonase (PG I and PG II). A heat-stable component that binds PG II to produce PG I has been isolated from tomato fruit. This component has been named polygalacturonase converter (PG converter). The PG converter has been purified by gel filtration, ion-exchange chromatography and chromatofocusing. It appears to be a protein with a relative molecular mass of 102000. It was readily inactivated by papain and pronase. The converter was labile at alkaline conditions, and treatment of PG I at pH 11 released free PG II. A similar factor with a lower molecular mass was extracted from tomato foliage.

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

USGS Publications Warehouse

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

1995-01-01

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

ION EXCHANGE SOFTENING: EFFECTS ON METAL CONCENTRATIONS

EPA Science Inventory

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

Qualitative analysis scheme based on the properties of ion exchangers (in French)

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

Machiroux, R.; Merciny, E.; Schreiber, A.

1973-01-01

A systematic scheme of qualitative analysis of some cations is presented. For didactic purposes the properties of cationic and anionic ion exchangers were used. At the present time, this scheme is limited to 23 ions, including Sr. (auth)

The mechanism of Cu+ transport ATPases: interaction with CU+ chaperones and the role of transient metal-binding sites.

PubMed

Padilla-Benavides, Teresita; McCann, Courtney J; Argüello, José M

2013-01-04

Cu(+)-ATPases are membrane proteins that couple the hydrolysis of ATP to the efflux of cytoplasmic Cu(+). In cells, soluble chaperone proteins bind and distribute cytoplasmic Cu(+), delivering the ion to the transmembrane metal-binding sites in the ATPase. The structure of Legionella pneumophila Cu(+)-ATPase (Gourdon, P., Liu, X. Y., Skjørringe, T., Morth, J. P., Møller, L. B., Pedersen, B. P., and Nissen, P. (2011) Nature 475, 59-64) shows that a kinked transmembrane segment forms a "platform" exposed to the cytoplasm. In addition, neighboring invariant Met, Asp, and Glu are located at the "entrance" of the ion path. Mutations of amino acids in these regions of the Archaeoglobus fulgidus Cu(+)-ATPase CopA do not affect ATPase activity in the presence of Cu(+) free in solution. However, Cu(+) bound to the corresponding chaperone (CopZ) could not activate the mutated ATPases, and in parallel experiments, CopZ was unable to transfer Cu(+) to CopA. Furthermore, mutation of a specific electronegative patch on the CopZ surface abolishes the ATPase activation and Cu(+) transference, indicating that the region is required for the CopZ-CopA interaction. Moreover, the data suggest that the interaction is driven by the complementation of the electropositive platform in the ATPase and the electronegative Cu(+) chaperone. This docking likely places the Cu(+) proximal to the conserved carboxyl and thiol groups in the entrance site that induce metal release from the chaperone via ligand exchange. The initial interaction of Cu(+) with the pump is transient because Cu(+) is transferred from the entrance site to transmembrane metal-binding sites involved in transmembrane translocation.

Proteasome Inhibition Contributed to the Cytotoxicity of Arenobufagin after Its Binding with Na, K-ATPase in Human Cervical Carcinoma HeLa Cells

PubMed Central

Zhen, Hong; Huang, Ming; Zheng, Xi; Feng, Lixing; Jiang, Baohong; Yang, Min; Wu, Wanying; Liu, Xuan; Guo, Dean

2016-01-01

Although the possibility of developing cardiac steroids/cardiac glycosides as novel cancer therapeutic agents has been recognized, the mechanism of their anticancer activity is still not clear enough. Toad venom extract containing bufadienolides, which belong to cardiac steroids, has actually long been used as traditional Chinese medicine in clinic for cancer therapy in China. The cytotoxicity of arenobufagin, a bufadienolide isolated from toad venom, on human cervical carcinoma HeLa cells was checked. And, the protein expression profile of control HeLa cells and HeLa cells treated with arenobufagin for 48 h was analyzed using two-dimensional electrophoresis, respectively. Differently expressed proteins in HeLa cells treated with arenobufagin were identified and the pathways related to these proteins were mapped from KEGG database. Computational molecular docking was performed to verify the binding of arenobufagin and Na, K-ATPase. The effects of arenobufagin on Na, K-ATPase activity and proteasome activity of HeLa cells were checked. The protein-protein interaction network between Na, K-ATPase and proteasome was constructed and the expression of possible intermediate proteins ataxin-1 and translationally-controlled tumor protein in HeLa cells treated with arenobufagin was then checked. Arenobufagin induced apoptosis and G2/M cell cycle arrest in HeLa cells. The cytotoxic effect of arenobufagin was associated with 25 differently expressed proteins including proteasome-related proteins, calcium ion binding-related proteins, oxidative stress-related proteins, metabolism-related enzymes and others. The results of computational molecular docking revealed that arenobufagin was bound in the cavity formed by the transmembrane alpha subunits of Na, K-ATPase, which blocked the pathway of extracellular Na+/K+ cation exchange and inhibited the function of ion exchange. Arenobufagin inhibited the activity of Na, K-ATPase and proteasome, decreased the expression of Na, K-ATPase α1 and α3 subunits and increased the expression of WEE1 in HeLa cells. Antibodies against Na, K-ATPase α1 and α3 subunits alone or combinated with arenobufagin also inhibited the activity of proteasome. Furthermore, the expression of the possible intermediate proteins ataxin-1 and translationally-controlled tumor protein was increased in HeLa cells treated with arenobufagin by flow cytometry analysis, respectively. These results indicated that arenobufagin might directly bind with Na, K-ATPase α1 and α3 subunits and the inhibitive effect of arenobufagin on proteasomal activity of HeLa cells might be related to its binding with Na, K-ATPase. PMID:27428326

Proteasome Inhibition Contributed to the Cytotoxicity of Arenobufagin after Its Binding with Na, K-ATPase in Human Cervical Carcinoma HeLa Cells.

PubMed

Yue, Qingxi; Zhen, Hong; Huang, Ming; Zheng, Xi; Feng, Lixing; Jiang, Baohong; Yang, Min; Wu, Wanying; Liu, Xuan; Guo, Dean

2016-01-01

Although the possibility of developing cardiac steroids/cardiac glycosides as novel cancer therapeutic agents has been recognized, the mechanism of their anticancer activity is still not clear enough. Toad venom extract containing bufadienolides, which belong to cardiac steroids, has actually long been used as traditional Chinese medicine in clinic for cancer therapy in China. The cytotoxicity of arenobufagin, a bufadienolide isolated from toad venom, on human cervical carcinoma HeLa cells was checked. And, the protein expression profile of control HeLa cells and HeLa cells treated with arenobufagin for 48 h was analyzed using two-dimensional electrophoresis, respectively. Differently expressed proteins in HeLa cells treated with arenobufagin were identified and the pathways related to these proteins were mapped from KEGG database. Computational molecular docking was performed to verify the binding of arenobufagin and Na, K-ATPase. The effects of arenobufagin on Na, K-ATPase activity and proteasome activity of HeLa cells were checked. The protein-protein interaction network between Na, K-ATPase and proteasome was constructed and the expression of possible intermediate proteins ataxin-1 and translationally-controlled tumor protein in HeLa cells treated with arenobufagin was then checked. Arenobufagin induced apoptosis and G2/M cell cycle arrest in HeLa cells. The cytotoxic effect of arenobufagin was associated with 25 differently expressed proteins including proteasome-related proteins, calcium ion binding-related proteins, oxidative stress-related proteins, metabolism-related enzymes and others. The results of computational molecular docking revealed that arenobufagin was bound in the cavity formed by the transmembrane alpha subunits of Na, K-ATPase, which blocked the pathway of extracellular Na+/K+ cation exchange and inhibited the function of ion exchange. Arenobufagin inhibited the activity of Na, K-ATPase and proteasome, decreased the expression of Na, K-ATPase α1 and α3 subunits and increased the expression of WEE1 in HeLa cells. Antibodies against Na, K-ATPase α1 and α3 subunits alone or combinated with arenobufagin also inhibited the activity of proteasome. Furthermore, the expression of the possible intermediate proteins ataxin-1 and translationally-controlled tumor protein was increased in HeLa cells treated with arenobufagin by flow cytometry analysis, respectively. These results indicated that arenobufagin might directly bind with Na, K-ATPase α1 and α3 subunits and the inhibitive effect of arenobufagin on proteasomal activity of HeLa cells might be related to its binding with Na, K-ATPase.

A new approach to evaluate natural zeolite ability to sorb lead (Pb) from aqueous solutions

NASA Astrophysics Data System (ADS)

Drosos, Evangelos I. P.; Karapanagioti, Hrissi K.

2013-04-01

Lead (Pb) is a hazardous pollutant commonly found in aquatic ecosystems. Among several methods available, the addition of sorbent amendments to soils or sediments is attractive, since its application is relatively simple, while it can also be cost effective when a low cost and re-usable sorbent is used; e.g. natural zeolites. Zeolites are crystalline aluminosilicates with a three-dimensional structure composed of a set of cavities occupied by large ions and water molecules. Zeolites can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+, which are rather loosely held and can readily be exchanged for others in an aqueous solution. Natural zeolites are capable of removing cations, such as lead, from aqueous solutions by ion exchange. There is a wide variation in the cation exchange capacity (CEC) of natural zeolites because of the different nature of various zeolites cage structures, natural structural defects, adsorbed ions, and their associated gangue minerals. Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, such as clays and feldspars, metals, quartz, or other zeolites as well. These impurities affect the CEC even for samples originated from the same region but from a different source. CEC of the material increases with decreasing impurity content. Potentially exchangeable ions in such impurities do not necessarily participate in ion exchange mechanism, while, in some cases, impurities may additionally block the access to active sites. For zeoliferous rocks having the same percentage of a zeolitic phase, the CEC increases with decreasing Si/Al ratio, as the more Si ions are substituted by Al ions, the more negative the valence of the matrix becomes. Sodium seems to be the most effective exchangeable ion for lead. On the contrary, it is unlikely that the potassium content of the zeolite would be substituted. A pretreatment with high concentration solutions of Na, such as 2 M NaCl, can significantly improve zeolite CEC by bringing the material to near homoionic form. pH and temperature are the critical parameters for using natural zeolites as sorbents. Zeolites should not be used in extremely acidic, neither in extremely basic pH conditions, except for very short times. The exchange of Pb, requires low solution pH, to avoid precipitation but not too low because the H+ are competitive ions for ion exchange; as a result the zeolite CEC related to Pb removal may be downgraded. If pH enters the basic range (e.g. pH>8), more aquatic complexes with lower positive valence than those prevailing in lower pH are produced; these complexes are less attracted by the negative charged zeolitic matrix. Pb uptake is favored at higher temperatures as ion exchange (including the diffusion of exchangeable ions inside the material and the medium, and vice versa) is an endothermic process. With the increase of temperature there is a decrease in hydration of all available exchangeable cations that eases the movement within the channels of the solid matrix. Additionally, the mobility of the potassium ions, present in the zeolitic material, also increases with the temperature resulting in enhanced CEC.

Effects of Thermal and Pressure Histories on the Chemical Strengthening of Sodium Aluminosilicate Glass

NASA Astrophysics Data System (ADS)

Svenson, Mouritz; Thirion, Lynn; Youngman, Randall; Mauro, John; Bauchy, Mathieu; Rzoska, Sylwester; Bockowski, Michal; Smedskjaer, Morten

2016-03-01

Glasses can be chemically strengthened through the ion exchange process, wherein smaller ions in the glass (e.g., Na+) are replaced by larger ions from a salt bath (e.g., K+). This develops a compressive stress (CS) on the glass surface, which, in turn, improves the damage resistance of the glass. The magnitude and depth of the generated CS depends on the thermal and pressure histories of the glass prior to ion exchange. In this study, we investigate the ion exchange-related properties (mutual diffusivity, CS, and hardness) of a sodium aluminosilicate glass, which has been densified through annealing below the initial fictive temperature of the glass or through pressure-quenching from the glass transition temperature at 1 GPa prior to ion exchange. We show that the rate of alkali interdiffusivity depends only on the density of the glass, rather than on the applied densification method. However, we also demonstrate that for a given density, the increase in CS and increase in hardness induced by ion exchange strongly depends on the densification method. Specifically, at constant density, the CS and hardness values achieved through thermal annealing are larger than those achieved through pressure-quenching. These results are discussed in relation to the structural changes in the environment of the network-modifier and the overall network densification.

Antimicrobial properties of zeolite-X and zeolite-A ion-exchanged with silver, copper, and zinc against a broad range of microorganisms.

PubMed

Demirci, Selami; Ustaoğlu, Zeynep; Yılmazer, Gonca Altın; Sahin, Fikrettin; Baç, Nurcan

2014-02-01

Zeolites are nanoporous alumina silicates composed of silicon, aluminum, and oxygen in a framework with cations, water within pores. Their cation contents can be exchanged with monovalent or divalent ions. In the present study, the antimicrobial (antibacterial, anticandidal, and antifungal) properties of zeolite type X and A, with different Al/Si ratio, ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions were investigated individually. The study presents the synthesis and manufacture of four different zeolite types characterized by scanning electron microscopy and X-ray diffraction. The ion loading capacity of the zeolites was examined and compared with the antimicrobial characteristics against a broad range of microorganisms including bacteria, yeast, and mold. It was observed that Ag(+) ion-loaded zeolites exhibited more antibacterial activity with respect to other metal ion-embedded zeolite samples. The results clearly support that various synthetic zeolites can be ion exchanged with Ag(+), Zn(2+), and Cu(2+) ions to acquire antimicrobial properties or ion-releasing characteristics to provide prolonged or stronger activity. The current study suggested that zeolite formulations could be combined with various materials used in manufacturing medical devices, surfaces, textiles, or household items where antimicrobial properties are required.

Synthesis of polymer ion-exchange hydrogels under γ - irradiation 60Co

NASA Astrophysics Data System (ADS)

Le, V. M.; Zhevnyak, V. D.; Pak, V. Kh; Ananev, V. A.; Borodin, U. V.

2015-04-01

We have reported earlier about the modification of ion-exchange hydrogel under the influence of gamma radiation. The optimal absorbed dose of irradiation had been choosen for radiation modification of polymer hydrogels by ionits to produce products with a high content of the gel - fractions and sufficient mechanical properties. The dependence of the static exchange capacity of hydrogels on the type of ionit and its fractional composition had been studied. The dependence of the static exchange capacity of the quantitative composition of the ionit in the volume of the hydrogel had been investigated. The ion-exchange medical eye lenses had been made under selected conditions of synthesis. Their sorption properties had been studied.

Action of some foreign cations and anions on the chloride permeability of frog muscle

PubMed Central

Hutter, O. F.; Warner, Anne E.

1967-01-01

1. Evidence for the existence in skeletal muscle of a specific cation binding system capable of lowering the chloride permeability was obtained by testing the effect of several metal ion species upon the efflux of 36Cl from frog muscles equilibrated in high-KCl solution. 2. Cu2+, Zn2+ and UO22+ ions, when present in concentrations of approximately 10-4 M in inactive wash solution at pH 7·4 slowed the efflux of 36Cl to half its original value. At pH 5·0, when the chloride permeability was already low as a consequence of hydrogen ion binding, these metal ions had little further effect. 3. Presence of Ni2+, Co2+, Pb2+, Ce3+ and La3+ in 10-4 M or higher concentrations had no detectable influence on the 36Cl efflux. Wide variations in Ca2+ concentration were similarly ineffective. 4. The influence of more adsorbable anions on the chloride permeability was examined at different pH values. Extracellular iodide greatly slowed the rapid efflux of 36Cl into alkaline solution. In acid solutions, when the chloride permeability was already low, the effect of iodide was less pronounced, but still demonstrable. The chloride permeability was consequently increased to a lesser extent by a rise in pH in the presence of iodide. 5. The efflux of iodide and bromide was measured at different pH values under conditions of self exchange. In alkaline solution the permeabilities to iodide and bromide were considerably lower than that to chloride. In acid solution the membrane differentiated less between anion species of different adsorbability. PMID:6040156

Properties of cupric ions in benzylamine oxidase from pig plasma as studied by magnetic-resonance and kinetic methods.

PubMed Central

Barker, R; Boden, N; Cayley, G; Charlton, S C; Henson, R; Holmes, M C; Kelly, I D; Knowles, P F

1979-01-01

Benzylamine oxidase from pig plasma has been studied by a variety of chemical and physical techniques. 1. Analytical ultracentrifugation, gel electrophoresis and isoelectric-focusing studies suggest that the enzyme is composed of two subunits with closely similar primary structures. 2. E.s.r. and n.m.r. measurements show that the enzyme contains two well-separated (greater than 0.6 nm) Cu2+ ions at chemically distinct sites. Each Cu2+ ion is coordinated by two water molecules, one 'axial' and the other 'equatorial'. Both water molecules undergo fast exchange (10(5)--10(8) s-1) with solvent and are deprotonated in the pH range 8--9, but only the equatorial water molecule is displaced by the inhibitors N3- and CN-. 3. Kinetic and e.s.r. measurements show that azide and cyanide compete against O2 binding and also make the two Cu2+ sites identical. It is concluded that Cu2+ must participate in the re-oxidation of reduced enzyme by molecular O2. PMID:218560

Statistical modeling of competitive threshold collision-induced dissociation

NASA Astrophysics Data System (ADS)

Rodgers, M. T.; Armentrout, P. B.

1998-08-01

Collision-induced dissociation of (R1OH)Li+(R2OH) with xenon is studied using guided ion beam mass spectrometry. R1OH and R2OH include the following molecules: water, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol. In all cases, the primary products formed correspond to endothermic loss of one of the neutral alcohols, with minor products that include those formed by ligand exchange and loss of both ligands. The cross-section thresholds are interpreted to yield 0 and 298 K bond energies for (R1OH)Li+-R2OH and relative Li+ binding affinities of the R1OH and R2OH ligands after accounting for the effects of multiple ion-molecule collisions, internal energy of the reactant ions, and dissociation lifetimes. We introduce a means to simultaneously analyze the cross sections for these competitive dissociations using statistical theories to predict the energy dependent branching ratio. Thermochemistry in good agreement with previous work is obtained in all cases. In essence, this statistical approach provides a detailed means of correcting for the "competitive shift" inherent in multichannel processes.

Location of Bromide Ions in Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

1998-01-01

Anions have been shown to play a dominant role in the crystallization of chicken egg white lysozyme from salt solutions. Previous studies employing X-ray crystallography had found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystal grown in bromide and chloride solutions. Five possible anion binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four of these sites corresponded to four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion binding sites in lysozyme remain unchanged, even when different anions and different crystal forms of lysozyme are employed.

Locations of Bromide Ions in Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

1998-01-01

Anions have been shown to play a dominant role in the crystallization of chicken egg-white lysozyme from salt solutions. Previous studies employing X-ray crystallography have found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystals grown in bromide and chloride solutions. Five possible anion-binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four further sites were found which corresponded to the four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion-binding sites in lysozyme remain unchanged even when different anions and different crystal forms of lysozyme are employed.

Influence of binding pH and protein solubility on the dynamic binding capacity in hydrophobic interaction chromatography.

PubMed

Baumann, Pascal; Baumgartner, Kai; Hubbuch, Jürgen

2015-05-29

Hydrophobic interaction chromatography (HIC) is one of the most frequently used purification methods in biopharmaceutical industry. A major drawback of HIC, however, is the rather low dynamic binding capacity (DBC) obtained when compared to e.g. ion exchange chromatography (IEX). The typical purification procedure for HIC includes binding at neutral pH, independently of the proteins nature and isoelectric point. Most approaches to process intensification are based on resin and salt screenings. In this paper a combination of protein solubility data and varying binding pH leads to a clear enhancement of dynamic binding capacity. This is shown for three proteins of acidic, neutral, and alkaline isoelectric points. High-throughput solubility screenings as well as miniaturized and parallelized breakthrough curves on Media Scout RoboColumns (Atoll, Germany) were conducted at pH 3-10 on a fully automated robotic workstation. The screening results show a correlation between the DBC and the operational pH, the protein's isoelectric point and the overall solubility. Also, an inverse relationship of DBC in HIC and the binding kinetics was observed. By changing the operational pH, the DBC could be increased up to 30% compared to the standard purification procedure performed at neutral pH. As structural changes of the protein are reported during HIC processes, the applied samples and the elution fractions were proven not to be irreversibly unfolded. Copyright © 2015 Elsevier B.V. All rights reserved.

Separation of hemicellulose-derived saccharides from wood hydrolysate by lime and ion exchange resin.

PubMed

Wang, Xiaojun; Zhuang, Jingshun; Fu, Yingjuan; Tian, Guoyu; Wang, Zhaojiang; Qin, Menghua

2016-04-01

A combined process of lime treatment and mixed bed ion exchange was proposed to separate hemicellulose-derived saccharides (HDS) from prehydrolysis liquor (PHL) of lignocellulose as value added products. The optimization of lime treatment achieved up to 44.2% removal of non-saccharide organic compounds (NSOC), mainly colloidal substances, with negligible HDS degradation at 0.5% lime level and subsequent neutralization by phosphoric acid. The residual NSOC and calcium ions in lime-treated PHL were eliminated by mixed bed ion exchange. The breakthrough curves of HDS and NSOC showed selective retention toward NSOC, leading to 75% HDS recovery with 95% purity at 17 bed volumes of exchange capacity. In addition, macroporous resin showed higher exchange capacity than gel resin as indicated by the triple processing volume. The remarkable selectivity of the combined process suggested the feasibility for HDS separation from PHL. Copyright © 2016 Elsevier Ltd. All rights reserved.

Predicting Salt Permeability Coefficients in Highly Swollen, Highly Charged Ion Exchange Membranes.

PubMed

Kamcev, Jovan; Paul, Donald R; Manning, Gerald S; Freeman, Benny D

2017-02-01

This study presents a framework for predicting salt permeability coefficients in ion exchange membranes in contact with an aqueous salt solution. The model, based on the solution-diffusion mechanism, was tested using experimental salt permeability data for a series of commercial ion exchange membranes. Equilibrium salt partition coefficients were calculated using a thermodynamic framework (i.e., Donnan theory), incorporating Manning's counterion condensation theory to calculate ion activity coefficients in the membrane phase and the Pitzer model to calculate ion activity coefficients in the solution phase. The model predicted NaCl partition coefficients in a cation exchange membrane and two anion exchange membranes, as well as MgCl 2 partition coefficients in a cation exchange membrane, remarkably well at higher external salt concentrations (>0.1 M) and reasonably well at lower external salt concentrations (<0.1 M) with no adjustable parameters. Membrane ion diffusion coefficients were calculated using a combination of the Mackie and Meares model, which assumes ion diffusion in water-swollen polymers is affected by a tortuosity factor, and a model developed by Manning to account for electrostatic effects. Agreement between experimental and predicted salt diffusion coefficients was good with no adjustable parameters. Calculated salt partition and diffusion coefficients were combined within the framework of the solution-diffusion model to predict salt permeability coefficients. Agreement between model and experimental data was remarkably good. Additionally, a simplified version of the model was used to elucidate connections between membrane structure (e.g., fixed charge group concentration) and salt transport properties.

Waste separation and pretreatment using crystalline silicotitanate ion exchangers

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

Tadros, M.E.; Miller, J.E.; Anthony, R.G.

1997-10-01

A new class of inorganic ion exchangers called crystalline silicotitanates (CSTs) has been developed jointly by Sandia National Laboratories and Texas A&M University to selectively remove Cs and other radionuclides from a wide spectrum of radioactive defense wastes. The CST exhibits high selectivity and affinity for Cs and Sr under a wide range of conditions. Tests show it can remove part-per-million concentrations of Cs{sup +} from highly alkaline, high-sodium simulated radioactive waste solutions modeled after those at Hanford, Oak Ridge, and Savannah River. The materials exhibit ion exchange properties based on ionic size selectivity. Specifically, crystalline lattice spacing is controlledmore » to be highly selective for Cs ions even in waste streams containing very high (5 to 10 M) concentrations of sodium. The CST technology is being demonstrated with actual waste at several DOE facilities. The use of inorganic ion exchangers. The inorganics are more resistant to chemical, thermal, and radiation degradation. Their high selectivities result in more efficient operations offering the possibility of a simple single-pass operation. In contrast, regenerable organic ion exchangers require additional processing equipment to handle the regeneration liquids and the eluant with the dissolved Cs.« less

Contact ion pair formation between hard acids and soft bases in aqueous solutions observed with 2DIR spectroscopy.

PubMed

Sun, Zheng; Zhang, Wenkai; Ji, Minbiao; Hartsock, Robert; Gaffney, Kelly J

2013-12-12

The interaction of charged species in aqueous solution has important implications for chemical, biological, and environmental processes. We have used 2DIR spectroscopy to study the equilibrium dynamics of thiocyanate chemical exchange between free ion (NCS(-)) and contact ion pair configurations (MNCS(+)), where M(2+) = Mg(2+) or Ca(2+). Detailed studies of the influence of anion concentration and anion speciation show that the chemical exchange observed with the 2DIR measurements results from NCS(-) exchanging with other anion species in the first solvation shell surrounding Mg(2+) or Ca(2+). The presence of chemical exchange in the 2DIR spectra provides an indirect, but robust, determinant of contact ion pair formation. We observe preferential contact ion pair formation between soft Lewis base anions and hard Lewis acid cations. This observation cannot be easily reconciled with Pearson's acid-base concept or Collins' Law of Matching Water Affinities. The anions that form contact ion pairs also correspond to the ions with an affinity for water and protein surfaces, so similar physical and chemical properties may control these distinct phenomena.

Effects of Iron Deficiency on Iron Binding and Internalization into Acidic Vacuoles in Dunaliella salina1[W][OA

PubMed Central

Paz, Yakov; Shimoni, Eyal; Weiss, Meira; Pick, Uri

2007-01-01

Uptake of iron in the halotolerant alga Dunaliella salina is mediated by a transferrin-like protein (TTf), which binds and internalizes Fe3+ ions. Recently, we found that iron deficiency induces a large enhancement of iron binding, which is associated with accumulation of three other plasma membrane proteins that associate with TTf. In this study, we characterized the kinetic properties of iron binding and internalization and identified the site of iron internalization. Iron deficiency induces a 4-fold increase in Fe binding, but only 50% enhancement in the rate of iron uptake and also increases the affinity for iron and bicarbonate, a coligand for iron binding. These results indicate that iron deprivation leads to accumulation and modification of iron-binding sites. Iron uptake in iron-sufficient cells is preceded by an apparent time lag, resulting from prebound iron, which can be eliminated by unloading iron-binding sites. Iron is tightly bound to surface-exposed sites and hardly exchanges with medium iron. All bound iron is subsequently internalized. Accumulation of iron inhibits further iron binding and internalization. The vacuolar inhibitor bafilomycin inhibits iron uptake and internalization. Internalized iron was localized by electron microscopy within vacuolar structures that were identified as acidic vacuoles. Iron internalization is accompanied by endocytosis of surface proteins into these acidic vacuoles. A novel kinetic mechanism for iron uptake is proposed, which includes two pools of bound/compartmentalized iron separated by a rate-limiting internalization stage. The major parameter that is modulated by iron deficiency is the iron-binding capacity. We propose that excessive iron binding in iron-deficient cells serves as a temporary reservoir for iron that is subsequently internalized. This mechanism is particularly suitable for organisms that are exposed to large fluctuations in iron availability. PMID:17513481

Study of Some Mineral Exchangers for Use in Water at High Temperature; ETUDE DE QUELQUES ECHANGEURS MINERAUX UTILISABLES DANS L'EAU A HAUTE TEMPERATURE

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

Hure, J.; Platzer, R.; Bittel, R.

1959-10-31

The study of the use of ion exchangers at high temperatures was made with a view to the purification of water in reactors. Natural ion exchangers with mineral structures (clay of the montmorillonite type), natural mineral compounds so treated as to give them the properties of ion exchangers (activated graphite), and synthetic mineral compounds (zirconium phosphates and hydroxides and thorium hydroxide) were investigated. The preparation of the minerals is described, and the results obtained with them are discussed in detail. (J.S.R.)

Ion temperature profiles in front of a negative planar electrode studied by a one-dimensional two-fluid model

NASA Astrophysics Data System (ADS)

Gyergyek, T.; Kovačič, J.

2016-06-01

Plasma-wall transition is studied by a one-dimensional steady state two-fluid model. Continuity and momentum exchange equations are used for the electrons, while the continuity, momentum exchange, and energy transport equation are used for the ions. Electrons are assumed to be isothermal. The closure of ion equations is made by the assumption that the heat flux is zero. The model equations are solved for potential, ion and electron density, and velocity and ion temperature as independent variables. The model includes coulomb collisions between ions and electrons and charge exchange collisions between ions and neutral atoms of the same species and same mass. The neutral atoms are assumed to be essentially at rest. The model is solved for finite ratio ɛ = /λ D L between the Debye length and λD and ionization length L in the pre-sheath and in the sheath at the same time. Charge exchange collisions heat the ions in the sheath and the pre-sheath. Even a small increase of the frequency of charge exchange collisions causes a substantial increase of ion temperature. Coulomb collisions have negligible effect on ion temperature in the pre-sheath, while in the sheath they cause a small cooling of ions. The increase of ɛ causes the increase of ion temperature. From the ion density and temperature profiles, the polytropic function κ is calculated according to its definition given by Kuhn et al. [Phys. Plasmas 13, 013503 (2006)]. The obtained profiles of κ indicate that the ion flow is isothermal only in a relatively narrow region in the pre-sheath, while close to the sheath edge and in the sheath it is closer to adiabatic. The ion sound velocity is space dependent and exhibits a maximum. This maximum indicates the location of the sheath edge only in the limit ɛ → 0 .

Calcineurin homologous protein as an essential cofactor for Na+/H+ exchangers.

PubMed

Pang, T; Su, X; Wakabayashi, S; Shigekawa, M

2001-05-18

The Na+/H+ exchangers (NHEs) comprise a family of transporters that catalyze cell functions such as regulation of the pH and volume of a cell and epithelial absorption of Na+ and bicarbonate. Ubiquitous calcineurin B homologous protein (CHP or p22) is co-localized and co-immunoprecipitated with expressed NHE1, NHE2, or NHE3 independently of its myristoylation and Ca2+ binding, and its binding site was identified as the juxtamembrane region within the carboxyl-terminal cytoplasmic domain of exchangers. CHP binding-defective mutations of NHE1-3 or CHP depletion by injection of the competitive CHP-binding region of NHE1 into Xenopus oocytes resulted in a dramatic reduction (>90%) in the Na+/H+ exchange activity. The data suggest that CHP serves as an essential cofactor, which supports the physiological activity of NHE family members.

Ion exchange phenomena

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

Bourg, I.C.; Sposito, G.

Ion exchange phenomena involve the population of readily exchangeable ions, the subset of adsorbed solutes that balance the intrinsic surface charge and can be readily replaced by major background electrolyte ions (Sposito, 2008). These phenomena have occupied a central place in soil chemistry research since Way (1850) first showed that potassium uptake by soils resulted in the release of an equal quantity of moles of charge of calcium and magnesium. Ion exchange phenomena are now routinely modeled in studies of soil formation (White et al., 2005), soil reclamation (Kopittke et al., 2006), soil fertilitization (Agbenin and Yakubu, 2006), colloidal dispersion/flocculationmore » (Charlet and Tournassat, 2005), the mechanics of argillaceous media (Gajo and Loret, 2007), aquitard pore water chemistry (Tournassat et al., 2008), and groundwater (Timms and Hendry, 2007; McNab et al., 2009) and contaminant hydrology (Chatterjee et al., 2008; van Oploo et al., 2008; Serrano et al., 2009).« less

Semi-aerobic stabilized landfill leachate treatment by ion exchange resin: isotherm and kinetic study

NASA Astrophysics Data System (ADS)

Zamri, Mohd Faiz Muaz Ahmad; Kamaruddin, Mohamad Anuar; Yusoff, Mohd Suffian; Aziz, Hamidi Abdul; Foo, Keng Yuen

2017-05-01

This study was carried out to investigate the treatability of ion exchange resin (Indion MB 6 SR) for the removal of chromium (VI), aluminium (III), zinc (II), copper (II), iron (II), and phosphate (PO4)3-, chemical oxygen demand (COD), ammonia nitrogen (NH3-N) and colour from semi-aerobic stabilized leachate by batch test. A range of ion exchange resin dosage was tested towards the removal efficiency of leachate parameters. It was observed that equilibrium data were best represented by the Langmuir model for metal ions and Freundlich was ideally fit for COD, NH3-N and colour. Intra particle diffusion model, pseudo first-order and pseudo second-order isotherm models were found ideally fit with correlation of the experimental data. The findings revealed that the models could describe the ion exchange kinetic behaviour efficiently, which further suggests comprehensive outlook for the future research in this field.

Atomic sites and stability of Cs+ captured within zeolitic nanocavities

PubMed Central

Yoshida, Kaname; Toyoura, Kazuaki; Matsunaga, Katsuyuki; Nakahira, Atsushi; Kurata, Hiroki; Ikuhara, Yumi H.; Sasaki, Yukichi

2013-01-01

Zeolites have potential application as ion-exchangers, catalysts and molecular sieves. Zeolites are once again drawing attention in Japan as stable adsorbents and solidification materials of fission products, such as 137Cs+ from damaged nuclear-power plants. Although there is a long history of scientific studies on the crystal structures and ion-exchange properties of zeolites for practical application, there are still open questions, at the atomic-level, on the physical and chemical origins of selective ion-exchange abilities of different cations and detailed atomic structures of exchanged cations inside the nanoscale cavities of zeolites. Here, the precise locations of Cs+ ions captured within A-type zeolite were analyzed using high-resolution electron microscopy. Together with theoretical calculations, the stable positions of absorbed Cs+ ions in the nanocavities are identified, and the bonding environment within the zeolitic framework is revealed to be a key factor that influences the locations of absorbed cations. PMID:23949184

Method of uranium reclamation from aqueous systems by reactive ion exchange. [US DOE patent application; anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands

DOEpatents

Maya, L.

1981-11-05

A reactive ion exchange method for separation and recovery of values of uranium, neptunium, plutonium, or americium from substantially neutral aqueous systems of said metals comprises contacting said system with an effective amount of a basic anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands to achieve nearly 100% sorption of said actinyl ion onto said resin and an aqueous system practically free of said actinyl ions. The method is operational over an extensive range of concentrations from about 10/sup -6/ M to 1.0 M actinyl ion and a pH range of about 4 to 7. The method has particulr application to treatment of waste streams from Purex-type nuclear fuel reprocessing facilities and hydrometallurgical processes involving U, Np, P, or Am.

Fe(+) chemical ionization of peptides.

PubMed

Speir, J P; Gorman, G S; Amster, I J

1993-02-01

Laser-desorbed peptide neutral molecules were allowed to react with Fe(+) in a Fourier transform mass spectrometer, using the technique of laser desorption/chemical ionization. The Fe(+) ions are formed by laser ablation of a steel target, as well as by dissociative charge-exchange ionization of ferrocene with Ne(+). Prior to reaction with laser-desorbed peptide molecules, Fe(+) ions undergo 20-100 thermalizin collisions with xenon to reduce the population of excited-state metal ion species. The Fe(+) ions that have not experienced thermalizing collisions undergo charge exchange with peptide molecules. Iron ions that undergo thermalizing collisions before they are allowed to react with peptides are found to undergo charge exchange and to form adduct species [M + Fe(+)] and fragment ions that result from the loss of small, stable molecules, such as H2O, CO, and CO2, from the metal ion-peptide complex.

Structures of the carbohydrate recognition domain of Ca2+-independent cargo receptors Emp46p and Emp47p.

PubMed

Satoh, Tadashi; Sato, Ken; Kanoh, Akira; Yamashita, Katsuko; Yamada, Yusuke; Igarashi, Noriyuki; Kato, Ryuichi; Nakano, Akihiko; Wakatsuki, Soichi

2006-04-14

Emp46p and Emp47p are type I membrane proteins, which cycle between the endoplasmic reticulum (ER) and the Golgi apparatus by vesicles coated with coat protein complexes I and II (COPI and COPII). They are considered to function as cargo receptors for exporting N-linked glycoproteins from the ER. We have determined crystal structures of the carbohydrate recognition domains (CRDs) of Emp46p and Emp47p of Saccharomyces cerevisiae, in the absence and presence of metal ions. Both proteins fold as a beta-sandwich, and resemble that of the mammalian ortholog, p58/ERGIC-53. However, the nature of metal binding is distinct from that of Ca(2+)-dependent p58/ERGIC-53. Interestingly, the CRD of Emp46p does not bind Ca(2+) ion but instead binds K(+) ion at the edge of a concave beta-sheet whose position is distinct from the corresponding site of the Ca(2+) ion in p58/ERGIC-53. Binding of K(+) ion to Emp46p appears essential for transport of a subset of glycoproteins because the Y131F mutant of Emp46p, which cannot bind K(+) ion fails to rescue the transport in disruptants of EMP46 and EMP47 genes. In contrast the CRD of Emp47p binds no metal ions at all. Furthermore, the CRD of Emp46p binds to glycoproteins carrying high mannosetype glycans and the is promoted by binding not the addition of Ca(2+) or K(+) ion in These results suggest that Emp46p can be regarded as a Ca(2+)-independent intracellular lectin at the ER exit sites.

Mono-manganese mechanism of the photosystem II water splitting reaction by a unique Mn4Ca cluster.

PubMed

Kusunoki, Masami

2007-06-01

The molecular mechanism of the water oxidation reaction in photosystem II (PSII) of green plants remains a great mystery in life science. This reaction is known to take place in the oxygen evolving complex (OEC) incorporating four manganese, one calcium and one chloride cofactors, that is light-driven to cycle four intermediates, designated S(0) through S(4), to produce four protons, five electrons and lastly one molecular oxygen, for indispensable resources in biosphere. Recent advancements of X-ray crystallography models established the existence of a catalytic Mn(4)Ca cluster ligated by seven protein amino acids, but its functional structure is not yet resolved. The (18)O exchange rates of two substrate water molecules were recently measured for four S(i)-state samples (i=0-3) leading to (34)O(2) and (36)O(2) formations, revealing asymmetric substrate binding sites significantly depending on the S(i)-state. In this paper, we present a chemically complete model for the Mn(4)Ca cluster and its surrounding enzyme field, which we found out from some possible models by using the hybrid density functional theoretic geometry optimization method to confirm good agreements with the 3.0 A resolution PSII model [B. Loll, J. Kern, W. Saenger, A. Zouni , J. Biesiadka, Nature 438 (2005) 1040-1044] and the S-state dependence of (18)O exchange rates [W. Hillier and T. Wydrzynski, Phys. Chem. Chem. Phys. 6 (2004) 4882-4889]. Furthermore, we have verified that two substrate water molecules are bound to asymmetric cis-positions on the terminal Mn ion being triply bridged (mu-oxo, mu-carboxylato, and a hydrogen bond) to the Mn(3)CaO(3)(OH) core, by developing a generalized theory of (18)O exchange kinetics in OEC to obtain an experimental evidence for the cross exchange pathway from the slow to the fast exchange process. Some important experimental data will be discussed in terms of this model and its possible tautomers, to suggest that a cofactor, Cl(-) ion, may be bound to CP43-Arg357 nearby Ca(2+) ion and that D1-His337 may be used to trap a released proton only in the S(2)-state.

Molecular mechanism of ATP binding and ion channel activation in P2X receptors

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

Hattori, Motoyuki; Gouaux, Eric

P2X receptors are trimeric ATP-activated ion channels permeable to Na{sup +}, K{sup +} and Ca{sup 2+}. The seven P2X receptor subtypes are implicated in physiological processes that include modulation of synaptic transmission, contraction of smooth muscle, secretion of chemical transmitters and regulation of immune responses. Despite the importance of P2X receptors in cellular physiology, the three-dimensional composition of the ATP-binding site, the structural mechanism of ATP-dependent ion channel gating and the architecture of the open ion channel pore are unknown. Here we report the crystal structure of the zebrafish P2X4 receptor in complex with ATP and a new structure ofmore » the apo receptor. The agonist-bound structure reveals a previously unseen ATP-binding motif and an open ion channel pore. ATP binding induces cleft closure of the nucleotide-binding pocket, flexing of the lower body {beta}-sheet and a radial expansion of the extracellular vestibule. The structural widening of the extracellular vestibule is directly coupled to the opening of the ion channel pore by way of an iris-like expansion of the transmembrane helices. The structural delineation of the ATP-binding site and the ion channel pore, together with the conformational changes associated with ion channel gating, will stimulate development of new pharmacological agents.« less

Graphane versus graphene: a computational investigation of the interaction of nucleobases, aminoacids, heterocycles, small molecules (CO2, H2O, NH3, CH4, H2), metal ions and onium ions.

PubMed

Umadevi, Deivasigamani; Narahari Sastry, G

2015-11-11

Graphane has emerged as a two-dimensional hydrocarbon with interesting physical properties and potential applications. Understanding the interaction of graphane with various molecules and ions is crucial to appreciate its potential applications. We investigated the interaction of nucleobases, aminoacids, saturated and unsaturated heterocycles, small molecules, metal ions and onium ions with graphane by using density functional theory calculations. The preferred orientations of these molecules and ions on the graphane surface have been analysed. The binding energies of graphane with these molecules have been compared with the corresponding binding energies of graphene. Our results reveal that graphane forms stable complexes with all the molecules and ions yet showing lesser binding affinity when compared to graphene. As an exemption, the preferential strong binding of H2O with graphane than graphene reveals the fact that graphane is more hydrophilic than graphene. Charge transfer between graphane and the molecules and ions have been found to be an important factor in determining the binding strength of the complexes. The effect of the interaction of these molecules and ions on the HOMO-LUMO energy gap of graphane has also been investigated.

Time resolved native ion-mobility mass spectrometry to monitor dynamics of IgG4 Fab arm exchange and "bispecific" monoclonal antibody formation.

PubMed

Debaene, François; Wagner-Rousset, Elsa; Colas, Olivier; Ayoub, Daniel; Corvaïa, Nathalie; Van Dorsselaer, Alain; Beck, Alain; Cianférani, Sarah

2013-10-15

Monoclonal antibodies (mAbs) and derivatives such as antibody-drug conjugates (ADC) and bispecific antibodies (bsAb), are the fastest growing class of human therapeutics. Most of the therapeutic antibodies currently on the market and in clinical trials are chimeric, humanized, and human immunoglobulin G1 (IgG1). An increasing number of IgG2s and IgG4s that have distinct structural and functional properties are also investigated to develop products that lack or have diminished antibody effector functions compared to IgG1. Importantly, wild type IgG4 has been shown to form half molecules (one heavy chain and one light chain) that lack interheavy chain disulfide bonds and form intrachain disulfide bonds. Moreover, IgG4 undergoes a process of Fab-arm exchange (FAE) in which the heavy chains of antibodies of different specificities can dissociate and recombine in bispecific antibodies both in vitro and in vivo. Here, native mass spectrometry (MS) and time-resolved traveling wave ion mobility MS (TWIM-MS) were used for the first time for online monitoring of FAE and bsAb formation using Hz6F4-2v3 and natalizumab, two humanized IgG4s which bind to human Junctional Adhesion Molecule-A (JAM-A) and alpha4 integrin, respectively. In addition, native MS analysis of bsAb/JAM-A immune complexes revealed that bsAb can bind up to two antigen molecules, confirming that the Hz6F4 family preferentially binds dimeric JAM-A. Our results illustrate how IM-MS can rapidly assess bsAb structural heterogeneity and be easily implemented into MS workflows for bsAb production follow up and bsAb/antigen complex characterization. Altogether, these results provide new MS-based methodologies for in-depth FAE and bsAb formation monitoring. Native MS and IM-MS will play an increasing role in next generation biopharmaceutical product characterization like bsAbs, antibody mixtures, and antibody-drug conjugates (ADC) as well as for biosimilar and biobetter antibodies.

Influences of Mutations on the Electrostatic Binding Free Energies of Chloride Ions in Escherichia Coli ClC

PubMed Central

Yu, Tao; Wang, Xiao-Qing; Sang, Jian-Ping; Pan, Chun-Xu; Zou, Xian-Wu; Chen, Tsung-Yu; Zou, Xiaoqin

2012-01-01

Mutations in ClC channel proteins may cause serious functional changes and even diseases. The function of ClC proteins mainly manifests as Cl− transport, which is related to the binding free energies of chloride ions. Therefore, the influence of a mutation on ClC function can be studied by investigating the mutational effect on the binding free energies of chloride ions. The present study provides quantitative and systematic investigations on the influences of residue mutations on the electrostatic binding free energies in Escherichia coli ClC (EcClC) proteins, using all-atom molecular dynamics simulations. It was found that the change of the electrostatic binding free energy decreases linearly with the increase of the residue-chloride ion distance for a mutation. This work reveals how changes in the charge of a mutated residue and in the distance between the mutated residue and the binding site govern the variations in the electrostatic binding free energies, and therefore influence the transport of chloride ions and conduction in EcClC. This work would facilitate our understanding of the mutational effects on transport of chloride ions and functions of ClC proteins, and provide a guideline to estimate which residue mutations will have great influences on ClC functions. PMID:22612693

Beyond the Hofmeister Series: Ion-Specific Effects on Proteins and Their Biological Functions.

PubMed

Okur, Halil I; Hladílková, Jana; Rembert, Kelvin B; Cho, Younhee; Heyda, Jan; Dzubiella, Joachim; Cremer, Paul S; Jungwirth, Pavel

2017-03-09

Ions differ in their ability to salt out proteins from solution as expressed in the lyotropic or Hofmeister series of cations and anions. Since its first formulation in 1888, this series has been invoked in a plethora of effects, going beyond the original salting out/salting in idea to include enzyme activities and the crystallization of proteins, as well as to processes not involving proteins like ion exchange, the surface tension of electrolytes, or bubble coalescence. Although it has been clear that the Hofmeister series is intimately connected to ion hydration in homogeneous and heterogeneous environments and to ion pairing, its molecular origin has not been fully understood. This situation could have been summarized as follows: Many chemists used the Hofmeister series as a mantra to put a label on ion-specific behavior in various environments, rather than to reach a molecular level understanding and, consequently, an ability to predict a particular effect of a given salt ion on proteins in solutions. In this Feature Article we show that the cationic and anionic Hofmeister series can now be rationalized primarily in terms of specific interactions of salt ions with the backbone and charged side chain groups at the protein surface in solution. At the same time, we demonstrate the limitations of separating Hofmeister effects into independent cationic and anionic contributions due to the electroneutrality condition, as well as specific ion pairing, leading to interactions of ions of opposite polarity. Finally, we outline the route beyond Hofmeister chemistry in the direction of understanding specific roles of ions in various biological functionalities, where generic Hofmeister-type interactions can be complemented or even overruled by particular steric arrangements in various ion binding sites.

Cooling field and temperature dependent exchange bias in Gd substituted YFe0.5Cr0.5O3

NASA Astrophysics Data System (ADS)

Singh, Karan; Mukherjee, K.

2018-04-01

We report the results of our investigation of cooling field and temperature dependence of exchange bias on Gd substituted mixed metal oxide YFe0.5Cr0.5O3. A negative exchange bias is observed in the Gd-substituted compounds, in contrast to the positive exchange bias in parent compound, YFe0.5Cr0.5O3 [1]. With the increase in Gd concentration it is noted that the exchange bias decreases. It was noted that the paramagnetic contribution from Gd ions plays the leading role in comparison to the antiferromagnetic type correlations among spins as is observed for the parent compound. Due to magnetic rare earth ion, additional exchange interaction of the form Gd-O-Fe/Cr dominates the magnetic interaction arising due to the transition metal ions, resulting in the reduction in exchange bias value.

The effect of ion-exchange purification on the determination of plutonium at the New Brunswick Laboratory

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

Mitchell, W.G.; Spaletto, M.I.; Lewis, K.

The method of plutonium (Pu) determination at the Brunswick Laboratory (NBL) consists of a combination of ion-exchange purification followed by controlled-potential coulometric analysis (IE/CPC). The present report's purpose is to quantify any detectable Pu loss occurring in the ion-exchange (IE) purification step which would cause a negative bias in the NBL method for Pu analysis. The magnitude of any such loss would be contained within the reproducibility (0.05%) of the IE/CPC method which utilizes a state-of-the-art autocoulometer developed at NBL. When the NBL IE/CPC method is used for Pu analysis, any loss in ion-exchange purification (<0.05%) is confounded with themore » repeatability of the ion-exchange and the precision of the CPC analysis technique (<0.05%). Consequently, to detect a bias in the IE/CPC method due to the IE alone using the IE/CPC method itself requires that many randomized analyses on a single material be performed over time and that statistical analysis of the data be performed. The initial approach described in this report to quantify any IE loss was an independent method, Isotope Dilution Mass Spectrometry; however, the number of analyses performed was insufficient to assign a statistically significant value to the IE loss (<0.02% of 10 mg samples of Pu). The second method used for quantifying any IE loss of Pu was multiple ion exchanges of the same Pu aliquant; the small number of analyses possible per individual IE together with the column-to-column variability over multiple ion exchanges prevented statistical detection of any loss of <0.05%. 12 refs.« less

Protein adsorption to poly(ethylenimine)-modified Sepharose FF: I. a critical ionic capacity for drastically enhanced capacity and uptake kinetics.

PubMed

Yu, Lin-Ling; Tao, Shi-Peng; Dong, Xiao-Yan; Sun, Yan

2013-08-30

To explore the details of protein uptake to polymer-grafted ion exchangers, Sepharose FF was modified with poly(ethylenimine) (PEI) to prepare anion exchanger of 10 different ionic capacities (ICs, 100-1220mmol/L). Adsorption equilibria and kinetics of bovine serum albumin (BSA) were then studied. It is found that ionic capacity, i.e., the coupling density of PEI, had significant effect on both adsorption capacity (qm) and effective protein diffusivity (De). With increasing ionic capacity, the qm value increased rapidly at IC<260mmol/L and then increased slowly till reaching a plateau at IC=600mmol/L. In the IC range of 100-600mmol/L, however, the De values kept at a low level (De/D0<0.07); it first decreased from 0.05±0.01 at IC=100mmol/L to 0.01±0.01 at IC=260mmol/L and then increased to 0.06±0.01 at IC=600mmol/L. Thereafter, sharp increases of the qm and De values [36% (from 201 to 273mg/mL) and 670% (from 0.06±0.01 to 0.49±0.04), respectively] were observed in the narrow range of IC from 600 to 740mmol/L. Finally, at IC>740mmol/L, the qm value decreased significantly while the De value increased moderately with increasing the IC. The results indicate that PEI chains played an important role in protein adsorption and transport. In brief, there was a critical IC (cIC) or PEI chain density, above which protein adsorption and transport behaviors changed drastically. The cIC was identified to be about 600mmol/L. Estimation of PEI grafting-layer thickness suggests that PEI chains formed an extended three-dimensional grafting-layer at IC>cIC, which provided high flexibility as well as accessibility of the chains for protein binding. Therefore, at IC>cIC, the adjacent PEI chains became close and flexible enough, leading to facilitated transport of adsorbed protein molecules by the interactions of neighboring chains mediated by the bound molecules. It is regarded as "chain delivery" effect. At the same time, improved accessibility of binding sites led the significant increase of binding capacity. The decrease of qm value at IC>740mmol/L is considered due to the decrease of effective porosity. The research has thus provided new insight into protein adsorption and transport in polymer-grafted ion-exchange media. Copyright © 2013 Elsevier B.V. All rights reserved.

Free Energy Wells and Barriers to Ion Transport Across Membranes

NASA Astrophysics Data System (ADS)

Rempe, Susan

2014-03-01

The flow of ions across cellular membranes is essential to many biological processes. Ion transport is also important in synthetic materials used as battery electrolytes. Transport often involves specific ions and fast conduction. To achieve those properties, ion conduction pathways must solvate specific ions by just the ``right amount.'' The right amount of solvation avoids ion traps due to deep free energy wells, and avoids ion block due to high free energy barriers. Ion channel proteins in cellular membranes demonstrate this subtle balance in solvation of specific ions. Using ab initio molecular simulations, we have interrogated the link between binding site structure and ion solvation free energies in biological ion binding sites. Our results emphasize the surprisingly important role of the environment that surrounds ion-binding sites for fast transport of specific ions. We acknowledge support from Sandia's LDRD program. Sandia National Labs is a multi-program laboratory operated by Sandia Corp., a wholly owned subsidiary of Lockheed Martin Corp., for the US DOE's NNSA under contract DE-AC04-94AL85000.

Self-regenerating column chromatography

DOEpatents

Park, Woo K.

1995-05-30

The present invention provides a process for treating both cations and anions by using a self-regenerating, multi-ionic exchange resin column system which requires no separate regeneration steps. The process involves alternating ion-exchange chromatography for cations and anions in a multi-ionic exchange column packed with a mixture of cation and anion exchange resins. The multi-ionic mixed-charge resin column works as a multi-function column, capable of independently processing either cationic or anionic exchange, or simultaneously processing both cationic and anionic exchanges. The major advantage offered by the alternating multi-function ion exchange process is the self-regeneration of the resins.

Ion Exchange Method - Diffusion Barrier Investigations

NASA Astrophysics Data System (ADS)

Pielak, G.; Szustakowski, M.; Kiezun, A.

1990-01-01

Ion exchange method is used to GRIN-rod lenses manufacturing. In this process the ion exchange occurs between bulk glass (rod) and a molten salt. It was find that diffusion barrier exists on a border of glass surface and molten salt. The investigations of this barrier show that it value varies with ion exchange time and process temperature. It was find that in the case when thalium glass rod was treated in KNO3, bath, the minimum of the potential after 24 h was in temperature of 407°C, after 48 h in 422°C, after 72 h in 438°C and so on. So there are the possibility to keep the minimum of diffusion barrier by changing the temperature of the process and then the effectiveness of ion exchange process is the most effective. The time needed to obtain suitable refractive index distribution in a process when temperature was linearly changed from 400°C to 460°C was shorter of about 30% compare with the process in which temperature was constant and equal 450°C.

A practical method for measuring the ion exchange capacity decrease of hydroxide exchange membranes during intrinsic degradation

NASA Astrophysics Data System (ADS)

Kreuer, Klaus-Dieter; Jannasch, Patric

2018-01-01

In this work we present a practical thermogravimetric method for quantifying the IEC (ion exchange capacity) decrease of hydroxide exchange membranes (HEMs) during intrinsic degradation mainly occurring through nucleophilic attack of the anion exchanging group by hydroxide ions. The method involves measuring weight changes under controlled temperature and relative humidity. These conditions are close to these in a fuel cell, i.e. the measured degradation rate includes all effects originating from the polymeric structure, the consumption of hydroxide ions and the release of water. In particular, this approach involves no added solvents or base, thereby avoiding inaccuracies that may arise in other methods due to the presence of solvents (other than water) or co-ions (such as Na+ or K+). We demonstrate the method by characterizing the decomposition of membranes consisting of poly(2,6-dimethyl-1,4-phenylene oxide) functionalized with trimethyl-pentyl-ammonium side chains. The decomposition rate is found to depend on temperature, relative humidity RH (controlling the hydration number λ) and the total water content (controlled by the actual IEC and RH).

Tuning the ion selectivity of tetrameric cation channels by changing the number of ion binding sites

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

Derebe, Mehabaw G.; Sauer, David B.; Zeng, Weizhong

2015-11-30

Selective ion conduction across ion channel pores is central to cellular physiology. To understand the underlying principles of ion selectivity in tetrameric cation channels, we engineered a set of cation channel pores based on the nonselective NaK channel and determined their structures to high resolution. These structures showcase an ensemble of selectivity filters with a various number of contiguous ion binding sites ranging from 2 to 4, with each individual site maintaining a geometry and ligand environment virtually identical to that of equivalent sites in K{sup +} channel selectivity filters. Combined with single channel electrophysiology, we show that only themore » channel with four ion binding sites is K{sup +} selective, whereas those with two or three are nonselective and permeate Na{sup +} and K{sup +} equally well. These observations strongly suggest that the number of contiguous ion binding sites in a single file is the key determinant of the channel's selectivity properties and the presence of four sites in K{sup +} channels is essential for highly selective and efficient permeation of K{sup +} ions.« less

Andrographolide derivatives inhibit guanine nucleotide exchange and abrogate oncogenic Ras function

PubMed Central

Hocker, Harrison J.; Cho, Kwang-Jin; Chen, Chung-Ying K.; Rambahal, Nandini; Sagineedu, Sreenivasa Rao; Shaari, Khozirah; Stanslas, Johnson; Hancock, John F.; Gorfe, Alemayehu A.

2013-01-01

Aberrant signaling by oncogenic mutant rat sarcoma (Ras) proteins occurs in ∼15% of all human tumors, yet direct inhibition of Ras by small molecules has remained elusive. Recently, several small-molecule ligands have been discovered that directly bind Ras and inhibit its function by interfering with exchange factor binding. However, it is unclear whether, or how, these ligands could lead to drugs that act against constitutively active oncogenic mutant Ras. Using a dynamics-based pocket identification scheme, ensemble docking, and innovative cell-based assays, here we show that andrographolide (AGP)—a bicyclic diterpenoid lactone isolated from Andrographis paniculata—and its benzylidene derivatives bind to transient pockets on Kirsten-Ras (K-Ras) and inhibit GDP–GTP exchange. As expected for inhibitors of exchange factor binding, AGP derivatives reduced GTP loading of wild-type K-Ras in response to acute EGF stimulation with a concomitant reduction in MAPK activation. Remarkably, however, prolonged treatment with AGP derivatives also reduced GTP loading of, and signal transmission by, oncogenic mutant K-RasG12V. In sum, the combined analysis of our computational and cell biology results show that AGP derivatives directly bind Ras, block GDP–GTP exchange, and inhibit both wild-type and oncogenic K-Ras signaling. Importantly, our findings not only show that nucleotide exchange factors are required for oncogenic Ras signaling but also demonstrate that inhibiting nucleotide exchange is a valid approach to abrogating the function of oncogenic mutant Ras. PMID:23737504

Parameter estimation for mathematical models of a nongastric H+(Na+)-K(+)(NH4+)-ATPase.

PubMed

Nadal-Quirós, Mónica; Moore, Leon C; Marcano, Mariano

2015-09-01

The role of nongastric H(+)-K(+)-ATPase (HKA) in ion homeostasis of macula densa (MD) cells is an open question. To begin to explore this issue, we developed two mathematical models that describe ion fluxes through a nongastric HKA. One model assumes a 1H(+):1K(+)-per-ATP stoichiometry; the other assumes a 2H(+):2K(+)-per-ATP stoichiometry. Both models include Na+ and NH4+ competitive binding with H+ and K+, respectively, a characteristic observed in vitro and in situ. Model rate constants were obtained by minimizing the distance between model and experimental outcomes. Both 1H(+)(1Na(+)):1K(+)(1NH4 (+))-per-ATP and 2H(+)(2Na(+)):2K(+)(2NH4 (+))-per-ATP models fit the experimental data well. Using both models, we simulated ion net fluxes as a function of cytosolic or luminal ion concentrations typical for the cortical thick ascending limb and MD region. We observed that (1) K+ and NH4+ flowed in the lumen-to-cytosol direction, (2) there was competitive behavior between luminal K+ and NH4+ and between cytosolic Na+ and H+, 3) ion fluxes were highly sensitive to changes in cytosolic Na+ or H+ concentrations, and 4) the transporter does mostly Na+ / K+ exchange under physiological conditions. These results support the concept that nongastric HKA may contribute to Na+ and pH homeostasis in MD cells. Furthermore, in both models, H+ flux reversed at a luminal pH that was <5.6. Such reversal led to Na+ / H+ exchange for a luminal pH of <2 and 4 in the 1:1-per-ATP and 2:2-per-ATP models, respectively. This suggests a novel role of nongastric HKA in cell Na+ homeostasis in the more acidic regions of the renal tubules. Copyright © 2015 the American Physiological Society.

Parameter estimation for mathematical models of a nongastric H+(Na+)-K+(NH4+)-ATPase

PubMed Central

Nadal-Quirós, Mónica; Moore, Leon C.

2015-01-01

The role of nongastric H+-K+-ATPase (HKA) in ion homeostasis of macula densa (MD) cells is an open question. To begin to explore this issue, we developed two mathematical models that describe ion fluxes through a nongastric HKA. One model assumes a 1H+:1K+-per-ATP stoichiometry; the other assumes a 2H+:2K+-per-ATP stoichiometry. Both models include Na+ and NH4+ competitive binding with H+ and K+, respectively, a characteristic observed in vitro and in situ. Model rate constants were obtained by minimizing the distance between model and experimental outcomes. Both 1H+(1Na+):1K+(1NH4+)-per-ATP and 2H+(2Na+):2K+(2NH4+)-per-ATP models fit the experimental data well. Using both models, we simulated ion net fluxes as a function of cytosolic or luminal ion concentrations typical for the cortical thick ascending limb and MD region. We observed that 1) K+ and NH4+ flowed in the lumen-to-cytosol direction, 2) there was competitive behavior between luminal K+ and NH4+ and between cytosolic Na+ and H+, 3) ion fluxes were highly sensitive to changes in cytosolic Na+ or H+ concentrations, and 4) the transporter does mostly Na+/K+ exchange under physiological conditions. These results support the concept that nongastric HKA may contribute to Na+ and pH homeostasis in MD cells. Furthermore, in both models, H+ flux reversed at a luminal pH that was <5.6. Such reversal led to Na+/H+ exchange for a luminal pH of <2 and 4 in the 1:1-per-ATP and 2:2-per-ATP models, respectively. This suggests a novel role of nongastric HKA in cell Na+ homeostasis in the more acidic regions of the renal tubules. PMID:26109090

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

PubMed

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

2003-03-01

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

IBiSA_Tools: A Computational Toolkit for Ion-Binding State Analysis in Molecular Dynamics Trajectories of Ion Channels.

PubMed

Kasahara, Kota; Kinoshita, Kengo

2016-01-01

Ion conduction mechanisms of ion channels are a long-standing conundrum. Although the molecular dynamics (MD) method has been extensively used to simulate ion conduction dynamics at the atomic level, analysis and interpretation of MD results are not straightforward due to complexity of the dynamics. In our previous reports, we proposed an analytical method called ion-binding state analysis to scrutinize and summarize ion conduction mechanisms by taking advantage of a variety of analytical protocols, e.g., the complex network analysis, sequence alignment, and hierarchical clustering. This approach effectively revealed the ion conduction mechanisms and their dependence on the conditions, i.e., ion concentration and membrane voltage. Here, we present an easy-to-use computational toolkit for ion-binding state analysis, called IBiSA_tools. This toolkit consists of a C++ program and a series of Python and R scripts. From the trajectory file of MD simulations and a structure file, users can generate several images and statistics of ion conduction processes. A complex network named ion-binding state graph is generated in a standard graph format (graph modeling language; GML), which can be visualized by standard network analyzers such as Cytoscape. As a tutorial, a trajectory of a 50 ns MD simulation of the Kv1.2 channel is also distributed with the toolkit. Users can trace the entire process of ion-binding state analysis step by step. The novel method for analysis of ion conduction mechanisms of ion channels can be easily used by means of IBiSA_tools. This software is distributed under an open source license at the following URL: http://www.ritsumei.ac.jp/~ktkshr/ibisa_tools/.

Transport of Zn(OH4)(2-) Ions Across a Polyolefin Microporous Membrane

DTIC Science & Technology

1992-12-22

studied using polarography and conductometry . Soluble Nafion as an ion exchange modifying agent was applied to the membrane by several techniques. The...polypropylene membranes was studied using polarography and conductometry . Soluble Nafion as an ion exchange modifying agent was applied to the membrane by

Cesium and strontium ion exchange on the framework titanium silicate M2Ti2O3SiO4.nH2O (M = H, Na).

PubMed

Solbrå, S; Allison, N; Waite, S; Mikhalovsky, S V; Bortun, A I; Bortun, L N; Clearfield, A

2001-02-01

The ion exchange properties of the titanium silicate, M2Ti2O3SiO4.nH2O (M = H, Na), toward stable and radioactive 137Cs+ and 89Sr2+, have been examined. By studying the cesium and strontium uptake in the presence of NaNO3, CaCl2, NaOH, and HNO3 (in the range of 0.01-6 M) the sodium titanium silicate was found to be an efficient Cs+ ion exchanger in acid, neutral, and alkaline media and an efficient Sr2+ ion exchanger in neutral and alkaline media, which makes it promising for treatment of contaminated environmental media and biological systems.

Multiscale Simulations Reveal Key Aspects of the Proton Transport Mechanism in the ClC-ec1 Antiporter

PubMed Central

Lee, Sangyun; Swanson, Jessica M.J.; Voth, Gregory A.

2016-01-01

Multiscale reactive molecular dynamics simulations are used to study proton transport through the central region of ClC-ec1, a widely studied ClC transporter that enables the stoichiometric exchange of 2 Cl– ions for 1 proton (H+). It has long been known that both Cl– and proton transport occur through partially congruent pathways, and that their exchange is strictly coupled. However, the nature of this coupling and the mechanism of antiporting remain topics of debate. Here multiscale simulations have been used to characterize proton transport between E203 (Gluin) and E148 (Gluex), the internal and external intermediate proton binding sites, respectively. Free energy profiles are presented, explicitly accounting for the binding of Cl– along the central pathway, the dynamically coupled hydration changes of the central region, and conformational changes of Gluin and Gluex. We find that proton transport between Gluin and Gluex is possible in both the presence and absence of Cl– in the central binding site, although it is facilitated by the anion presence. These results support the notion that the requisite coupling between Cl– and proton transport occurs elsewhere (e.g., during proton uptake or release). In addition, proton transport is explored in the E203K mutant, which maintains proton permeation despite the substitution of a basic residue for Gluin. This collection of calculations provides for the first time, to our knowledge, a detailed picture of the proton transport mechanism in the central region of ClC-ec1 at a molecular level. PMID:27028643

Corrosion of steel drums containing cemented ion-exchange resins as intermediate level nuclear waste

NASA Astrophysics Data System (ADS)

Duffó, G. S.; Farina, S. B.; Schulz, F. M.

2013-07-01

Exhausted ion-exchange resins used in nuclear reactors are immobilized by cementation before being stored. They are contained in steel drums that may undergo internal corrosion depending on the presence of certain contaminants. The objective of this work is to evaluate the corrosion susceptibility of steel drums in contact with cemented ion-exchange resins with different aggressive species. The corrosion potential and the corrosion rate of the steel, and the electrical resistivity of the matrix were monitored for 900 days. Results show that the cementation of ion-exchange resins seems not to pose special risks regarding the corrosion of the steel drums. The corrosion rate of the steel in contact with cemented ion-exchange resins in the absence of contaminants or in the presence of 2.3 wt.% sulphate content remains low (less than 0.1 μm/year) during the whole period of the study (900 days). The presence of chloride ions increases the corrosion rate of the steel at the beginning of the exposure but, after 1 year, the corrosion rate drops abruptly reaching a value close to 0.1 μm/year. This is probably due to the lack of water to sustain the corrosion process. When applying the results obtained in the present work to estimate the corrosion depth of the steel drums containing the cemented radioactive waste after a period of 300 years, it is found that in the most unfavourable case (high chloride contamination), the corrosion penetration will be considerably lower than the thickness of the wall of the steel drums. Cementation of ion-exchange resins does not seem to pose special risks regarding the corrosion of the steel drums that contained them; even in the case the matrix is highly contaminated with chloride ions.

Truly incomplete and complex exchanges in prematurely condensed chromosomes of human fibroblasts exposed in vitro to energetic heavy ions

NASA Technical Reports Server (NTRS)

Wu, Honglu; Durante, Marco; Furusawa, Yoshiya; George, Kerry; Kawata, Tetsuya; Cucinotta, Francis A.

2003-01-01

Confluent human fibroblast cells (AG1522) were irradiated with gamma rays, 490 MeV/nucleon silicon ions, or iron ions at either 200 or 500 MeV/nucleon. The cells were allowed to repair at 37 degrees C for 24 h after exposure, and a chemically induced premature chromosome condensation (PCC) technique was used to condense chromosomes in the G2 phase of the cell cycle. Incomplete and complex exchanges were analyzed in the irradiated samples. To verify that chromosomal breaks were truly unrejoined, chromosome aberrations were analyzed using a combination of whole-chromosome specific probes and probes specific for the telomere region of the chromosome. Results showed that the frequency of unrejoined chromosome breaks was higher after irradiation with the heavy ions of high LET, and consequently the ratio of incomplete to complete exchanges increased steadily with LET up to 440 keV/microm, the highest LET included in the present study. For samples exposed to 200 MeV/nucleon iron ions, chromosome aberrations were analyzed using the multicolor FISH (mFISH) technique, which allows identification of both complex and truly incomplete exchanges. Results of the mFISH study showed that 0.7 and 3 Gy iron ions produced similar ratios of complex to simple exchanges and incomplete to complete exchanges; these ratios were higher than those obtained after exposure to 6 Gy gamma rays. After 0.7 Gy of iron ions, most complex aberrations were found to involve three or four chromosomes, which is a likely indication of the maximum number of chromosome domains traversed by a single iron-ion track.

The human mitochondrial single-stranded DNA-binding protein displays distinct kinetics and thermodynamics of DNA binding and exchange

PubMed Central

Qian, Yufeng; Johnson, Kenneth A.

2017-01-01

The human mitochondrial ssDNA-binding protein (mtSSB) is a homotetrameric protein, involved in mtDNA replication and maintenance. Although mtSSB is structurally similar to SSB from Escherichia coli (EcoSSB), it lacks the C-terminal disordered domain, and little is known about the biophysics of mtSSB–ssDNA interactions. Here, we characterized the kinetics and thermodynamics of mtSSB binding to ssDNA by equilibrium titrations and stopped-flow kinetic measurements. We show that the mtSSB tetramer can bind to ssDNA in two distinct binding modes: (SSB)30 and (SSB)60, defined by DNA binding site sizes of 30 and 60 nucleotides, respectively. We found that the binding mode is modulated by magnesium ion and NaCl concentration, but unlike EcoSSB, the mtSSB does not show negative intersubunit cooperativity. Global fitting of both the equilibrium and kinetic data afforded estimates for the rate and equilibrium constants governing the formation of (SSB)60 and (SSB)30 complexes and for the transitions between the two binding modes. We found that the mtSSB tetramer binds to ssDNA with a rate constant near the diffusion limit (2 × 109 m−1 s−1) and that longer DNA (≥60 nucleotides) rapidly wraps around all four monomers, as revealed by FRET assays. We also show that the mtSSB tetramer can directly transfer from one ssDNA molecule to another via an intermediate with two DNA molecules bound to the mtSSB. In conclusion, our results indicate that human mtSSB shares many physicochemical properties with EcoSSB and that the differences may be explained by the lack of an acidic, disordered C-terminal tail in human mtSSB protein. PMID:28615444

Effects of ionic compositions of the medium on monosodium glutamate binding to taste epithelial cells.

PubMed

Hayashi, Y; Tsunenari, T; Mori, T

1999-03-01

Monosodium glutamate and nucleotides are umami taste substances in animals and have a synergistic effect on each other. We studied the ligand-binding properties of the glutamate receptors in taste epithelial cells isolated from bovine tongue. Specific glutamate binding was observed in an enriched suspension of taste receptor cells in Hanks' balanced salt solution, while no specific glutamate binding was apparent in the absence of divalent ions or when the cells had been depolarized by a high content of potassium in Hanks' balanced salt solution. There was no significant difference between the release of glutamate under depolarized or divalent ion-free conditions and under normal conditions. However, glutamate was easily released from the depolarized cells in the absence of divalent ions. These data suggest that the binding of glutamate to receptors depends on divalent ions, which also have an effect on maintaining binding between glutamate and receptors.

UREA/ammonium ion removal system for the orbiting frog otolith experiment. [ion exchange resins for water treatment during space missions

NASA Technical Reports Server (NTRS)

Schulz, J. R.; Anselmi, R. T.

1976-01-01

The feasibility of using free urease enzyme and ANGC-101 ion exchange resin to remove urea and ammonium ion for space system waste water applications was studied. Specifically examined is the prevention of urea and ammonia toxicity in a 30-day Orbiting Frog Otolith (OFO) flight experiment. It is shown that free urease enzyme used in conjunction with ANGC-101 ion-exchange resin and pH control can control urea and amonium ion concentration in unbuffered recirculating water. In addition, the resin does not adversely effect the bullfrogs by lowering the concentration of cations below critical minimum levels. Further investigations on bioburden control, frog waste excretion on an OFO diet, a trade-off analysis of methods of automating the urea/ammonium ion removal system and fabrication and test of a semiautomated breadboard were recommended as continuing efforts. Photographs of test equipment and test animals are shown.

Dynamics of radiocesium exchange and interstratification in anhydrous clay interlayers: Bridging the atom and single crystal scales

NASA Astrophysics Data System (ADS)

Lammers, L. N.; Pestana, L. R.; Schaettle, K. B.; Head-Gordon, T.

2016-12-01

High structural charge clay minerals govern the transport and retention of radiocesium in soils and clay-rich geologic repositories. Cation exchange capacities in these phases are typically assumed to be limited to fast-exchanging basal and high-affinity edge sites, while ions in anhydrous interlayers, usually K+, are considered non-exchangeable. However, recent high resolution imaging and spectroscopic studies have demonstrated that Cs ions can in fact exchange with interlayer K without the formation of a hydrated intermediate.1,2 These exchange reactions result in sharp exchange fronts wherein K+ ions are completely replaced by Cs+ at the exchange interface, and the rate of exchange varies from layer to layer, resulting in the formation of interstratified structures (i.e., randomly alternating layers of exchanged and pristine interlayers). Currently, this process cannot be explained by any known exchange mechanism, and consequently, no kinetic expressions are available to account for this phenomenon in models of subsurface radiocesium fate and transport. We present a mesoscale model for direct exchange in anhydrous clay interlayers that is based on the kinetics of single ion migration events. Single atom migration kinetics derived from density functional theory (DFT) calculations are used as inputs to kinetic Monte Carlo (kMC) simulations, which capture the collective dynamics of the exchange process over length- and timescales relevant for implementation in reactive transport models. Potential energy surfaces derived from DFT demonstrate that exchange of Cs+ for K+ in anhydrous interlayers lowers the energy barrier to K ion migration by 145 kJ/mol, leading to a positive feedback mechanism that generates atomically sharp exchange fronts. Our work demonstrates the application of "coarse-graining" techniques to develop models for processes with characteristic length- and timescales not accessible by direct atomistic simulation. 1 Okumura T. et al. (2014) Direct observation of cesium at the interlayer region in phlogopite mica. Microscopy 63(1), 65-72. 2 Fuller A. J. et al. (2015) Caesium incorporation and retention in illite interlayers. Appl. Clay Sci. 108, 128-134.

Rate theory of solvent exchange and kinetics of Li(+) - BF4 (-)/PF6 (-) ion pairs in acetonitrile.

PubMed

Dang, Liem X; Chang, Tsun-Mei

2016-09-07

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li(+) and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li(+) in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li(+)-[BF4] and Li(+)-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li(+). We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li(+)-[BF4] and Li(+)-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

Rate theory of solvent exchange and kinetics of Li+ - BF4-/PF6- ion pairs in acetonitrile

NASA Astrophysics Data System (ADS)

Dang, Liem X.; Chang, Tsun-Mei

2016-09-01

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li+ and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li+ in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li+-[BF4] and Li+-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li+. We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li+-[BF4] and Li+-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

Spectroscopic characterization of metal bound phytochelatin analogue (Glu-Cys)4-Gly.

PubMed

Cheng, Yongsheng; Yan, Yong-Bin; Liu, Jinyuan

2005-10-01

The metal ion binding properties of a phytochelatin (PC) analogue, (Glu-Cys)4-Gly (named as EC4), have been studied by a divalent metal ion binding assay monitored by UV-visible spectroscopy, circular dichroism and NMR spectroscopy. Spectro- photometric titration with different divalent metal ions have revealed that the stiochoimetry of metal-bound EC4 was 1:1, and its metal binding affinities with different divalent metal ions in the order of Cd(II)>Cu(II)>Zn(II)>Pb(II)>Ni(II)>Co(II). UV-visible spectroscopic analysis of metal complexes indicated that four sulfur atoms in cysteine residues are attributable to ligand-to-metal charge transfer (LMCT) between divalent metal ions and EC4, and further confirmed by 1D H1 NMR study and Circular Dichroism. In addition, Circular Dichroism spectra of both free and metal-bound forms of EC4 revealed that metal coordination drives the nonapeptide chain to fold into a turned conformation. The comprehensive analysis of spectroscopic properties of the nonapeptide complexed with metal ions not only provides a fundamental description of the metal ion binding properties of PC analogue, but also shows a correlation between metal binding affinity of PC analogue and the induction activity of metal ions.

Intermolecular electron-transfer mechanisms via quantitative structures and ion-pair equilibria for self-exchange of anionic (dinitrobenzenide) donors.

PubMed

Rosokha, Sergiy V; Lü, Jian-Ming; Newton, Marshall D; Kochi, Jay K

2005-05-25

Definitive X-ray structures of "separated" versus "contact" ion pairs, together with their spectral (UV-NIR, ESR) characterizations, provide the quantitative basis for evaluating the complex equilibria and intrinsic (self-exchange) electron-transfer rates for the potassium salts of p-dinitrobenzene radical anion (DNB(-)). Three principal types of ion pairs, K(L)(+)DNB(-), are designated as Classes S, M, and C via the specific ligation of K(+) with different macrocyclic polyether ligands (L). For Class S, the self-exchange rate constant for the separated ion pair (SIP) is essentially the same as that of the "free" anion, and we conclude that dinitrobenzenide reactivity is unaffected when the interionic distance in the separated ion pair is r(SIP) > or =6 Angstroms. For Class M, the dynamic equilibrium between the contact ion pair (with r(CIP) = 2.7 Angstroms) and its separated ion pair is quantitatively evaluated, and the rather minor fraction of SIP is nonetheless the principal contributor to the overall electron-transfer kinetics. For Class C, the SIP rate is limited by the slow rate of CIP right arrow over left arrow SIP interconversion, and the self-exchange proceeds via the contact ion pair by default. Theoretically, the electron-transfer rate constant for the separated ion pair is well-accommodated by the Marcus/Sutin two-state formulation when the precursor in Scheme 2 is identified as the "separated" inner-sphere complex (IS(SIP)) of cofacial DNB(-)/DNB dyads. By contrast, the significantly slower rate of self-exchange via the contact ion pair requires an associative mechanism (Scheme 3) in which the electron-transfer rate is strongly governed by cationic mobility of K(L)(+) within the "contact" precursor complex (IS(CIP)) according to the kinetics in Scheme 4.

Measurement of 15N longitudinal relaxation rates in 15NH4+ spin systems to characterise rotational correlation times and chemical exchange

NASA Astrophysics Data System (ADS)

Hansen, D. Flemming

2017-06-01

Many chemical and biological processes rely on the movement of monovalent cations and an understanding of such processes can therefore only be achieved by characterising the dynamics of the involved ions. It has recently been shown that 15N-ammonium can be used as a proxy for potassium to probe potassium binding in bio-molecules such as DNA quadruplexes and enzymes. Moreover, equations have been derived to describe the time-evolution of 15N-based spin density operator elements of 15NH4+ spin systems. Herein NMR pulse sequences are derived to select specific spin density matrix elements of the 15NH4+ spin system and to measure their longitudinal relaxation in order to characterise the rotational correlation time of the 15NH4+ ion as well as report on chemical exchange events of the 15NH4+ ion. Applications to 15NH4+ in acidic aqueous solutions are used to cross-validate the developed pulse sequence while measurements of spin-relaxation rates of 15NH4+ bound to a 41 kDa domain of the bacterial Hsp70 homologue DnaK are presented to show the general applicability of the derived pulse sequence. The rotational correlation time obtained for 15N-ammonium bound to DnaK is similar to the correlation time that describes the rotation about the threefold axis of a methyl group. The methodology presented here provides, together with the previous theoretical framework, an important step towards characterising the motional properties of cations in macromolecular systems.

High-throughput process development: determination of dynamic binding capacity using microtiter filter plates filled with chromatography resin.

PubMed

Bergander, Tryggve; Nilsson-Välimaa, Kristina; Oberg, Katarina; Lacki, Karol M

2008-01-01

Steadily increasing demand for more efficient and more affordable biomolecule-based therapies put a significant burden on biopharma companies to reduce the cost of R&D activities associated with introduction of a new drug to the market. Reducing the time required to develop a purification process would be one option to address the high cost issue. The reduction in time can be accomplished if more efficient methods/tools are available for process development work, including high-throughput techniques. This paper addresses the transitions from traditional column-based process development to a modern high-throughput approach utilizing microtiter filter plates filled with a well-defined volume of chromatography resin. The approach is based on implementing the well-known batch uptake principle into microtiter plate geometry. Two variants of the proposed approach, allowing for either qualitative or quantitative estimation of dynamic binding capacity as a function of residence time, are described. Examples of quantitative estimation of dynamic binding capacities of human polyclonal IgG on MabSelect SuRe and of qualitative estimation of dynamic binding capacity of amyloglucosidase on a prototype of Capto DEAE weak ion exchanger are given. The proposed high-throughput method for determination of dynamic binding capacity significantly reduces time and sample consumption as compared to a traditional method utilizing packed chromatography columns without sacrificing the accuracy of data obtained.

Mixed-mode sorption of hydroxylated atrazine degradation products to sell: A mechanism for bound residue

USGS Publications Warehouse

Lerch, R.N.; Thurman, E.M.; Kruger, E.L.

1997-01-01

This study tested the hypothesis that sorption of hydroxylated atrazine degradation products (HADPs: hydroxyatrazine, HA; deethylhydroxyatrazine, DEHA; and deisopropylhydroxyatrazine, DIHA) to soils occurs by mixed-mode binding resulting from two simultaneous mechanisms: (1) cation exchange and (2) hydrophobic interaction. The objective was to use liquid chromatography and soil extraction experiments to show that mixed-mode binding is the mechanism controlling HADP sorption to soils and is also a mechanism for bound residue. Overall, HADP binding to solid-phase extraction (SPE) sorbents occurred in the order: cation exchange >> octadecyl (C18) >> cyanopropyl. Binding to cation exchange SPE and to a high-performance liquid chromatograph octyl (C8) column showed evidence for mixed-mode binding. Comparison of soil extracted by 0.5 M KH2P04, pH 7.5, or 25% aqueous CH3CN showed that, for HA and DIHA, cation exchange was a more important binding mechanism to soils than hydrophobic interaction. Based on differences between several extractants, the extent of HADP mixed-mode binding to soil occurred in the following order: HA > DIHA > DEHA. Mixed-mode extraction recovered 42.8% of bound atrazine residues from aged soil, and 88% of this fraction was identified as HADPs. Thus, a significant portion of bound atrazine residues in soils is sorbed by the mixed-mode binding mechanisms.

Yeast enolase: mechanism of activation by metal ions.

PubMed

Brewer, J M

1981-01-01

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

The use of laboratory-determined ion exchange parameters in the predictive modelling of field-scale major cation migration in groundwater over a 40-year period.

PubMed

Carlyle, Harriet F; Tellam, John H; Parker, Karen E

2004-01-01

An attempt has been made to estimate quantitatively cation concentration changes as estuary water invades a Triassic Sandstone aquifer in northwest England. Cation exchange capacities and selectivity coefficients for Na(+), K(+), Ca(2+), and Mg(2+) were measured in the laboratory using standard techniques. Selectivity coefficients were also determined using a method involving optimized back-calculation from flushing experiments, thus permitting better representation of field conditions; in all cases, the Gaines-Thomas/constant cation exchange capacity (CEC) model was found to be a reasonable, though not perfect, first description. The exchange parameters interpreted from the laboratory experiments were used in a one-dimensional reactive transport mixing cell model, and predictions compared with field pumping well data (Cl and hardness spanning a period of around 40 years, and full major ion analyses in approximately 1980). The concentration patterns predicted using Gaines-Thomas exchange with calcite equilibrium were similar to the observed patterns, but the concentrations of the divalent ions were significantly overestimated, as were 1980 sulphate concentrations, and 1980 alkalinity concentrations were underestimated. Including representation of sulphate reduction in the estuarine alluvium failed to replicate 1980 HCO(3) and pH values. However, by including partial CO(2) degassing following sulphate reduction, a process for which there is 34S and 18O evidence from a previous study, a good match for SO(4), HCO(3), and pH was attained. Using this modified estuary water and averaged values from the laboratory ion exchange parameter determinations, good predictions for the field cation data were obtained. It is concluded that the Gaines-Thomas/constant exchange capacity model with averaged parameter values can be used successfully in ion exchange predictions in this aquifer at a regional scale and over extended time scales, despite the numerous assumptions inherent in the approach; this has also been found to be the case in the few other published studies of regional ion exchanging flow.

The use of laboratory-determined ion exchange parameters in the predictive modelling of field-scale major cation migration in groundwater over a 40-year period

NASA Astrophysics Data System (ADS)

Carlyle, Harriet F.; Tellam, John H.; Parker, Karen E.

2004-01-01

An attempt has been made to estimate quantitatively cation concentration changes as estuary water invades a Triassic Sandstone aquifer in northwest England. Cation exchange capacities and selectivity coefficients for Na +, K +, Ca 2+, and Mg 2+ were measured in the laboratory using standard techniques. Selectivity coefficients were also determined using a method involving optimized back-calculation from flushing experiments, thus permitting better representation of field conditions; in all cases, the Gaines-Thomas/constant cation exchange capacity (CEC) model was found to be a reasonable, though not perfect, first description. The exchange parameters interpreted from the laboratory experiments were used in a one-dimensional reactive transport mixing cell model, and predictions compared with field pumping well data (Cl and hardness spanning a period of around 40 years, and full major ion analyses in ˜1980). The concentration patterns predicted using Gaines-Thomas exchange with calcite equilibrium were similar to the observed patterns, but the concentrations of the divalent ions were significantly overestimated, as were 1980 sulphate concentrations, and 1980 alkalinity concentrations were underestimated. Including representation of sulphate reduction in the estuarine alluvium failed to replicate 1980 HCO 3 and pH values. However, by including partial CO 2 degassing following sulphate reduction, a process for which there is 34S and 18O evidence from a previous study, a good match for SO 4, HCO 3, and pH was attained. Using this modified estuary water and averaged values from the laboratory ion exchange parameter determinations, good predictions for the field cation data were obtained. It is concluded that the Gaines-Thomas/constant exchange capacity model with averaged parameter values can be used successfully in ion exchange predictions in this aquifer at a regional scale and over extended time scales, despite the numerous assumptions inherent in the approach; this has also been found to be the case in the few other published studies of regional ion exchanging flow.

Ion transport in the microporous titanosilicate ETS-10.

PubMed

Wei, Ta-Chen; Hillhouse, Hugh W

2006-07-20

Impedance spectroscopy was used to investigate ion transport in the microporous crystalline framework titanosilicate ETS-10 in the frequency range from 1 Hz to 10 MHz. These data were compared to measured data from the microporous aluminosilicate zeolite X. Na-ETS-10 was found to have a lower activation energy for ion conduction than that of NaX, 58.5 kJ/mol compared to 66.8 kJ/mol. However, the dc conductivity and ion hopping rate for Na-ETS-10 were also lower than NaX. This was found to be due to the smaller entropy contribution in Na-ETS-10 because of its high cation site occupancy. This was verified by ion exchanging Na(+) with Cu(2+) in both microporous frameworks. This exchange decreases the cation site occupancy and reduces correlation effects. The exchanged Cu-ETS-10 was found to have both lower activation energy and higher ionic conductivity than CuX. Zeolite X has the highest ion conductivity among the zeolites, and thus the data shown here indicate that ETS-10 has more facile transport of higher valence cations which may be important for ion-exchange, environmental remediation of radionucleotides, and nanofabrication.

Binding characteristics of copper and cadmium by cyanobacterium Spirulina platensis.

PubMed

Fang, Linchuan; Zhou, Chen; Cai, Peng; Chen, Wenli; Rong, Xingmin; Dai, Ke; Liang, Wei; Gu, Ji-Dong; Huang, Qiaoyun

2011-06-15

Cyanobacteria are promising biosorbent for heavy metals in bioremediation. Although sequestration of metals by cyanobacteria is known, the actual mechanisms and ligands involved are not very well understood. The binding characteristics of Cu(II) and Cd(II) by the cyanobacterium Spirulina platensis were investigated using a combination of chemical modifications, batch adsorption experiments, Fourier transform infrared (FTIR) spectroscopy and X-ray absorption fine structure (XAFS) spectroscopy. A significant increase in Cu(II) and Cd(II) binding was observed in the range of pH 3.5-5.0. Dramatical decrease in adsorption of Cu(II) and Cd(II) was observed after methanol esterification of the nonliving cells demonstrating that carboxyl functional groups play an important role in the binding of metals by S. platensis. The desorption rate of Cu(II) and Cd(II) from S. platensis surface was 72.7-80.7% and 53.7-58.0% by EDTA and NH(4)NO(3), respectively, indicating that ion exchange and complexation are the dominating mechanisms for Cu(II) and Cd(II) adsorption. XAFS analysis provided further evidence on the inner-sphere complexation of Cu by carboxyl ligands and showed that Cu is complexed by two 5-membered chelate rings on S. platensis surface. Copyright © 2011 Elsevier B.V. All rights reserved.

Investigation of the electrostatic and hydration properties of DNA minor groove-binding by a heterocyclic diamidine by osmotic pressure.

PubMed

Erlitzki, Noa; Huang, Kenneth; Xhani, Suela; Farahat, Abdelbasset A; Kumar, Arvind; Boykin, David W; Poon, Gregory M K

2017-12-01

Previous investigations of sequence-specific DNA binding by model minor groove-binding compounds showed that the ligand/DNA complex was destabilized in the presence of compatible co-solutes. Inhibition was interpreted in terms of osmotic stress theory as the uptake of significant numbers of excess water molecules from bulk solvent upon complex formation. Here, we interrogated the AT-specific DNA complex formed with the symmetric heterocyclic diamidine DB1976 as a model for minor groove DNA recognition using both ionic (NaCl) and non-ionic cosolutes (ethylene glycol, glycine betaine, maltose, nicotinamide, urea). While the non-ionic cosolutes all destabilized the ligand/DNA complex, their quantitative effects were heterogeneous in a cosolute- and salt-dependent manner. Perturbation with NaCl in the absence of non-ionic cosolute showed that preferential hydration water was released upon formation of the DB1976/DNA complex. As salt probes counter-ion release from charged groups such as the DNA backbone, we propose that the preferential hydration uptake in DB1976/DNA binding observed in the presence of osmolytes reflects the exchange of preferentially bound cosolute with hydration water in the environs of the bound DNA, rather than a net uptake of hydration waters by the complex. Copyright © 2017 Elsevier B.V. All rights reserved.

Identification of residues that control Li+ versus Na+ dependent Ca2+ exchange at the transport site of the mitochondrial NCLX.

PubMed

Roy, Soumitra; Dey, Kuntal; Hershfinkel, Michal; Ohana, Ehud; Sekler, Israel

2017-06-01

The Na + /Ca 2+ /Li + exchanger (NCLX) is a member of the Na + /Ca 2+ exchanger family. NCLX is unique in its capacity to transport both Na + and Li + , unlike other members, which are Na + selective. The major aim of this study was twofold, i.e., to identify NCLX residues that confer Li + or Na + selective Ca 2+ transport and map their putative location on NCLX cation transport site. We combined molecular modeling to map transport site of NCLX with euryarchaeal H + /Ca 2+ exchanger, CAX_Af, and fluorescence analysis to monitor Li + versus Na + dependent mitochondrial Ca 2+ efflux of transport site mutants of NCLX in permeabilized cells. Mutation of Asn149, Pro152, Asp153, Gly176, Asn467, Ser468, Gly494 and Asn498 partially or strongly abolished mitochondrial Ca 2+ exchange activity in intact cells. In permeabilized cells, N149A, P152A, D153A, N467Q, S468T and G494S demonstrated normal Li + /Ca 2+ exchange activity but a reduced Na + /Ca 2+ exchange activity. On the other hand, D471A showed dramatically reduced Li + /Ca 2+ exchange, but Na + /Ca 2+ exchange activity was unaffected. Finally, simultaneous mutation of four putative Ca 2+ binding residues was required to completely abolish both Na + /Ca 2+ and Li + /Ca 2+ exchange activities. We identified distinct Na + and Li + selective residues in the NCLX transport site. We propose that functional segregation in Li + and Na + sites reflects the functional properties of NCLX required for Ca 2+ exchange under the unique membrane potential and ion gradient across the inner mitochondrial membrane. The results of this study provide functional insights into the unique Li + and Na + selectivity of the mitochondrial exchanger. This article is part of a Special Issue entitled: ECS Meeting edited by Claus Heizmann, Joachim Krebs and Jacques Haiech. Copyright © 2017 Elsevier B.V. All rights reserved.

The crystal structures of the psychrophilic subtilisin S41 and the mesophilic subtilisin Sph reveal the same calcium-loaded state.

PubMed

Almog, Orna; González, Ana; Godin, Noa; de Leeuw, Marina; Mekel, Marlene J; Klein, Daniela; Braun, Sergei; Shoham, Gil; Walter, Richard L

2009-02-01

We determine and compare the crystal structure of two proteases belonging to the subtilisin superfamily: S41, a cold-adapted serine protease produced by Antarctic bacilli, at 1.4 A resolution and Sph, a mesophilic serine protease produced by Bacillus sphaericus, at 0.8 A resolution. The purpose of this comparison was to find out whether multiple calcium ion binding is a molecular factor responsible for the adaptation of S41 to extreme low temperatures. We find that these two subtilisins have the same subtilisin fold with a root mean square between the two structures of 0.54 A. The final models for S41 and Sph include a calcium-loaded state of five ions bound to each of these two subtilisin molecules. None of these calcium-binding sites correlate with the high affinity known binding site (site A) found for other subtilisins. Structural analysis of the five calcium-binding sites found in these two crystal structures indicate that three of the binding sites have two side chains of an acidic residue coordinating the calcium ion, whereas the other two binding sites have either a main-chain carbonyl, or only one acidic residue side chain coordinating the calcium ion. Thus, we conclude that three of the sites are of high affinity toward calcium ions, whereas the other two are of low affinity. Because Sph is a mesophilic subtilisin and S41 is a psychrophilic subtilisin, but both crystal structures were found to bind five calcium ions, we suggest that multiple calcium ion binding is not responsible for the adaptation of S41 to low temperatures. Copyright 2008 Wiley-Liss, Inc.

Electrochemically Controlled Ion-exchange Property of Carbon Nanotubes/Polypyrrole Nanocomposite in Various Electrolyte Solutions

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

Choi, Daiwon; Zhu, Chengzhou; Fu, Shaofang

2016-09-15

The electrochemically controlled ion-exchange properties of multi-wall carbon nanotube (MWNT)/electronically conductive polypyrrole (PPy) polymer composite in the various electrolyte solutions have been investigated. The ion-exchange behavior, rate and capacity of the electrochemically deposited polypyrrole with and without carbon nanotube (CNT) were compared and characterized using cyclic voltammetry (CV), chronoamperometry (CA), electrochemical quartz crystal microbalance (EQCM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). It has been found that the presence of carbon nanotube backbone resulted in improvement in ion-exchange rate, stability of polypyrrole, and higher anion loading capacity per PPy due to higher surface area, electronic conductivity, porous structuremore » of thin film, and thinner film thickness providing shorter diffusion path. Chronoamperometric studies show that electrically switched anion exchange could be completed more than 10 times faster than pure PPy thin film. The anion selectivity of CNT/PPy film is demonstrated using X-ray photoelectron spectroscopy (XPS).« less

Antimicrobial Activity of Silver Ions Released from Zeolites Immobilized on Cellulose Nanofiber Mats.

PubMed

Rieger, Katrina A; Cho, Hong Je; Yeung, Hiu Fai; Fan, Wei; Schiffman, Jessica D

2016-02-10

In this study, we exploit the high silver ion exchange capability of Linde Type A (LTA) zeolites and present, for the first time, electrospun nanofiber mats decorated with in-house synthesized silver (Ag(+)) ion exchanged zeolites that function as molecular delivery vehicles. LTA-Large zeolites with a particle size of 6.0 μm were grown on the surface of the cellulose nanofiber mats, whereas LTA-Small zeolites (0.2 μm) and three-dimensionally ordered mesoporous-imprinted (LTA-Meso) zeolites (0.5 μm) were attached to the surface of the cellulose nanofiber mats postsynthesis. After the three zeolite/nanofiber mat assemblies were ion-exchanged with Ag(+) ions, their ion release profiles and ability to inactivate Escherichia coli (E. coli) K12 were evaluated as a function of time. LTA-Large zeolites immobilized on the nanofiber mats displayed more than an 11 times greater E. coli K12 inactivation than the Ag-LTA-Large zeolites that were not immobilized on the nanofiber mats. This study demonstrates that by decorating nanometer to micrometer scale Ag(+) ion-exchanged zeolites on the surface of high porosity, hydrophilic cellulose nanofiber mats, we can achieve a tunable release of Ag(+) ions that inactivate bacteria faster and are more practical to use in applications over powder zeolites.

Co2+-exchange mechanism of birnessite and its application for the removal of Pb2+ and As(III).

PubMed

Yin, Hui; Liu, Fan; Feng, Xionghan; Liu, Mingming; Tan, Wenfeng; Qiu, Guohong

2011-11-30

Co-containing birnessites were obtained by ion exchange at different initial concentrations of Co(2+). Ion exchange of Co(2+) had little effect on birnessite crystal structure and micromorphology, but resulted in an increase in specific surface areas from 19.26 to 33.35 m(2)g(-1), and a decrease in both crystallinity and manganese average oxidation state. It was due to that Mn(IV) in the layer structure was reduced to Mn(III) during the oxidation process of Co(2+) to Co(III). The hydroxyl groups on the surface of Co-containing birnessites gradually decreased with an increase of Co/Mn molar ratio owing to the occupance of Co(III) into vacancies and the location of large amounts of Co(2+/3+) and Mn(2+/3+) above/below the vacant sites. This greatly accounted for the monotonous reduction in Pb(2+) adsorption capacity, from 2538 mmol kg(-1) for the unmodified birnessite to 1500 mmol kg(-1) for the Co(2+) ion-exchanged birnessite with a Co/Mn molar ratio of 0.16. The amount of As(III) oxidized by birnessite was enhanced after ion exchange, but the apparent initial reaction rate was greatly decreased. The present work demonstrates that Co(2+) ion exchange has great influence on the adsorption and oxidation behavior of inorganic toxic metal ions by birnessite in water environments. Copyright © 2011 Elsevier B.V. All rights reserved.

The geochemical evolution of aqueous sodium in the Black Creek Aquifer, Horry and Georgetown counties, South Carolina

USGS Publications Warehouse

Zack, Allen L.; Roberts, Ivan

1988-01-01

The Black Creek aquifer contains dilute seawater near the North Carolina State line, probably the result of incomplete flushing of ancient seawater. Data do not indicate that the dilute seawater has migrated toward areas of fresh ground-water withdrawals. The concentration of chloride in ground-water samples ranges from 5 to 720 milligrams per liter and that of sodium from 160 to 690 milligrams per liter. Ion-exchange reactions (sodium for calcium and fluoride for hydroxyl) occur with the calcium carbonate dissolution reaction which produces calcium, bicarbonate, and hydroxyl ions. The reaction sequence and stoichiometry result in an aqueous solution in which the sum of bicarbonate and chloride equivalents per liter is equal to the equivalents per liter of sodium. Calcium ions are exchanged for sodium ions derived from sodium-rich clays upgradient of the dilute seawater. The cation-exchange reaction equilibrates at a sodium concentration of 280 milligrams per liter. Amounts of sodium greater than 280 milligrams per liter are contributed from dilute seawater. The cation-exchange reaction approaches an equilibrium which represents a mass-action limit in terms of the ratio of sodium to calcium in solution versus the ratio of exchangeable sodium to calcium on clay surfaces. Where the limit of calcium carbonate solubility is approached and dissolution ceases, some precipitation of calcite probably takes place. The dissolution of calcite exposes fossil shark teeth which release fluoride ions to the ground water through anion exchange with aqueous hydroxyl ions.

Effect of Monovalent Ion Parameters on Molecular Dynamics Simulations of G-Quadruplexes.

PubMed

Havrila, Marek; Stadlbauer, Petr; Islam, Barira; Otyepka, Michal; Šponer, Jiří

2017-08-08

G-quadruplexes (GQs) are key noncanonical DNA and RNA architectures stabilized by desolvated monovalent cations present in their central channels. We analyze extended atomistic molecular dynamics simulations (∼580 μs in total) of GQs with 11 monovalent cation parametrizations, assessing GQ overall structural stability, dynamics of internal cations, and distortions of the G-tetrad geometries. Majority of simulations were executed with the SPC/E water model; however, test simulations with TIP3P and OPC water models are also reported. The identity and parametrization of ions strongly affect behavior of a tetramolecular d[GGG] 4 GQ, which is unstable with several ion parametrizations. The remaining studied RNA and DNA GQs are structurally stable, though the G-tetrad geometries are always deformed by bifurcated H-bonding in a parametrization-specific manner. Thus, basic 10-μs-scale simulations of fully folded GQs can be safely done with a number of cation parametrizations. However, there are parametrization-specific differences and basic force-field errors affecting the quantitative description of ion-tetrad interactions, which may significantly affect studies of the ion-binding processes and description of the GQ folding landscape. Our d[GGG] 4 simulations indirectly suggest that such studies will also be sensitive to the water models. During exchanges with bulk water, the Na + ions move inside the GQs in a concerted manner, while larger relocations of the K + ions are typically separated. We suggest that the Joung-Cheatham SPC/E K + parameters represent a safe choice in simulation studies of GQs, though variation of ion parameters can be used for specific simulation goals.

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo; E, Sook Yen

2018-05-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. [Figure not available: see fulltext.

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data.

PubMed

Hamuro, Yoshitomo; E, Sook Yen

2018-05-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. Graphical Abstract ᅟ.

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo; E, Sook Yen

2018-03-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. [Figure not available: see fulltext.

Estimate of the frequency of true incomplete exchanges in human lymphocytes exposed to 1 GeV/u Fe ions in vitro

NASA Technical Reports Server (NTRS)

Wu, H.; George, K.; Yang, T. C.

1999-01-01

PURPOSE: To study the frequency of true incomplete exchanges induced by high-LET radiation. MATERIALS AND METHODS: Human lymphocytes were exposed to 1 GeV/u Fe ions (LET = 140 keV/microm). Chromosome aberrations were analysed by a fluorescence in situ hybridization using a combination of whole-chromosome-specific probes and human telomere probes. Chromosomes 1, 3 and 4 were investigated. RESULTS: The percentage of incomplete exchanges was between 23 and 29% if telomere signals were not considered. The percentage decreased to approximately 10% after ruling out false incomplete exchanges containing telomere signals. The final estimation of true incomplete exchanges was <10%. CONCLUSION: Within a degree of uncertainty, the percentage of true incomplete exchanges in 1 GeV/u Fe ion-irradiated human lymphocytes was similar to that induced by gamma rays.

Fate of 90Sr and U(VI) in Dounreay sediments following saline inundation and erosion.

PubMed

Eagling, Jane; Worsfold, Paul J; Blake, William H; Keith-Roach, Miranda J

2013-08-01

There is concern that sea level rise associated with projected climate change will lead to the inundation, flooding and erosion of soils and sediments contaminated with radionuclides at coastal nuclear sites, such as Dounreay (UK), with seawater. Here batch and column experiments were designed to simulate these scenarios and sequential extractions were used to identify the key radionuclide solid phase associations. Strontium was exchangeable and was mobilised rapidly by ion exchange with seawater Mg(2+) in both batch and column experiments. In contrast, U was more strongly bound to the sediments and mobilisation was initially limited by the influence of the sediment on the pH of the water. Release was only observed when the pH increased above 6.9, suggesting that the formation of soluble U(VI)-carbonate species was important. Under dynamic flow conditions, long term release was significant (47%), but controlled by slow desorption kinetics from a range of binding sites. Copyright © 2013 Elsevier Ltd. All rights reserved.

In-vitro evaluation of ion-exchange microspheres for the sustained release of liposomal-adenoviral conjugates.

PubMed

Steel, Jason C; Cavanagh, Heather M A; Burton, Mark A; Dingwall, Daniel; Kalle, Wouter H J

2004-03-24

This study looks at the development of a novel combination vector consisting of adenovirus conjugated to liposomes (AL complexes) bound to cation-exchanging microspheres (MAL complexes). With adenovirus having a net negative charge and the liposomes a net positive charge it was possible to modify the net charge of the AL complexes by varying the concentrations of adenovirus to liposomes. The modification of the net charge resulted in altered binding and release characteristics. Of the complexes tested, the 5:1 and 2:1 ratio AL complexes were able to be efficiently bound by the microspheres and exhibited sustained release over 24 h. The 1:1 and 1:2 AL complexes, however, bound poorly to the microspheres and were rapidly released. In addition the MAL complexes also were able to reduce the toxicity of the AL complexes, which was seen with the 10:1 ratio. The AL complexes showed considerably more toxicity alone than in combination with microspheres, highlighting a potential benefit of this vector.

Preparation of cation exchanger from lemon and sorption of divalent heavy metals.

PubMed

Arslanoglu, Hasan; Soner Altundogan, H; Tumen, Fikret

2008-05-01

A cation exchanging material was developed from lemon by modifying the pectic-cellulosic substances in the lemon peel by lemon juice having citric acid. For this purpose, chopped lemon removed from seeds and yellow skin was heated in two stages, firstly at 50 degrees C for 24h and subsequently at 120 degrees C for 2h. The material obtained was ground, repeatedly washed with water and dried. Lemon peel and lemon resin obtained were characterized through physicochemical analyses and FTIR spectroscopy. Heavy metal binding performance of this material was determined by removal tests conducted by using 10mM solutions of divalent metals. Experimental results show that the resin prepared from lemon is effective especially for Pb and Cu removals. For a lemon resin dosage of 10 g l(-1), sorption affinity of divalent metal ions is found to be in an order of Pb>Cu>Ni>Fe>Cd>Zn>Co>Mn. Typically, sorption capacities are about 0.87 and 0.43 mmol g(-1) for Pb and Mn, respectively.

A differential scanning calorimetric study of the effects of metal ions, substrate/product, substrate analogues and chaotropic anions on the thermal denaturation of yeast enolase 1.

PubMed

Brewer, J M; Wampler, J E

2001-03-14

The thermal denaturation of yeast enolase 1 was studied by differential scanning calorimetry (DSC) under conditions of subunit association/dissociation, enzymatic activity or substrate binding without turnover and substrate analogue binding. Subunit association stabilizes the enzyme, that is, the enzyme dissociates before denaturing. The conformational change produced by conformational metal ion binding increases thermal stability by reducing subunit dissociation. 'Substrate' or analogue binding additionally stabilizes the enzyme, irrespective of whether turnover is occurring, perhaps in part by the same mechanism. More strongly bound metal ions also stabilize the enzyme more, which we interpret as consistent with metal ion loss before denaturation, though possibly the denaturation pathway is different in the absence of metal ion. We suggest that some of the stabilization by 'substrate' and analogue binding is owing to the closure of moveable polypeptide loops about the active site, producing a more 'closed' and hence thermostable conformation.

Ion temperatures in HIP-1 and SUMMA from charge-exchange neutral optical emission spectra

NASA Technical Reports Server (NTRS)

Patch, R. W.; Lauver, M. R.

1976-01-01

Ion temperatures were obtained from observations of the H sub alpha, D sub alpha, and He 587.6 nm lines emitted from hydrogen, deuterium, and helium plasmas in the SUMMA and HIP-1 mirror devices at Lewis Research Center. Steady state discharges were formed by applying a radially inward dc electric field between cylindrical or annular anodes and hollow cathodes located at the peaks of the mirrors. The ion temperatures were found from the Doppler broadening of the charge-exchange components of spectral lines. A statistical method was developed for obtaining scaling relations of ion temperature as a function of current, voltage, and magnetic flux density. Derivations are given that take into account triangular monochromator slit functions, loss cones, and superimposed charge-exchange processes. In addition, the Doppler broadening was found to be sensitive to the influence of drift on charge-exchange cross section. The effects of finite ion-cyclotron radius, cascading, and delayed emission are reviewed.

Sodium channel selectivity and conduction: Prokaryotes have devised their own molecular strategy

PubMed Central

Finol-Urdaneta, Rocio K.; Wang, Yibo; Al-Sabi, Ahmed; Zhao, Chunfeng

2014-01-01

Striking structural differences between voltage-gated sodium (Nav) channels from prokaryotes (homotetramers) and eukaryotes (asymmetric, four-domain proteins) suggest the likelihood of different molecular mechanisms for common functions. For these two channel families, our data show similar selectivity sequences among alkali cations (relative permeability, Pion/PNa) and asymmetric, bi-ionic reversal potentials when the Na/K gradient is reversed. We performed coordinated experimental and computational studies, respectively, on the prokaryotic Nav channels NaChBac and NavAb. NaChBac shows an “anomalous,” nonmonotonic mole-fraction dependence in the presence of certain sodium–potassium mixtures; to our knowledge, no comparable observation has been reported for eukaryotic Nav channels. NaChBac’s preferential selectivity for sodium is reduced either by partial titration of its highly charged selectivity filter, when extracellular pH is lowered from 7.4 to 5.8, or by perturbation—likely steric—associated with a nominally electro-neutral substitution in the selectivity filter (E191D). Although no single molecular feature or energetic parameter appears to dominate, our atomistic simulations, based on the published NavAb crystal structure, revealed factors that may contribute to the normally observed selectivity for Na over K. These include: (a) a thermodynamic penalty to exchange one K+ for one Na+ in the wild-type (WT) channel, increasing the relative likelihood of Na+ occupying the binding site; (b) a small tendency toward weaker ion binding to the selectivity filter in Na–K mixtures, consistent with the higher conductance observed with both sodium and potassium present; and (c) integrated 1-D potentials of mean force for sodium or potassium movement that show less separation for the less selective E/D mutant than for WT. Overall, tight binding of a single favored ion to the selectivity filter, together with crucial inter-ion interactions within the pore, suggests that prokaryotic Nav channels use a selective strategy more akin to those of eukaryotic calcium and potassium channels than that of eukaryotic Nav channels. PMID:24420772

Hyaluronate-binding proteins of murine brain.

PubMed

Marks, M S; Chi-Rosso, G; Toole, B P

1990-01-01

The distribution of hyaluronate-binding activity was determined in the soluble and membrane fractions derived from adult mouse brain by sonication in low-ionic-strength buffer. Approximately 60% of the total activity was recovered in the soluble fraction and 33% in membrane fractions. In both cases, the hyaluronate-binding activities were found to be of high affinity (KD = 10(-9) M), specific for hyaluronate, and glycoprotein in nature. Most of the hyaluronate-binding activity from the soluble fraction chromatographed in the void volume of Sepharose CL-4B and CL-6B. Approximately 50% of this activity was highly negatively charged, eluting from diethylaminoethyl (DEAE)-cellulose in 0.5 M NaCl, and contained chondroitin sulfate chains. This latter material also reacted with antibodies raised against cartilage link protein and the core protein of cartilage proteoglycan. Thus, the binding and physical characteristics of this hyaluronate-binding activity are consistent with those of a chondroitin sulfate proteoglycan aggregate similar to that found in cartilage. A 500-fold purification of this proteoglycan-like, hyaluronate-binding material was achieved by wheat germ agglutinin affinity chromatography, molecular sieve chromatography on Sepharose CL-6B, and ion exchange chromatography on DEAE-cellulose. Another class of hyaluronate-binding material (25-50% of that recovered) eluted from DEAE with 0.24 M NaCl; this material had the properties of a complex glycoprotein, did not contain chondroitin sulfate, and did not react with the antibodies against cartilage link protein and proteoglycan. Thus, adult mouse brain contains at least three different forms of hyaluronate-binding macromolecules. Two of these have properties similar to the link protein and proteoglycan of cartilage proteoglycan aggregates; the third is distinguishable from these entities.

A dye-binding assay for measurement of the binding of Cu(II) to proteins.

PubMed

Wilkinson-White, Lorna E; Easterbrook-Smith, Simon B

2008-10-01

We analysed the theory of the coupled equilibria between a metal ion, a metal ion-binding dye and a metal ion-binding protein in order to develop a procedure for estimating the apparent affinity constant of a metal ion:protein complex. This can be done by analysing from measurements of the change in the concentration of the metal ion:dye complex with variation in the concentration of either the metal ion or the protein. Using experimentally determined values for the affinity constant of Cu(II) for the dye, 2-(5-bromo-2-pyridylaxo)-5-(N-propyl-N-sulfopropylamino) aniline (5-Br-PSAA), this procedure was used to estimate the apparent affinity constants for formation of Cu(II):transthyretin, yielding values which were in agreement with literature values. An apparent affinity constant for Cu(II) binding to alpha-synuclein of approximately 1 x 10(9)M(-1) was obtained from measurements of tyrosine fluorescence quenching by Cu(II). This value was in good agreement with that obtained using 5-Br-PSAA. Our analysis and data therefore show that measurement of changes in the equilibria between Cu(II) and 5-Br-PSAA by Cu(II)-binding proteins provides a general procedure for estimating the affinities of proteins for Cu(II).

Coexisting stable conformations of gaseous protein ions.

PubMed Central

Suckau, D; Shi, Y; Beu, S C; Senko, M W; Quinn, J P; Wampler, F M; McLafferty, F W

1993-01-01

For further insight into the role of solvent in protein conformer stabilization, the structural and dynamic properties of protein ions in vacuo have been probed by hydrogen-deuterium exchange in a Fourier-transform mass spectrometer. Multiply charged ions generated by electrospray ionization of five proteins show exchange reactions with 2H2O at 10(-7) torr (1 torr = 133.3 Pa) exhibiting pseudo-first-order kinetics. Gas-phase compactness of the S-S cross-linked RNase A relative to denatured S-derivatized RNase A is indicated by exchange of 35 and 135 hydrogen atoms, respectively. For pure cytochrome c ions, the existence of at least three distinct gaseous conformers is indicated by the substantially different values--52, 113, and 74--of reactive H atoms; the observation of these same values for ions of a number--2, 7, and 5, respectively--of different charge states indicates conformational insensitivity to coulombic forces. For each of these conformers, the compactness in vacuo indicated by these values corresponds directly to that of a known conformer structure in the solution from which the conformer ions are produced by electrospray. S-derivatized RNase A ions also exist as at least two gaseous conformers exchanging 50-140 H atoms. Gaseous conformer ions are isometrically stable for hours; removal of solvent greatly increases conformational rigidity. More specific ion-molecule reactions could provide further details of conformer structures. Images PMID:8381533

Neutral dynamics and ion energy transport in MST plasma

NASA Astrophysics Data System (ADS)

Xing, Zichuan; Nornberg, Mark; den Hartog, Daniel; Kumar, Santosh; Anderson, Jay

2015-11-01

Neutral dynamics can have a significant effect on ion energy transport through charge exchange collisions. Whereas previously charge exchange was considered a direct loss mechanism in MST plasmas, new analysis indicates that significant thermal charge exchange neutrals are reionized. Further, the temperatures of the neutral species in the core of the plasma are suspected to be much higher than room temperature, which has a large effect on ion energy losses due to charge exchange. The DEGAS2 Monte Carlo simulation code is applied to the MST reversed field pinch experiment to estimate the density and temperature profile of the neutral species. The result is then used to further examine the effect of the neutral species on ion energy transport in improved confinement plasmas. This enables the development of a model that accounts for collisional equilibration between species, classical convective and conductive energy transport, and energy loss due to charge exchange collisions. The goal is to quantify classical, stochastic, and anomalous ion heating and transport in RFP plasmas. Work supported by the US DOE. DEGAS2 is provided by PPPL and STRAHL is provided by Ralph Dux of the Max-Planck-Institut fur Plasmaphysik.

Ion Exchange Polymeric Coatings for Selective Capacitive Deionization

NASA Astrophysics Data System (ADS)

Jain, Amit; Kim, Jun; Li, Qilin; Verduzco, Rafael

Capacitive deionization (CDI) is an energy-efficient technology for adsorbing and removing scalants and foulants from water by utilizing electric potential between porous carbon electrodes. Currently, industrial application of CDI is limited to low salinity waters due to the limited absorption capacities of carbon electrodes. However, CDI can potentially be used as a low-cost approach to selectively remove divalent ions from high salinity water. Divalent ions such as sulfonates and carbonates cause scaling and thus performance deterioration of membrane-based desalination systems. In this work, we investigated ion-exchange polymer coatings for use in a membrane capacitive deionization (MCDI) process for selective removal of divalent ions. Poly-Vinyl Alcohol (PVA) base polymer was crosslinked and charged using sulfo-succinic acid (SSA) to give a cation exchange layer. 50 um thick standalone polymer films had a permeability of 4.25*10-7 cm2/s for 10mM NaCl feed. Experiments on electrodes with as low as 10 υm thick coating of cation exchange polymer are under progress and will be evaluated on the basis of their selective salt removal efficiency and charge efficiency, and in future we will extend this work to sulfonated block copolymers and anion exchange polymers.

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

USGS Publications Warehouse

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

1998-01-01

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

Cooperative binding modes of Cu(II) in prion protein

NASA Astrophysics Data System (ADS)

Hodak, Miroslav; Chisnell, Robin; Lu, Wenchang; Bernholc, Jerry

2007-03-01

The misfolding of the prion protein, PrP, is responsible for a group of neurodegenerative diseases including mad cow disease and Creutzfeldt-Jakob disease. It is known that the PrP can efficiently bind copper ions; four high-affinity binding sites located in the octarepeat region of PrP are now well known. Recent experiments suggest that at low copper concentrations new binding modes, in which one copper ion is shared between two or more binding sites, are possible. Using our hybrid Thomas-Fermi/DFT computational scheme, which is well suited for simulations of biomolecules in solution, we investigate the geometries and energetics of two, three and four binding sites cooperatively binding one copper ion. These geometries are then used as inputs for classical molecular dynamics simulations. We find that copper binding affects the secondary structure of the PrP and that it stabilizes the unstructured (unfolded) part of the protein.

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study.

PubMed

Eklund, Lars; Hofer, Thomas S; Pribil, Andreas B; Rode, Bernd M; Persson, Ingmar

2012-05-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) Å by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.

Steady-State Ion Beam Modeling with MICHELLE

NASA Astrophysics Data System (ADS)

Petillo, John

2003-10-01

There is a need to efficiently model ion beam physics for ion implantation, chemical vapor deposition, and ion thrusters. Common to all is the need for three-dimensional (3D) simulation of volumetric ion sources, ion acceleration, and optics, with the ability to model charge exchange of the ion beam with a background neutral gas. The two pieces of physics stand out as significant are the modeling of the volumetric source and charge exchange. In the MICHELLE code, the method for modeling the plasma sheath in ion sources assumes that the electron distribution function is a Maxwellian function of electrostatic potential over electron temperature. Charge exchange is the process by which a neutral background gas with a "fast" charged particle streaming through exchanges its electron with the charged particle. An efficient method for capturing this is essential, and the model presented is based on semi-empirical collision cross section functions. This appears to be the first steady-state 3D algorithm of its type to contain multiple generations of charge exchange, work with multiple species and multiple charge state beam/source particles simultaneously, take into account the self-consistent space charge effects, and track the subsequent fast neutral particles. The solution used by MICHELLE is to combine finite element analysis with particle-in-cell (PIC) methods. The basic physics model is based on the equilibrium steady-state application of the electrostatic particle-in-cell (PIC) approximation employing a conformal computational mesh. The foundation stems from the same basic model introduced in codes such as EGUN. Here, Poisson's equation is used to self-consistently include the effects of space charge on the fields, and the relativistic Lorentz equation is used to integrate the particle trajectories through those fields. The presentation will consider the complexity of modeling ion thrusters.

Aqueous alkali halide solutions: can osmotic coefficients be explained on the basis of the ionic sizes alone?

PubMed

Kalyuzhnyi, Yu V; Vlachy, Vojko; Dill, Ken A

2010-06-21

We use the AMSA, associative mean spherical theory of associative fluids, to study ion-ion interactions in explicit water. We model water molecules as hard spheres with four off-center square-well sites and ions as charged hard spheres with sticky sites that bind to water molecules or other ions. We consider alkali halide salts. The choice of model parameters is based on two premises: (i) The strength of the interaction between a monovalent ion and a water molecule is inversely proportional to the ionic (crystal) diameter sigma(i). Smaller ions bind to water more strongly than larger ions do, taking into account the asymmetry of the cation-water and anion-water interactions. (ii) The number of contacts an ion can make is proportional to sigma2(i). In short, small ions bind waters strongly, but only a few of them. Large ions bind waters weakly, but many of them. When both a monovalent cation and anion are large, it yields a small osmotic coefficient of the salt, since the water molecules avoid the space in between large ions. On the other hand, salts formed from one small and one large ion remain hydrated and their osmotic coefficient is high. The osmotic coefficients, calculated using this model in combination with the integral equation theory developed for associative fluids, follow the experimental trends, including the unusual behavior of caesium salts.

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ELUTION OF URANIUM VALUES FROM ION EXCHANGE RESINS

DOEpatents

Kennedy, R.H.

1959-11-24

A process is described for eluting complex uranium ions absorbed on ion exchange resins. The resin is subjected to the action of an aqueous eluting solution contuining sulfuric acid and an alkali metal, ammonium, or magnesium chloride or nitrate, the elution being carried out until the desired amount of the uranium is removed from the resin.

Characterization of an atomic hydrogen source for charge exchange experiments

DOE PAGES

Leutenegger, M. A.; Beiersdorfer, P.; Betancourt-Martinez, G. L.; ...

2016-07-02

Here, we characterized the dissociation fraction of a thermal dissociation atomic hydrogen source by injecting the mixed atomic and molecular output of the source into an electron beam ion trap containing highly charged ions and recording the x-ray spectrum generated by charge exchange using a high-resolution x-ray calorimeter spectrometer. We exploit the fact that the charge exchange state-selective capture cross sections are very different for atomic and molecular hydrogen incident on the same ions, enabling a clear spectroscopic diagnostic of the neutral species.

Rupture loop annex ion exchange RLAIX vault deactivation

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

Ham, J.E.; Harris, D.L., Westinghouse Hanford

This engineering report documents the deactivation, stabilization and final conditions of the Rupture Loop Annex Ion Exchange (RLAIX) Vault located northwest of the 309 Building`s Plutonium Recycle Test Reactor (PRTR). Twelve ion exchange columns, piping debris, and column liquid were removed from the vault, packaged and shipped for disposal. The vault walls and floor were decontaminated, and portions of the vault were painted to fix loose contamination. Process piping and drains were plugged, and the cover blocks and rain cover were installed. Upon closure,the vault was empty, stabilized, isolated.

Grafted methylenediphosphonate ion exchange resins

DOEpatents

Trochimcznk, Andrzej W.; Gatrone, Ralph C.; Alexandratos, Spiro; Horwitz, E. Philip

1998-01-27

An ion exchange resin is disclosed that is comprised of an insoluble copolymer onto which are grafted pendent groups that provide 1.0 to about 10 mmol/g dry weight phosphorous. The pendent groups have the formula ##STR1## wherein R is hydrogen, a cation or mixtures thereof; and R.sup.1 is hydrogen or an C.sub.1 -C.sub.2 alkyl group. The resin also contains zero to about 5 mmol/g dry weight of pendent aromatic sulfonate groups. Processes for making and using an ion exchange-resin are also disclosed.

Grafted methylenediphosphonate ion exchange resins

DOEpatents

Trochimcznk, A.W.; Gatrone, R.C.; Alexandratos, S.; Horwitz, E.P.

1997-04-08

An ion exchange resin is disclosed that is comprised of an insoluble copolymer onto which are grafted pendent groups that provide 1.0 to about 10 mmol/g dry weight phosphorus. The pendent groups have the formula as shown in the patent wherein R is hydrogen, a cation or mixtures thereof; and R{sup 1} is hydrogen or an C{sub 1}-C{sub 2} alkyl group. The resin also contains zero to about 5 mmol/g dry weight of pendent aromatic sulfonate groups. Processes for making and using an ion exchange resin are also disclosed.

Grafted methylenediphosphonate ion exchange resins

DOEpatents

Trochimcznk, Andrzej W.; Gatrone, Ralph C.; Alexandratos, Spiro; Horwitz, E. Philip

1997-01-01

An ion exchange resin is disclosed that is comprised of an insoluble copolymer onto which are grafted pendent groups that provide 1.0 to about 10 mmol/g dry weight phosphorous. The pendent groups have the formula ##STR1## wherein R is hydrogen, a cation or mixtures thereof; and R.sup.1 is hydrogen or an C.sub.1 -C.sub.2 alkyl group. The resin also contains zero to about 5 mmol/g dry weight of pendent aromatic sulfonate groups. Processes for making and using an ion exchange resin are also disclosed.

Evaluation of iron-binding activity of collagen peptides prepared from the scales of four cultivated fishes in Taiwan.

PubMed

Huang, Chun-Yung; Wu, Chien-Hui; Yang, Jing-Iong; Li, Ying-Han; Kuo, Jen-Min

2015-12-01

Iron deficiency is one of the most concerning deficiency problems in the world. It may generate several adverse effects such as iron deficiency anemia (IDA) and reduced physical and intellectual working capacity. The aim of this study is to evaluate the Fe(II)-binding activity of collagen peptides from fishery by-products. Lates calcarifer, Mugil cephalus, Chanos chanos, and Oreochromis spp are four major cultivated fishes in Taiwan; thousands of scales of these fish are wasted without valuable utilization. In this study, scales of these fish were hydrolyzed by papain plus flavourzyme. Collagen peptides were obtained and compared for their Fe(II)-binding activity. Collagen peptides from Chanos chanos showed the highest Fe(II)-binding activity, followed by those from Lates calcarifer and Mugil cephalus; that from Oreochromis spp exhibited the lowest one. Fe(II)-binding activity of collagen peptides from fish scales was also confirmed with a dialysis method. Molecular weight (MW) distributions of the collagen peptides from scales of four fish are all < 10 kDa, and averaged 1.3 kDa. Hydrolysates of fish scales were further partially purified with ion exchange chromatography. Fractions having Fe(II)-binding activity were obtained and their activity compared. Data obtained showed that collagen peptides from fish scales did have Fe(II)-binding activity. This is the first observation elucidating fish scale collagen possessing this functionality. The results from this study also indicated that collagen peptides from fish scales could be applied in industry as a bioresource. Copyright © 2014. Published by Elsevier B.V.

Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers

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

Tsai, Tsung-Han; Ertem, S. Piril; Maes, Ashley M.

2015-01-28

Random copolymers of isoprene and 4-vinylbenzyl chloride (VBCl) with varying compositions were synthesized via nitroxide-mediated polymerization. Subsequent quaternization afforded solvent processable and cross-linkable ionomers with a wide range of ion exchange capacities (IECs). Solution cast membranes were thermally cross-linked to form anion exchange membranes. Cross-linking was achieved by taking advantage of the unsaturations on the polyisoprene backbone, without added cross-linkers. A strong correlation was found between water uptake and ion conductivity of the membranes: conductivities of the membranes with IECs beyond a critical value were found to be constant related to their high water absorption. Environmentally controlled small-angle X-ray scatteringmore » experiments revealed a correlation between the average distance between ionic clusters and the ion conductivity, indicating that a well-connected network of ion clusters is necessary for efficient ion conduction and high ion conductivity.« less

Use of magnetic circular dichroism to study dinuclear metallohydrolases and the corresponding biomimetics.

PubMed

Larrabee, James A; Schenk, Gerhard; Mitić, Nataša; Riley, Mark J

2015-09-01

Magnetic circular dichroism (MCD) is a convenient technique for providing structural and mechanistic insight into enzymatic systems in solution. The focus of this review is on aspects of geometric and electronic structure that can be determined by MCD, and how this method can further our understanding of enzymatic mechanisms. Dinuclear Co(II) systems that catalyse hydrolytic reactions were selected to illustrate the approach. These systems all contain active sites with similar structures consisting of two Co(II) ions bridged by one or two carboxylates and a water or hydroxide. In most of these active sites one Co(II) is five-coordinate and one is six-coordinate, with differing binding affinities. It is shown how MCD can be used to determine which binding site--five or six-coordinate--has the greater affinity. Importantly, zero-field-splitting data and magnetic exchange coupling constants may be determined from the temperature and field dependence of MCD data. The relevance of these data to the function of the enzymatic systems is discussed.

Developing a polymeric sensor to monitor intracellular conditions

NASA Astrophysics Data System (ADS)

Mudarri, Timothy C.; Leo, Donald J.; Wood, Brett C.; Shires, Peter K.

2004-07-01

Ionic electroactive polymers have been developed as mechanical sensors or actuators, taking advantage of the electromechanical coupling of the materials. This research attempts to take advantage of the chemomechanical and chemoelectrical coupling by characterizing the transient response as the polymer undergoes an ion exchange, thus using the polymer for ionic sensing. Nafion is a biocompatible material, and an implantable polymeric ion sensor which has applications in the biomedical field for bone healing research. An ion sensor and a strain gauge could determine the effects of motion allowed at the fracture site, thus improving rehabilitation procedures for bone fractures. The charge sensitivity of the material and the capacitance of the material were analyzed to determine the transient response. Both measures indicate a change when immersed in ionic salt solutions. It is demonstrated that measuring the capacitance is the best indicator of an ion exchange. Relative to a flat response in deionized water (+/-2%), the capacitance of the polymer exhibits an exponential decay of ~25% of its peak when placed in a salt solution. A linear correlation between the time constant of the decay and the ionic size of the exchanging ion was developed that could reasonably predict a diffusing ion. Tests using an energy dispersive spectrometer (EDS) indicate that 90% of the exchange occurs in the first 20 minutes, shown by both capacitance decay and an atomic level scan. The diffusion rate time constant was found to within 0.3% of the capacitance time constant, confirming the ability of capacitance to measure ion exchange.

Tuning a High Transmission Ion Guide to Prevent Gas-Phase Proton Exchange During H/D Exchange MS Analysis.

PubMed

Guttman, Miklos; Wales, Thomas E; Whittington, Dale; Engen, John R; Brown, Jeffery M; Lee, Kelly K

2016-04-01

Hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for protein structural analysis has been adopted for many purposes, including biopharmaceutical development. One of the benefits of examining amide proton exchange by mass spectrometry is that it can readily resolve different exchange regimes, as evidenced by either binomial or bimodal isotope patterns. By careful analysis of the isotope pattern during exchange, more insight can be obtained on protein behavior in solution. However, one must be sure that any observed bimodal isotope patterns are not artifacts of analysis and are reflective of the true behavior in solution. Sample carryover and certain stationary phases are known as potential sources of bimodal artifacts. Here, we describe an additional undocumented source of deuterium loss resulting in artificial bimodal patterns for certain highly charged peptides. We demonstrate that this phenomenon is predominantly due to gas-phase proton exchange between peptides and bulk solvent within the initial stages of high-transmission conjoined ion guides. Minor adjustments of the ion guide settings, as reported here, eliminate the phenomenon without sacrificing signal intensity. Such gas-phase deuterium loss should be appreciated for all HDX-MS studies using such ion optics, even for routine studies not focused on interpreting bimodal spectra. Graphical Abstract ᅟ.

Bismuth generator method

DOEpatents

Bray, Lane Allan; DesChane, Jaquetta R.

1998-01-01

A method for separating .sup.213 Bi from a solution of radionuclides wherein the solution contains a concentration of the chloride ions and hydrogen ions adjusted to allow the formation of a chloride complex. The solution is then brought into contact with an anion exchange resin, whereupon .sup.213 Bi is absorbed from the solution and adhered onto the anion exchange resin in the chloride complex. Other non-absorbing radionuclides such as .sup.225 Ra, .sup.225 Ac, and .sup.221 Fr, along with HCl are removed from the anion exchange resin with a scrub solution. The .sup.213 Bi is removed from the anion exchange resin by washing the anion exchange resin with a stripping solution free of chloride ions and with a reduced hydrogen ion concentration which breaks the chloride anionic complex, releasing the .sup.213 Bi as a cation. In a preferred embodiment of the present invention, the anion exchange resin is provided as a thin membrane, allowing for extremely rapid adherence and stripping of the .sup.213 Bi. A preferred stripping solution for purification of .sup.213 Bi for use in medical applications includes sodium acetate, pH 5.5. A protein conjugated with bifunctional chelating agents in vivo with the NaOAc, to receive the .sup.213 Bi as it is being released from the anion exchange resin.

Bismuth generator method

DOEpatents

Bray, L.A.; DesChane, J.R.

1998-05-05

A method is described for separating {sup 213}Bi from a solution of radionuclides wherein the solution contains a concentration of the chloride ions and hydrogen ions adjusted to allow the formation of a chloride complex. The solution is then brought into contact with an anion exchange resin, whereupon {sup 213}Bi is absorbed from the solution and adhered onto the anion exchange resin in the chloride complex. Other non-absorbing radionuclides such as {sup 225}Ra, {sup 225}Ac, and {sup 221}Fr, along with HCl are removed from the anion exchange resin with a scrub solution. The {sup 213}Bi is removed from the anion exchange resin by washing the anion exchange resin with a stripping solution free of chloride ions and with a reduced hydrogen ion concentration which breaks the chloride anionic complex, releasing the {sup 213}Bi as a cation. In a preferred embodiment of the present invention, the anion exchange resin is provided as a thin membrane, allowing for extremely rapid adherence and stripping of the {sup 213}Bi. A preferred stripping solution for purification of {sup 213}Bi for use in medical applications includes sodium acetate, pH 5.5. A protein conjugated with bifunctional chelating agents in vivo with the NaOAc receives the {sup 213}Bi as it is being released from the anion exchange resin. 10 figs.

A VARIABLE REACTIVITY MODEL FOR ION BINDING TO ENVIRONMENTAL SORBENTS

EPA Science Inventory

The conceptual and mathematical basis for a new general-composite modeling approach for ion binding to environmental sorbents is presented. The work extends the Simple Metal Sorption (SiMS) model previously presented for metal and proton binding to humic substances. A surface com...

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.

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.

Theoretical study of metal noble-gas positive ions

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

Screening of biologically important Zn2 + by a chemosensor with fluorescent turn on-off mechanism

NASA Astrophysics Data System (ADS)

Khan, Tanveer A.; Sheoran, Monika; Nikhil Raj M., Venkata; Jain, Surbhi; Gupta, Diksha; Naik, Sunil G.

2018-01-01

Reported herein the synthesis, characterization and biologically important zinc ion binding propensity of a weakly fluorescent chemosensor, 4-methyl-2,6-bis((E)-(2-(4-phenylthiazol-2-yl)hydrazono)methyl)phenol (1). 1H NMR spectroscopic titration experiment reveals the binding knack of 1 to the essential Zn2 +. The photo-physical studies of 1 exhibit an enhancement in the fluorescence by several folds upon binding with the zinc ions attributed to PET-off process, with a binding constant value of 5.22 × 103 M- 1. 1 exhibits an excellent detection range for Zn2 + with lower detection limit value of 2.31 × 10- 8 M. The selectivity of 1 was studied with various mono and divalent metal cations and it was observed that most cations either quenches the fluorescence or remains unchanged except for Cd2 +, which shows a slight enhancement in fluorescence intensity of 1. The ratiometric displacement of Cd2 + ions by Zn2 + ions shows an excellent selectivity towards in-situ detection of Zn2 + ions. Photo-physical studies also support the reversible binding of 1 to Zn2 + ions having on and off mechanism in presence of EDTA. Such recognition of the biologically important zinc ions finds potential application in live cell imaging.

Specificity in cationic interaction with poly(N-isopropylacrylamide).

PubMed

Du, Hongbo; Wickramasinghe, Sumith Ranil; Qian, Xianghong

2013-05-02

Classical molecular dynamics (MD) simulations were conducted for PNIPAM in 1 M monovalent alkali chloride salt solutions as well as in 0.5 M divalent Mg(2+) and Ca(2+) chloride salt solutions. It was found that the strength for the direct alkali ion-amide O binding is strongly correlated with the size of the ionic radius. The smallest Li(+) ion binds strongest to amide O, and the largest Cs(+) ion has the weakest interaction with the amide bond. For the divalent Mg(2+) and Ca(2+) ions, their interactions with the amide bond are weak and appear to be mediated by the water molecules, particularly in the case of Mg(2+), resulting from their strong hydration. The direct binding between the cations and amide O requires partial desovlation of the ions that is energetically unfavorable for Mg(2+) and also to a great extent for Ca(2+). The higher cation charge makes the electrostatic interaction more favorable but the dehydration process less favorable. This competition between electrostatic interaction and the dehydration process largely dictates whether the direct binding between the cation and amide O is energetically preferred or not. For monovalent alkali ions, it is energetically preferred to bind directly with the amide O. Moreover, Li(+) ion is also found to associate strongly with the hydrophobic residues on PNIPAM.

Control of Ion Selectivity in LeuT: Two Na+ Binding Sites with two different mechanisms

PubMed Central

Noskov, Sergei Y.; Roux, Benoît

2016-01-01

The x-ray structure of LeuT, a bacterial homologue of Na+/Cl−-dependent neurotransmitter transporter, provides a great opportunity to better understand the molecular basis of monovalent cation selectivity in ion-coupled transporters. LeuT possesses two ion-binding sites, NA1 and NA2, which are highly selective for Na+. Extensive all-atom free energy molecular dynamics simulations of LeuT embedded in an explicit membrane are performed at different temperatures and various occupancy states of the binding sites to dissect the molecular mechanism of ion selectivity. The results show that the two binding sites display robust selectivity for Na+ over K+ or Li+, the competing ions of most similar radii. Of particular interest, the mechanism primarily responsible for selectivity for each of the two binding sites appears to be different. In site NA1, selectivity for Na+ over K+ arises predominantly from the strong electrostatic field arising from the negatively charged carboxylate group of the leucine substrate coordinating the ion directly. In site NA2, which comprises only neutral ligands, selectivity for Na+ is enforced by the local structural restraints arising from the hydrogen-bonding network and the covalent connectivity of the poly-peptide chain surrounding the ion according to a snug-fit mechanism. PMID:18280500

Unidirectional Flux Balance of Monovalent Ions in Cells with Na/Na and Li/Na Exchange: Experimental and Computational Studies on Lymphoid U937 Cells

PubMed Central

Vereninov, Igor A.; Yurinskaya, Valentina E.; Model, Michael A.; Vereninov, Alexey A.

2016-01-01

Monovalent ion traffic across the cell membrane occurs via various pathways. Evaluation of individual fluxes in whole cell is hampered by their strong interdependence. This difficulty can be overcome by computational analysis of the whole cell flux balance. However, the previous computational studies disregarded ion movement of the self-exchange type. We have taken this exchange into account. The developed software allows determination of unidirectional fluxes of all monovalent ions via the major pathways both under the balanced state and during transient processes. We show how the problem of finding the rate coefficients can be solved by measurement of monovalent ion concentrations and some of the fluxes. Interdependence of fluxes due to the mandatory conditions of electroneutrality and osmotic balance and due to specific effects can be discriminated, enabling one to identify specific changes in ion transfer machinery under varied conditions. To test the effectiveness of the developed approach we made use of the fact that Li/Na exchange is known to be an analogue of the coupled Na/Na exchange. Thus, we compared the predicted and experimental data obtained on U937 cells under varied Li+ concentrations and following inhibition of the sodium pump with ouabain. We found that the coupled Na/Na exchange in U937 cells comprises a significant portion of the entire Na+ turnover. The data showed that the loading of the sodium pump by Li/Na exchange involved in the secondary active Li+ transport at 1–10 mM external Li+ is small. This result may be extrapolated to similar Li+ and Na+ flux relationships in erythrocytes and other cells in patients treated with Li+ in therapeutic doses. The developed computational approach is applicable for studying various cells and can be useful in education for demonstrating the effects of individual transporters and channels on ion gradients, cell water content and membrane potential. PMID:27159324

Characterisation of landfill leachate by EEM-PARAFAC-SOM during physical-chemical treatment by coagulation-flocculation, activated carbon adsorption and ion exchange.

PubMed

Oloibiri, Violet; De Coninck, Sam; Chys, Michael; Demeestere, Kristof; Van Hulle, Stijn W H

2017-11-01

The combination of fluorescence excitation-emission matrices (EEM), parallel factor analysis (PARAFAC) and self-organizing maps (SOM) is shown to be a powerful tool in the follow up of dissolved organic matter (DOM) removal from landfill leachate by physical-chemical treatment consisting of coagulation, granular activated carbon (GAC) and ion exchange. Using PARAFAC, three DOM components were identified: C1 representing humic/fulvic-like compounds; C2 representing tryptophan-like compounds; and C3 representing humic-like compounds. Coagulation with ferric chloride (FeCl 3 ) at a dose of 7 g/L reduced the maximum fluorescence of C1, C2 and C3 by 52%, 17% and 15% respectively, while polyaluminium chloride (PACl) reduced C1 only by 7% at the same dose. DOM removal during GAC and ion exchange treatment of raw and coagulated leachate exhibited different profiles. At less than 2 bed volumes (BV) of treatment, the humic components C1 and C3 were rapidly removed, whereas at BV ≥ 2 the tryptophan-like component C2 was preferentially removed. Overall, leachate treated with coagulation +10.6 BV GAC +10.6 BV ion exchange showed the highest removal of C1 (39% - FeCl 3 , 8% - PACl), C2 (74% - FeCl 3 , 68% - PACl) and no C3 removal; whereas only 52% C2 and no C1 and C3 removal was observed in raw leachate treated with 10.6 BV GAC + 10.6 BV ion exchange only. Analysis of PARAFAC-derived components with SOM revealed that coagulation, GAC and ion exchange can treat leachate at least 50% longer than only GAC and ion exchange before the fluorescence composition of leachate remains unchanged. Copyright © 2017 Elsevier Ltd. All rights reserved.

Monitoring Ras Interactions with the Nucleotide Exchange Factor Son of Sevenless (Sos) Using Site-specific NMR Reporter Signals and Intrinsic Fluorescence*

PubMed Central

Vo, Uybach; Vajpai, Navratna; Flavell, Liz; Bobby, Romel; Breeze, Alexander L.; Embrey, Kevin J.; Golovanov, Alexander P.

2016-01-01

The activity of Ras is controlled by the interconversion between GTP- and GDP-bound forms partly regulated by the binding of the guanine nucleotide exchange factor Son of Sevenless (Sos). The details of Sos binding, leading to nucleotide exchange and subsequent dissociation of the complex, are not completely understood. Here, we used uniformly 15N-labeled Ras as well as [13C]methyl-Met,Ile-labeled Sos for observing site-specific details of Ras-Sos interactions in solution. Binding of various forms of Ras (loaded with GDP and mimics of GTP or nucleotide-free) at the allosteric and catalytic sites of Sos was comprehensively characterized by monitoring signal perturbations in the NMR spectra. The overall affinity of binding between these protein variants as well as their selected functional mutants was also investigated using intrinsic fluorescence. The data support a positive feedback activation of Sos by Ras·GTP with Ras·GTP binding as a substrate for the catalytic site of activated Sos more weakly than Ras·GDP, suggesting that Sos should actively promote unidirectional GDP → GTP exchange on Ras in preference of passive homonucleotide exchange. Ras·GDP weakly binds to the catalytic but not to the allosteric site of Sos. This confirms that Ras·GDP cannot properly activate Sos at the allosteric site. The novel site-specific assay described may be useful for design of drugs aimed at perturbing Ras-Sos interactions. PMID:26565026

Cooling field and ion-beam bombardment effects on exchange bias behavior in NiFe/(Ni,Fe)O bilayers.

PubMed

Lin, K W; Wei, M R; Guo, J Y

2009-03-01

The dependence of the cooling field and the ion-beam bombardment on the exchange bias effects in NiFe/(Ni,Fe)O bilayers were investigated. The positive exchange bias was found in the zero-field-cooled (ZFC) process whereas a negative exchange bias occurred in the FC process. The increased exchange field, H(ex) with increasing (Ni,Fe)O thicknesses indicates the thicker the AF (Ni,Fe)O, the stronger the exchange coupling between the NiFe layer and the (Ni,Fe)O layer. In addition, the dependence of the H(ex) (ZFC vs. FC) on the (Ni,Fe)O thicknesses reflects the competition between the applied magnetic field and the (Ni,Fe)O surface layer exchange coupled to the NiFe layer. Further, an unusual oscillating exchange bias was observed in NiFe/(Ni,Fe)O bilayers that results from the surface of the (Ni,Fe)O layer being bombarded with different Ar-ion energies using End-Hall deposition voltages (V(EH)) from 0 to 150 V. The behavior of the H(ex) and the H(c) with the V(EH) is attributed to the surface spin reorientation that is due to moderate ion-beam bombardment effects on the surface of the (Ni,Fe)O layer. Whether the (Ni,Fe)O antiferromagnetic spins are coupled to the NiFe moments antiferromagnetically or ferromagnetically changes the sign of the exchange bias.

Modeling the adsorption of hydrogen, sodium, chloride and phthalate on goethite using a strict charge-neutral ion-exchange theory.

PubMed

Schulthess, Cristian P; Ndu, Udonna

2017-01-01

Simultaneous adsorption modeling of four ions was predicted with a strict net charge-neutral ion-exchange theory and its corresponding equilibrium and mass balance equations. An important key to the success of this approach was the proper collection of all the data, particularly the proton adsorption data, and the inclusion of variable concentrations of conjugate ions from the experimental pH adjustments. Using IExFit software, the ion-exchange model used here predicted the competitive retention of several ions on goethite by assuming that the co-adsorption or desorption of all ions occurred in the correct stoichiometries needed to maintain electroneutrality. This approach also revealed that the retention strength of Cl- ions on goethite increases in the presence of phthalate ions. That is, an anion-anion enhancement effect was observed. The retention of Cl- ions was much weaker than phthalate ions, and this also resulted in a higher sensitivity of the Cl- ions toward minor variations in the surface reactivity. The proposed model uses four goethite surface sites. The drop in retention of phthalate ions at low pH was fully described here as resulting from competitive Cl- reactions, which were introduced in increasing concentrations into the matrix as the conjugate base to the acid added to lower the pH.

Free-bound electron exchange contribution to l-split atomic structure in dense plasmas

NASA Astrophysics Data System (ADS)

Bennadji, K.; Rosmej, F.; Lisitsa, V. S.

2013-11-01

An analytical expression for the exchange energy between the bound electron in hydrogen-like ions and the free electrons of plasma is proposed. Two limiting cases are identified: 1) the low temperature limit where the energy depends linearly on density and on the ion charge as 1/Z2 but does not depend on the temperature itself, 2) the high temperature limit where the energy depends on temperature as 1/T but does not depend on the ion charge. These two regimes are separated by a characteristic temperature (T∗ = 4Z2Ry) which is a universal parameter depending only on the charge Z of the ions. We presented numerical results for aluminum: the exchange energy contributes about 15% to the total plasma energy and can reach an order of 10-4 of the total transition energy. Comparison to the Local-density Approximation (Kohn-Sham) exchange energy shows a good agreement.

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

Russell, Renee L.; Fiskum, Sandra K.; Smoot, Margaret R.

Washington River Protection Solutions (WRPS) is developing a Low-Activity Waste Pretreatment System (LAWPS) to provide low-activity waste (LAW) directly to the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste Facility for immobilization. The pretreatment that will be conducted on tank waste supernate at the LAWPS facility entails filtration to remove entrained solids and cesium (Cs) ion exchange to remove Cs from the product sent to the WTP. Currently, spherical resorcinol-formaldehyde (sRF) resin (Microbeads AS, Skedsmokorset, Norway) is the Cs ion exchange resin of choice. Most work on Cs ion exchange efficacy in Hanford tank waste has been conductedmore » at nominally 5 M sodium (Na). WRPS is examining the possibility of processing supernatant at high Na concentrations—up to 8 M Na—to maximize processing efficiency through the LAWPS. Minimal Cs ion exchange work has been conducted at 6 M and 8 M Na concentrations..« less

A Charge-Exchange Neutral Particle Analyzer for an Inertial Electrostatic Confinement Fusion Device

NASA Astrophysics Data System (ADS)

Becerra, Gabriel; Kulcinski, Gerald; Santarius, John; Emmert, Gilbert

2013-10-01

An electrostatic energy analyzer for outgoing charge-exchange neutral particles has been designed and constructed for application on HELIOS, an inertial electrostatic confinement (IEC) fusion device designed for advanced fuel studies. Ions are extracted from an external helicon plasma source and subsequently accelerated radially into an electrostatic potential well set up by a semi-transparent cathode grid inside the HELIOS spherical chamber. Analysis of fast neutrals produced by charge exchange between energetic ions and background gas yields information on primary ion energy spectra, as well as a quantitative measure of charge exchange as an energy loss mechanism in IEC devices. Preliminary data with helium is used to benchmark the two-charge-state helium formalism of VICTER, a numerical code on spherically convergent ion flow, as it relates to IEC operation with helium-3 fuel. Research supported by the Greatbatch Foundation.

Polarizability, volume expansion, and stress contributions to the refractive index change of Cu+-Na+ ion exchanged waveguides in glass.

PubMed

Oven, Robert

2011-09-10

The refractive index of optical waveguides formed by electric field assisted Cu(+)-Na(+) ion exchange in two types of glass is measured. Assuming, as in a previously published work, that the observed refractive index increase is solely due to polarizability changes, the difference in electronic polarizability between Cu(+) and Na(+) ions is determined by applying the Lorentz-Lorenz equation to the data. In our work, the concentration of exchanged ions, which is a necessary input to the Lorentz-Lorenz equation, is determined by combining optical data and electrical data obtained during the exchange. Values for the electronic polarizability difference are in agreement with that in the literature. However, when a correction is made, taking into consideration the measured volume expansion and stress in the glass, the calculated electronic polarizability difference is shown to increase by 19%.

Exchange, interpretation, and database-search of ion mobility spectra supported by data format JCAMP-DX

NASA Technical Reports Server (NTRS)

Baumback, J. I.; Davies, A. N.; Vonirmer, A.; Lampen, P. H.

1995-01-01

To assist peak assignment in ion mobility spectrometry it is important to have quality reference data. The reference collection should be stored in a database system which is capable of being searched using spectral or substance information. We propose to build such a database customized for ion mobility spectra. To start off with it is important to quickly reach a critical mass of data in the collection. We wish to obtain as many spectra combined with their IMS parameters as possible. Spectra suppliers will be rewarded for their participation with access to the database. To make the data exchange between users and system administration possible, it is important to define a file format specially made for the requirements of ion mobility spectra. The format should be computer readable and flexible enough for extensive comments to be included. In this document we propose a data exchange format, and we would like you to give comments on it. For the international data exchange it is important, to have a standard data exchange format. We propose to base the definition of this format on the JCAMP-DX protocol, which was developed for the exchange of infrared spectra. This standard made by the Joint Committee on Atomic and Molecular Physical Data is of a flexible design. The aim of this paper is to adopt JCAMP-DX to the special requirements of ion mobility spectra.

FOURTH ANNUAL REPORT ON DISTRIBUTION STUDIES BETWEEN MELTS AND SOLID PHASES USING RADIOACTIVE TRACERS

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

Ward, R.; Orr, W.C.; Katz, L.

Cerium(III) ion in a barium chloride flux does not readily exchangs with any of the ions in solid BaZrO/sub 3/ or BaTiO/sub 3/. It reacts to form new solid phases, which are identified, and does not enter the original crystal lattices at an appreciable rate. The strontium was found to exchange at a measurable rate with barium in BaTiO/sub 3/ and with the corresponding ions in alkaline-earth zirconates. Results of a series of equilibrium and rate measurements were interpreted to ahow that the exchange produces an additional solid phase, SrTiO/sub 3/, rather than the mixed phase, or solid solution, thatmore » ndght have been expected. The significance of this observation is discussed. The self-exchange of yttnium ions between a solid compound of yttrium and an alkali chloride flux in which yttrium chloride is dissolved appears in the systems studied to depend primaaily on the solubility of the solid. Exchange is rapid and complete in the case of yttrium oxychlonide, which is soluble to the extent of 0.6%, but is limited to the surface of yttrium chromium oxide, which has no measurable solubility in the flux. The introduction of yttrium ion vacancies in the lattice of yttrium chromium oxide has no detectable effect in promoting exchange. (For preceding period see NYO-3279.) (auth)« less

Nonbonded interactions in membrane active cyclic biopolymers. IV - Cation dependence

NASA Technical Reports Server (NTRS)

Radhakrishnan, R.; Srinivasan, S.; Prasad, C. V.; Brinda, S. R.; Macelroy, R. D.; Sundaram, K.

1980-01-01

Interactions of valinomycin and form of its analogs in several conformations with the central ions Li(+), Na(+), K(+), Rb(+) and Cs(+) are investigated as part of a study of the specific preference of valinomycin for potassium and the mechanisms of carrier-mediated ion transport across membranes. Ion binding energies and conformational potential energies are calculated taking into account polarization energy formulas and repulsive energy between the central ion and the ligand atoms for conformations representing various stages in ion capture and release for each of the two ring chiralities of valinomycin and its analogs. Results allow the prediction of the chirality and conformation most likely to be observed for a given analog, and may be used to synthesize analogs with a desired rigidity or flexibility. The binding energies with the alkali metal cations are found to decrease with increasing ion size, and to be smaller than the corresponding ion hydration energies. It is pointed out that the observed potassium preference may be explainable in terms of differences between binding and hydration energies. Binding energies are also noted to depend on ligand conformation.

Modeling of salt and pH gradient elution in ion-exchange chromatography.

PubMed

Schmidt, Michael; Hafner, Mathias; Frech, Christian

2014-01-01

The separation of proteins by internally and externally generated pH gradients in chromatofocusing on ion-exchange columns is a well-established analytical method with a large number of applications. In this work, a stoichiometric displacement model was used to describe the retention behavior of lysozyme on SP Sepharose FF and a monoclonal antibody on Fractogel SO3 (S) in linear salt and pH gradient elution. The pH dependence of the binding charge B in the linear gradient elution model is introduced using a protein net charge model, while the pH dependence of the equilibrium constant is based on a thermodynamic approach. The model parameter and pH dependences are calculated from linear salt gradient elutions at different pH values as well as from linear pH gradient elutions at different fixed salt concentrations. The application of the model for the well-characterized protein lysozyme resulted in almost identical model parameters based on either linear salt or pH gradient elution data. For the antibody, only the approach based on linear pH gradients is feasible because of the limited pH range useful for salt gradient elution. The application of the model for the separation of an acid variant of the antibody from the major monomeric form is discussed. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiheteromacrocycles that Complex Metal Ions. Ninth Progress Report (includes results of last three years), 1 May 1980 -- 30 April 1983

DOE R&D Accomplishments Database

Cram, D. J.

1982-09-15

The overall objective of this research is to design, synthesize, and evaluate cyclic and polycyclic host organic compounds for the abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The hope is to synthesize new classes of compounds useful in the separation of metal ions, their complexes, and their clusters.

Free Energy Landscape and Multiple Folding Pathways of an H-Type RNA Pseudoknot

PubMed Central

Bian, Yunqiang; Zhang, Jian; Wang, Jun; Wang, Jihua; Wang, Wei

2015-01-01

How RNA sequences fold to specific tertiary structures is one of the key problems for understanding their dynamics and functions. Here, we study the folding process of an H-type RNA pseudoknot by performing a large-scale all-atom MD simulation and bias-exchange metadynamics. The folding free energy landscapes are obtained and several folding intermediates are identified. It is suggested that the folding occurs via multiple mechanisms, including a step-wise mechanism starting either from the first helix or the second, and a cooperative mechanism with both helices forming simultaneously. Despite of the multiple mechanism nature, the ensemble folding kinetics estimated from a Markov state model is single-exponential. It is also found that the correlation between folding and binding of metal ions is significant, and the bound ions mediate long-range interactions in the intermediate structures. Non-native interactions are found to be dominant in the unfolded state and also present in some intermediates, possibly hinder the folding process of the RNA. PMID:26030098

Thermal dissociation of ions limits the degree of the gas-phase H/D exchange at the atmospheric pressure.

PubMed

Kostyukevich, Y; Kononikhin, A; Popov, I; Nikolaev, E

2017-04-01

We present the application of the extended desolvating capillaries for increasing the degree of the gas-phase hydrogen/deuterium exchange reaction at atmospheric pressure. The use of the extended capillaries results in the increase of the time that ions spend in the high pressure region, what leads to the significant improvement of the efficiency of the reaction. For the small protein ubiquitin, it was observed that for the same temperature, the number of exchanges increases with the decrease of the charge state so that the lowest charge state can exchange twice the number of hydrogen than the highest one. With the increase of the temperature, the difference decreases, and eventually, the number of exchanges equalizes for all charge states. The value of this temperature and the corresponding number of exchanges depend on the geometric parameters of the capillary. Further increase of the temperature leads to the thermal dissociation of the protein ion. The observed b/y fragments are identical to those produced by collision-induced dissociation performed in the ion trap. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

The effect of a confining unit on the geochemical evolution of ground water in the Upper Floridan aquifer system

USGS Publications Warehouse

Wicks, C.M.; Herman, J.S.

1994-01-01

In west-central Florida, sections of the Upper Floridan aquifer system range in character from confined to leaky to unconfined. The confining unit is the Hawthorn Formation, a clay-rich sequence. The presence or absence of the Hawthorn Formation affects the geochemical evolution of the ground water in the Upper Floridan aquifer system. Mass-balance and mass-transfer models suggest that, in unconfined areas, the geochemical reactions are dolomite dissolution, ion exchange (Mg for Na, K), sulfate reduction, calcite dissolution, and CO2 exchange. In the areas in which the Hawthorn Formation is leaky, the evolution of the ground water is accounted for by ion exchange, sulfate reduction, calcite dissolution, and CO2 exchange. In the confined areas, no ion exchange and only limited sulfate reduction occur, and the chemical character of the ground water is consistent with dolomite and gypsum dissolution, calcite precipitation, and CO2 ingassing. The Hawthorn Formation acts both as a physical barrier to the transport of CO2 and organic matter and as a source of ion-exchange sites, but the carbonate-mineral reactions are largely unaffected by the extent of confinement of the Upper Floridan aquifer. ?? 1994.

Secondary water pore formation for proton transport in a ClC exchanger revealed by an atomistic molecular-dynamics simulation.

PubMed

Ko, Youn Jo; Jo, Won Ho

2010-05-19

Several prokaryotic ClC proteins have been demonstrated to function as exchangers that transport both chloride ions and protons simultaneously in opposite directions. However, the path of the proton through the ClC exchanger, and how the protein brings about the coupled movement of both ions are still unknown. In this work, we use an atomistic molecular dynamics (MD) simulation to demonstrate that a previously unknown secondary water pore is formed inside an Escherichia coli ClC exchanger. The secondary water pore is bifurcated from the chloride ion pathway at E148. From the systematic simulations, we determined that the glutamate residue exposed to the intracellular solution, E203, plays an important role as a trigger for the formation of the secondary water pore, and that the highly conserved tyrosine residue Y445 functions as a barrier that separates the proton from the chloride ion pathways. Based on our simulation results, we conclude that protons in the ClC exchanger are conducted via a water network through the secondary water pore, and we propose a new mechanism for the coupled transport of chloride ions and protons. It has been reported that several members of ClC proteins are not just channels that simply transport chloride ions across lipid bilayers; rather, they are exchangers that transport both the chloride ion and proton in opposite directions. However, the ion transit pathways and the mechanism of the coupled movement of these two ions have not yet been unveiled. In this article, we report a new finding (to our knowledge) of a water pore inside a prokaryotic ClC protein as revealed by computer simulation. This water pore is bifurcated from the putative chloride ion, and water molecules inside the new pore connect two glutamate residues that are known to be key residues for proton transport. On the basis of our simulation results, we conclude that the water wire that is formed inside the newly found pore acts as a proton pathway, which enables us to resolve many problems that could not be addressed by previous experimental studies. Copyright 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Metal binding proteins, recombinant host cells and methods

DOEpatents

Summers, Anne O.; Caguiat, Jonathan J.

2004-06-15

The present disclosure provides artificial heavy metal binding proteins termed chelons by the inventors. These chelons bind cadmium and/or mercuric ions with relatively high affinity. Also disclosed are coding sequences, recombinant DNA molecules and recombinant host cells comprising those recombinant DNA molecules for expression of the chelon proteins. In the recombinant host cells or transgenic plants, the chelons can be used to bind heavy metals taken up from contaminated soil, groundwater or irrigation water and to concentrate and sequester those ions. Recombinant enteric bacteria can be used within the gastrointestinal tracts of animals or humans exposed to toxic metal ions such as mercury and/or cadmium, where the chelon recombinantly expressed in chosen in accordance with the ion to be rededicated. Alternatively, the chelons can be immobilized to solid supports to bind and concentrate heavy metals from a contaminated aqueous medium including biological fluids.

17 CFR 230.402 - Number of copies; binding; signatures.

Code of Federal Regulations, 2010 CFR

2010-04-01

...; signatures. 230.402 Section 230.402 Commodity and Securities Exchanges SECURITIES AND EXCHANGE COMMISSION...; binding; signatures. (a) Three copies of the complete registration statement, including exhibits and all... bound and may contain facsimile versions of manual signatures in accordance with paragraph (e) of this...

Three-grid accelerator system for an ion propulsion engine

NASA Technical Reports Server (NTRS)

Brophy, John R. (Inventor)

1994-01-01

An apparatus is presented for an ion engine comprising a three-grid accelerator system with the decelerator grid biased negative of the beam plasma. This arrangement substantially reduces the charge-exchange ion current reaching the accelerator grid at high tank pressures, which minimizes erosion of the accelerator grid due to charge exchange ion sputtering, known to be the major accelerator grid wear mechanism. An improved method for life testing ion engines is also provided using the disclosed apparatus. In addition, the invention can also be applied in materials processing.

Truly Incomplete and Complex Chromosomal Exchanges in Human Fibroblast Cells Exposed In Situ to Energetic Heavy Ions

NASA Technical Reports Server (NTRS)

Wu, Honglu; Durante, marco; Furusawa, Yoshiya; George, Kerry; Kawata, Tetsuya; Cucinotta, Francis A.

2003-01-01

Confluent human fibroblast cells (AG 1522) were irradiated with gamma rays, 490 MeV/nucleon Si, or with Fe ions at either 200 or 500 MeV/nucleon. The cells were allowed to repair at 37 C for 24 hours after exposure, and a chemically induced premature chromosome condensation (PCC) technique was used to condense chromosomes in the G2 phase of the cell cycle. Incomplete and complex exchanges were analyzed in the irradiated samples. In order to verify that chromosomal breaks were truly unrejoined, chromosome aberrations were analyzed using a combination of whole chromosome specific probes and probes specific for the telomere region of the chromosome. Results showed that the frequency of unrejoined chromosome breaks was higher after high-LET radiation, and consequently, the ratio of incomplete to complete exchanges increased steadily with LET up to 440 keV/micron, the highest LET value in the present study. For samples exposed to 200 MeV/nucleon Fe ions, chromosome aberrations were analyzed using the multicolor FISH (mFISH) technique that allow identification of both complex and truly incomplete exchanges. Results of the mFISH study showed that 0.7 and 3 Gy dose of the Fe ions produced similar ratios of complex to simple exchanges and incomplete to complete exchanges, values for which were higher than those obtained after a 6 Gy gamma exposure. After 0.7 Gy of Fe ions, most complex aberrations were found to involve three or four chromosomes, which is a likely indication of the maximum number of chromosome domains traversed by a single Fe ion track.

Synthesis, characterization and application of ion exchange resin as a slow-release fertilizer for wheat cultivation in space

NASA Astrophysics Data System (ADS)

Li, Bowei; Dong, Chen; Chu, Zhengpei; Zhang, Weizhe; Wang, Minjuan; Liu, Hong; Xie, Beizhen

2016-10-01

In addition to the bio-regenerative air revitalization, water recycling and waste management systems and their associated challenges, enhancing the crop yield with less fertilizer input for sustainable food production in space is also a challenge that needs to be overcome. The purpose of this study is to investigate the feasibility of applying ion exchange resin as a slow-release fertilizer for wheat cultivation in space. Strong-acid cationic exchange resins and weak-base anion exchange resins soaked in 1X, 5X, 10X and 15X Hoagland nutrient solutions, respectively, were used as fertilizers in clinoptilolite to cultivate wheat plants, and the morphological and physiological characteristics of the wheat plants were studied and compared with that of the wheat planted in vermiculite and nutrient solutions. The results showed that more ions were attached on the surface of the ion exchange resins as the solution concentration increased. After 14 days, the fresh weight of wheat planted in the ion exchange resin-clinoptilolite (IER-clinoptilolite) treated with 10X and 15X solutions were 190% and 192% higher than that of wheat planted in nutrient solution with the same concentration. Chlorophyll content of wheat plants cultivated in the two kinds of solid medium is significantly higher than that of liquid cultivation. The lowest peroxidase (POD) activity and malondialdehyde (MDA) contents of wheat plants cultivated in the IER-clinoptilolite appeared on the 14th day. According to all the experimental data, it's promising to produce slow-release nutrient fertilizer by using strong-acid cationic exchange resins and weak-base anion exchange resins for wheat cultivation in space.