Crystal structures and DFT calculations of mixed chloride-azide zinc(II) and chloride-isocyanate cadmium(II) complexes with the condensation product of 2-quinolinecarboxaldehyde and Girard's T reagent

NASA Astrophysics Data System (ADS)

Anđelković, Katarina; Pevec, Andrej; Grubišić, Sonja; Turel, Iztok; Čobeljić, Božidar; Milenković, Milica R.; Keškić, Tanja; Radanović, Dušanka

2018-06-01

The mixed chloride-azide [ZnL(N3)1.65Cl0.35] (1) and chloride-isocyanate [CdL(NCO)1.64Cl0.36] (2) complexes with the condensation product of 2-quinolinecarboxaldehyde and trimethylammonium acetohydrazide chloride (Girard's T reagent) (HLCl) have been prepared and characterized by X-ray crystallography. In complexes 1 and 2, Zn1 and Cd1 ions, respectively, are five-coordinated in a distorted square based pyramidal geometry with NNO set of donor atoms of deprotonated hydrazone ligand and two monodentate ligands N3- and/or N3- and Cl- in the case of 1 and OCN- and/or OCN- and Cl- in the case of 2. The structural parameters of 1 and 2 have been discussed in relation to those of previously reported M(II) complexes with the same hydrazone ligand. Density functional theory calculations have been employed to study the interaction between the Zn2+ and Cd2+ ions and ligands. High affinity of ligands towards the Zn2+ and Cd2+ ions are predicted for both complexes.

A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

NASA Astrophysics Data System (ADS)

Usher, Al; McPhail, D. C.; Brugger, Joël

2009-06-01

The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl 3Br] -, [AuCl 2Br 2] -, [AuBr 3Cl] - and [AuBr 4] -; [AuCl 3(OH)] -, [AuCl 2(OH) 2] -, [AuCl(OH) 3] - and [Au(OH) 4] -; and [AuBr 3(OH)] -, [AuBr 2(OH) 2] - and [AuBr(OH) 3] -. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl (4-n)(OH) n] - series of complexes ( n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I -) was found to be unstable in the presence of Au(III), oxidizing rapidly to I 2(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0.05. The results of our study increase the understanding of gold aqueous geochemistry, with the potential to lead to new methods for mineral exploration, hydrometallurgy and medicine.

Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

PubMed

Greathouse, Jeffery A; Cygan, Randall T

2006-06-15

Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water oxygen density near the pyrophyllite surface is similar to the other cases, but the hydrogen density profile indicates reduced hydrogen bonding between adsorbed water molecules and the surface.

A selective optical sensor based on [9]mercuracarborand-3, a new type of ionophore with a chloride complexing cavity

NASA Technical Reports Server (NTRS)

Badr, I. H.; Johnson, R. D.; Diaz, M.; Hawthorne, M. F.; Bachas, L. G.; Daunert, S. (Principal Investigator)

2000-01-01

A highly selective optical sensor for chloride, based on the multidentate Lewis acid ionophore [9]mercuracarborand-3, is described herein. This sensor is constructed by embedding the mercuracarborand ionophore, a suitable pH-sensitive lipophilic dye, and lipophilic cationic sites in a plasticized polymeric membrane. The multiple complementary interactions offered by the preorganized complexing cavity of [9]mercuracarborand-3 is shown to control the anion selectivity pattern of the optical film. The film exhibits a significantly enhanced selectivity for chloride over a variety of lipophilic anions such as perchlorate, nitrate, salicylate, and thiocyanate. Furthermore, the optical selectivity coefficients obtained for chloride over other biologically relevant anions are shown to meet the selectivity requirements for the determination of chloride in physiological fluids, unlike previously reported chloride optical sensors. In addition, the optical film responds to chloride reversibly over a wide dynamic range (16 microM-136 mM) with fast response and recovery times.

Single and double C-Cl-activation of methylene chloride by P,N-ligand coordinated rhodium complexes.

PubMed

Blank, Benoît; Glatz, Germund; Kempe, Rhett

2009-02-02

Two in one: The simultaneous formation of bimetallic mu-methylene bridged Rh(III) complexes as well as dimeric Rh(III) complexes with terminal chloromethyl groups is observed for P,N-ligand stabilized Rh(I) complexes by C-Cl bond activation of methylene chloride. A mechanistic proposal for the formation of both activation products is also discussed. The synthesis of Rh(I) complexes with P-functionalized aminopyridine ligands is reported as well as the first simultaneous observation of a single and double activation of C-Cl bonds of methylene chloride affording both a dimeric Rh(III) complex bearing terminal CH(2)Cl groups in addition to a binuclear Rh(III) complex with a bridging mu-CH(2) group. The structures of the oxidative addition products were obtained by X-ray diffraction studies and NMR experiments were performed to elucidate some aspects of the reaction pathway.

Health Assessment Document for Vinylidene Chloride (Final Report, 1983)

EPA Science Inventory

Vinylidene chloride is a highly reactive, flammable, clear colorless liquid. In the absence of chemical inhibitors, it can produce violently explosive, complex peroxides. The estimated, ambient air level of vinylidene chloride in urban-suburban areas of the United States is 20 mi...

Characterization of the Unusual Product from the Reaction between Cobalt(II) Chloride, Ethane-1,2-diamine, and Hydrochloric Acid: An Undergraduate Project Involving an Unknown Metal Complex.

ERIC Educational Resources Information Center

Curtis, Neil F.; And Others

1986-01-01

Discusses the need for student research-type chemistry projects based upon "unknown" metal complexes. Describes an experiment involving the product from the reaction between cobalt(II) chloride, ethane-1,2-diamine (en) and concentrated hydrochloric acid. Outlines the preparation of the cobalt complex, along with procedure, results and…

Rheological characterization of solutions and thin films made from amylose-hexadecylammonium chloride inclusion complexes and polyvinyl alcohol

USDA-ARS?s Scientific Manuscript database

The rheological properties of aqueous solutions and films made from blends of polyvinyl alcohol (PVOH) and amylose-hexadecylammonium chloride inclusion complexes (Hex-Am) were investigated to better understand the polymer interactions and processing parameters. Aqueous solutions of Hex-Am displayed ...

[Determination of Chloride Salt Solution by NIR Spectroscopy].

PubMed

Zhang, Bin; Chen, Jian-hong; Jiao, Ming-xing

2015-07-01

Determination of chloride salt solution by near infrared spectrum plays a very important role in Biomedicine. The near infrared spectrum analysis of Sodium chloride, potassium chloride, calcium chloride aqueous solution shows that the concentration change of chloride salt can affect hydrogen bond, resulting in the variation of near infrared spectrum of water. The temperature influence on NIR spectrum has been decreased by choosing reasonable wavelength range and the wavelength where the temperature effects are zero (isosbestic point). Chlorine salt prediction model was established based on partial least squares method and used for predicting the concentration of the chlorine ion. The impact on near infrared spectrum of the cation ionic radius, the number of ionic charge, the complex effect of ionic in water has also discussed in this article and the reason of every factor are analysed. Experimental results show that the temperature and concentration will affect the near-infrared spectrum of the solution, It is found that the effect of temperature plays the dominant role at low concentrations of chlorine salt; rather, the ionic dominates at high concentration. Chloride complexes are formed in aqueous solution, It has an effect on hydrogen bond of water combining with the cations in chlorine salt solution, Comparing different chloride solutions at the same concentration, the destruction effects of chloride complexes and catnions on the hydrogen bond of water increases in the sequences: CaCl2 >NaCl>KC. The modeling result shows that the determination coefficients (R2) = 99.97%, the root mean square error of cross validation (RM- SECV) = 4.51, and the residual prediction deviation (RPD) = 62.7, it meets the daily requirements of biochemical detection accuracy.

Interaction of palladium ions with the skin.

PubMed

Santucci, B; Cristaudo, A; Cannistraci, C; Picardo, M

1995-08-01

87 subjects sensitive to both nickel sulfate and palladium-chloride pet., were contemporaneously patch retested to nickel sulfate 5% pet., metallic palladium chloride 1% pet. and to palladium chloride 1% aq. Whilst all subjects reacted to nickel sulfate and palladium chloride pet., only 3 reacted to palladium chloride aq. No positive reactions were found to metallic palladium. The negative results to palladium chloride aq. are probably due to the formation of a new palladium ion (PdCl4)2-, achieved on adding an amount of hydrocloric acid to the aqueous solution of PdCl2. The findings seem to demonstrate that the allergic reaction to palladium depends on the arrangement of the metal electrons. The sensitization to palladium does not seem to be dependent on the element itself but on the complexes formed by the different compounds. The concomitant reactions to nickel and palladium ions could be dependent on the generation of similar complexes between the ions and the skin proteins.

Remediation of cadmium- and lead-contaminated agricultural soil by composite washing with chlorides and citric acid.

PubMed

Li, Yu-jiao; Hu, Peng-jie; Zhao, Jie; Dong, Chang-xun

2015-04-01

Composite washing of cadmium (Cd)- and lead (Pb)-contaminated agricultural soil from Hunan province in China using mixtures of chlorides (FeCl3, CaCl2) and citric acid (CA) was investigated. The concentrations of composite washing agents for metal removal were optimized. Sequential extraction was conducted to study the changes in metal fractions after soil washing. The removal of two metals at optimum concentration was reached. Using FeCl3 mixed with CA, 44% of Cd and 23% of Pb were removed, and 49 and 32% by CaCl2 mixed with CA, respectively. The mechanism of composite washing was postulated. A mixture of chlorides and CA enhanced metal extraction from soil through the formation of metal-chloride and metal-citrate complexes. CA in extract solutions promoted the formation of metal-chloride complexes and reduced the solution pH. Composite washing reduced Cd and Pb in Fe-Mn oxide forms significantly. Chlorides and CA exerted a synergistic effect on metal extraction during composite washing.

Hafnium(IV) chloride complexes with chelating β-ketiminate ligands: Synthesis, spectroscopic characterization and volatility study

NASA Astrophysics Data System (ADS)

Patil, Siddappa A.; Medina, Phillip A.; Antic, Aleks; Ziller, Joseph W.; Vohs, Jason K.; Fahlman, Bradley D.

2015-09-01

The synthesis and characterization of four new β-ketiminate hafnium(IV) chloride complexes dichloro-bis[4-(phenylamido)pent-3-en-2-one]-hafnium (4a), dichloro-bis[4-(4-methylphenylamido)pent-3-en-2-one]-hafnium (4b), dichloro-bis[4-(4-methoxyphenylamido)pent-3-en-2-one]-hafnium (4c), and dichloro-bis[4-(4-chlorophenylamido)pent-3-en-2-one]-hafnium (4d) are reported. All the complexes (4a-d) were characterized by spectroscopic methods (1H NMR, 13C NMR, IR), and elemental analysis while the compound 4c was further examined by single-crystal X-ray diffraction, revealing that the complex is monomer with the hafnium center in octahedral coordination environment and oxygens of the chelating N-O ligands are trans to each other and the chloride ligands are in a cis arrangement. Volatile trends are established for four new β-ketiminate hafnium(IV) chloride complexes (4a-d). Sublimation enthalpies (ΔHsub) were calculated from thermogravimetric analysis (TGA) data, which show that, the dependence of ΔHsub on the molecular weight (4a-c) and inductive effects from chlorine (4d).

Encapsulated chloride coordinating with two in-in protons of bridgehead amines in an octaprotonated azacryptand

PubMed Central

Saeed, Musabbir A.; Fronczek, Frank R.; Hossain, Md. Alamgir

2010-01-01

An encapsulated chloride in a thiophene-based cryptand is bridged with the two in-in protons of tertiary amines with a N…Cl− distance of 3.048(3) Å, similar to that observed in the chloride complex of Park and Simmons’ katapinand. PMID:19841792

Water-assisted dehalogenation of thionyl chloride in the presence of water molecules.

PubMed

Yeung, Chi Shun; Ng, Ping Leung; Guan, Xiangguo; Phillips, David Lee

2010-04-01

A second-order Møller-Plesset perturbation theory (MP2) and density functional theory (DFT) investigation of the dehalogenation reactions of thionyl chloride is reported, in which water molecules (up to seven) were explicitly involved in the reaction complex. The dehalogenation processes of thionyl chloride were found to be dramatically catalyzed by water molecules. The reaction rate became significantly faster as more water molecules became involved in the reaction complex. The dehalogenation processes can be reasonably simulated by the gas-phase water cluster models, which reveals that water molecules can help to solvate the thionyl chloride molecules and activate the release of the Cl(-) leaving group. The computed activation energies were used to compare the calculations to available experimental data.

Surface aspects of pitting and stress corrosion cracking

NASA Technical Reports Server (NTRS)

Truhan, J. S., Jr.; Hehemann, R. F.

1977-01-01

The pitting and stress corrosion cracking of a stable austenitic stainless steel in aqueous chloride environments were investigated using a secondary ion mass spectrometer as the primary experimental technique. The surface concentration of hydrogen, oxygen, the hydroxide, and chloride ion, magnesium or sodium, chromium and nickel were measured as a function of potential in both aqueous sodium chloride and magnesium chloride environments at room temperature and boiling temperatures. It was found that, under anodic conditions, a sharp increase in the chloride concentration was observed to occur for all environmental conditions. The increase may be associated with the formation of an iron chloride complex. Higher localized chloride concentrations at pits and cracks were also detected with an electron microprobe.

Method for the regeneration of spent molten zinc chloride

DOEpatents

Zielke, Clyde W.; Rosenhoover, William A.

1981-01-01

In a process for regenerating spent molten zinc chloride which has been used in the hydrocracking of coal or ash-containing polynuclear aromatic hydrocarbonaceous materials derived therefrom and which contains zinc chloride, zinc oxide, zinc oxide complexes and ash-containing carbonaceous residue, by incinerating the spent molten zinc chloride to vaporize the zinc chloride for subsequent condensation to produce a purified molten zinc chloride: an improvement comprising the use of clay in the incineration zone to suppress the vaporization of metals other than zinc. Optionally water is used in conjunction with the clay to further suppress the vaporization of metals other than zinc.

URANIUM RECOVERY AND PURIFICATION PROCESS AND PRODUCTION OF HIGH PURITY URANIUM TETRAFLUORIDE

DOEpatents

Bailes, R.H.; Long, R.S.; Grinstead, R.R.

1957-09-17

A process is described wherein an anionic exchange technique is employed to separate uramium from a large variety of impurities. Very efficient and economical purification of contamimated uranium can be achieved by treatment of the contaminated uranium to produce a solution containing a high concentration of chloride. Under these conditions the uranium exists as an aniomic chloride complex. Then the uranium chloride complex is adsorbed from the solution on an aniomic exchange resin, whereby a portion of the impurities remain in the solution and others are retained with the uramium by the resin. The adsorbed impurities are then removed by washing the resin with pure concentrated hydrochloric acid, after which operation the uranium is eluted with pure water yielding an acidic uranyl chloride solution of high purity.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non-Polar Solvents by using Conductometry.

PubMed

Iseda, Kazuya; Kokado, Kenta; Sada, Kazuki

2018-03-01

In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride ( TBACl ) ion-pair salt to the free ions through complexation with meso -octamethylcalix[4]pyrrole ( CP ), which is a well-known receptor for chloride anions. In the presence of CP , the conductivity of TBACl increases in various non-polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non-polar solvents. In other words, CP recognizes chloride as an ion-paired salt as well as a free anion in non-polar solvents. Additionally, the TBA(CP - Cl ) complex exhibited a considerably lower ion-pairing constant ( K ip ) than TBACl in non-polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli-responsive soft materials in organic solvents using coulombic forces.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non‐Polar Solvents by using Conductometry

PubMed Central

Iseda, Kazuya

2018-01-01

Abstract In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride (TBACl) ion‐pair salt to the free ions through complexation with meso‐octamethylcalix[4]pyrrole (CP), which is a well‐known receptor for chloride anions. In the presence of CP, the conductivity of TBACl increases in various non‐polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non‐polar solvents. In other words, CP recognizes chloride as an ion‐paired salt as well as a free anion in non‐polar solvents. Additionally, the TBA(CP–Cl) complex exhibited a considerably lower ion‐pairing constant (K ip) than TBACl in non‐polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli‐responsive soft materials in organic solvents using coulombic forces. PMID:29610717

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.

Study of Synthesis of N-Nitroborazine Compounds. I. Nitryl Chloride as Nitrating Agent.

DTIC Science & Technology

dinitrogen tetroxide (N2O4) as the solid complexes of boron trifluoride (BF3). Nearly water-white nitryl chloride was obtained in this manner. A tinge of...yellow was attributed to the presence of chlorine . The reaction of nitryl chloride with a model compound, lithium dimethylamide, was found to yield

Syntheses, Characterization, Resolution, and Biological Studies of Coordination Compounds of Aspartic Acid and Glycine

PubMed Central

Akinkunmi, Ezekiel; Ojo, Isaac; Adebajo, Clement; Isabirye, David

2017-01-01

Enantiomerically enriched coordination compounds of aspartic acid and racemic mixtures of coordination compounds of glycine metal-ligand ratio 1 : 3 were synthesized and characterized using infrared and UV-Vis spectrophotometric techniques and magnetic susceptibility measurements. Five of the complexes were resolved using (+)-cis-dichlorobis(ethylenediamine)cobalt(III) chloride, (+)-bis(glycinato)(1,10-phenanthroline)cobalt(III) chloride, and (+)-tris(1,10-phenanthroline)nickel(II) chloride as resolving agents. The antimicrobial and cytotoxic activities of these complexes were then determined. The results obtained indicated that aspartic acid and glycine coordinated in a bidentate fashion. The enantiomeric purity of the compounds was in the range of 22.10–32.10%, with (+)-cis-dichlorobis(ethylenediamine)cobalt(III) complex as the more efficient resolving agent. The resolved complexes exhibited better activity in some cases compared to the parent complexes for both biological activities. It was therefore inferred that although the increase in the lipophilicity of the complexes may assist in the permeability of the complexes through the cell membrane of the pathogens, the enantiomeric purity of the complexes is also of importance in their activity as antimicrobial and cytotoxic agents. PMID:28293149

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.

Pentamethylcyclopentadienyl-rhodium and iridium complexes containing (N^N and N^O) bound chloroquine analogue ligands: synthesis, characterization and antimalarial properties.

PubMed

Ekengard, Erik; Kumar, Kamlesh; Fogeron, Thibault; de Kock, Carmen; Smith, Peter J; Haukka, Matti; Monari, Magda; Nordlander, Ebbe

2016-03-07

The synthesis and characterization of twenty new pentamethylcyclopentadienyl-rhodium and iridium complexes containing N^N and N^O-chelating chloroquine analogue ligands are described. The in vitro antimalarial activity of the new ligands as well as the complexes was evaluated against the chloroquine sensitive (CQS) NF54 and the chloroquine resistant (CQR) Dd2 strains of Plasmodium falciparum. The antimalarial activity was found to be good to moderate; although all complexes are less active than artesunate, some of the ligands and complexes showed better activity than chloroquine (CQ). In particular, rhodium complexes were found to be considerably more active than iridium complexes against the CQS NF54 strain. Salicylaldimine Schiff base ligands having electron-withdrawing groups (F, Cl, Br, I and NO2) in para position of the salicyl moiety and their rhodium complexes showed good antiplasmodial activity against both the CQS-NF54 and the CQR-Dd2 strains. The crystal structures of (η(5)-pentamethylcyclopentadienyl){N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)} chlororhodium(III) chloride and (η(5)-pentamethylcyclopentadienyl){(4-chloro-2-(((2-((7-chloroquinolin-4-yl)amino)ethyl)imino)methyl)phenolate)}chlororhodium(III) chloride are reported. The crystallization of the amino-pyridyl complex (η(5)-pentamethylcyclopentadienyl){(N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)}chloroiridium(III) chloride in acetone resulted in the formation of the imino-pyridyl derivative (η(5)-pentamethylcyclopentadienyl){(N1-(7-chloroquinolin-4-yl)-N2-(pyridin-2-ylmethylene)ethane-1,2-diamine)}chloroiridium(III) chloride, the crystal structure of which is also reported.

Polynuclear complexes of copper(I) halides: coordination chemistry and catalytic transformations of alkynes

NASA Astrophysics Data System (ADS)

Mykhalichko, B. M.; Temkin, Oleg N.; Mys'kiv, M. G.

2000-11-01

Characteristic features of the coordination chemistry of Cu(I) and mechanisms of catalytic conversions of alkynes in the CuCl-MCl-H2O-HC≡CR system (MCl is alkali metal or ammonium chloride or amine hydrochloride; R=H, CH2OH, CH=CH2, etc.) are analysed based on studies of the compositions and structures of copper(I) chloride (bromide) complexes, alkyne π-complexes and ethynyl organometallic polynuclear compounds formed in this system in solutions and in the crystalline state. The role of polynuclear complexes in various reactions of alkynes is discussed. The bibliography includes 149 references.

Bifunctional Asymmetric Catalysis with Hydrogen Chloride: Enantioselective Ring-Opening of Aziridines Catalyzed by a Phosphinothiourea

PubMed Central

Mita, Tsuyoshi; Jacobsen, Eric N.

2009-01-01

Ring-opening of aziridines with hydrogen chloride to form β-chloroamine derivatives is catalyzed by a chiral phosphinothiourea derivative in high yields and with high enantioselectivities. On the basis of 31P NMR studies, activation of HCl appears to proceed via quantitative protonation of the catalyst to afford a phosphonium chloride complex. PMID:20161432

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

NASA Astrophysics Data System (ADS)

Rudnik, Ewa; Włoch, Grzegorz

2013-01-01

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

Ruthenium(η⁶,η¹-arene-CH₂-NHC) Catalysts for Direct Arylation of 2-Phenylpyridine with (Hetero)Aryl Chlorides in Water.

PubMed

Kaloğlu, Nazan; Özdemir, İsmail; Gürbüz, Nevin; Arslan, Hakan; Dixneuf, Pierre H

2018-03-13

A series of new benzimidazolium halides were synthesized in good yields as unsymmetrical N -heterocyclic carbene (NHC) precursors containing the N-CH₂-arene group. The benzimidazolium halides were readily converted into ruthenium(II)-NHC complexes with the general formula [RuCl₂(η⁶,η¹-arene-CH₂-NHC)]. The structures of all new compounds were characterized by ¹H NMR (Nuclear Magnetic Resonance), 13 C NMR, FT-IR (Fourier Transform Infrared) spectroscopy and elemental analysis techniques. The single crystal structure of one benzimidazole ruthenium complex, 2b , was determined. The complex is best thought of as containing an octahedrally coordinated Ru center with the arene residue occupying three sites, the remaining sites being occupied by a (carbene)C-Ru bond and two Ru-Cl bonds. The catalytic activity of [RuCl₂(η⁶,η ¹ -arene-CH₂-NHC)] complexes was evaluated in the direct (hetero)arylation of 2-phenylpyridine with (hetero)aryl chlorides in water as the nontoxic reaction medium. These results show that catalysts 2a and 2b were the best for monoarylation with simple phenyl and tolyl chlorides. For functional aryl chlorides, 2d , 2e , and 2c appeared to be the most efficient.

Role of second-sphere coordination in anion binding: Synthesis, characterization and X-ray structure of hexaamminecobalt(III) chloride hydrogen phthalate trihydrate and sodium hexaamminecobalt(III) benzoate monohydrate

NASA Astrophysics Data System (ADS)

Sharma, Raj Pal; Bala, Ritu; Sharma, Rajni; Kariuki, B. M.; Rychlewska, Urszula; Warżajtis, Beata

2005-06-01

In an effort to utilize [Co(NH 3) 6] 3+cation as a new host for carboxylate ions, orange coloured crystalline solids of composition [Co(NH 3) 6]Cl(C 8H 5O 4) 2·3H 2O ( 1) and Na[Co(NH 3) 6](C 7H 5O 2) 4·H 2O ( 2) were obtained by reacting hot aqueous solutions of hexaamminecobalt(III) chloride with potassium hydrogen phthalate and sodium benzoate in 1:3 molar ratio, respectively. The title complex salts were characterized by elemental analyses and spectroscopic studies (IR, UV/Visible and NMR). Single crystal X-ray structure determinations revealed the formation of second-sphere coordination complexes based on hydrogen bond interactions. In complex salt 1 only two out of three ionisable chloride ions present in [Co(NH 3) 6]Cl 3 were replaced by two CHO4- ions whereas in complex salt 2 all the three ionisable chloride ions present in [Co(NH 3) 6]Cl 3 were replaced and the final product was an adduct with another mole of sodium benzoate in solid state. The crystal lattice is stabilized by electrostatic forces of attraction and predominantly N-H⋯O interactions.

Gold(I) Complexes of the Geminal Phosphinoborane tBu2PCH2BPh2.

PubMed

Boom, Devin H A; Ehlers, Andreas W; Nieger, Martin; Devillard, Marc; Bouhadir, Ghenwa; Bourissou, Didier; Slootweg, J Chris

2018-04-30

In this work, we explored the coordination properties of the geminal phosphinoborane t Bu 2 PCH 2 BPh 2 ( 2 ) toward different gold(I) precursors. The reaction of 2 with an equimolar amount of the sulfur-based complex (Me 2 S)AuCl resulted in displacement of the SMe 2 ligand and formation of linear phosphine gold(I) chloride 3 . Using an excess of ligand 2 , bisligated complex 4 was formed and showed dynamic behavior at room temperature. Changing the gold(I) metal precursor to the phosphorus-based complex, (Ph 3 P)AuCl impacted the coordination behavior of ligand 2 . Namely, the reaction of ligand 2 with (Ph 3 P)AuCl led to the heterolytic cleavage of the gold-chloride bond, which is favored over PPh 3 ligand displacement. To the best of our knowledge, 2 is the first example of a P/B-ambiphilic ligand capable of cleaving the gold-chloride bond. The coordination chemistry of 2 was further analyzed by density functional theory calculations.

Controlling First-Row Catalysts: Amination of Aryl and Heteroaryl Chlorides and Bromides with Primary Aliphatic Amines Catalyzed by a BINAP-Ligated Single-Component Ni(0) Complex

PubMed Central

2015-01-01

First-row metal complexes often undergo undesirable one-electron redox processes during two-electron steps of catalytic cycles. We report the amination of aryl chlorides and bromides with primary aliphatic amines catalyzed by a well-defined, single-component nickel precursor (BINAP)Ni(η2-NC-Ph) (BINAP = 2,2′-bis(biphenylphosphino)-1,1′-binaphthalene) that minimizes the formation of Ni(I) species and (BINAP)2Ni. The scope of the reaction encompasses electronically varied aryl chlorides and nitrogen-containing heteroaryl chlorides, including pyridine, quinoline, and isoquinoline derivatives. Mechanistic studies support the catalytic cycle involving a Ni(0)/Ni(II) couple for this nickel-catalyzed amination and are inconsistent with a Ni(I) halide intermediate. Monitoring the reaction mixture by 31P NMR spectroscopy identified (BINAP)Ni(η2-NC-Ph) as the resting state of the catalyst in the amination of both aryl chlorides and bromides. Kinetic studies showed that the amination of aryl chlorides and bromides is first order in both catalyst and aryl halide and zero order in base and amine. The reaction of a representative aryl chloride is inverse first order in PhCN, but the reaction of a representative aryl bromide is zero order in PhCN. This difference in the order of the reaction in PhCN indicates that the aryl chloride reacts with (BINAP)Ni(0), formed by dissociation PhCN from (BINAP)Ni(η2-NC-Ph), but the aryl bromide directly reacts with (BINAP)Ni(η2-NC-Ph). The overall kinetic behavior is consistent with turnover-limiting oxidative addition of the aryl halide to Ni(0). Several pathways for catalyst decomposition were identified, such as the formation of the catalytically inactive bis(amine)-ligated arylnickel(II) chloride, (BINAP)2Ni(0), and the Ni(I) species [(BINAP)Ni(μ-Cl)]2. By using a well-defined nickel complex as catalyst, the formation of (BINAP)2Ni(0) is avoided and the formation of the Ni(I) species [(BINAP)Ni(μ-Cl)]2 is minimized. PMID:24397570

Rapid fixation of methylene chloride by a macrocyclic amine.

PubMed

Lee, Jung-Jae; Stanger, Keith J; Noll, Bruce C; Gonzalez, Carlos; Marquez, Manuel; Smith, Bradley D

2005-03-30

A simple macrocyclic amine is alkylated by methylene chloride to give a quaternary ammonium chloride salt. When methylene chloride is the solvent, the reaction exhibits pseudo-first-order kinetics, and the reaction half-life at 25.0 degrees C is 2.0 min. The reaction half-life for a structurally related, acyclic amine is approximately 50 000 times longer. Detailed calculations favor a mechanism where the methylene chloride associates with the macrocycle to form an activated prereaction complex. The macrocyclic nitrogen subsequently attacks the methylene chloride with a classic SN2 trajectory, and although the carbon-chlorine bond breaks, the chloride leaving group does not separate from the newly formed cationic macrocycle, such that the product is a tightly associated ion-pair. X-ray crystal structures of the starting amine and the product salt, as well as kinetic data, support this mechanism.

GKI chloride in water, analysis method. GKI boron in water, analysis method

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

Morriss, L.L.

1979-05-01

Procedures for the chemical analysis of chlorides and boron in water are presented. Chlorides can be titrated with mercuric nitrate to form mercuric chloride. At pH 2.3 to 2.8, diphenylcarbazone indicates the end point of this titration by formation of a purple complex with mercury ions. When a sample of water containing boron is acidified and evaporated in the presence of curcumin, a red colored product called rosocyanine is formed. This is dissolved and can be measured photometrically or visually. (DMC)

Molybdenum chloride catalysts for Z-selective olefin metathesis reactions

NASA Astrophysics Data System (ADS)

Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.

2017-01-01

The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

SOLVENT EXTRACTION PROCESS FOR URANIUM FROM CHLORIDE SOLUTIONS

DOEpatents

Blake, C.A. Jr.; Brown, K.B.; Horner, D.E.

1960-05-24

An improvement was made in a uranium extraction process wherein the organic extractant is a phosphine oxide. An aqueous solution containing phosphate ions or sulfate ions together with uranium is provided with a source of chloride ions during the extraction step. The presence of the chloride ions enables a phosphine oxide to extract uranium in the presence of strong uranium- complexing ions such as phosphate or sulfate ions.

Intrinsic Resistance of Burkholderia cepacia Complex to Benzalkonium Chloride

PubMed Central

Ahn, Youngbeom; Kim, Jeong Myeong; Kweon, Ohgew; Kim, Seong-Jae; Jones, Richard C.; Woodling, Kellie; Gamboa da Costa, Gonçalo; LiPuma, John J.; Hussong, David; Marasa, Bernard S.

2016-01-01

ABSTRACT Pharmaceutical products that are contaminated with Burkholderia cepacia complex (BCC) bacteria may pose serious consequences to vulnerable patients. Benzyldimethylalkylammonium chloride (BZK) cationic surfactants are extensively used in medical applications and have been implicated in the coselection of antimicrobial resistance. The ability of BCC to degrade BZK, tetradecyldimethylbenzylammonium chloride (C14BDMA-Cl), dodecyldimethylbenzylammonium chloride (C12BDMA-Cl), decyldimethylbenzylammonium chloride (C10BDMA-Cl), hexyldimethylbenzylammonium chloride, and benzyltrimethylammonium chloride was determined by incubation in 1/10-diluted tryptic soy broth (TSB) to determine if BCC bacteria have the ability to survive and inactivate these disinfectants. With BZK, C14BDMA-Cl, and C12BDMA-Cl, inhibition of the growth of 20 BCC strains was observed in disinfectant solutions that ranged from 64 to 256 µg/ml. The efflux pump inhibitor carbonyl cyanide m-chlorophenylhydrazone increased the sensitivity of bacteria to 64 µg/ml BZK. The 20 BCC strains grew well in 1/10-diluted TSB medium with BZK, C12BDMA-Cl, and C10BDMA-Cl; they absorbed and degraded the compounds in 7 days. Formation of benzyldimethylamine and benzylmethylamine as the initial metabolites suggested that the cleavage of the C alkyl-N bond occurred as the first step of BZK degradation by BCC bacteria. Proteomic data confirmed the observed efflux activity and metabolic inactivation via biodegradation in terms of BZK resistance of BCC bacteria, which suggests that the two main resistance mechanisms are intrinsic and widespread. PMID:27879334

Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

PubMed

Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

2017-07-18

The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amination with Pd-NHC complexes: rate and computational studies involving substituted aniline substrates.

PubMed

Hoi, Ka Hou; Çalimsiz, Selçuk; Froese, Robert D J; Hopkinson, Alan C; Organ, Michael G

2012-01-02

The amination of aryl chlorides with various aniline derivatives using the N-heterocyclic carbene-based Pd complexes Pd-PEPPSI-IPr and Pd-PEPPSI-IPent (PEPPSI=pyridine, enhanced precatalyst, preparation, stabilization, and initiation; IPr=diisopropylphenylimidazolium derivative; IPent= diisopentylphenylimidazolium derivative) has been studied. Rate studies have shown a reliance on the aryl chloride to be electron poor, although oxidative addition is not rate limiting. Anilines couple best when they are electron rich, which would seem to discount deprotonation of the intermediate metal ammonium complex as being rate limiting in favour of reductive elimination. In previous studies with secondary amines using PEPPSI complexes, deprotonation was proposed to be the slow step in the cycle. These experimental findings relating to mechanism were corroborated by computation. Pd-PEPPSI-IPr and the more hindered Pd-PEPPSI-IPent catalysts were used to couple deactivated aryl chlorides with electron poor anilines; while the IPr catalysis was sluggish, the IPent catalyst performed extremely well, again showing the high reactivity of this broadly useful catalyst. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold(I) Complexes of the Geminal Phosphinoborane tBu2PCH2BPh2

PubMed Central

2018-01-01

In this work, we explored the coordination properties of the geminal phosphinoborane tBu2PCH2BPh2 (2) toward different gold(I) precursors. The reaction of 2 with an equimolar amount of the sulfur-based complex (Me2S)AuCl resulted in displacement of the SMe2 ligand and formation of linear phosphine gold(I) chloride 3. Using an excess of ligand 2, bisligated complex 4 was formed and showed dynamic behavior at room temperature. Changing the gold(I) metal precursor to the phosphorus-based complex, (Ph3P)AuCl impacted the coordination behavior of ligand 2. Namely, the reaction of ligand 2 with (Ph3P)AuCl led to the heterolytic cleavage of the gold–chloride bond, which is favored over PPh3 ligand displacement. To the best of our knowledge, 2 is the first example of a P/B-ambiphilic ligand capable of cleaving the gold–chloride bond. The coordination chemistry of 2 was further analyzed by density functional theory calculations. PMID:29732451

Regio- and Stereospecific Formation of Protected Allylic Alcohols via Zirconium-Mediated SN2' Substitution of Allylic Chlorides

PubMed Central

Fox, Richard J.; Lalic, Gojko; Bergman, Robert G.

2008-01-01

A new, highly regio- and stereospecific SN2' substitution reaction between a zirconium oxo complex and allylic chloride has been achieved. The resulting allylic alcohol or TBS-protected allylic ether products were isolated in good to excellent yields with a wide range of E-allylic chlorides. A mechanism for the SN2' allylic substitution consistent with kinetic, stereochemical and secondary isotope effect studies was proposed. PMID:17973391

Modernization at the Y-12 National Security Complex: A Case for Additional Experimental Benchmarks

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

Thornbury, M. L.; Juarez, C.; Krass, A. W.

Efforts are underway at the Y-12 National Security Complex (Y-12) to modernize the recovery, purification, and consolidation of un-irradiated, highly enriched uranium metal. Successful integration of advanced technology such as Electrorefining (ER) eliminates many of the intermediate chemistry systems and processes that are the current and historical basis of the nuclear fuel cycle at Y-12. The cost of operations, the inventory of hazardous chemicals, and the volume of waste are significantly reduced by ER. It also introduces unique material forms and compositions related to the chemistry of chloride salts for further consideration in safety analysis and engineering. The work hereinmore » briefly describes recent investigations of nuclear criticality for 235UO2Cl2 (uranyl chloride) and 6LiCl (lithium chloride) in aqueous solution. Of particular interest is the minimum critical mass of highly enriched uranium as a function of the molar ratio of 6Li to 235U. The work herein also briefly describes recent investigations of nuclear criticality for 235U metal reflected by salt mixtures of 6LiCl or 7LiCl (lithium chloride), KCl (potassium chloride), and 235UCl3 or 238UCl3 (uranium tri-chloride). Computational methods for analysis of nuclear criticality safety and published nuclear data are employed in the absence of directly relevant experimental criticality benchmarks.« less

Microorganisms and methods for degrading plant cell walls and complex hydrocarbons

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

Polne-Fuller, M.

1991-09-24

This patent describes a biologically pure multinucleated marine amoeba having the identifying characteristics of ATCC 40319. The amoeba being capable of digesting algal cell walls and having the further capacity to degrade paraffin, wax, polyethylene, polypropylene, polyvinyl chloride polyvinylidene di-chloride and mixtures thereof.

Rhodium(I)-Complexes Catalyzed 1,4-Conjugate Addition of Arylzinc Chlorides to N-Boc-4-pyridone.

PubMed

Guo, Fenghai; McGilvary, Matthew A; Jeffries, Malcolm C; Graves, Briana N; Graham, Shekinah A; Wu, Yuelin

2017-05-01

Rhodium(I)-complexes catalyzed the 1,4-conjugate addition of arylzinc chlorides to N -Boc-4-pyridone in the presence of chlorotrimethylsilane (TMSCl). A combination of [RhCl(C₂H₄)₂]₂ and BINAP was determined to be the most effective catalyst to promote the 1,4-conjugate addition reactions of arylzinc chlorides to N -Boc-4-pyridone. A broad scope of arylzinc reagents with both electron-withdrawing and electron-donating substituents on the aromatic ring successfully underwent 1,4-conjugate addition to N -Boc-4-pyridone to afford versatile 1,4-adducts 2-substituted-2,3-dihydropyridones in good to excellent yields (up to 91%) and excellent ee (up to 96%) when ( S )-BINAP was used as chiral ligand.

α, α', α", α'"- meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents

DOE PAGES

Williams, Neil J.; Bryantsev, Vyacheslav S.; Custelcean, Radu; ...

2016-01-29

α, α', α", α'"- meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parent meso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative 2 complexes with tributylmethylammonium chloride in chloroform more strongly than does 1 as shown by NMR titrations. However, 1 and 2 exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA +(1 or 2)Cl – inmore » both NMR and extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand 2 and its complex with tetramethylammonium chloride. In addition, the free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with 2 in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially.« less

α, α', α", α'"- meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents

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

Williams, Neil J.; Bryantsev, Vyacheslav S.; Custelcean, Radu

α, α', α", α'"- meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parent meso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative 2 complexes with tributylmethylammonium chloride in chloroform more strongly than does 1 as shown by NMR titrations. However, 1 and 2 exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA +(1 or 2)Cl – inmore » both NMR and extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand 2 and its complex with tetramethylammonium chloride. In addition, the free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with 2 in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially.« less

The Use of Electrospray Mass Spectrometry to Determine Speciation in a Dynamic Combinatorial Library for Anion Recognition

PubMed Central

Phillips, Hazel I A; Chernikov, Aleksey V; Fletcher, Nicholas C; Ashcroft, Alison E; Ault, James R; Filby, Maria H; Wilson, Andrew J

2012-01-01

The composition of a dynamic mixture of similar 2,2′-bipyridine complexes of iron(II) bearing either an amide (5-benzylamido-2,2′-bipyridine and 5-(2-methoxyethane)amido-2,2′-bipyridine) or an ester (2,2′-bipyridine-5-carboxylic acid benzylester and 2,2′-bipyridine-5-carboxylic acid 2-methoxyethane ester) side chain have been evaluated by electrospray mass spectroscopy in acetonitrile. The time taken for the complexes to come to equilibrium appears to be dependent on the counteranion, with chloride causing a rapid redistribution of two preformed heteroleptic complexes (of the order of 1 hour), whereas the time it takes in the presence of tetrafluoroborate salts is in excess of 24 h. Similarly the final distribution of products is dependent on the anion present, with the presence of chloride, and to a lesser extent bromide, preferring three amide-functionalized ligands, and a slight preference for an appended benzyl over a methoxyethyl group. Furthermore, for the first time, this study shows that the distribution of a dynamic library of metal complexes monitored by ESI-MS can adapt following the introduction of a different anion, in this case tetrabutylammonium chloride to give the most favoured heteroleptic complex despite the increasing ionic strength of the solution. PMID:22996943

Hydrothermal transport and deposition of the rare earth elements by fluorine-bearing aqueous liquids

NASA Astrophysics Data System (ADS)

Migdisov, Art A.; Williams-Jones, A. E.

2014-12-01

New technologies, particularly those designed to address environmental concerns, have created a great demand for the rare earth elements (REE), and focused considerable attention on the processes by which they are concentrated to economically exploitable levels in the Earth's crust. There is widespread agreement that hydrothermal fluids played an important role in the formation of the world's largest economic REE deposit, i.e. Bayan Obo, China. Until recently, many researchers have assumed that hydrothermal transport of the REE in fluorine-bearing ore-forming systems occurs mainly due to the formation of REE-fluoride complexes. Consequently, hydrothermal models for REE concentration have commonly involved depositional mechanisms based on saturation of the fluid with REE minerals due to destabilization of REE-fluoride complexes. Here, we demonstrate that these complexes are insignificant in REE transport, and that the above models are therefore flawed. The strong association of H+ and F- as HF° and low solubility of REE-F solids greatly limit transport of the REE as fluoride complexes. However, this limitation does not apply to REE-chloride complexes. Because of this, the high concentration of Cl- in the ore fluids, and the relatively high stability of REE-chloride complexes, the latter can transport appreciable concentrations of REE at low pH. The limitation also does not apply to sulphate complexes and in some fluids, the concentration of sulphate may be sufficient to transport significant concentrations of REE as sulphate complexes, particularly at weakly acidic pH. This article proposes new models for hydrothermal REE deposition based on the transport of the REE as chloride and sulphate complexes.

Fluorinated tripodal receptors for potentiometric chloride detection in biological fluids.

PubMed

Pankratova, Nadezda; Cuartero, Maria; Jowett, Laura A; Howe, Ethan N W; Gale, Philip A; Bakker, Eric; Crespo, Gastón A

2018-01-15

Fluorinated tripodal compounds were recently reported to be efficient transmembrane transporters for a series of inorganic anions. In particular, this class of receptors has been shown to be suitable for the effective complexation of chloride, nitrate, bicarbonate and sulfate anions via hydrogen bonding. The potentiometric properties of urea and thiourea-based fluorinated tripodal receptors are explored here for the first time, in light of the need for reliable sensors for chloride monitoring in undiluted biological fluids. The ion selective electrode (ISE) membranes with tren-based tris-urea bis(CF 3 ) tripodal compound (ionophore I) were found to exhibit the best selectivity for chloride over major lipophilic anions such as salicylate ( [Formula: see text] ) and thiocyanate ( [Formula: see text] ). Ionophore I-based ISEs were successfully applied for chloride determination in undiluted human serum as well as artificial serum sample, the slope of the linear calibration at the relevant background of interfering ions being close to Nernstian (49.8±1.7mV). The results of potentiometric measurements were confirmed by argentometric titration. Moreover, the ionophore I-based ISE membrane was shown to exhibit a very good long-term stability of potentiometric performance over the period of 10 weeks. Nuclear magnetic resonance (NMR) titrations, potentiometric sandwich membrane experiments and density functional theory (DFT) computational studies were performed to determine the binding constants and suggest 1:1 complexation stoichiometry for the ionophore I with chloride as well as salicylate. Copyright © 2017 Elsevier B.V. All rights reserved.

Form of Dietary Methylmercury does not Affect Total Mercury Accumulation in the Tissues of Zebra Finch.

PubMed

Varian-Ramos, Claire W; Whitney, Margaret; Rice, Gary W; Cristol, Daniel A

2017-07-01

Exposure to mercury in humans, other mammals, and birds is primarily dietary, with mercury in the methylated form and bound to cysteine in the tissues of prey items. Yet dosing studies are generally carried out using methylmercury chloride. Here we tested whether the accumulation of total mercury in zebra finch blood, egg, muscle, liver, kidney or brain differed depending on whether dietary mercury was complexed with chloride or cysteine. We found no effect of form of mercury on tissue accumulation. Some previous studies have found lower accumulation of mercury in tissues of animals fed complexed mercury. Much remains to be understood about what happens to ingested mercury once it enters the intestines, but our results suggest that dietary studies using methylmercury chloride in birds will produce similar tissue accumulation levels to those using methylmercury cysteine.

Anion-induced reconstitution of a self-assembling system to express a chloride-binding Co10L15 pentagonal prism.

PubMed

Riddell, Imogen A; Smulders, Maarten M J; Clegg, Jack K; Hristova, Yana R; Breiner, Boris; Thoburn, John D; Nitschke, Jonathan R

2012-09-01

Biochemical systems are adaptable, capable of reconstitution at all levels to achieve the functions associated with life. Synthetic chemical systems are more limited in their ability to reorganize to achieve new functions; they can reconfigure to bind an added substrate (template effect) or one binding event may modulate a receptor's affinity for a second substrate (allosteric effect). Here we describe a synthetic chemical system that is capable of structural reconstitution on receipt of one anionic signal (perchlorate) to create a tight binding pocket for another anion (chloride). The complex, barrel-like structure of the chloride receptor is templated by five perchlorate anions. This second-order templation phenomenon allows chemical networks to be envisaged that express more complex responses to chemical signals than is currently feasible.

Great Salt Lake Composition and Rare Earth Speciation Analysis

DOE Data Explorer

Jiao, Yongqin; Lammers, Laura; Brewer, Aaron

2017-04-19

We have conducted aqueous speciation analyses of the Great Salt Lake (GSL) brine sample (Table 1) and a mock geo sample (Table 2) spiked with 1 ppb Tb and 100 ppb Tb. The GSL speciation (Figure 1) aligns with our basic speciation expectations that strong carbonate complexes would form at mid to higher pH's. Although we expected strong aqueous complexes with fluorides at neutral pH and with chlorides, and hydroxides at low pH, we observe that the dominant species in the low to mid pH range to be Tb3+ as a free ion. Still, we do see the presence of fluoride and chloride complexes within the expected low to mid pH range.

A cAMP-Regulated Chloride Channel in Lymphocytes that is Affected in Cystic Fibrosis

NASA Astrophysics Data System (ADS)

Chen, Jennifer H.; Schulman, Howard; Gardner, Phyllis

1989-02-01

A defect in regulation of a chloride channel appears to be the molecular basis for cystic fibrosis (CF), a common lethal genetic disease. It is shown here that a chloride channel with kinetic and regulatory properties similar to those described for secretory epithelial cells is present in both T and B lymphocyte cell lines. The regulation of the channels by adenosine 3',5'-monophosphate (cAMP)--dependent protein kinase in transformed B cells from CF patients is defective. Thus, lymphocytes may be an accessible source of CF tissue for study of this defect, for cloning of the chloride channel complex, and for diagnosis of the disease.

Combined time-resolved laser fluorescence spectroscopy and extended X-ray absorption fine structure spectroscopy study on the complexation of trivalent actinides with chloride at T = 25-200 °C.

PubMed

Skerencak-Frech, Andrej; Fröhlich, Daniel R; Rothe, Jörg; Dardenne, Kathy; Panak, Petra J

2014-01-21

The complexation of trivalent actinides (An(III)) with chloride is studied in the temperature range from 25 to 200 °C by spectroscopic methods. Time-resolved laser fluorescence spectroscopy (TRLFS) is applied to determine the thermodynamic data of Cm(III)-Cl(-) complexes, while extended X-ray absorption fine structure spectroscopy (EXAFS) is used to determine the structural data of the respective Am(III) complexes. The experiments are performed in a custom-built high-temperature cell which is modified for the respective spectroscopic technique. The TRLFS results show that at 25 °C the speciation is dominated mainly by the Cm(3+) aquo ion. Only a minor fraction of the CmCl(2+) complex is present in solution. As the temperature increases, the fraction of this species decreases further. Simultaneously, the fraction of the CmCl2(+) complex increases strongly with the temperature. Also, the CmCl3 complex is formed to a minor extent at T > 160 °C. The conditional stability constant log β'2 is determined as a function of the temperature and extrapolated to zero ionic strength with the specific ion interaction theory approach. The log β°2(T) values increase by more than 3 orders of magnitude in the studied temperature range. The temperature dependency of log β°2 is fitted by the extended van't Hoff equation to determine ΔrH°m, ΔrS°m, and ΔrC°p,m. The EXAFS results support these findings. The results confirm the absence of americium(III) chloride complexes at T = 25 and 90 °C ([Am(III)] = 10(-3) m, [Cl(-)] = 3.0 m), and the spectra are described by 9-10 oxygen atoms at a distance of 2.44-2.48 Å. At T = 200 °C two chloride ligands are present in the inner coordination sphere of Am(III) at a distance of 2.78 Å.

The role of chloride in the mechanism of O(2) activation at the mononuclear nonheme Fe(II) center of the halogenase HctB.

PubMed

Pratter, Sarah M; Light, Kenneth M; Solomon, Edward I; Straganz, Grit D

2014-07-02

Mononuclear nonheme Fe(II) (MNH) and α-ketoglutarate (α-KG) dependent halogenases activate O2 to perform oxidative halogenations of activated and nonactivated carbon centers. While the mechanism of halide incorporation into a substrate has been investigated, the mechanism by which halogenases prevent oxidations in the absence of chloride is still obscure. Here, we characterize the impact of chloride on the metal center coordination and reactivity of the fatty acyl-halogenase HctB. Stopped-flow kinetic studies show that the oxidative transformation of the Fe(II)-α-KG-enzyme complex is >200-fold accelerated by saturating concentrations of chloride in both the absence and presence of a covalently bound substrate. By contrast, the presence of substrate, which generally brings about O2 activation at enzymatic MNH centers, only has an ∼10-fold effect in the absence of chloride. Circular dichroism (CD) and magnetic CD (MCD) studies demonstrate that chloride binding triggers changes in the metal center ligation: chloride binding induces the proper binding of the substrate as shown by variable-temperature, variable-field (VTVH) MCD studies of non-α-KG-containing forms and the conversion from six-coordinate (6C) to 5C/6C mixtures when α-KG is bound. In the presence of substrate, a site with square pyramidal five-coordinate (5C) geometry is observed, which is required for O2 activation at enzymatic MNH centers. In the absence of substrate an unusual trigonal bipyramidal site is formed, which accounts for the observed slow, uncoupled reactivity. Molecular dynamics simulations suggest that the binding of chloride to the metal center of HctB leads to a conformational change in the enzyme that makes the active site more accessible to the substrate and thus facilitates the formation of the catalytically competent enzyme-substrate complex. Results are discussed in relation to other MNH dependent halogenases.

The Microwave Spectrum of Argon-Vinyl Chloride

NASA Astrophysics Data System (ADS)

Leung, Helen O.; Marshall, Mark D.

2011-06-01

Through the systematic comparison of the structures of a series of complexes formed between protic acid and fluorine substituted ethylenes, we have been able to observe how tuning the properties of the functional groups (F and H atoms) in ethylene using additional F atoms causes these groups to compete or cooperate with each other in intermolecular interactions. A necessary step for expanding our work in the next natural direction by examining the effects of the less electronegative, but more polarizable Cl atom is the determination of the structures of protic acid-vinyl chloride complexes. Since the rich microwave spectrum of Ar-vinyl chloride has not previously been reported, it is essential to first characterize this rare gas complex. We have observed strong b-type and weak a-type transitions for both 35Cl and 37Cl versions of this species, all of which appear to be doubled. Although ab initio calculations suggest a sufficiently large value of μ_c, c-type lines remain elusive. Indeed, these same calculations reveal the presence of several minima on the interaction potential energy surface, which may provide an explanation.

Experimental study of iron-chloride complexing in hydrothermal fluids

USGS Publications Warehouse

Fein, J.B.; Hemley, J.J.; d'Angelo, W. M.; Komninou, A.; Sverjensky, D.A.

1992-01-01

Mineral assemblage solubilities were measured in cold-seal pressure vessels as a function of pressure, temperature, and potassium chloride concentration in order to determine the nature and thermodynamic properties of iron-chloride complexes under hydrothermal conditions. The assemblage pyritepyrrhotite-magnetite was used to buffer f{hook}S2 and f{hook}O2, and K+ H+ ratios were buffered at reasonable geologic values using the assemblage potassium feldspar-muscovite (or andalusite)-quartz. The pressure-temperature ranges were 0.5-2.0 kbar and 300-600??C, and initial fluid compositions ranged from 0.01-2.0 molal KCl. With all other factors constant, the concentration of iron in solution increases with increasing temperature, with decreasing pressure, and with increasing total potassium chloride concentration. Changes in iron concentrations as a function of KCl concentration, in conjunction with charge balance, mass action, and mass balance constraints on the system, place constraints on the stoichiometry of the important iron-chloride complexes under each of the experimental conditions. Using least-squared linear regression fits to determine these slopes, the calculations yield values for the average ligand numbers that are in the range 1.2-1.9, with uncertainties ranging from ??0.1-0.6 at the several PT conditions considered. The slopes of the regressed fits to the data suggest that both FeCl+ and FeCl20 are important in the experimental fluids, with FeCl20 becoming dominant at the higher temperatures. Theoretical calculations, however, indicate that FeCl+ does not contribute significantly to the solubility. Because of the large uncertainties associated with some of the calculated average ligand numbers, we base our data analysis on the theoretical calculations. A statistical analysis is applied to the solubility data in order to determine the values and uncertainties of the dissociation constant for FeCl20 that best fit the data at each of the experimental pressures and temperatures. The calculated stability of FeCl20 increases with increasing temperature and total chloride concentration, and with decreasing pressure. The values of the dissociation constant of FeCl20that are calculated in this study are in moderately good agreement with FeCl20dissociation constants from other studies of iron-chloride complexing in supercritical fluids. Differences are likely due to different assumptions made concerning activity coefficients of aqueous species. Log kd values for full dissociation of FeCl20 at 0.5 kbar-300??C-and at 1 kbar-400, 500, and 600??C, respectively-are -3.75 ?? 0.40, -6.25 ?? 0.10, -9.19 ?? 0.44, and -13.29 ?? 0.09. ?? 1992.

Peat porewater chloride concentration profiles in the Everglades during wet/dry cycles from January 1996 to June 1998: Field measurements and theoretical analysis

USGS Publications Warehouse

Reddy, M.M.; Reddy, M.B.; Kipp, K.L.; Burman, A.; Schuster, P.; Rawlik, P.S.

2008-01-01

Water quality is a key aspect of the Everglades Restoration Project, the largest water reclamation and ecosystem management project proposed in the United States. Movement of nutrients and contaminants to and from Everglades peat porewater could have important consequences for Everglades water quality and ecosystem restoration activities. In a study of Everglades porewater, we observed complex, seasonally variable peat porewater chloride concentration profiles at several locations. Analyses and interpretation of these changing peat porewater chloride concentration profiles identifies processes controlling conservative solute movement at the peat-surface water interface, that is, solutes whose transport is minimally affected by chemical and biological reactions. We examine, with an advection-diffusion model, how alternating wet and dry climatic conditions in the Florida Everglades mediate movement of chloride between peat porewater and marsh surface water. Changing surface water-chloride concentrations alter gradients at the interface between peat and overlying water and hence alter chloride flux across that interface. Surface water chloride concentrations at two frequently monitored sites vary with marsh water depth, and a transfer function was developed to describe daily marsh surface water chloride concentration as a function of marsh water depth. Model results demonstrate that porewater chloride concentrations are driven by changing surface water chloride concentrations, and a sensitivity analysis suggests that inclusion of advective transport in the model improves the agreement between the calculated and the observed chloride concentration profiles. Copyright ?? 2007 John Wiley & Sons, Ltd.

Palladium pincer complex catalyzed stannyl and silyl transfer to propargylic substrates: synthetic scope and mechanism.

PubMed

Kjellgren, Johan; Sundén, Henrik; Szabó, Kálmán J

2005-02-16

Pincer complex catalyzed substitution of various propargylic substrates could be achieved using tin- and silicon-based dimetallic reagents to obtain propargyl- and allenylstannanes and silanes. These reactions involving chloride, mesylate, and epoxide substrates could be carried out under mild conditions, and therefore many functionalities (such as COOEt, OR, OH, NR, and NAc) are tolerated. It was shown that pincer catalysts with electron-supplying ligands, such as NCN, SCS, and SeCSe complexes, display the highest catalytic activity. The catalytic substitution of secondary propargyl chlorides and primary propargyl chlorides with electron-withdrawing substituents proceeds with high regioselectivity providing the allenyl product. Opening of the propargyl epoxides takes place with an excellent stereo- and regioselectivity to give stereodefined allenylstannanes. Silylstannanes as dimetallic reagents undergo an exclusive silyl transfer to the propargylic substrate affording allenylsilanes with high regioselectivity. According to our mechanistic studies, the key intermediate of the reaction is an organostannane (or silane)-coordinated pincer complex, which is formed from the dimetallic reagent and the corresponding pincer complex catalyst. DFT modeling studies have shown that the trimethylstannyl functionality is transferred to the propargylic substrate in a single reaction step with high allenyl selectivity. Inspection of the TS structures reveals that the trimethylstannyl group transfer is initiated by the attack of the palladium-tin sigma-bond electrons on the propargylic substrate. This is a novel mechanism in palladium chemistry, which is based on the unique topology of the pincer complex catalysts.

Chloride supporting electrolytes for all-vanadium redox flow batteries.

PubMed

Kim, Soowhan; Vijayakumar, M; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Chen, Feng; Hu, Jianzhi; Li, Liyu; Yang, Zhenguo

2011-10-28

This paper examines vanadium chloride solutions as electrolytes for an all-vanadium redox flow battery. The chloride solutions were capable of dissolving more than 2.3 M vanadium at varied valence states and remained stable at 0-50 °C. The improved stability appeared due to the formation of a vanadium dinuclear [V(2)O(3)·4H(2)O](4+) or a dinuclear-chloro complex [V(2)O(3)Cl·3H(2)O](3+) in the solutions over a wide temperature range. The all-vanadium redox flow batteries with the chloride electrolytes demonstrated excellent reversibility and fairly high efficiencies. Only negligible, if any, gas evolution was observed. The improved energy capacity and good performance, along with the ease in heat management, would lead to substantial reduction in capital cost and life-cycle cost, making the vanadium chloride redox flow battery a promising candidate for stationary applications. This journal is © the Owner Societies 2011

Synthesis, Characterization and Antibacterial Activity of 1,4-di[ aminomethylene carboxyl] phenylene (H2L) and its Complexes Co(II), Cu (II), Zn(II) and Cd (II)

NASA Astrophysics Data System (ADS)

Sultan, J. S.; Fezea, S. M.; Mousa, F. H.

2018-05-01

A binucleating tetradentate Schiff base ligand, 1,4- di[amino methylene carboxylic] phenylene (H2L) and its forth new binuclear complexes [Co(II), Cu(II), Zn(II) and Cd(II)] were prepared via reaction metal (II) chloride with ligand (H2L) using 2:1 (M:L) in ethanol solvent. The new ligand (H2L) and its complexes were characterized by elemental microanalysis (C.H.N), atomic absorption, chloride content, molar conductance’s magnetic susceptibility, FTIR UV- Vis spectral and, 1H, 13 C- NMR (for H2L). The antibacterial activity with bacteria activity with bacteria, Staphylococcus aureus, Bacillus and Esccherichia Coli were studied.

Structure and Bonding in Uranyl(VI) Peroxide and Crown Ether Complexes; Comparison of Quantum Chemical and Experimental Data.

PubMed

Vallet, Valérie; Grenthe, Ingmar

2017-12-18

The structure, chemical bonding, and thermodynamics of alkali ions in M[12-crown-4] + , M[15-crown-5] + , and M[18-crown-6] + , M[UO 2 (O 2 )(OH 2 ) 2 ] + 4,5 , and M[UO 2 (O 2 )(OH)(OH 2 )] n 1-n (n = 4, 5) complexes have been explored by using quantum chemical (QC) calculations at the ab initio level. The chemical bonding has been studied in the gas phase in order to eliminate solvent effects. QTAIM analysis demonstrates features that are very similar in all complexes and typical for electrostatic M-O bonds, but with the M-O bonds in the uranyl peroxide systems about 20 kJ mol -1 stronger than in the corresponding crown ether complexes. The regular decrease in bond strength with increasing M-O bond distance is consistent with predominantly electrostatic contributions. Energy decomposition of the reaction energies in the gas phase and solvent demonstrates that the predominant component of the total attractive (ΔE elec + ΔE orb ) energy contribution is the electrostatic component. There are no steric constraints for coordination of large cations to small rings, because the M + ions are located outside the ring plane, [O n ], formed by the oxygen donors in the ligands; coordination of ions smaller than the ligand cavity results in longer than normal M-O distances or in a change in the number of bonds, both resulting in weaker complexes. The Gibbs energies, enthalpies, and entropies of reaction calculated using the conductor-like screening model, COSMO, to account for solvent effects deviate significantly from experimental values in water, while those in acetonitrile are in much better agreement. Factors that might affect the selectivity are discussed, but our conclusion is that present QC methods are not accurate enough to describe the rather small differences in selectivity, which only amount to 5-10 kJ mol -1 . We can, however, conclude on the basis of QC and experimental data that M[crown ether] + complexes in the strongly coordinating water solvent are of outer-sphere type, [M(OH 2 ) n + ][crown ether], while those in weakly coordinating acetonitrile are of inner-sphere type, [M-crown ether] + . The observation that the M[UO 2 (O 2 )(OH)(OH 2 )] n 1-n complexes are more stable in solution than those of M[crown ether] + is an effect of the different charges of the rings.

Chloride channels as tools for developing selective insecticides.

PubMed

Bloomquist, Jeffrey R

2003-12-01

Ligand-gated chloride channels underlie inhibition in excitable membranes and are proven target sites for insecticides. The gamma-aminobutyric acid (GABA(1)) receptor/chloride ionophore complex is the primary site of action for a number of currently used insecticides, such as lindane, endosulfan, and fipronil. These compounds act as antagonists by stabilizing nonconducting conformations of the chloride channel. Blockage of the GABA-gated chloride channel reduces neuronal inhibition, which leads to hyperexcitation of the central nervous system, convulsions, and death. We recently investigated the mode of action of the silphinenes, plant-derived natural compounds that structurally resemble picrotoxinin. These materials antagonize the action of GABA on insect neurons and block GABA-mediated chloride uptake into mouse brain synaptoneurosomes in a noncompetitive manner. In mammals, avermectins have a blocking action on the GABA-gated chloride channel consistent with a coarse tremor, whereas at longer times and higher concentrations, activation of the channel suppresses neuronal activity. Invertebrates display ataxia, paralysis, and death as the predominant signs of poisoning, with a glutamate-gated chloride channel playing a major role. Additional target sites for the avermectins or other chloride channel-directed compounds might include receptors gated by histamine, serotonin, or acetylcholine.The voltage-sensitive chloride channels form another large gene family of chloride channels. Voltage-dependent chloride channels are involved in a number of physiological processes including: maintenance of electrical excitability, chloride ion secretion and resorption, intravesicular acidification, and cell volume regulation. A subset of these channels is affected by convulsants and insecticides in mammals, although the role they play in acute lethality in insects is unclear. Given the wide range of functions that they mediate, these channels are also potential targets for insecticide development. Copyright 2003 Wiley-Liss, Inc.

Spectrophotometric complexation of cephalosporins with palladium (II) chloride in aqueous and non-aqueous solvents

NASA Astrophysics Data System (ADS)

Bagheri Gh., A.; Yosefi rad, A.; Rezvani, M.; Roshanzamir, S.

2012-04-01

The complexation reaction of cephalosporins namely cefotaxime (CTX), cefuroxime (CRX), and cefazolin (CEFAZ) with palladium (II) ions have been studied in water and DMF in 25 °C by the spectrophotometric methods. The method is based on the formation of yellow to yellowish brown complex between palladium (II) chloride and the investigated cephalosporins in the presence of sodium lauryl sulfate (SLS) as surfactant. The complexation process was optimized in terms of pH, temperature and contact time. The stoichiometry of all the complexes was found to be 2:1 (metal ion/ligand) for CTX, CRX, and 1:2 for CEFAZ. The stoichiometry of palladium (II)-cephalosporins was estimated by mole ratio and continuous variation methods and emphasized by the KINFIT program. These drugs could be determined by measuring the absorbance of each complex at its specific λmax. The results obtained are in good agreement with those obtained using the official methods. The proposed method was successfully applied for the determination of these compounds in their dosage forms.

Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions.

PubMed

Qi, Xinghao; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

2018-02-20

The electron-rich silylene Co(i) chloride 5 was obtained through the reaction of CoCl(PMe 3 ) 3 with chlorosilylene. Complex 5 reacted with 1,3-siladiazole HSiMe(NCH 2 PPh 2 ) 2 C 6 H 4 to give the silylene Co(iii) hydride 6 through chelate-assisted Si-H activation. To the best of our knowledge, complex 6 is the first example of Co(iii) hydride supported by N-heterocyclic silylene. Complexes 5 and 6 were fully characterized by spectroscopic methods and X-ray diffraction analysis. Complex 6 was used as an efficient precatalyst for Kumada cross-coupling reactions. Compared with the related complex 3 supported by only trimethylphosphine, complex 6 as a catalyst supported by both chlorosilylene and trimethylphosphine exhibits a more efficient performance for the Kumada cross-coupling reactions. A novel catalytic radical mechanism was suggested and experimentally verified. As an intermediate silylene cobalt(ii) chloride 6d was isolated and structurally characterized.

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.

Gold(I) Carbenoids: On‐Demand Access to Gold(I) Carbenes in Solution

PubMed Central

Sarria Toro, Juan M.; García‐Morales, Cristina; Raducan, Mihai; Smirnova, Ekaterina S.

2017-01-01

Abstract Chloromethylgold(I) complexes of phosphine, phosphite, and N‐heterocyclic carbene ligands are easily synthesized by reaction of trimethylsilyldiazomethane with the corresponding gold chloride precursors. Activation of these gold(I) carbenoids with a variety of chloride scavengers promotes reactivity typical of metallocarbenes in solution, namely homocoupling to ethylene, olefin cyclopropanation, and Buchner ring expansion of benzene. PMID:28090747

Transition metal coordination chemistry ofN,N-bis(2-{pyrid-2-ylethyl})hydroxylamine.

PubMed

Belock, Christopher W; Cetin, Anil; Barone, Natalie V; Ziegler, Christopher J

2008-08-18

Although directly relevant to metal mediated biological nitrification as well as the coordination chemistry of peroxide, the metal complexes of hydroxylamines and their functionalized variants remain largely unexplored. The chelating hydroxylamine ligand N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine can be readily generated via a solvent free reaction in high purity; however, the ligand is prone to decomposition which can hamper metal reaction. N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine forms stable complexes with chromium(III), manganese(II), nickel(II), and cadmium(II) ions, coordinating in a side-on mode in the case of chromium and via the nitrogen in the case of the latter three metal ions. The hydroxylamine ligand can also be reduced to form N,N-bis(2-{pyrid-2-ylethyl})amine upon exposure to a stoichiometric amount of the metal salts cobalt(II) nitrate, vanadium(III) chloride, and iron(II) chloride. In the reaction with cobalt nitrate, the reduced ligand then chelates to the metal to form [N,N-bis(2-{pyrid-2-ylethyl})amine]dinitrocobalt(II). Upon reaction with vanadium(III) chloride and iron(III) chloride, the reduced ligand is isolated as the protonated free base, resulting from a metal-mediated decomposition reaction.

Numerical Modeling of Local Penetration of Chloride-Containing Medium into Construction Elements Made of Reinforced Concrete

NASA Astrophysics Data System (ADS)

Ovchinnikov, I. I.; Snezhkina, O. V.; Ovchinnikov, I. G.

2017-11-01

The task of modeling the kinetics of chloride-containing medium penetration into construction elements out of reinforced concrete that have partially damaged anti-corrosion protective coatings is being discussed. As a result, chlorides penetrate the construction element via local surface areas which leads to irregularities between chloride dispersion volumes. The kinetics of chloride penetration is described by the equation of diffusion to solve which the CONDUCT software complex by professor S. Patankar was used. The methodology used to solve the diffusional equation is described. The results of the evaluation of concentration field in the axial section of a cylindrical construction element, which was centrally reinforced, are given. The chloride diffusion was symmetrical to the axis, the medium was applied through the central ring area equal to one third of the side surface area while the rest of the surface was isolated. It was shown that the methodology of evaluation and its algorithm allow one to evaluate the concentration field of chlorides in reinforced concrete structural elements under local or asymmetrical action of the chloride - containing medium. The example given illustrates that after a certain time interval critical the concentration of chlorides develops even in protected areas which are located far from the initial damaged area. This means that the corrosion destruction of reinforced elements develops not only in the immediate damage area, but also further away from it.

Concentration determination of methyl magnesium chloride and other Grignard reagents by potentiometric titration with in-line characterization of reaction species by FTIR spectroscopy.

PubMed

Chen, Yadan; Wang, Tao; Helmy, Roy; Zhou, George X; LoBrutto, Rosario

2002-07-01

A potentiometric titration method for methyl magnesium chloride and other Grignard reagents based on the reaction with 2-butanol in THF has been developed and validated. The method employs a commercially available platinum electrode, using an electrolyte compatible with non-aqueous solvents. Well-defined titration curves were obtained, along with excellent method precision. The endpoint was precisely determined based on the first derivative of the titration curve. Different solvents such as THF, diethyl ether and methylene chloride provided similar results with regard to sharpness of the endpoint and method precision. The method was applied to a wide array of Grignard reagents including methyl magnesium bromide, ethyl magnesium chloride, propyl magnesium chloride, vinyl magnesium chloride, phenyl magnesium chloride, and benzyl magnesium chloride with similar precision and accuracy. Application of in-line FTIR was demonstrated for in situ monitoring of the titration reaction, allowing characterization of the reaction species. An authentic spectrum of the MeMgCl-THF complex was obtained using spectral subtraction and the vibrational absorbance bands were identified. FTIR also provided an alternative for detecting the titration endpoint, and the titration results so obtained, provided a cross-validation of the accuracy of the potentiometric titration.

Multilinear analysis of Time-Resolved Laser-Induced Fluorescence Spectra of U(VI) containing natural water samples

NASA Astrophysics Data System (ADS)

Višňák, Jakub; Steudtner, Robin; Kassahun, Andrea; Hoth, Nils

2017-09-01

Natural waters' uranium level monitoring is of great importance for health and environmental protection. One possible detection method is the Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS), which offers the possibility to distinguish different uranium species. The analytical identification of aqueous uranium species in natural water samples is of distinct importance since individual species differ significantly in sorption properties and mobility in the environment. Samples originate from former uranium mine sites and have been provided by Wismut GmbH, Germany. They have been characterized by total elemental concentrations and TRLFS spectra. Uranium in the samples is supposed to be in form of uranyl(VI) complexes mostly with carbonate (CO32- ) and bicarbonate (HCO3- ) and to lesser extend with sulphate (SO42- ), arsenate (AsO43- ), hydroxo (OH- ), nitrate (NO3- ) and other ligands. Presence of alkaline earth metal dications (M = Ca2+ , Mg2+ , Sr2+ ) will cause most of uranyl to prefer ternary complex species, e.g. Mn(UO2)(CO3)32n-4 (n ɛ {1; 2}). From species quenching the luminescence, Cl- and Fe2+ should be mentioned. Measurement has been done under cryogenic conditions to increase the luminescence signal. Data analysis has been based on Singular Value Decomposition and monoexponential fit of corresponding loadings (for separate TRLFS spectra, the "Factor analysis of Time Series" (FATS) method) and Parallel Factor Analysis (PARAFAC, all data analysed simultaneously). From individual component spectra, excitation energies T00, uranyl symmetric mode vibrational frequencies ωgs and excitation driven U-Oyl bond elongation ΔR have been determined and compared with quasirelativistic (TD)DFT/B3LYP theoretical predictions to cross -check experimental data interpretation. Note to the reader: Several errors have been produced in the initial version of this article. This new version published on 23 October 2017 contains all the corrections.

Mechanisms of gold bioaccumulation by filamentous cyanobacteria from gold(III)-chloride complex.

PubMed

Lengke, Maggy F; Ravel, Bruce; Fleet, Michael E; Wanger, Gregory; Gordon, Robert A; Southam, Gordon

2006-10-15

The mechanisms of gold bioaccumulation by cyanobacteria (Plectonema boryanum UTEX 485) from gold(III)-chloride solutions have been studied at three gold concentrations (0.8,1.7, and 7.6 mM) at 25 degrees C, using both fixed-time laboratory and real-time synchrotron radiation absorption spectroscopy (XAS) experiments. Interaction of cyanobacteria with aqueous gold(III)-chloride initially promoted the precipitation of nanoparticles of amorphous gold(I)-sulfide at the cell walls, and finally deposited metallic gold in the form of octahedral (111) platelets (approximately 10 nm to 6 microm) near cell surfaces and in solutions. The XAS results confirm that the reduction mechanism of gold(III)-chloride to metallic gold by cyanobacteria involves the formation of an intermediate Au(I) species, gold(I)-sulfide.

Aqueous chloride stress corrosion cracking of titanium - A comparison with environmental hydrogen embrittlement

NASA Technical Reports Server (NTRS)

Nelson, H. G.

1974-01-01

The physical characteristics of stress corrosion cracking of titanium in an aqueous chloride environment are compared with those of embrittlement of titanium by a gaseous hydrogen environment in an effort to help contribute to the understanding of the possible role of hydrogen in the complex stress corrosion cracking process. Based on previous studies, the two forms of embrittlement are shown to be similar at low hydrogen pressures (100 N/sq m) but dissimilar at higher hydrogen pressures. In an effort to quantify this comparison, tests were conducted in an aqueous chloride solution using the same material and test techniques as had previously been employed in a gaseous hydrogen environment. The results of these tests strongly support models based on hydrogen as the embrittling species in an aqueous chloride environment.

[CNN]-pincer nickel(II) complexes of N-heterocyclic carbene (NHC): synthesis and catalysis of the Kumada reaction of unactivated C-Cl bonds.

PubMed

Sun, Yunqiang; Li, Xiaoyan; Sun, Hongjian

2014-07-07

Three novel [CNN]-pincer nickel(ii) complexes with NHC-amine arms were synthesized in three steps. Complex was proven to be an efficient catalyst for the Kumada coupling of aryl chlorides or aryl dichlorides under mild conditions.

Hexaammine Complexes of Cr(III) and Co(III): A Spectral Study.

ERIC Educational Resources Information Center

Brown, D. R.; Pavlis, R. R.

1985-01-01

Procedures are provided for experiments containing complex ions with octahedral symmetry, hexaamminecobalt(III) chloride and hexaamminechromium(III) nitrate, so students can interpret fully the ultra violet/visible spectra of the complex cations in terms of the ligand field parameters, 10 "Dq," the Racah interelectron repulsion parameters, "B,"…

Diaquachloro-tris(ethyl-p-Aminobenzoate)copper(II) Chloride: Synthesis, Characterization and In Vitro Investigation of Antibacterial Activity

NASA Astrophysics Data System (ADS)

Rahardjo, S. B.; Lestari, W. W.; Syaima, H.

2017-07-01

The new complex of [Cu(benz)3(H2O)2Cl]Cl has been synthesized in 1:4 mole ratio of CuCl2·2H2O and ethyl-p-aminobenzoate (benz) in ethanol at room temperature. The complex was characterized by UV-Vis and infrared spectroscopy, Atomic Absorption Spectroscopy (AAS), thermal analysis, magnetic measurement and molar conductivity. Infrared spectra indicated that benz was coordinated to the metal ion through nitrogen of primary amine group. Water molecules and chloride ion were also coordinated to Cu(II). CuCl2·2H2O, benz, and Cu(II) complex were screened for investigating in vitro antibacterial activity against Staphylococcus aureus and Escherichia coli using a modified Kirby-Bauer method.

On the behaviour of biradicaloid [P(μ-NTer)]2 towards Lewis acids and bases.

PubMed

Hinz, Alexander; Schulz, Axel; Villinger, Alexander

2016-05-07

The well-known diphosphadiazane-1,3-diyl [P(μ-NTer)]2 (Ter = 2,6-bis(2,4,6-trimethyl-phenyl)-phenyl) was treated with Lewis bases such as N-heterocyclic carbenes and Lewis acids e.g. gold(i) chloride complexes. In the reaction with the Lewis base, fragmentation of the P2N2 framework was observed, yielding a salt of the type [(NHC)2P](+)[(TerN)2P](-) in a clean reaction. The reaction of [P(μ-NTer)]2 with gold(i) chloride afforded 1 : 1 and 1 : 2 complexes. The dinuclear complex [(ClAu)2P(μ-NTer)2P] displays a bridging P atom between both gold centers, as has been observed for P based zwitterions.

Synthesis of Two New Group 13 Benzoato-Chloro Complexes: A Structural Study of Gallium and Indium Chelating Carboxylates

NASA Technical Reports Server (NTRS)

Duraj, Stan A.; Hepp, Aloysius F.; Woloszynek, Robert; Protasiewicz, John D.; Dequeant, Michael; Ren, Tong

2010-01-01

Two new heteroleptic chelated-benzoato gallium (III) and indium (III) complexes have been prepared and structurally characterized. The molecular structures of [GaCl2(4-Mepy)2(O2CPh)]4-Mepy (1) and [InCl(4-Mepy)2(O2CPh)2]4-Mepy (2) have been determined by single-crystal x-ray diffraction. The gallium compound (1) is a distorted octahedron with cis-chloride ligands co-planar with the chelating benzoate and the 4-methylpyridines trans to each other. This is the first example of a Ga(III) structure with a chelating benzoate. The indium compound (2) is a distorted pentagonal bipyramid with two chelating benzoates, one 4-methylpyridine in the plane and a chloride trans to the other 4-methylpyridine. The indium bis-benzoate is an unusual example of a seven-coordinate structure with classical ligands. Both complexes, which due to the chelates, could also be described as pseudo-trigonal bipyramidal, include a three-bladed motif with three roughly parallel aromatic rings that along with a solvent of crystallization and electron-withdrawing chloride ligand(s) stabilize the solid-state structures.

Spectral and thermal studies with anti-fungal aspects of some organotin(IV) complexes with nitrogen and sulphur donor ligands derived from 2-phenylethylamine

NASA Astrophysics Data System (ADS)

Singh, Rajeev; Kaushik, N. K.

2008-11-01

Some complexes of 2-phenylethyl dithiocarbamate, thiohydrazides and thiodiamines with dibenzyltin(IV) chloride, tribenzyltin(IV) chloride and di( para-chlorobenzyl)tin(IV) dichloride have been synthesized and investigated in 1:2 and 1:1 molar ratio. The dithiocarbamate ligand act as monoanionic bidentate and thiohydrazide, thiodiamines act as neutral bidentate ligand. The synthesized complexes have been characterized by elemental analysis and molecular weight determination studies and their bonding pattern suggested on the basis of electronic, infrared, 1H and 13C NMR spectroscopy. Using thermogravimetric (TG) and differential thermal analysis (DTA) various thermodynamic and kinetic parameters viz. reaction order ( n), apparent activation energy ( Ea), apparent activation entropy ( S#) and heat of reaction (Δ H) have been calculated and correlated with the structural aspects for solid-state decomposition of complexes. The ligands and their tin complexes have also been screened for their fungitoxicity activity against Rhizoctonia solanii and Sclerotium rolfsii and their ED 50 values calculated.

Spectral and thermal studies with anti-fungal aspects of some organotin(IV) complexes with nitrogen and sulphur donor ligands derived from 2-phenylethylamine.

PubMed

Singh, Rajeev; Kaushik, N K

2008-11-15

Some complexes of 2-phenylethyl dithiocarbamate, thiohydrazides and thiodiamines with dibenzyltin(IV) chloride, tribenzyltin(IV) chloride and di(para-chlorobenzyl)tin(IV) dichloride have been synthesized and investigated in 1:2 and 1:1 molar ratio. The dithiocarbamate ligand act as monoanionic bidentate and thiohydrazide, thiodiamines act as neutral bidentate ligand. The synthesized complexes have been characterized by elemental analysis and molecular weight determination studies and their bonding pattern suggested on the basis of electronic, infrared, 1H and 13C NMR spectroscopy. Using thermogravimetric (TG) and differential thermal analysis (DTA) various thermodynamic and kinetic parameters viz. reaction order (n), apparent activation energy (Ea), apparent activation entropy (S#) and heat of reaction (DeltaH) have been calculated and correlated with the structural aspects for solid-state decomposition of complexes. The ligands and their tin complexes have also been screened for their fungitoxicity activity against Rhizoctonia solanii and Sclerotium rolfsii and their ED50 values calculated.

The Copper-nicotinamide complex: sustainable applications in coupling and cycloaddition reactions

EPA Science Inventory

Crystalline copper (II)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.

An Alternative Preparation of 1-(N,N-Dimethylaminomethyl)-1′-(diphenylphosphanyl)ferrocene: Synthesis and Structural Characterization of AuI and PdII Complexes with this Hybrid Ligand

PubMed Central

Štěpnička, Petr; Zábranský, Martin; Císařová, Ivana

2012-01-01

1-(N,N-Dimethylaminomethyl)-1′-(diphenylphosphanyl)ferrocene (1) was synthesized in good yield by lithiation of 1-bromo-1′-(diphenylphosphanyl)ferrocene and subsequent reaction with Eschenmoser's salt (dimethylmethylideneammonium iodide). Making use of an easily accessible, nontoxic starting material, this procedure represents a convenient alternative to the original synthetic protocol based on stepwise lithiation/functionalization of 1,1′-bis(tributylstannyl)ferrocene and reductive amination [M. E. Wright, Organometallics 1990, 9, 853–856]. Compound 1 has typical hybrid-donor properties. When reacted with [AuCl(tht)] (tht=tetrahydrothiophene), it afforded the expected AuI phosphane complex [AuCl(1-κP)] (2). An attempted removal of the chloride ligand from 2 with AgClO4 produced an ill-defined material formulated as Au(1)ClO4. The uncoordinated amine substituent reacted with traces of hydrogen chloride formed by slow decomposition typically occurring in solution. In this manner, complexes [AuCl(Ph2PfcCH2NHMe2)]Cl (3, fc=ferrocene-1,1′-diyl) and [AuCl(Ph2PfcCH2NHMe2)]ClO4 (4) were isolated from crystallizations experiments with 2 and Au(1)ClO4, respectively. On a larger scale, complex 3 was prepared easily from 2 and hydrogen chloride. The course of reactions between [PdCl2(cod)] (cod=cycloocta-1,5-diene) and 1 were found to depend on the ligand-to-metal ratio. Whereas the reaction with two equivalents of 1 afforded bis(phosphane) complex trans-[PdCl2(1-κP)2] (5), that of a Pd:P ratio 1:1 produced ligand-bridged dimer [(μ-1)PdCl2]2 (6). With hydrogen chloride, complex 6 reacted to afford zwitterionic complex [PdCl3(1H-κP)] (7), which was also formed when ligand 1 and [PdCl2(cod)] were allowed to react slowly by liquid-phase diffusion of their chloroform solutions. The compounds were characterized by spectroscopic methods (multinuclear NMR and ESI–MS), and the molecular structures of complex 2–4, 6⋅2CHCl3 and 7⋅1.5CHCl3 were determined by single-crystal X-ray diffraction analysis. PMID:24551494

Ionic Fluorine Chemistry.

DTIC Science & Technology

SOLID ROCKET OXIDIZERS, *LIQUID ROCKET OXIDIZERS, CHLORATES, FLUORIDES, ACETONES, CHLORINE COMPOUNDS, NITROSO COMPOUNDS, *HALOGEN COMPOUNDS, ADDITION REACTIONS, CESIUM COMPOUNDS, CHLORIDES, COMPLEX COMPOUNDS

Unfolding of a ClC chloride transporter retains memory of its evolutionary history.

PubMed

Min, Duyoung; Jefferson, Robert E; Qi, Yifei; Wang, Jing Yang; Arbing, Mark A; Im, Wonpil; Bowie, James U

2018-05-01

ClC chloride channels and transporters are important for chloride homeostasis in species from bacteria to human. Mutations in ClC proteins cause genetically inherited diseases, some of which are likely to involve folding defects. The ClC proteins present a challenging and unusual biological folding problem because they are large membrane proteins possessing a complex architecture, with many reentrant helices that go only partway through membrane and loop back out. Here we were able to examine the unfolding of the Escherichia coli ClC transporter, ClC-ec1, using single-molecule forced unfolding methods. We found that the protein could be separated into two stable halves that unfolded independently. The independence of the two domains is consistent with an evolutionary model in which the two halves arose from independently folding subunits that later fused together. Maintaining smaller folding domains of lesser complexity within large membrane proteins may be an advantageous strategy to avoid misfolding traps.

Zinc complexation in chloride-rich hydrothermal fluids (25-600 °C): A thermodynamic model derived from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Mei, Yuan; Sherman, David M.; Liu, Weihua; Etschmann, Barbara; Testemale, Denis; Brugger, Joël

2015-02-01

The solubility of zinc minerals in hydrothermal fluids is enhanced by chloride complexation of Zn2+. Thermodynamic models of these complexation reactions are central to models of Zn transport and ore formation. However, existing thermodynamic models, derived from solubility measurements, are inconsistent with spectroscopic measurements of Zn speciation. Here, we used ab initio molecular dynamics simulations (with the PBE exchange-correlation functional) to predict the speciation of Zn-Cl complexes from 25 to 600 °C. We also obtained in situ XAS measurements of Zn-Cl solutions at 30-600 °C. Qualitatively, the simulations reproduced the main features derived from in situ XANES and EXAFS measurements: octahedral to tetrahedral transition with increasing temperature and salinity, stability of ZnCl42- at high chloride concentration up to ⩾500 °C, and increasing stability of the trigonal planar [ZnCl3]- complex at high temperature. Having confirmed the dominant species, we directly determined the stability constants for the Zn-Cl complexes using thermodynamic integration along constrained Zn-Cl distances in a series of MD simulations. We corrected our stability constants to infinite dilution using the b-dot model for the activity coefficients of the solute species. In order to compare the ab initio results with experiments, we need to re-model the existing solubility data using the species we identified in our MD simulations. The stability constants derived from refitting published experimental data are in reasonable agreement with those we obtained using ab initio MD simulations. Our new thermodynamic model accurately predicts the experimentally observed changes in ZnO(s) and ZnCO3(s) solubility as a function of chloride concentration from 200 (Psat) to 600 °C (2000 bar). This study demonstrates that metal speciation and geologically useful stability constants can be derived for species in hydrothermal fluids from ab initio MD simulations even at the generalized gradient approximation for exchange-correlation. We caution, however, that simulations are mostly reliable at high T where ligand exchange is fast enough to yield thermodynamic averages over the timescales of the simulations.

The speciation and transport of palladium in hydrothermal fluids: Experimental modeling and thermodynamic constraints

NASA Astrophysics Data System (ADS)

Tagirov, Boris R.; Baranova, Nina N.; Zotov, Alexandr V.; Akinfiev, Nikolay N.; Polotnyanko, Natalya A.; Shikina, Nadezhda D.; Koroleva, Lyudmila A.; Shvarov, Yuri V.; Bastrakov, Evgeniy N.

2013-09-01

The solubility of PdO(cr) was measured in NaOH (to 0.1m, mol/kg H2O) solutions at 400 °C, 1 kbar, and the solubility of Pd(cr) was determined at 400-500 °C, 1 kbar in acidic chloride solutions (to 1.5m NaCl) buffered with respect to hydrogen. The Pd electrode potential Eo(PdCl42-)/Pd for the reaction PdCl42- + 2e- = Pd(cr) + 4 Cl- was determined at 50 and 70 °C in 1m chloride solutions. These data, together with reliable literature values, were used for calculation of the standard thermodynamic properties and the formation constants for Pd-OH, Pd-Cl, and Pd-S-HS complexes within the framework of the revised Helgeson-Kirkham-Flowers model. It was found that PdCl3- and PdCl42- become the most important Pd complexes in high temperature (t > 300 °C), chloride-rich fluids, and PdCl42- predominates at m(Cl) > 0.1. The stability of Pd-Cl complexes increases sharply with increase in temperature. The near-neutral chloride-sulfide solutions (1m NaCl, <0.1m Stot) can transport Pd at ppm concentration levels at t ⩾ 600 °C, whereas decrease in temperature and increase in pH can lead to effective deposition of Pd minerals. The stability of Pd-S-HS complexes (Pd(°, Pd(HS)3- and PdS(HS)2-) decreases with increase in temperature. Therefore, the role of these complexes in hydrothermal transport of palladium is restricted to the low temperature solutions (t < 100 °C) and sulfur can be considered an efficient depositing agent for Pd. The calculated HKF Equation of State parameters were used to predict thermodynamic properties of Pd2+, Pd-OH, Pd-Cl, and Pd-S-HS complexes to 700 °C, 2 kbar. These parameters are incorporated into the FreeGs web-enabled database (http://www-b.ga.gov.au/minerals/research/methodology/geofluids/thermo/calculator/search.jsp) that can be used for geochemical application of thermodynamic data obtained in the present study.

Flow injection spectrophotometric method for chloride determination in natural waters using Hg(SCN)(2) immobilized in epoxy resin.

PubMed

Silva, Claudineia R; Vieira, Heberth J; Canaes, Larissa S; Nóbrega, Joaquim A; Fatibello-Filho, Orlando

2005-02-28

A flow injection (FI) spectrophotometric method was proposed for the determination of chloride ion in natural waters. The determination of chloride was carried out by reaction with Hg(SCN)(2) immobilized in an epoxy resin bead in a solid-phase reactor (SPR) and the thiocyanate ions released were determined spectrophotometrically at 480nm after complexing reaction with Fe(III). The analytical curve for chloride was linear in the concentration range from 5.6 x 10(-5) to 2.2 x 10(-4)moll(-1) with a detection limit of 1.4 x 10(-5)moll(-1). The relative standard deviation (R.S.D.) was 2.2% for a solution containing 2.2 x 10(-4)moll(-1) (n = 10). The simple manifold allows a routine analytical frequency of 100 determinations per hour. The main advantage of the developed method is the 400% reduction of the Hg waste solution generated when compared to conventional methods for chloride determination based on the same spectrophotometric reaction.

Aqueous chloride stress corrosion cracking of titanium: A comparison with environmental hydrogen embrittlement

NASA Technical Reports Server (NTRS)

Nelson, H. G.

1973-01-01

The physical characteristics of stress corrosion cracking of titanium in an aqueous chloride environment are compared with those of embrittlement of titanium by a gaseous hydrogen environment in an effort to help contribute to the understanding of the possible role of hydrogen in the complex stress corrosion cracking process. Based on previous studies, the two forms of embrittlement are shown to be similar at low hydrogen pressures (100 N/sqm) but dissimilar at higher hydrogen pressures. In an effort to quantify this comparison, tests were conducted in an aqueous chloride solution using the same material and test techniques as had previously been employed in a gaseous hydrogen environment. The results of these tests strongly support models based on hydrogen as the embrittling species in an aqueous chloride environment. Further, it is shown that if hydrogen is the causal species, the effective hydrogen fugacity at the surface of titanium exposed to an aqueous chloride environment is equivalent to a molecular hydrogen pressure of approximately 10 N/sqm.

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, Lane A.; Ryan, Jack L.

1999-01-01

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the 22.sup.9 Th or 2.sup.27 Ac "cow" radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium; lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture; are removed from the mixture on the chloride form anion exchange column.

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, L.A.; Ryan, J.L.

1999-03-23

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the {sup 229}Th or {sup 227}Ac ``cow`` radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium, lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture are removed from the mixture on the chloride form anion exchange column. 8 figs.

Intermetallic communication in titanium(IV) ferrocenyldiketonates.

PubMed

Dulatas, Lea T; Brown, Seth N; Ojomo, Edema; Noll, Bruce C; Cavo, Matthew J; Holt, Paul B; Wopperer, Matthew M

2009-11-16

A tetradentate bis(ferrocenyldiketonate) ligand, Fc(2)BobH(2), is prepared via Claisen condensation of acetylferrocene and 2,2'-biphenyldiacetyl chloride, and is metalated with titanium(IV) isopropoxide to give (Fc(2)Bob)Ti(O(i)Pr)(2) in good yield. The isopropoxide groups are replaced with di(4-nitrophenyl)phosphate groups on treatment with the corresponding acid, and with chlorides on treatment with trimethylsilyl chloride. Metathesis with catechol leads to the bis(o-hydroxyphenoxide) complex rather than the chelating catecholate complex. Hydrolysis selectively gives the mu-oxo trimer (Delta,Delta,Delta)/(Lambda,Lambda,Lambda)-{(Fc(2)Bob)Ti(mu-O)}(3). The solid-state structures of the mu-oxo trimer and the bis(o-hydroxyphenoxide) complex show that the ferrocene substituents are oriented proximal to the biphenyl backbone rather than pointed out toward the exogenous groups. The complexes show dramatic changes in color depending on the bound anions, ranging from the red isopropoxide (lambda(max) = 489 nm) to the green bis(di(4-nitrophenyl)phosphate) (lambda(max) = 653 nm). The oxidation potentials of the ferrocenes show modest shifts based on the titanium environment, but the redox potentials of the two ferrocenes are never separated by more than 60 mV. These results and those of density-functional theory (DFT) calculations indicate that the titanium interacts principally with the lowest unoccupied molecular orbital (LUMO) of the ferrocenyldiketonate and very little with its highest occupied molecular orbital (HOMO).

Targeting antioxidant pathways with ferrocenylated N-heterocyclic carbene supported gold(i) complexes in A549 lung cancer cells† †Electronic supplementary information (ESI) available. CCDC 1419940 and 1419941. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03519h

PubMed Central

McCall, R.; Sidoran, K. J.; Magda, D.; Mitchell, N. A.; Bielawski, C. W.; Lynch, V. M.; Sessler, J. L.

2016-01-01

Ferrocene containing N-heterocyclic carbene (NHC) ligated gold(i) complexes of the type [Au(NHC)2]+ were prepared and found to be capable of regulating the formation of reactive oxygen species (ROS) via multiple mechanisms. Single crystal X-ray analysis of bis(1-(ferrocenylmethyl)-3-mesitylimidazol-2-ylidene)-gold(i) chloride (5) and bis(1,3-di(ferrocenylmethyl)imidazol-2-ylidene)-gold(i) chloride (6) revealed a quasi-linear geometry around the gold(i) centers (i.e., the C–Au–C bond angle were measured to be ∼177° and all the Au–Ccarbene bonds distances were in the range of 2.00 (7)–2.03 (1) Å). A series of cell studies indicated that cell proliferation inhibition and ROS generation were directly proportional to the amount of ferrocene contained within the [Au(NHC)2]+ complexes (IC50 of 6 < 5 < bis(1-benzyl-3-mesitylimidazol-2-ylidene)-gold(i) chloride (4)). Complexes 4–6 were also confirmed to inhibit thioredoxin reductase as inferred from lipoate reduction assays and increased chelatable intracellular zinc concentrations. RNA microarray gene expression assays revealed that 6 induces endoplasmic reticulum stress response pathways as a result of ROS increase. PMID:26918111

Synthesis, spectroscopic and thermal studies of the copper(II) aspartame chloride complex

NASA Astrophysics Data System (ADS)

Çakır, S.; Coşkun, E.; Naumov, P.; Biçer, E.; Bulut, İ.; İçbudak, H.; Çakır, O.

2002-08-01

Aspartame adduct of copper(II) chloride Cu(Asp) 2Cl 2·2H 2O (Asp=aspartame) is synthesized and characterized by elemental analysis, FT IR, UV/vis, ESR spectroscopies, TG, DTG, DTA measurements and molecular mechanics calculations. Aqueous solution of the green solid absorbs strongly at 774 and 367 nm. According to the FT IR spectra, the aspartame moiety coordinates to the copper(II) ion via its carboxylate ends, whereas the ammonium terminal groups give rise to hydrogen bonding network with the water, the chloride ions or neighboring carboxylate groups. The results suggest tetragonally distorted octahedral environment of the copper ions.

Ecological and Taxonomic Features of Actinomycetal Complexes in Soils of the Lake Elton Basin

NASA Astrophysics Data System (ADS)

Zenova, G. M.; Dubrova, M. S.; Kuznetsova, A. I.; Gracheva, T. A.; Manucharova, N. A.; Zvyagintsev, D. G.

2016-02-01

In the sor (playa) solonchaks of chloride and sulfate-chloride salinity (the content of readily soluble salts is 0.9-1.0%) in the delta of the Khara River discharging into Lake Elton, the number of mycelial actinobacteria (actinomycetes) is low ((2-3) × 103 CFU/g of soil). At a distance from the water's edge, these soils are substituted for the light chestnut ones, for which an elevated number of actinomycetes (an order of magnitude higher than in the sor solonchaks) and a wider generic spectrum are characteristic. The actinomycetal complex is included the Streptomyces and Micromonospora genera, whereas in the sor solonchaks around the lake, representatives of Micromonospora were not found.

Diverse reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) towards alkali metal, group 9 metal, and coinage metal precursors† †Electronic supplementary information (ESI) available: Experimental and calculation details, and crystallographic information for 2, 3, 4, 6, 8. CCDC 1038665, 1038666, 1038667, 1011534, and 1011533. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00404g Click here for additional data file. Click here for additional data file.

PubMed Central

Kong, Lingbing; Ganguly, Rakesh; Li, Yongxin

2015-01-01

The reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) 1 towards metal precursors and its coordination chemistry were comprehensively studied. While the boron center in 1 is reluctant to coordinate to the alkali metals in their trifluoromethanesulfonate salts (MOTf) (M = Li, Na, K), the unprecedented compound 2 containing two L2PhB: units linked by a cyclic Li(OTf)2Li spacer was obtained from the reaction of 1 with LiOTf. Treatment of 1 with group 9 metal complexes [MCl(COD)]2 (M = Rh, Ir) afforded the first zwitterionic rhodium(i)–boronium complex 3 and the iridium(iii)–borane complex 4, respectively. The reaction pathway may involve C–H activation followed by proton migration from the metals to the boron center, demonstrating the first example of the deprotonation of metal hydrides by a basic boron. In the reactions with coinage metals, 1 could act as a two-electron reducing agent towards the metal chlorides MCl (M = Cu, Ag, Au). Meanwhile, the reaction of 1 with gold chloride supported by a N-heterocyclic carbene (NHC) produced a heteroleptic cationic gold complex [(L2PhB)Au(NHC)]Cl (6) featuring both carbene and L2PhB: ligands on the gold atom. In contrast, an isolable gold chloride complex (L2PhB)AuCl (8) was obtained by direct complexation between 1 and triphenylphosphine-gold chloride via ligand exchange. X-ray diffraction analysis and computational studies revealed the nature of the B:→Au bonding interaction in complexes 6 and 8. Natural Population Analysis (NPA) and Natural Bond Orbital (NBO) analysis support the strong σ-donating property of the L2PhB: ligand. Moreover, preliminary studies showed that complex 8 can serve as an efficient precatalyst for the addition of X–H (X = N, O, C) to alkynes under ambient conditions, demonstrating the first application of a metal complex featuring a neutral boron-based ligand in catalysis. PMID:29308167

Reactions of guanine with methyl chloride and methyl bromide: O6-methylation versus charge transfer complex formation

NASA Astrophysics Data System (ADS)

Shukla, P. K.; Mishra, P. C.; Suhai, S.

Density functional theory (DFT) at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels was employed to study O6-methylation of guanine due to its reactions with methyl chloride and methyl bromide and to obtain explanation as to why the methyl halides cause genotoxicity and possess mutagenic and carcinogenic properties. Geometries of the various isolated species involved in the reactions, reactant complexes (RCs), and product complexes (PCs) were optimized in gas phase. Transition states connecting the reactant complexes with the product complexes were also optimized in gas phase at the same levels of theory. The reactant complexes, product complexes, and transition states were solvated in aqueous media using the polarizable continuum model (PCM) of the self-consistent reaction field theory. Zero-point energy (ZPE) correction to total energy and the corresponding thermal energy correction to enthalpy were made in each case. The reactant complexes of the keto form of guanine with methyl chloride and methyl bromide in water are appreciably more stable than the corresponding complexes involving the enol form of guanine. The nature of binding in the product complexes was found to be of the charge transfer type (O6mG+ · X-, X dbond Cl, Br). Binding of HCl, HBr, and H2O molecules to the PCs obtained with the keto form of guanine did not alter the positions of the halide anions in the PCs, and the charge transfer character of the PCs was also not modified due to this binding. Further, the complexes obtained due to the binding of HCl, HBr, and H2O molecules to the PCs had greater stability than the isolated PCs. The reaction barriers involved in the formation of PCs were found to be quite high (?50 kcal/mol). Mechanisms of genotoxicity, mutagenesis and carcinogenesis caused by the methyl halides appear to involve charge transfer-type complex formation. Thus the mechanisms of these processes involving the methyl halides appear to be quite different from those that involve the other strongly carcinogenic methylating agents.

Safety of trivalent chromium complexes: no evidence for DNA damage in human HaCaT keratinocytes.

PubMed

Hininger, Isabelle; Benaraba, Rachida; Osman, Mireille; Faure, Henri; Marie Roussel, Anne; Anderson, Richard A

2007-06-15

Several studies have demonstrated beneficial effects of supplemental trivalent Cr in subjects with reduced insulin sensitivity with no documented signs of toxicity. However, recent studies have questioned the safety of supplemental trivalent Cr complexes. The objective of this study was to evaluate the cytotoxic and genotoxic potential of the Cr(III) complexes (histidinate, picolinate, and chloride) used as nutrient supplements compared with Cr(VI) dichromate. The cytotoxic and genotoxic effects of the Cr complexes were assessed in human HaCaT keratinocytes. The concentrations of Cr required to decrease cell viability were assessed by determining the ability of a keratinocyte cell line (HaCaT) to reduce tetrazolium dye, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide. DNA damage using the Comet assay and the production of 8-hydroxy-2'-deoxyguanosine were also determined with and without hydrogen peroxide-induced stress. The LC50 for human cultured HaCaT keratinocytes was 50 microM for hexavalent sodium dichromate and more than 120-fold higher for Cr chloride (6 mM) and Cr histidinate (10 mM). For Cr picolinate at saturating concentration (120 microM) the LC50 was not attained. High Cr(III) concentrations, 250 microM Cr as Cr chloride and Cr histidinate and 120 microM Cr picolinate (highest amount soluble in the system), not only did not result in oxidative DNA damage but exhibited protective antioxidant effects when cells were exposed to hydrogen peroxide-induced oxidative stress. These data further support the low toxicity of trivalent Cr complexes used in nutrient supplements.

Photosensitized generation of singlet oxygen by rhenium(I) complex

NASA Astrophysics Data System (ADS)

Burchinov, A. N.; Kiselev, V. M.; Penni, A. A.; Khistyaeva, V. V.

2015-12-01

The photosensitized generation of singlet oxygen in solutions of rhenium(I) complex fac-[Re(bipy)(CO)3NCCH3]+OTf-, where bipy=2,2'-bipyridine, in chloride methylene and carbon tetrachloride under continuous LED irradiation in the UV and visible ranges has been investigated.

Crystal structure of cis-tetra-aqua-dichlorido-cobalt(II) sulfolane disolvate.

PubMed

Boudraa, Mhamed; Bouacida, Sofiane; Bouchareb, Hasna; Merazig, Hocine; Chtoun, El Hossain

2015-02-01

In the title compound, [CoCl2(H2O)4]·2C4H8SO2, the Co(II) cation is located on the twofold rotation axis and is coordinated by four water mol-ecules and two adjacent chloride ligands in a slightly distorted octa-hedral coordination environment. The cisoid angles are in the range 83.27 (5)-99.66 (2)°. The three transoid angles deviate significantly from the ideal linear angle. The crystal packing can be described as a linear arrangement of complex units along c formed by bifurcated O-H⋯Cl hydrogen bonds between two water mol-ecules from one complex unit towards one chloride ligand of the neighbouring complex. Two solvent mol-ecules per complex are attached to this infinite chain via O-H⋯O hydrogen bonds in which water mol-ecules act as the hydrogen-bond donor and sulfolane O atoms as the hydrogen-bond acceptor sites.

High-temperature corrosion of metals in the salt and metallic melts containing rare earths

NASA Astrophysics Data System (ADS)

Karpov, V. V.; Abramov, A. V.; Zhilyakov, A. Yu.; Belikov, S. V.; Volkovich, V. A.; Polovov, I. B.; Rebrin, O. I.

2016-09-01

A complex of independent methods was employed to study the corrosion resistance of molybdenum, zirconium, tantalum and tungsten in chloride, chloride-fluoride and fluoride-oxide melts based on LiCl, CaCl2, NaCl- KCl, LiF, and containing rare earths. Tests were conducted for 30 h at 750-1050 °C. The metals showed excellent corrosion resistance in fused chlorides (the corrosion rates were below 0.0005 g/(m2 h). Despite the presence of chemically active fluoride ions in the chloride-fluoride melts, the metals studied also showed very low corrosion rates, except molybdenum, for which the rate of corrosion was 0,8 g/(m2 h). The corrosion resistance of tantalum was considerably reduced in the fluoride-oxide melts; the corrosion rate was over 1 g/(m2 h) corresponding to the 8-th grade of stability and placing tantalum to the group of "low stability" materials.

Interactions of chloride and formate at the donor and the acceptor side of photosystem II.

PubMed

Jajoo, Anjana; Bharti, Sudhakar; Kawamori, Asako

2005-02-01

Chloride is required for the maximum activity of the oxygen evolving complex (OEC) while formate inhibits the function of OEC. On the basis of the measurements of oxygen evolution rates and the S(2) state multiline EPR signal, an interaction between the action of chloride and formate at the donor side of PS II has been suggested. Moreover, the Fe(2)+Q-A EPR signals were measured to investigate a common binding site of both these anions at the PS II acceptor side. Other monovalent anions like bromide, nitrate etc. could influence the effects of formate to a small extent at the donor side of PS II, but not significantly at the acceptor side of PS II. The results presented in this paper clearly suggest a competitive binding of formate and chloride at the PS II acceptor side.

[Prevention of ventricular fibrillation with the aid of protopine in animal experiments].

PubMed

Burtsev, V N; Dormidontov, E N; Saliaev, V N

1978-04-01

The anti-arrhythmic activity of protopin, quinidine and novocainamide infused intravenously as a preventive and relieving measure was studied in acute experiments on rats with calcium chloride and aconitic arrhythmia. In myocardial fibrillation induced by calcium chloride the contents in the rat heart of adrenalin, noradrenaline, dopa and dopamine were studied by spectrofluorimetry before and after the use of protopin. It was established that in the size of its minimum effective doses which arrest or prevent calcium chloride and aconitic arrhythmias in rats protopin is two to three times more potent than quinidine and novocainamide. The mechanism of the anti-arrhythmic effect of protopin in calcium chloride and aconitic arrhythmias is complex and is due to the suppression of the foci of heterotopic stimulation, decrease in excitability of the myocardial cells and normalization of the catecholamine content in the myocardium.

Experimental evidence for the participation of deep eutectic solvents in silver chloride crystal formation at low temperature

NASA Astrophysics Data System (ADS)

Bhatt, Jitkumar; Mondal, Dibyendu; Prasad, Kamalesh

2016-05-01

Deep eutectic solvents (DESs) obtained by the complexation of choline chloride (ChoCl) as hydrogen bond acceptor and hydrogen bond donors such as ethylene glycol (ChoCl-EG 1:2) and glycerol (ChoCl-Gly 1:2) were used as media for the formation of AgCl crystals. Although formation of AgCl crystals was observed in both the solvents but the rate of formation of crystals was faster in ChoCl-EG 1:2 at low temperature (4-5 °C). In the crystals, cholinium cations were found to be present with chloride ions bridged with Ag ions resulting generation of 1D network of AgCl2 anions.

Interaction of N-hydroxyurea with strong proton donors: HCl and HF

NASA Astrophysics Data System (ADS)

Sałdyka, Magdalena

2014-11-01

An infrared spectroscopic and MP2/6-311++G(2d,2p) study of strong hydrogen bonded complexes of N-hydroxyurea (NH2CONHOH) with hydrogen halides (HCl and HF) trapped in solid argon matrices is reported. 1:1 and 1:2 complexes between N-hydroxyurea and hydrogen chloride, hydrogen fluoride have been identified in the NH2CONHOH/HCl/Ar, NH2CONHOH/HF/Ar matrices, respectively; their structures were determined by comparison of the spectra with the results of calculations. In the 1:1 complexes, identified for both hydrogen halide molecules, the cyclic structure stabilized by the X-H⋯O and N-H⋯X bonds is present; for the NH2CONHOH⋯HF system another isomeric 1:1 complex is also observed. Two 1:2 complexes were identified for the N-hydroxyurea-hydrogen chloride system characterised by the Cl-H⋯O and N-H⋯Cl bonds. The results of the study evidence that N-hydroxyurea is an oxygen base in the gas-phase with the carbonyl group as the strongest proton acceptor centre in the molecule.

High-efficiency emitting materials based on phenylquinoline/carbazole-based compounds for organic light emitting diode applications

NASA Astrophysics Data System (ADS)

Jin, Sung-Ho

2009-08-01

Highly efficient light-emitting materials based on phenylquinoline-carbazole derivative has been synthesized for organic-light emitting diodes (OLEDs). The materials form high quality amorphous thin films by thermal evaporation and the energy levels can be easily adjusted by the introduction of different electron donating and electron withdrawing groups on carbazoylphenylquinoline. Non-doped deep-blue OLEDs using Et-CVz-PhQ as the emitter show bright emission (CIE coordinates, x=0.156, y=0.093) with an external quantum efficiency of 2.45 %. Furthermore, the material works as an excellent host material for BCzVBi to get high-performance OLEDs with excellent deep-blue CIE coordinates (x=0.155, y=0.157), high power efficiency (5.98 lm/W), and high external quantum efficiency (5.22 %). Cyclometalated Ir(III) μ-chloride bridged dimers were synthesized by iridium trichloride hydrate with an excess of our developed deep-blue emitter, Et-CVz-PhQ. The Ir(III) complexes were prepared by the dimers with the corresponding ancillary ligands. The chloride bridged diiridium complexes can be easily converted to mononuclear Ir(III) complexes by replacing the two bridging chlorides with bidentate monoanionic ancillary ligands. Among the various types of ancillary ligands, we firstly used picolinic acid N-oxide, including picolinic acid and acetylacetone as an ancillary ligands for Ir(III) complexes. The PhOLEDs also shows reasonably high brightness and good luminance efficiency of 20,000 cd/m2 and 12 cd/A, respectively.

Activity of phosphino palladium(II) and platinum(II) complexes against HIV-1 and Mycobacterium tuberculosis.

PubMed

Gama, Ntombenhle H; Elkhadir, Afag Y F; Gordhan, Bhavna G; Kana, Bavesh D; Darkwa, James; Meyer, Debra

2016-08-01

Treatment of human immunodeficiency virus (HIV) is currently complicated by increased prevalence of co-infection with Mycobacterium tuberculosis. The development of drug candidates that offer the simultaneous management of HIV and tuberculosis (TB) would be of great benefit in the holistic treatment of HIV/AIDS, especially in sub-Saharan Africa which has the highest global prevalence of HIV-TB coinfection. Bis(diphenylphosphino)-2-pyridylpalladium(II) chloride (1), bis(diphenylphosphino)-2-pyridylplatinum(II) chloride (2), bis(diphenylphosphino)-2-ethylpyridylpalladium(II) chloride (3) and bis(diphenylphosphino)-2-ethylpyridylplatinum(II) (4) were investigated for the inhibition of HIV-1 through interactions with the viral protease. The complexes were subsequently assessed for biological potency against Mycobacterium tuberculosis H37Rv by determining the minimal inhibitory concentration (MIC) using broth microdilution. Complex (3) showed the most significant and competitive inhibition of HIV-1 protease (p = 0.014 at 100 µM). Further studies on its in vitro effects on whole virus showed reduced viral infectivity by over 80 % at 63 µM (p < 0.05). In addition, the complex inhibited the growth of Mycobacterium tuberculosis at an MIC of 5 µM and was non-toxic to host cells at all active concentrations (assessed by tetrazolium dye and real time cell electronic sensing). In vitro evidence is provided here for the possibility of utilizing a single metal-based compound for the treatment of HIV/AIDS and TB.

Response of single bacterial cells to stress gives rise to complex history dependence at the population level

PubMed Central

Mathis, Roland; Ackermann, Martin

2016-01-01

Most bacteria live in ever-changing environments where periods of stress are common. One fundamental question is whether individual bacterial cells have an increased tolerance to stress if they recently have been exposed to lower levels of the same stressor. To address this question, we worked with the bacterium Caulobacter crescentus and asked whether exposure to a moderate concentration of sodium chloride would affect survival during later exposure to a higher concentration. We found that the effects measured at the population level depended in a surprising and complex way on the time interval between the two exposure events: The effect of the first exposure on survival of the second exposure was positive for some time intervals but negative for others. We hypothesized that the complex pattern of history dependence at the population level was a consequence of the responses of individual cells to sodium chloride that we observed: (i) exposure to moderate concentrations of sodium chloride caused delays in cell division and led to cell-cycle synchronization, and (ii) whether a bacterium would survive subsequent exposure to higher concentrations was dependent on the cell-cycle state. Using computational modeling, we demonstrated that indeed the combination of these two effects could explain the complex patterns of history dependence observed at the population level. Our insight into how the behavior of single cells scales up to processes at the population level provides a perspective on how organisms operate in dynamic environments with fluctuating stress exposure. PMID:26960998

Thermal treatment effects imposed on solid DNA cationic lipid complex with hexadecyltrimethylammonium chloride, observed by variable angle spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Nizioł, Jacek

2014-12-01

DNA cationic lipid complexes are materials of properties required for applications in organic electronics and optoelectronics. Often, their thermal stability demonstrated by thermogravimetry is cited in the literature as important issue. However, little is known about processes occurring in heated solid DNA cationic lipid complexes. In frame of this work, thin films of Deoxyribonucleic acid-hexadecyltrimethylammonium chloride (DNA-CTMA) were deposited on silicon wafers. Samples were thermally annealed, and simultaneously, their optical functions were measured by spectroscopic ellipsometry. At lower temperatures, thermal expansion coefficient of solid DNA-CTMA was negative, but at higher temperatures positive. Thermally induced modification of absorption spectrum in UV-vis was observed. It occurred at a range of temperatures higher than this of DNA denaturation in solution. The observed phenomenon was irreversible, at least in time scale of the experiment (one day).

Experimental evidence for blue-shifted hydrogen bonding in the fluoroform-hydrogen chloride complex: a matrix-isolation infrared and ab initio study.

PubMed

Gopi, R; Ramanathan, N; Sundararajan, K

2014-07-24

The 1:1 hydrogen-bonded complex of fluoroform and hydrogen chloride was studied using matrix-isolation infrared spectroscopy and ab initio computations. Using B3LYP and MP2 levels of theory with 6-311++G(d,p) and aug-cc-pVDZ basis sets, the structures of the complexes and their energies were computed. For the 1:1 CHF3-HCl complexes, ab initio computations showed two minima, one cyclic and the other acyclic. The cyclic complex was found to have C-H · · · Cl and C-F · · · H interactions, where CHF3 and HCl sub-molecules act as proton donor and proton acceptor, respectively. The second minimum corresponded to an acyclic complex stabilized only by the C-F · · · H interaction, in which CHF3 is the proton acceptor. Experimentally, we could trap the 1:1 CHF3-HCl cyclic complex in an argon matrix, where a blue-shift in the C-H stretching mode of the CHF3 sub-molecule was observed. To understand the nature of the interactions, Atoms in Molecules and Natural Bond Orbital analyses were carried out to unravel the reasons for blue-shifting of the C-H stretching frequency in these complexes.

Protonation of Different Goethite Surfaces - Unified Models for NaNO3 and NaCl Media.

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

Lutzenkirchen, Johannes; Boily, Jean F.; Gunneriusson, Lars

2008-01-01

Acid-base titration data for two goethites samples in sodium nitrate and sodium chloride media are discussed. The data are modelled based on various surface complexation models in the framework of the MUlti SIte Complexation (MUSIC) model. Various assumptions with respect to the goethite morphology are considered in determining the site density of the surface functional groups. The results from the various model applications are not statistically significant in terms of goodness of fit. More importantly, various published assumptions with respect to the goethite morphology (i.e. the contributions of different crystal planes and their repercussions on the “overall” site densities ofmore » the various surface functional groups) do not significantly affect the final model parameters. The simultaneous fit of the chloride and nitrate data results in electrolyte binding constants, which are applicable over a wide range of electrolyte concentrations including mixtures of chloride and nitrate. Model parameters for the high surface area goethite sample are in excellent agreement with parameters that were independently obtained by another group on different goethite titration data sets.« less

DNA interaction studies of new nano metal based anticancer agent: validation by spectroscopic methods

NASA Astrophysics Data System (ADS)

Tabassum, Sartaj; Sharma, Girish Chandra; Arjmand, Farukh; Azam, Ameer

2010-05-01

A new nano dimensional heterobimetallic Cu-Sn containing complex as a potential drug candidate was designed, synthesized and characterized by analytical and spectral methods. The electronic absorption and electron paramagnetic resonance parameters of the complex revealed that the Cu(II) ion exhibits a square pyramidal geometry with the two pyrazole nitrogen atoms, the amine nitrogen atom and the carboxylate oxygen of the phenyl glycine chloride ligand located at the equatorial sites and the coordinated chloride ion occupying an apical position. 119Sn NMR spectral data showed a hexa-coordinated environment around the Sn(IV) metal ion. TEM, AFM and XRD measurements illustrate that the complex could induce the condensation of CT-DNA to a particulate nanostructure. The interaction of the Cu-Sn complex with CT-DNA was investigated by UV-vis absorption and emission spectroscopy, as well as cyclic voltammetric measurements. The results indicated that the complex interacts with DNA through an electrostatic mode of binding with an intrinsic binding constant Kb = 8.42 × 104 M - 1. The Cu-Sn complex exhibits effective cleavage of pBR322 plasmid DNA by an oxidative cleavage mechanism, monitored at different concentrations both in the absence and in the presence of reducing agents.

DEVELOPMENT OF IMPROVED TITANIUM ORGANIC COMPOUNDS FOR USE AS HYDRAULIC FLUIDS

DTIC Science & Technology

HYDRAULIC FLUIDS, *METALORGANIC COMPOUNDS, *TITANATES, *TITANIUM COMPOUNDS, ALKYL RADICALS, CATALYSTS , CHLORIDES, COMPLEX COMPOUNDS, FLUIDS, PHOSPHORIC ACIDS, PROPYL RADICALS, VISCOSITY, ZINC COMPOUNDS

Effect of clay in controlling the non-fluorescence H-dimeric states of a cationic dye Nile Blue Chloride (NBC) in hybrid Langmuir-Blodgett (LB) film

NASA Astrophysics Data System (ADS)

Debnath, Chandan; Shil, Ashis; Hussain, S. A.; Bhattacharjee, D.

2018-01-01

Present communication reports the effect of amphiphilic matrices and nano-clay platelets on the aggregation properties of a water soluble cationic fluorescent dye Nile Blue Chloride (NBC) in Langmuir-Blodgett (LB) films. In-situ Brewster Angle Microscopic (BAM) studies showed distinct domain structures of complex and hybrid Langmuir monolayer at the air-water interface. UV-vis absorption spectra showed non-fluorescent H-dimeric band in concentrated aqueous solution of NBC and in complex LB film of NBC with stearic acid. By changing various parameters, a great control over H-dimeric states has been achieved in clay incorporated hybrid LB films. These films can act as efficient fluorescence probe.

Quantifying loading, toxic concentrations, and systemic persistence of chloride in a contemporary mixed-land-use watershed using an experimental watershed approach.

PubMed

Hubbart, J A; Kellner, E; Hooper, L W; Zeiger, S

2017-03-01

A nested-scale experimental watershed study was implemented to quantify loading and persistence of chloride in an urbanizing, mixed-land-use watershed. A Midwest USA (Missouri) watershed was partitioned into five sub-basins with contrasting dominant land use. Streamwater was tested for chloride concentration four days per week from October 2009 through May 2014 at each site. Monitoring sites included co-located gauging and climate stations recording variables at 30-minute intervals. Results indicate significant (p<0.01) differences in chloride concentrations and loading between sites. Loading consistently increased from the forested headwaters (average=507kgday -1 ) to primarily urban watershed terminus (average=7501kgday -1 ). Chloride concentrations were highest (average=83.9mgL -1 ) with the greatest frequency of acutely toxic conditions (i.e. 860mgL -1 ) mid-watershed. This finding is in-part attributable to the ratio of chloride application to streamflow volume (i.e. increasing flow volume with stream distance resulted in chloride dilution, offsetting increased percent urban land use with stream distance). Results highlight the important, yet often confounding, interactions between pollutant loading and flow dynamics. Chloride peaks occurred during late winter/early spring melting periods, implicating road salt application as the primary contributor to the chloride regime. Floodplain groundwater analysis indicated seasonal sink/source relationships between the stream and floodplain, which could contribute to chronic toxicity and persistent low Cl - concentrations in streamwater year-round. Results hold important implications for resource managers wishing to mitigate water quality and aquatic habitat degradation, and suggest important water quality limitations to stream restoration success in complex urban aquatic ecosystems. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of reinforcement mesh configuration for improvement of concrete durability

NASA Astrophysics Data System (ADS)

Pan, Chong-gen; Jin, Wei-liang; Mao, Jiang-hong; Zhang, Hua; Sun, Li-hao; Wei, Dong

2017-10-01

Steel bar in concrete structures under harsh environmental conditions, such as chlorine corrosion, seriously affects its service life. Bidirectional electromigration rehabilitation (BIEM) is a new method of repair technology for reinforced concrete structures in such chloride corrosion environments. By applying the BIEM, chloride ions can be removed from the concrete and the migrating corrosion inhibit can be moved to the steel surface. In conventional engineering, the concrete structure is often configured with a multi-layer steel mesh. However, the effect of the BIEM in such structures has not yet been investigated. In this paper, the relevant simulation test is carried out to study the migration law of chloride ions and the migrating corrosion inhibitor in a concrete specimen with complex steel mesh under different energizing modes. The results show that the efficiency of the BIEM increases 50% in both the monolayer steel mesh and the double-layer steel mesh. By using the single-sided BIEM, 87% of the chloride ions are removed from the steel surface. The different step modes can affect the chloride ion removal. The chloride ions within the range of the reinforcement protective cover are easier to be removed than those in the concrete between the two layers of steel mesh. However, the amount of migrating corrosion inhibitor is larger in the latter circumstances.

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

Kleinlein, Claudia; Zheng, Shao-Liang; Betley, Theodore A.

Three ferric dipyrromethene complexes featuring different ancillary ligands were synthesized by one electron oxidation of ferrous precursors. Four-coordinate iron complexes of the type ( ArL)FeX 2 [ ArL = 1,9-(2,4,6-Ph 3C 6H 2) 2-5-mesityldipyrromethene] with X = Cl or tBuO were prepared and found to be high-spin (S = 5/2), as determined by superconducting quantum interference device magnetometry, electron paramagnetic resonance, and 57Fe Mössbauer spectroscopy. The ancillary ligand substitution was found to affect both ground state and excited properties of the ferric complexes examined. While each ferric complex displays reversible reduction and oxidation events, each alkoxide for chloride substitution resultsmore » in a nearly 600 mV cathodic shift of the Fe III/II couple. The oxidation event remains largely unaffected by the ancillary ligand substitution and is likely dipyrrin-centered. While the alkoxide substituted ferric species largely retain the color of their ferrous precursors, characteristic of dipyrrin-based ligand-to-ligand charge transfer (LLCT), the dichloride ferric complex loses the prominent dipyrrin chromophore, taking on a deep green color. Time-dependent density functional theory analyses indicate the weaker-field chloride ligands allow substantial configuration mixing of ligand-to-metal charge transfer into the LLCT bands, giving rise to the color changes observed. Furthermore, the higher degree of covalency between the alkoxide ferric centers is manifest in the observed reactivity. Delocalization of spin density onto the tert-butoxide ligand in ( ArL)FeCl(O tBu) is evidenced by hydrogen atom abstraction to yield ( ArL)FeCl and HOtBu in the presence of substrates containing weak C–H bonds, whereas the chloride ( ArL)FeCl 2 analogue does not react under these conditions.« less

Complexes of metal chlorides with proton donors — promising polyfunctional catalysts for electrophilic processes

NASA Astrophysics Data System (ADS)

Minsker, Karl S.; Ivanova, S. R.; Biglova, Raisa Z.

1995-05-01

The Bronsted acids formed as a result of the interaction of aluminium chlorides with Group I and II metal chlorides in the presence of proton-donating compounds are promising polyfunctional catalysts for electrophilic processes (polymerisation, depolymerisation and degradation of macromolecules, alkylation, desulfurisation, and hydrogenation). The factor determing the electrophilic activity and selectivity of the action of the catalysts is their acidity. This makes it possible to predict the direction of the changes in the activity and selectivity of the catalyst in specific chemical processes in conformity with the opposite variation rule: with increase in the acidity of the electrophilic catalyst, their activity increases but the selectivity of their action diminishes. The bibliography includes 72 references.

Structure of thallium(III) chloride, bromide, and cyanide complexes in aqueous solution

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

Blixt, J.; Glaser, J.; Sandstroem, M.

1995-05-10

The structures of the hydrated thallium(III) halide and pseudohalide complexes, [TlX{sub n}(OH{sub 2}){sub m}]{sup (3-d)+}, X = Cl, Br, CN, in aqueous solution have been studied by a combination of X-ray absorption fine structure spectroscopy (XAFS), large-angle X-ray scattering (LAXS), and vibrational spectroscopic (Raman and IR) techniques including far-infrared studies of aqueous solutions and some solid phases with known structures. The vibrational Tl-X frequencies of all complexes are reported, force constants are calculated using normal coordinate analysis, and assignments are given. The structural results are consistent with octahedral six-coordination for the cationic complexes Tl(OH{sub 2}){sub 6}{sup 3$PLU}, TlX(OH{sub 2}){sub 5}{supmore » 2+}, and trans-TlX{sub 2}(OH{sub 2}){sub 4}{sup +}. The coordination geometry changes to trigonal bipyramidal for the neutral TlBr{sub 3}(OH{sub 2}){sub 2} complex and possibly also for TlCl{sub 3}(OH{sub 2}){sub 2}. The TlX{sub 4}{sup -} complexes are all tetrahedral. Higher chloride complexes, TlCl{sub 5}(OH{sub 2}){sup 2-} and TlCl{sub 6}{sup 3-}, are formed and have again octahedral coordination geometry. 65 refs., 7 figs., 5 tabs.« less

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides - II. Effects of chloride and sulfate

USGS Publications Warehouse

Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

2004-01-01

Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg]i=0.5 mM on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl- concentration ([Cl-]) range 10-5 to 10-2 M, lowering Hg surface coverages on goethite, ??-alumina, and bayerite from 0.42 to 0.07 ??mol/m2, 0.06 to 0.006 ??mol/m2, and 0.55 to 0.39 ??mol/m2 ([Cl -]=10-5 to 10-3 M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl2 complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl-] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg2Cl2 species and the precipitation of calomel, Hg 2Cl2(s). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO42-]) range 10-5 to 0.9 M, increasing Hg surface coverages on goethite, ??-alumina, and bayerite from 0.39 to 0.45 ??mol/m2, 0.11 to 0.38 ??mol/m2, and 0.36 to 3.33 ??mol/m2, respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO42-] and in the Hg-goethite-chloride system. ?? 2003 Elsevier Inc. All rights reserved.

Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

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

Wintergerst, Mr. Matthieu; Levitskaia, Tatiana G.; Moyer, Bruce A

Solvent-extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs cesium salt and receptor concentration, indicating the formation of an ionpaired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent-extraction system, with either chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride than for themore » cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.« less

Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

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

Wintergerst, Mr. Matthieu; Levitskaia, Tatiana G.; Moyer, Bruce A

Solvent extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs. cesium salt and receptor concentration, indicating the formation of an ion-paired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent extraction system, either with chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride thanmore » for the cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a very polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion-pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.« less

Collective hydration dynamics of guanidinium chloride solutions and its possible role in protein denaturation: a terahertz spectroscopic study.

PubMed

Samanta, Nirnay; Mahanta, Debasish Das; Mitra, Rajib Kumar

2014-11-14

The remarkable ability of guanidinium chloride (GdmCl) to denature proteins is a well studied yet controversial phenomenon; the exact molecular mechanism is still debatable, especially the role of hydration dynamics, which has been paid less attention. In the present contribution, we have addressed the issue of whether the collective hydrogen bond dynamics of water gets perturbed in the presence of GdmCl and its possible impact on the denaturation of a globular protein human serum albumin (HSA), using terahertz (THz) time domain spectroscopy (TTDS) in the frequency range of 0.3-2.0 THz. The collective hydrogen bond dynamics is determined by fitting the obtained complex dielectric response in a multiple Debye relaxation model. To compare the results, the studies were extended to two more salts: tetramethylguanidinium chloride (TMGdmCl) and sodium chloride (NaCl). It was concluded that the change in hydration dynamics plays a definite role in the protein denaturation process.

Highly Reactive, General and Long-Lived Catalysts for Palladium-Catalyzed Amination of Heteroaryl and Aryl Chlorides, Bromides and Iodides: Scope and Structure-Activity Relationships

PubMed Central

Shen, Qilong; Ogata, Tokutaro; Hartwig, John F.

2010-01-01

We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts for the amination of heteroaryl and aryl chlorides, bromides and iodides containing sterically hindered chelating alkylphosphines. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides and iodides occur to completion with 0.0005-0.05 mol % catalysts. A comparison of the reactivity of this catalyst for coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes. PMID:18444639

Evidence of a two-step process and pathway dependency in the thermodynamics of poly(diallyldimethylammonium chloride)/poly(sodium acrylate) complexation.

PubMed

Vitorazi, L; Ould-Moussa, N; Sekar, S; Fresnais, J; Loh, W; Chapel, J-P; Berret, J-F

2014-12-21

Recent studies have pointed out the importance of polyelectrolyte assembly in the elaboration of innovative nanomaterials. Beyond their structures, many important questions on the thermodynamics of association remain unanswered. Here, we investigate the complexation between poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium acrylate) (PANa) chains using a combination of three techniques: isothermal titration calorimetry (ITC), static and dynamic light scattering and electrophoresis. Upon addition of PDADMAC to PANa or vice-versa, the results obtained by the different techniques agree well with each other, and reveal a two-step process. The primary process is the formation of highly charged polyelectrolyte complexes of size 100 nm. The secondary process is the transition towards a coacervate phase made of rich and poor polymer droplets. The binding isotherms measured are accounted for using a phenomenological model that provides the thermodynamic parameters for each reaction. Small positive enthalpies and large positive entropies consistent with a counterion release scenario are found throughout this study. Furthermore, this work stresses the importance of the underestimated formulation pathway or mixing order in polyelectrolyte complexation.

Nanoscale supramolecular ordering in gel-surfactant complexes: Sodium alkyl sulfates in poly(diallyldimethylammonium chloride)

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

Sokolov, E.L.; Yeh, F.; Khokhlov, A.

1996-12-25

Studies of slightly cross-linked polycationic gels interacting with anionic surfactants have been performed by using random copolymers of poly(diallyldimethylammonium chloride) (PDADMACl) and polyacrylamide (PAAm) with varying content of PDADMACl and degree of cross-linking. Gel samples which had been fully swollen in water were placed in aqueous solutions of sodium alkyl sulfates (octyl(SOS), decyl-(SDCS), dodecyl (SDS), tetradecyl (STS), and hexyl (SHS) sulfates). The degree of the sample volume contraction depends on the PDADMACl content. The collapsed gel-surfactant complexes were studied using synchrotron small-angle X-ray scattering. All studied samples containing PDADMACl exhibited pronounced supramolecular nanostructures. The gel-SDCS complex exhibited a cubic structuremore » with a periodicity (7.75 nm) of approximately 4 times the surfactant molecular length, while the gel-SDS, gel-STS, and gel-SHS complexes showed hexagonal supramolecular ordering with a periodicity of approximately 2 times the surfactant molecular length. The d spacing of the longest periodicity in the complexes was dependent on the PDADMACl content and the surfactant. The d spacing generally increased with decreasing PDADMACl (charge) content and increasing number of carbon atoms in the surfactant alkyl chain. 20 refs., 11 figs., 5 tabs.« less

The "chloride theory", a unifying hypothesis for renal handling and body fluid distribution in heart failure pathophysiology.

PubMed

Kataoka, Hajime

2017-07-01

Body fluid volume regulation is a complex process involving the interaction of various afferent (sensory) and neurohumoral efferent (effector) mechanisms. Historically, most studies focused on the body fluid dynamics in heart failure (HF) status through control of the balance of sodium, potassium, and water in the body, and maintaining arterial circulatory integrity is central to a unifying hypothesis of body fluid regulation in HF pathophysiology. The pathophysiologic background of the biochemical determinants of vascular volume in HF status, however, has not been known. I recently demonstrated that changes in vascular and red blood cell volumes are independently associated with the serum chloride concentration, but not the serum sodium concentration, during worsening HF and its recovery. Based on these observations and the established central role of chloride in the renin-angiotensin-aldosterone system, I propose a unifying hypothesis of the "chloride theory" for HF pathophysiology, which states that changes in the serum chloride concentration are the primary determinant of changes in plasma volume and the renin-angiotensin-aldosterone system under worsening HF and therapeutic resolution of worsening HF. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis, characterization and biocidal activities of heterobimetallic complexes having tin(IV) as a padlock

NASA Astrophysics Data System (ADS)

Husain, Ahmad; Nami, Shahab A. A.; Siddiqi, K. S.

2010-04-01

A mononuclear precursor complex, [(CH 3) 2Sn(tpdtc)] and several of its heterobimetallic derivatives of the type, [(CH 3) 2Sn(tpdtc)]MCl 2 have been synthesized by the simple addition reaction of transition metal chlorides, MCl 2· nH 2O where tpdtc = tetraethylenepentamine bis(dithiocarbamate) anion, M = Fe(II), Co(II), Ni(II), Cu(II) and Zn(II). The synthesized complexes have been systematically characterized by the physicochemical and spectroscopic techniques. A square-pyramidal geometry has been proposed for all the transition metal atoms with chloride ions occupying the axial while the three nitrogen atoms occupying the equatorial positions. A symmetrical bidentate coordination has been observed for the dithiocarbamato moiety leading to the formation of 18 member cavity. The thermal studies reveal that the mononuclear complex decomposes in three stages while its heterobimetallic analog exhibits a simple two-stage profile. The conductivity measurement data (1 mmol solution) implies a non-electrolytic behavior for all the complexes as evident by their low conductivity values obtained at room temperature. The heterobimetallic complexes have also been tested against the bacterial ( Escherichia coli and Pseudomonas aeruginosa) and antifungal strains ( Aspergillus niger and Fusarium oxysporum). All the complexes were found to be active against the test organisms and maximum activity was found for [(CH 3) 2Sn(tpdtc)]CuCl 2 complex.

Crystal structures of the psychrophilic alpha-amylase from Alteromonas haloplanctis in its native form and complexed with an inhibitor.

PubMed Central

Aghajari, N.; Feller, G.; Gerday, C.; Haser, R.

1998-01-01

Alteromonas haloplanctis is a bacterium that flourishes in Antarctic sea-water and it is considered as an extreme psychrophile. We have determined the crystal structures of the alpha-amylase (AHA) secreted by this bacterium, in its native state to 2.0 angstroms resolution as well as in complex with Tris to 1.85 angstroms resolution. The structure of AHA, which is the first experimentally determined three-dimensional structure of a psychrophilic enzyme, resembles those of other known alpha-amylases of various origins with a surprisingly greatest similarity to mammalian alpha-amylases. AHA contains a chloride ion which activates the hydrolytic cleavage of substrate alpha-1,4-glycosidic bonds. The chloride binding site is situated approximately 5 angstroms from the active site which is characterized by a triad of acid residues (Asp 174, Glu 200, Asp 264). These are all involved in firm binding of the Tris moiety. A reaction mechanism for substrate hydrolysis is proposed on the basis of the Tris inhibitor binding and the chloride activation. A trio of residues (Ser 303, His 337, Glu 19) having a striking spatial resemblance with serine-protease like catalytic triads was found approximately 22 angstroms from the active site. We found that this triad is equally present in other chloride dependent alpha-amylases, and suggest that it could be responsible for autoproteolytic events observed in solution for this cold adapted alpha-amylase. PMID:9541387

Adsorption of Rh(III) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion-exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Wang, Jinchao; Zhang, Yongjian; Guo, Zhanchen

2010-07-15

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Rh(III) ions contained in the chloride solutions obtained, thermodynamic and kinetics studies for adsorption of Rh(III) complexes from the chloride solutions on an anionic exchange resin Diaion WA21J were carried out. Rh, Pd, Pt, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The distribution coefficients (K(d)) of Rh(III) decreased with the increase in initial Rh(III) concentration or in adsorption temperature. The isothermal adsorption of Rh(III) was found to fit Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 6.39, 6.61 and 5.81 mg/g for temperatures 18, 28 and 40 degrees C, respectively. The apparent adsorption energy of Rh was about -7.6 kJ/mol and thus Rh(III) adsorption was a physical type. The experimental data obtained could be better simulated by pseudo-first-order kinetic model and the activation energy obtained was 6.54 J/mol. The adsorption rate of Rh(III) was controlled by intraparticle diffusion in most of time of adsorption process. 2010 Elsevier B.V. All rights reserved.

Analysis of function-related interactions of ATP, sodium and potassium ions with Na+- and K+-transporting ATPase studied with a thiol reagent as tool.

PubMed

Grosse, R; Eckert, K; Malur, J; Repke, K R

1978-01-01

The paper describes the interaction of ATP, Na+ and K+ with (NaK)-ATPase exploiting the inactivation by reaction with NBD-chloride as an analytical tool for the evaluation of enzyme ligandation with the various effectors. 1. The inactivation of (NaK)-ATPase by reaction with NBD-chloride showing under all conditions studied a pseudo first-order rate rests on the alkylation of thiol groups in or near catalytic centre. ATP bound to catalytic centre prevents from enzyme inactivation by NDD-chloride through protection of these thiol groups from alkylation. Na+ and K+ affect the reactivity of the thiol groups towards NBD-chloride either indirectly via influencing ATP binding or more directly via changing the conformation of catalytic centre. Proceeding from these interrelations, the interaction of the various effectors with the enzyme was analyzed. 2. The K'D-values of various nucleotides determined by our approach correspond to the values obtained by independent methods. As shown for the first time, two catalytic centres per enzyme molecule exist. They exhibit high or low affinity to both ATP and ADP apparently caused by anticooperative interaction of the half-units of the enzyme through intersubunit communication ("half-of-the-sites reactivity"). 3. In the absence of ATP, Na+ or K+ ligandation of (NaK)-ATPase produce opposite effects on the reactivity of the thiol groups of catalytic centres reflecting different changes of their conformation. This corresponds to the well-known antagonistic effect of Na+ and K+ on some partial reactions of (NaK)-ATPase. The Na+ and K+ concentrations required to change thiol reactivity are rather high, i.e. the ionophoric centres for both Na+ and K+ are not readily accessible for cation complexation in the absence of enzyme complexation with ATP. 4. Na+ being without effect on ATP binding to the enzyme also does not influence the inactivating reaction with NBD-chloride while K+ by decreasing ATP binding dramatically decreases the protective effect of ATP. The K+ affinity of the enzyme-ATP complex is by more than two orders of magnitude higher than that of free enzyme. Na+ ligandation of the K+-liganded enzyme-ATP complex reverses the effect of K+ ligandation and produces a protective effect which distinctly surpasses that of the complexation of free enzyme with ATP. Hence, the enzyme molecule carries simultaneously ionophoric centres for both Na+ and K+. 5. The findings that per enzyme molecule ionophoric centres for Na+ and K+, and two catalytic centres with anticooperative interaction coexist corroborate the corresponding basic predictions of the flip-flop concept of (NaK)-ATPase pump mechanism, and explain some peculiar kinetic features of transport and enzyme activities of (NaK)-ATPase.

N-acetylglyoxylic amide bearing a nitrophenyl group as anion receptors: NMR and X-ray investigations on anion binding and selectivity

NASA Astrophysics Data System (ADS)

Suryanti, Venty; Bhadbhade, Mohan; Black, David StC; Kumar, Naresh

2017-10-01

N-Nitrophenylglyoxylic amides 1 and 2 in presence of tetrabutylammonium cation (TBA) act as receptors for anions HSO4-, Cl-, Br- and NO3- as investigated by NMR studies. The receptors formed 1:1 host-guest complexes in solution. X-ray structure of 1 along with TBA that bind a chloride anion is reported. Molecule 1 showed the highest selectivity for HSO4- anion over others measured. X-ray structure of the bound Cl- revealed a pocket containing the anion making strong (Nsbnd H⋯Cl) and weak hydrogen bonds (Csbnd H⋯Cl) that contribute to the recognition of the chloride anion. Nsbnd H and Csbnd H hydrogen bonds resulted in a relatively strong binding for chloride ions.

The Preparation and Structural Characterization of Three Structural Types of Gallium Compounds Derived from Gallium (II) Chloride

NASA Technical Reports Server (NTRS)

Gordon, Edward M.; Hepp, Aloysius F.; Duraj. Stan A.; Habash, Tuhfeh S.; Fanwick, Phillip E.; Schupp, John D.; Eckles, William E.; Long, Shawn

1997-01-01

The three compounds Ga2Cl4(4-mepy)2 (1),[GaCl2(4-mepy)4]GaCl4x1/2(4-mepy); (2) and GaCl2(4-mepy)2(S2CNEt2); (3) (4-mepy= 4-methylpyridine) have been prepared from reactions of gallium (II) chloride in 4-methylpyridine and characterized by single-crystal X-ray analysis. Small variations in the reaction conditions for gallium(II) chloride can produce crystals with substantially different structural properties. The three compounds described here encompass a neutral gallium(II) dimer in which each gallium is four-coordinate, an ionic compound containing both anionic and cationic gallium complex ions with different coordination numbers and a neutral six-coordinate heteroleptic

Health hazards in the production and processing of some fibers, resins, and plastics in Bulgaria.

PubMed Central

Spassovski, M

1976-01-01

Results of the toxicological studies of working conditions, general and professional morbidity, and complex examinations carried out on workers engaged in the production of polyamides, polyacrylonitrile fibers, polyester fibers and poly (vinyl chloride) resin, urea-formaldehyde glue, glass fibre materials and polyurethane resins are given. An extremely high occupational hazard for workers in the production of poly (vinyl chloride) resin and porous materials from polyurethane resins and urea-formaldehyde glue has been established. Cases of vinyl chloride disease, poisoning from formaldehyde, isocyanates, and styrene were noted. Prophylactic measures were taken in Bulgaria to lessen the occupational hazard in the productions as set forth included limitation of the work day to 6 hr, free food, additional bonus and leave, and annual physical examinations of workers. PMID:1026405

Synthesis of phosphatidylcholine: an improved method without using the cadmium chloride complex of sn-glycero-3-phosphocholine.

PubMed

Ichihara, Ken'ichi; Iwasaki, Hitomi; Ueda, Kaori; Takizawa, Ryoko; Naito, Hideko; Tomosugi, Mitsuhiro

2005-10-01

An improved safe method that does not contaminate the environment with cadmium chloride, a toxic heavy metal salt, was developed for the synthesis of phosphatidylcholine (PC). PC was synthesized from sn-glycero-3-phosphocholine (GPC) and fatty acid in one step under mild conditions without the use of cadmium chloride. GPC was prepared from egg yolk PC and adsorbed by kieselguhr in a Teflon vessel. The GPC on kieselguhr was acylated with fatty acid in the presence of two reagents, dicyclohexylcarbodiimide for synthesis of fatty acid anhydride and 4-dimethylaminopyridine as an acylating catalyst, at 30 degrees C overnight. The PC thus produced was purified by silica gel column chromatography. The yield of dioleoyl PC was 90% based on the starting material, GPC.

Advanced intermediate temperature sodium copper chloride battery

NASA Astrophysics Data System (ADS)

Yang, Li-Ping; Liu, Xiao-Min; Zhang, Yi-Wei; Yang, Hui; Shen, Xiao-Dong

2014-12-01

Sodium metal chloride batteries, also called as ZEBRA batteries, possess many merits such as low cost, high energy density and high safety, but their high operation temperature (270-350 °C) may cause several issues and limit their applications. Therefore, decreasing the operation temperature is of great importance in order to broaden their usage. Using a room temperature ionic liquid (RTIL) catholyte composed of sodium chloride buffered 1-ethyl-3-methylimidazolium chloride-aluminum chloride and a dense β″-aluminates solid electrolyte film with 500 micron thickness, we report an intermediate temperature sodium copper chloride battery which can be operated at only 150 °C, therefore alleviating the corrosion issues, improving the material compatibilities and reducing the operating complexities associated with the conventional ZEBRA batteries. The RTIL presents a high ionic conductivity (0.247 S cm-1) at 150 °C and a wide electrochemical window (-2.6 to 2.18 vs. Al3+/Al). With the discharge plateau at 2.64 V toward sodium and the specific capacity of 285 mAh g-1, this intermediate temperature battery exhibits an energy density (750 mWh g-1) comparable to the conventional ZEBRA batteries (728-785 mWh g-1) and superior to commercialized Li-ion batteries (550-680 mWh g-1), making it very attractive for renewable energy integration and other grid related applications.

The enthalpies of interactions of Ca2+(aq) and C2O{4/2-} (aq) ions in complexon solutions: Competition between complexation and precipitation

NASA Astrophysics Data System (ADS)

Kustov, A. V.; Smirnova, N. L.; Berezin, B. D.; Trostin, V. N.

2010-04-01

The thermal effects of mixing of aqueous calcium chloride with sodium citrate and ethylenedi-aminetetraacetate in the absence and presence of sodium oxalate have been measured at 25°C. The thermal effects of dilution of aqueous calcium chloride solutions were determined. The thermal effects of calcium oxalate precipitation and formation of calcium complexes with citrate and ethylenediaminetetraacetate ions were calculated. The 1% solution of sodium citrate inhibited the formation of CaC2O4 (s); in a 1% solution of sodium ethylenediaminetetraacetate with [Ca2+][C2O{4/2-}] > 10-5, the endothermal formation of the [CaEdta]2- complex quickly changed to exothermal precipitation. The 3 and 5% solutions of complexons showed a pronounced inhibiting effect on the formation of urinary stones even when the concentration of calcium and oxalate ions in solution exceeded the product of solubility of CaC2O4 by four and more orders of magnitude.

Quantitative determination of some pharmaceutical piperazine derivatives through complexation with iron(III) chloride.

PubMed

Abou-Attia, F M; Issa, Y M; Abdel-Gawad, F M; Abdel-Hamid, S M

2003-08-01

A simple, accurate and sensitive spectrophotometric method has been developed for the determination of three pharmaceutical piperazine derivatives, namely ketoconazole (KC), trimetazidine hydrochloride (TMH) and piribedil (PD). This method is based on the formation of yellow orange complexes between iron(III) chloride and the investigated drugs. The optimum reaction conditions, spectral characteristics, conditional stability constants and composition of the water soluble complexes have been established. The method permits the determination of KC, TMH and PD over a concentration range 1-15, 1-12 and 1-12 microg ml(-1), respectively. Sandell sensitivity is found to be 0.016, 0.013 and 0.013 microg cm(-2) for KC, TMH and PD, respectively. The method was sensitive, simple, reproducible and accurate within +/-1.5%. The method is applicable to the assay of the three drugs under investigation in different dosage forms and the results are in good agreement with those obtained by the official methods (USP and JP).

Pyrrolidine dithiocarbamate-zinc(II) and -copper(II) complexes induce apoptosis in tumor cells by inhibiting the proteasomal activity☆

PubMed Central

Milacic, Vesna; Chen, Di; Giovagnini, Lorena; Diez, Alejandro; Fregona, Dolores; Dou, Q. Ping

2013-01-01

Zinc and copper are trace elements essential for proper folding, stabilization and catalytic activity of many metalloenzymes in living organisms. However, disturbed zinc and copper homeostasis is reported in many types of cancer. We have previously demonstrated that copper complexes induced proteasome inhibition and apoptosis in cultured human cancer cells. In the current study we hypothesized that zinc complexes could also inhibit the proteasomal chymotrypsin-like activity responsible for subsequent apoptosis induction. We first showed that zinc(II) chloride was able to inhibit the chymotrypsin-like activity of a purified 20S proteasome with an IC50 value of 13.8 μM, which was less potent than copper(II) chloride (IC50 5.3 μM). We then compared the potencies of a pyrrolidine dithiocarbamate (PyDT)-zinc(II) complex and a PyDT-copper(II) complex to inhibit cellular proteasomal activity, suppress proliferation and induce apoptosis in various human breast and prostate cancer cell lines. Consistently, zinc complex was less potent than copper complex in inhibiting the proteasome and inducing apoptosis. Additionally, zinc and copper complexes appear to use somewhat different mechanisms to kill tumor cells. Zinc complexes were able to activate calpain-, but not caspase-3-dependent pathway, while copper complexes were able to induce activation of both proteases. Furthermore, the potencies of these PyDT-metal complexes depend on the nature of metals and also on the ratio of PyDT to the metal ion within the complex, which probably affects their stability and availability for interacting with and inhibiting the proteasome in tumor cells. PMID:18501397

Morphological, spectroscopic and thermal studies of samarium chloride coordinated single crystal grown by slow evaporation method

NASA Astrophysics Data System (ADS)

Slathia, Goldy; Raina, Bindu; Gupta, Rashmi; Bamzai, K. K.

2018-05-01

The synthesis of samarium chloride coordinated single crystal was carried out at room temperature by slow evaporation method. The crystal possesses a well defined hexagonal morphology with six symmetrically equivalent growth sectors separated by growth boundaries. The theoretical morphology has been established by structural approach using Bravaise-Friedele-Donnaye-Harker (BFDH) law. Fourier transform infra red spectroscopy was carried in order to study the geometry and structure of the crystal. The detailed thermogravimetric analysis elucidates the thermal stability of the complex.

Software User’s Manual for the RAILCAR4.1 Toxic Industrial Chemical Source Characterization Program

DTIC Science & Technology

2015-04-01

average cloud area during formation as half of the final cloud area of  Dc2/4.    Since the equations for these parameters can be quite  complex , the...hydrogen chloride  propane (LPG)  chlorine  hydrogen  cyanide  sulfur dioxide  chlorine dioxide  hydrogen fluoride  sulfuric acid  cyanogen chloride

Experimental autologous immune deposit nephritis in rats associated with mercuric chloride administration.

PubMed

Kelchner, J; McIntosh, J R; Boedecker, E; Guggenheim, S; McIntosh, R M

1976-09-15

Serial administration of mercuric chloride to rats was followed by development of antibodies to tubular basement membrane and renal tubular epithelial antigen (RTE) and glomerulonephritis characterized by granular deposits of hosts IgG, C3 and RTE along the glomerular capillary walls. The glomerular fixed antibody was directed against RTE. These studies suggest that tubular injury by mercury may lead to release of RTE and autosensitization and subsequent antibody production to this antigen result in formation of and glomerular deposition of circulating immunopathogenic complexes (RTE-anti-RTE) and glomerular morphologic alterations.

Crystal structure of a mixed-ligand dinuclear Ba-Zn complex with 2-meth-oxy-ethanol having tri-phenyl-acetate and chloride bridges.

PubMed

Utko, Józef; Sobocińska, Maria; Dobrzyńska, Danuta; Lis, Tadeusz

2015-07-01

The dinuclear barium-zinc complex, μ-chlorido-1:2κ(2) Cl:Cl-chlorido-2κCl-bis-(2-meth-oxy-ethanol-1κO)bis-(2-meth-oxy-ethanol-1κ(2) O,O')bis-(μ-tri-phenyl-acetato-1:2κ(2) O:O')bariumzinc, [BaZn(C20H15O2)2Cl2(C3H8O2)4], has been synthesized by the reaction of barium tri-phenyl-acetate, anhydrous zinc chloride and 2-meth-oxy-ethanol in the presence of toluene. The barium and zinc metal cations in the dinuclear complex are linked via one chloride anion and carboxyl-ate O atoms of the tri-phenyl-acetate ligands, giving a Ba⋯Zn separation of 3.9335 (11) Å. The irregular nine-coordinate BaO8Cl coordination centres comprise eight O-atom donors, six of them from 2-meth-oxy-ethanol ligands (four from two bidentate O,O'-chelate inter-actions and two from monodentate inter-actions), two from bridging tri-phenyl-acetate ligands and one from a bridging Cl donor. The distorted tetra-hedral coordination sphere of zinc comprises two O-atom donors from the tri-phenyl-acetate ligands and two Cl donors (one bridging and one terminal). In the crystal, O-H⋯Cl, O-H⋯O and C-H⋯Cl inter-molecular inter-actions form a layered structure, lying parallel to (001).

The cystic fibrosis transmembrane recruiter the alter ego of CFTR as a multi-kinase anchor.

PubMed

Mehta, Anil

2007-11-01

This review focuses on a newly discovered interaction between protein kinases involved in cellular energetics, a process that may be disturbed in cystic fibrosis for unknown reasons. I propose a new model where kinase-mediated cellular transmission of energy provides mechanistic insight to a latent role of the cystic fibrosis transmembrane conductance regulator (CFTR). I suggest that CFTR acts as a multi-kinase recruiter to the apical epithelial membrane. My group finds that, in the cytosol, two protein kinases involved in cell energy homeostasis, nucleoside diphosphate kinase (NDPK) and AMP-activated kinase (AMPK), bind one another. Preliminary data suggest that both can also bind CFTR (function unclear). The disrupted role of this CFTR-kinase complex as 'membrane transmitter to the cell' is proposed as an alternative paradigm to the conventional ion transport mediated and CFTR/chloride-centric view of cystic fibrosis pathogenesis. Chloride remains important, but instead, chloride-induced control of the phosphohistidine content of one kinase component (NDPK, via a multi-kinase complex that also includes a third kinase, CK2; formerly casein kinase 2). I suggest that this complex provides the necessary near-equilibrium conditions needed for efficient transmission of phosphate energy to proteins controlling cellular energetics. Crucially, a new role for CFTR as a kinase controller is proposed with ionic concentration acting as a signal. The model posits a regulatory control relay for energy sensing involving a cascade of protein kinases bound to CFTR.

Mechanisms on the Impacts of Alkalinity, pH, and Chloride on Persulfate-Based Groundwater Remediation.

PubMed

Li, Wei; Orozco, Ruben; Camargos, Natalia; Liu, Haizhou

2017-04-04

Persulfate (S 2 O 8 2- )-based in situ chemical oxidation (ISCO) has gained more attention in recent years due to the generation of highly reactive and selective sulfate radical (SO 4 •- ). This study examined the effects of important groundwater chemical parameters, i.e., alkalinity, pH, and chloride on benzene degradation via heterogeneous persulfate activation by three Fe(III)- and Mn(IV)-containing aquifer minerals: ferrihydrite, goethite, and pyrolusite. A comprehensive kinetic model was established to elucidate the mechanisms of radical generation and mineral surface complexation. Results showed that an increase of alkalinity up to 10 meq/L decreased the rates of persulfate decomposition and benzene degradation, which was associated with the formation of unreactive surface carbonato complexes. An increase in pH generally accelerated persulfate decomposition due to enhanced formation of reactive surface hydroxo complexation. A change in the chloride level up to 5 mM had a negligibly effect on the reaction kinetics. Kinetics modeling also suggested that SO 4 •- was transformed to hydroxyl radical (HO • ) and carbonate radical (CO 3 •- ) at higher pHs. Furthermore, the yields of two major products of benzene oxidation, i.e., phenol and aldehyde, were positively correlated with the branching ratio of SO 4 •- reacting with benzene, but inversely correlated with that of HO • or CO 3 •- , indicating that SO 4 •- preferentially oxidized benzene via pathways involving fewer hydroxylation steps compared to HO • or CO 3 •- .

Infrared spectra of proton transfer complexes of the cycleanine alkaloid in solid state

NASA Astrophysics Data System (ADS)

Kasende, Okuma E.; de Waal, D.

2003-01-01

Proton transfer complexes obtained between the cycleanine alkaloid and hydrogen chloride, hydrogen bromide and nitric acids have been investigated by infrared spectroscopic technique between 4000 and 400 cm -1 in KBr. The vibrational perturbations brought about by proton transfer complex formation, discussed in terms of preferred site of interaction, show that the proton of the inorganic acids is transferred to cycleanine through one of its N sites.

MgCl 2 : The Key Ingredient to Improve Chloride Containing Electrolytes for Rechargeable Magnesium-Ion Batteries

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

Pan, Baofei; Huang, Jinhua; Sa, Niya

The effect of MgCl2 on a series of chloride containing magnesium electrolytes was investigated. In the presence of extra MgCl2, the electrochemical properties of Grignard reagents (RMgCl, R = Ph, Et, iPr) were significantly improved, and the advance of MgCl2 was further demonstrated in Mg-Mo6S8 rechargeable batteries with improved capacities and much smaller over-potentials. MgCl2 was then further proven to be powerful reagent to improve the performance of well-established strong Lewis acid derived magnesium electrolytes including the “all-phenyl” complex (APC) and alkoxide-based magnesium electrolytes. The results suggest that MgCl2 salt is a very important species to benefit all chloride containingmore » electrolytes for rechargeable magnesium-ion batteries.« less

Projection structure of a ClC-type chloride channel at 6.5Å resolution

NASA Astrophysics Data System (ADS)

Mindell, Joseph A.; Maduke, Merritt; Miller, Christopher; Grigorieff, Nikolaus

2001-01-01

Virtually all cells in all eukaryotic organisms express ion channels of the ClC type, the only known molecular family of chloride-ion-selective channels. The diversity of ClC channels highlights the multitude and range of functions served by gated chloride-ion conduction in biological membranes, such as controlling electrical excitability in skeletal muscle, maintaining systemic blood pressure, acidifying endosomal compartments, and regulating electrical responses of GABA (γ-aminobutyric acid)-containing interneurons in the central nervous system. Previously, we expressed and purified a prokaryotic ClC channel homologue. Here we report the formation of two-dimensional crystals of this ClC channel protein reconstituted into phospholipid bilayer membranes. Cryo-electron microscopic analysis of these crystals yields a projection structure at 6.5Å resolution, which shows off-axis water-filled pores within the dimeric channel complex.

Adsorption of Pd(II) complexes from chloride solutions obtained by leaching chlorinated spent automotive catalysts on ion exchange resin Diaion WA21J.

PubMed

Shen, Shaobo; Pan, Tonglin; Liu, Xinqiang; Yuan, Lei; Zhang, Yongjian; Wang, Jinchao; Guo, Zhanchen

2010-05-01

It was found that Rh, Pd and Pt contained in the spent ceramic automotive catalysts could be effectively extracted by dry chlorination with chlorine. In order to concentrate Pd(II) contained in the chloride solution obtained from the dry chlorination process, thermodynamic and kinetics studies for adsorption of Pd(II) complexes from the chloride solutions on anionic exchange resin Diaion WA21J were carried out. It was found that Pd, Pt, Rh, Al, Fe, Si, Zn and Pb from the chloride solution could be adsorbed on the resin. The isothermal adsorption of Pd(II) was found to fit Freundlich, Langmuir and Dubinin-Kaganer-Radushkevich models under the adsorption conditions. The adsorption of Pd(II) on the resin was favorable according to the values of 1/n and R(L) from Freundlich and Langmuir adsorption isotherms, respectively. The maximum monolayer adsorption capacities Q(max) based on Langmuir adsorption isotherms were 5.70, 4.84 and 4.05 mg/g and the corresponding value X(m) based on Dubinin-Kaganer-Radushkevich were 5.55, 4.69 and 4.01 mg/g at temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. The apparent adsorption energies (E(ad)) based on Dubinin-Kaganer-Radushkevich isotherm were -15.43, -16.22 and -23.57 kJ/mol for the temperatures 18 degrees C, 28 degrees C and 40 degrees C, respectively. Chemical adsorption was a main mechanism involved in the adsorption process. Pd(II) adsorption on the resin could be accelerated by increasing the adsorption temperature. The adsorption of Pd(II) from the chloride solution on the resin underwent pseudo-first order kinetic process and the apparent adsorption activation energy E(a) was 15.0 kJ/mol. The intra-particle diffusion was a main rate controlling step in the Pd(II) adsorption process under the adsorption conditions. Copyright 2010 Elsevier Inc. All rights reserved.

Molecular Dynamics Simulations of Adsorption of Poly(acrylic acid) and Poly(methacrylic acid) on Dodecyltrimethylammonium Chloride Micelle in Water: Effect of Charge Density.

PubMed

Sulatha, Muralidharan S; Natarajan, Upendra

2015-09-24

We have investigated the interaction of dodecyltrimethylammonium chloride (DoTA) micelle with weak polyelectrolytes, poly(acrylic acid) and poly(methacrylic acid). Anionic as well as un-ionized forms of the polyelectrolytes were studied. Polyelectrolyte-surfactant complexes were formed within 5-11 ns of the simulation time and were found to be stable. Association is driven purely by electrostatic interactions for anionic chains whereas dispersion interactions also play a dominant role in the case of un-ionized chains. Surfactant headgroup nitrogen atoms are in close contact with the carboxylic oxygens of the polyelectrolyte chain at a distance of 0.35 nm. In the complexes, the polyelectrolyte chains are adsorbed on to the hydrophilic micellar surface and do not penetrate into the hydrophobic core of the micelle. Polyacrylate chain shows higher affinity for complex formation with DoTA as compared to polymethacrylate chain. Anionic polyelectrolyte chains show higher interaction strength as compared to corresponding un-ionized chains. Anionic chains act as polymeric counterion in the complexes, resulting in the displacement of counterions (Na(+) and Cl(-)) into the bulk solution. Anionic chains show distinct shrinkage upon adsorption onto the micelle. Detailed information about the microscopic structure and binding characteristics of these complexes is in agreement with available experimental literature.

Degradation of magnesium and its alloys: dependence on the composition of the synthetic biological media.

PubMed

Mueller, Wolf-Dieter; de Mele, Monica Fernández Lorenzo; Nascimento, Maria Lucia; Zeddies, Miriam

2009-08-01

Magnesium and its alloys are highly degradable metals that are potentially useful as biomaterials, especially in orthopaedic and cardiovascular applications. However, the in vivo corrosion has proved to be too high. Because of the complexity of in vivo conditions, a careful study of the corrosion of magnesium in synthetic solutions that simulate the in vivo environment is necessary as a first approach to predict the actual in vivo situation. The aim of this work was to evaluate the influence of the electrolyte composition on the corrosion behavior of magnesium and two Mg-alloys in synthetic biological media. Pure magnesium and its alloys (AZ31 and LAE442) were employed in the experiments. Electrochemical potentiodynamic polarization curves were recorded in sodium chloride and PBS electrolytes with different chloride ion and albumin concentration. Optical and SEM observations complemented by EDX analysis were made. The results showed that magnesium corrosion is localized in chloride- and albumin-containing buffer solutions. They also showed that the chloride concentration and the presence of buffer and protein strongly affect the electrochemical behavior of magnesium and magnesium alloys.

Effect of chloride ions on the corrosion behavior of low-alloy steel containing copper and antimony in sulfuric acid solution

NASA Astrophysics Data System (ADS)

Park, Sun-Ah; Kim, Seon-Hong; Yoo, Yun-Ha; Kim, Jung-Gu

2015-05-01

The influence of the addition of HCl on the corrosion behavior of low-alloy steel containing copper and antimony was investigated using electrochemical (potentiodynamic and potentiostatic polarization tests, and electrochemical impedance spectroscopy) and weight loss tests in a 1.6M H2SO4 solution with different concentrations of hydrochloric acid (0.00, 0.08, 0.15 and 0.20 M HCl) at 60 °C. The result showed that the corrosion rate decreased with increasing HCl by the formation of protective layers. SEM, EDS and XPS examinations of the corroded surfaces after the immersion test indicated that the corrosion production layer formed in the solution containing HCl was highly comprised of metallic Cu, Cu chloride and metallic (Fe, Cu, Sb) compounds. The corrosion resistance was improved by the Cu-enriched layer, in which chloride ions are an accelerator for cupric ion reduction during copper deposition. Furthermore, cuprous and antimonious chloride species are complex salts for cuprous ions adsorbed on the surface during copper deposition.

Adduct simplification in the analysis of cyanobacterial toxins by matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Howard, Karen L; Boyer, Gregory L

2007-01-01

A novel method for simplifying adduct patterns to improve the detection and identification of peptide toxins using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry is presented. Addition of 200 microM zinc sulfate heptahydrate (ZnSO(4) . 7H(2)O) to samples prior to spotting on the target enhances detection of the protonated molecule while suppressing competing adducts. This produces a highly simplified spectrum with the potential to enhance quantitative analysis, particularly for complex samples. The resulting improvement in total signal strength and reduction in the coefficient of variation (from 31.1% to 5.2% for microcystin-LR) further enhance the potential for sensitive and accurate quantitation. Other potential additives tested, including 18-crown-6 ether, alkali metal salts (lithium chloride, sodium chloride, potassium chloride), and other transition metal salts (silver chloride, silver nitrate, copper(II) nitrate, copper(II) sulfate, zinc acetate), were unable to achieve comparable results. Application of this technique to the analysis of several microcystins, potent peptide hepatotoxins from cyanobacteria, is illustrated. Copyright (c) 2007 John Wiley & Sons, Ltd.

First-Principles Molecular Dynamics Study of a Deep Eutectic Solvent: Choline Chloride/Urea and Its Mixture with Water

DOE PAGES

Fetisov, Evgenii O.; Harwood, David B.; Kuo, I-Feng William; ...

2017-12-07

First-principles molecular dynamics simulations in the canonical ensemble at temperatures of 333 and 363 K and at the corresponding experimental densities are carried out to investigate the behavior of the 1:2 choline chloride/urea (reline) deep eutectic solvent and its equimolar mixture with water. Analysis of atom–atom radial and spatial distribution functions and of the H-bond network reveals the microheterogeneous structure of these complex liquid mixtures. In neat reline, the structure is governed by strong H-bonds of the trans- and cis-H atoms of urea to the chloride ion. In hydrous reline, water competes for the anions, and the H atoms ofmore » urea have similar propensities to bond to the chloride ions and the O atoms of urea and water. Finally, the vibrational spectra exhibit relatively broad peaks reflecting the heterogeneity of the environment. Although the 100 ps trajectories allow only for a qualitative assessment of transport properties, the simulations indicate that water is more mobile than the other species and its addition also fosters faster motion of urea.« less

Synthesis and characterization of an effective organic/inorganic hybrid green corrosion inhibitive complex based on zinc acetate/Urtica Dioica

NASA Astrophysics Data System (ADS)

Salehi, E.; Naderi, Reza; Ramezanzadeh, B.

2017-02-01

This study aims at synthesis and characterization of an effective corrosion inhibitive complex based on zinc acetate/Urtica Dioica (ZnA-U.D) for corrosion protection of mild steel in chloride solution. The chemical structure and morphology of the complex were characterized by Fourier transform infrared spectroscopy (FT-IR), UV-vis, thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The corrosion protection performance of the mild steel samples dipped in 3.5 wt.% NaCl solutions with and without ZnA-U.D extract was investigated by visual observations, open circuit potential (OCP) measurements, electrochemical impedance spectroscopy (EIS) and polarization test. Results revealed that the ZnA successfully chelated with organic inhibitive compounds (i.e Quercetin, Quinic acid, Caffeic acid, Hystamine and Serotonin) present in the U.D extract. The electrochemical measurements revealed the effective inhibition action of ZnA-U.D complex in the sodium chloride solution on the mild steel. The synergistic effect between Zn2+ and organic compounds present in the U.D extract resulted in protective film deposition on the steel surface, which was proved by SEM and XPS analyses.

Cytotoxic effects of nanosilver are highly dependent on the chloride concentration and the presence of organic compounds in the cell culture media.

PubMed

Kaiser, Jean-Pierre; Roesslein, Matthias; Diener, Liliane; Wichser, Adrian; Nowack, Bernd; Wick, Peter

2017-01-06

Nanosilver shows great promise for use in industrial, consumer or medical products because of its antimicrobial properties. However, the underlying mechanisms of the effects of silver nanoparticles on human cells are still controversial. Therefore, in the present study the influence of the chloride concentration and different serum content of culture media on the cytotoxic effects of nanosilver was systematically evaluated. Our results show that nanosilver toxicity was strongly affected by the composition of the culture media. The chloride concentration, as well as the carbon content affected the silver agglomeration and the complex formation. But also the dissolution of nanosilver and the availability of free silver ions (Ag + ) were severely affected by the compositions of the culture media. Cells, only exposed to silver particles in suspension and dissolved silver complexes, did not show any effects under all conditions. Nanosilver agglomerates and silver complexes were not very soluble. Thus, cells growing on the bottom of the culture dishes were exposed to sedimented nanosilver agglomerates and precipitated silver complexes. Locally, the concentration of silver on the cell surface was very high, much higher compared the silver concentration in the bulk solution. The cytotoxic effects of nanosilver are therefore a combination of precipitated silver complexes and organic silver compounds rather than free silver ions. Silver coatings are used in health care products due to their bacteriostatic or antibacterial properties. The assessment of the toxicity of a certain compound is mostly done using in vitro assays. Therefore, cytotoxicity studies of nanosilver using human cell cultures have to be undertaken under well controlled and understood cultivations conditions in order to improve the compatibility of different studies. Especially when eukaryotic versus prokaryotic systems are compared for the evaluation of the use of nanosilver as antibacterial coatings for implants in order to prevent bacterial colonization.

On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

USGS Publications Warehouse

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

2007-01-01

Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 ?? 0.2 to 1.7 ?? 0.3 in the 0.006m chloride solution and from 0.9 ?? 0.7 to 1.8 ?? 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500????C range. Conversely, the number of H2O ligands of Gd(H2O)??-nCln+3-n complexes decreases steadily from 8.9 ?? 0.4 to 5.8 ?? 0.7 in the 0.006m GdCl3 aqueous solution and from 9.0 ?? 0.5 to 5.3 ?? 1.0 in the 0.1m GdCl3 aqueous solution at temperatures from 25 to 500????C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH2 bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction (??? 0.005??A??/100????C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids. ?? 2006 Elsevier B.V. All rights reserved.

Cytotoxic hydrogen bridged ruthenium quinaldamide complexes showing induced cancer cell death by apoptosis.

PubMed

Lord, Rianne M; Allison, Simon J; Rafferty, Karen; Ghandhi, Laura; Pask, Christopher M; McGowan, Patrick C

2016-08-16

This report presents the first known p-cymene ruthenium quinaldamide complexes which are stabilised by a hydrogen-bridging atom, [{(p-cym)Ru(II)X(N,N)}{H(+)}{(N,N)XRu(II)(p-cym)}][PF6] (N,N = functionalised quinaldamide and X = Cl or Br). These complexes are formed by a reaction of [p-cymRu(μ-X)2]2 with a functionalised quinaldamide ligand. When filtered over NH4PF6, and under aerobic conditions the equilibrium of NH4PF6 ⇔ NH3 + HPF6 enables incorporation of HPF6 and the stabilisation of two monomeric ruthenium complexes by a bridging H(+), which are counter-balanced by a PF6 counterion. X-ray crystallographic analysis is presented for six new structures with OO distances of 2.420(4)-2.448(15) Å, which is significant for strong hydrogen bonds. Chemosensitivity studies against HCT116, A2780 and cisplatin-resistant A2780cis human cancer cells showed the ruthenium complexes with a bromide ancillary ligand to be more potent than those with a chloride ligand. The 4'-fluoro compounds show a reduction in potency for both chloride and bromide complexes against all cell lines, but an increase in selectivity towards cancer cells compared to non-cancer ARPE-19 cells, with a selectivity index >1. Mechanistic studies showed a clear correlation between IC50 values and induction of cell death by apoptosis.

The contribution of raised intraneuronal chloride to epileptic network activity.

PubMed

Alfonsa, Hannah; Merricks, Edward M; Codadu, Neela K; Cunningham, Mark O; Deisseroth, Karl; Racca, Claudia; Trevelyan, Andrew J

2015-05-20

Altered inhibitory function is an important facet of epileptic pathology. A key concept is that GABAergic activity can become excitatory if intraneuronal chloride rises. However, it has proved difficult to separate the role of raised chloride from other contributory factors in complex network phenomena, such as epileptic pathology. Therefore, we asked what patterns of activity are associated with chloride dysregulation by making novel use of Halorhodopsin to load clusters of mouse pyramidal cells artificially with Cl(-). Brief (1-10 s) activation of Halorhodopsin caused substantial positive shifts in the GABAergic reversal potential that were proportional to the charge transfer during the illumination and in adult neocortical pyramidal neurons decayed with a time constant of τ = 8.0 ± 2.8s. At the network level, these positive shifts in EGABA produced a transient rise in network excitability, with many distinctive features of epileptic foci, including high-frequency oscillations with evidence of out-of-phase firing (Ibarz et al., 2010). We show how such firing patterns can arise from quite small shifts in the mean intracellular Cl(-) level, within heterogeneous neuronal populations. Notably, however, chloride loading by itself did not trigger full ictal events, even with additional electrical stimulation to the underlying white matter. In contrast, when performed in combination with low, subepileptic levels of 4-aminopyridine, Halorhodopsin activation rapidly induced full ictal activity. These results suggest that chloride loading has at most an adjunctive role in ictogenesis. Our simulations also show how chloride loading can affect the jitter of action potential timing associated with imminent recruitment to an ictal event (Netoff and Schiff, 2002). Copyright © 2015 Alfonsa et al.

Synchrotron speciation of silver and zinc oxide nanoparticles aged in a kaolin suspension.

PubMed

Scheckel, Kirk G; Luxton, Todd P; El Badawy, Amro M; Impellitteri, Christopher A; Tolaymat, Thabet M

2010-02-15

Assessments of the environmental fate and mobility of nanoparticles must consider the behavior of nanoparticles in relevant environmental systems that may result in speciation changes over time. Environmental conditions may act on nanoparticles to change their size, shape, and surface chemistry. Changing these basic characteristics of nanoparticles may result in a final reaction product that is significantly different than the initial nanomaterial. As such, basing long-term risk and toxicity on the initial properties of a nanomaterial may lead to erroneous conclusions if nanoparticles change upon release to the environment. The influence of aging on the speciation and chemical stability of silver and zinc oxide nanoparticles in kaolin suspensions was examined in batch reactors for up to 18 months. Silver nanoparticles remained unchanged in sodium nitrate suspensions; however, silver chloride was identified with the metallic silver nanoparticles in sodium chloride suspensions and may be attributed to an in situ silver chloride surface coating. Zinc oxide nanoparticles were rapidly converted via destabilization/dissolution mechanisms to Zn(2+) inner-sphere sorption complexes within 1 day of reaction and these sorption complexes were maintained through the 12 month aging processes. Chemical and physical alteration of nanomaterials in the environment must be examined to understand fate, mobility, and toxicology.

21 CFR 178.3290 - Chromic chloride complexes.

Code of Federal Regulations, 2014 CFR

2014-04-01

... square inch of closure area. (b) The packaging container which has its closure area treated with the release agent shall have a capacity of not less than 120 grams of food per square inch of such treated...

Thailand's downstream projects proliferate

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

Not Available

1991-06-03

Thailand continues to press expansion and modernization of its downstream sector. Among recent developments: Construction of an olefins unit at Thailand's second major petrochemical complex and a worldscale aromatics unit in Thailand is threatened by rising costs. Thailand's National Petrochemical Corp (NPC) let a 9 billion yen contract to Mitsui Engineering and Shipbuilding Co. and C. Itoh and Co. for a dual fuel cogeneration power plant at its Mab Ta Phud, Rayong province, petrochemical complex. Financing is in place to flash a green light for a $530 million Belgian-Thai joint venture sponsoring a worldscale polyvinyl chloride/vinyl chloride monomer plant inmore » Thailand. Work is more than 50% complete on the $345 million second phase expansion of Thai Oil's Sri Racha refinery in Chon Buri province. Petroleum Authority of Thailand (PTT) endorsed a plan to install two more natural gas processing plants in Thailand to meet rapidly growing domestic demand for petroleum gas.« less

Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

PubMed Central

Barendt, Timothy A.; Docker, Andrew; Marques, Igor; Félix, Vítor

2016-01-01

Abstract The synthesis of the first halogen bonding [3]rotaxane host system containing a bis‐iodo triazolium‐bis‐naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo‐triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion–rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the 1H NMR anion binding results. PMID:27436297

Aqueous photochemical reactions of chloride, bromide, and iodide ions in a diode-array spectrophotometer. Autoinhibition in the photolysis of iodide ions.

PubMed

Kalmár, József; Dóka, Éva; Lente, Gábor; Fábián, István

2014-03-28

The aqueous photoreactions of three halide ions (chloride, bromide and iodide) were studied using a diode array spectrophotometer to drive and detect the process at the same time. The concentration and pH dependences of the halogen formation rates were studied in detail. The experimental data were interpreted by improving earlier models where the cage complex of a halogen atom and an electron has a central role. The triiodide ion was shown to exert a strong inhibiting effect on the reaction sequence leading to its own formation. An assumed chemical reaction between the triiodide ion and the cage complex interpreted the strong autoinhibition effect. It is shown that there is a real danger of unwanted interference from the photoreactions of halide ions when halide salts are used as supporting electrolytes in spectrophotometric experiments using a relatively high intensity UV light source.

General and mild Ni(0)-catalyzed α-arylation of ketones using aryl chlorides.

PubMed

Fernández-Salas, José A; Marelli, Enrico; Cordes, David B; Slawin, Alexandra M Z; Nolan, Steven P

2015-03-02

A general methodology for the α-arylation of ketones using a nickel catalyst has been developed. The new well-defined [Ni(IPr*)(cin)Cl] (1 c) pre-catalyst showed great efficiency for this transformation, allowing the coupling of a wide range of ketones, including acetophenone derivatives, with various functionalised aryl chlorides. This cinnamyl-based Ni-N-heterocyclic carbene (NHC) complex has demonstrated a different behaviour to previously reported NHC-Ni catalysts. Preliminary mechanistic studies suggest a Ni(0)/Ni(II) catalytic cycle to be at play. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium-catalyzed cross-coupling of aryl chlorides and triflates with sodium cyanate: A practical synthesis of unsymmetrical ureas

PubMed Central

Vinogradova, Ekaterina V.; Fors, Brett P.; Buchwald, Stephen L.

2012-01-01

An efficient method for palladium-catalyzed cross-coupling of aryl chlorides and triflates with sodium cyanate is reported. The protocol allows for the synthesis of unsymmetrical N,N'-di- and N,N,N'-trisubstituted ureas in one pot, and is tolerant of a wide range of functional groups. Insight into the mechanism of aryl isocyanate formation is gleaned through studies of the transmetallation and reductive elimination steps of the reaction, including the first demonstration of reductive elimination from an arylpalladium isocyanate complex to produce an aryl isocyanate. PMID:22716197

Rare earth gas laser

DOEpatents

Krupke, W.F.

1975-10-31

A high energy gas laser with light output in the infrared or visible region of the spectrum is described. Laser action is obtained by generating vapors of rare earth halides, particularly neodymium iodide or, to a lesser extent, neodymium bromide, and disposing the rare earth vapor medium in a resonant cavity at elevated temperatures; e.g., approximately 1200/sup 0/ to 1400/sup 0/K. A particularly preferred gaseous medium is one involving a complex of aluminum chloride and neodymium chloride, which exhibits tremendously enhanced vapor pressure compared to the rare earth halides per se, and provides comparable increases in stored energy densities.

Synthesis, and spectroscopic studies of charge transfer complex of 1,2-dimethylimidazole as an electron donor with π-acceptor 2,4-dinitro-1-naphthol in different polar solvents

NASA Astrophysics Data System (ADS)

Miyan, Lal; Khan, Ishaat M.; Ahmad, Afaq

2015-07-01

The charge transfer (CT) complex of 1,2-dimethylimidazole (DMI) as an electron donor with π acceptor 2,4-dinitro-1-naphthol (DNN) has been studied spectrophotometrically in different solvents like chloroform, acetonitrile, methanol, methylene chloride, etc. at room temperature. The CT complex which is formed through the transfer of lone pair electrons from DMI to DNN exhibits well resolved CT bands and the regions of these bands were remarkably different from those of the donor and acceptor. The stoichiometry of the CT complex was found to be 1:1 by a straight-line method between donor and acceptor with maximum absorption bands. The novel CT complex has been characterized by FTIR, TGA-DTA, powder XRD, 1H NMR and 13C NMR spectroscopic techniques. The Benesi-Hildebrand equation has been used to determine the formation constant (KCT), molar extinction coefficient (εCT), standard gibbs free energy (ΔG°) and other physical parameters of the CT complex. The formation constant recorded higher values and molar extinction coefficient recorded lower values in chloroform compared with methylene chloride, methanol and acetonitrile, confirming the strong interaction between the molecular orbital's of donor and acceptor in the ground state in less polar solvent. This CT complex has been studied by absorption spectra of donor 1,2-dimethylimidazole (DMI) and acceptor 2,4-dinitro-1-naphthol (DNN) by using the spectrophotometric technique in various solvents at room temperature.

A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

DOE PAGES

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

2016-05-23

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

Preparation and Quality Control of the [153Sm]-Samarium Maltolate Complex as a Lanthanide Mobilization Product in Rats

PubMed Central

Naseri, Zohreh; Hakimi, Amir; Jalilian, Amir R.; Nemati Kharat, Ali; Bahrami-Samani, Ali; Ghannadi-Maragheh, Mohammad

2011-01-01

Development of lanthanide detoxification agents and protocols is of great importance in management of overdoses. Due to safety of maltol as a detoxifying agent in metal overloads, it can be used as a lanthanide detoxifying agent. In order to demonstrate the biodistribution of final complex, [153Sm]-samarium maltolate was prepared using Sm-153 chloride (radiochemical purity >99.9%; ITLC and specific activity). The stability of the labeled compound was determined in the final solution up to 24h as well as the partition coefficient. Biodistribution studies of Sm-153 chloride, [153Sm]-samarium maltolate were carried out in wild-type rats comparing the critical organ uptakes. Comparative study for Sm3+ cation and the labeled compound was conducted up to 48 h, demonstrating a more rapid wash out for the labeled compound. The effective and biological half lives of 2.3 h and 2.46h were calculated for the complex. The data suggest the detoxification property of maltol formulation for lanthanide overdoses. PMID:21773065

In-situ complex with by-product HCl and release chloride ions to dissolve aramid.

PubMed

Dai, Yu; Cheng, Zheng; Yuan, Yihao; Meng, Chenbo; Qin, Jiaqiang; Liu, Xiangyang

2018-06-20

Because of the strong hydrogen-bond interaction among macromolecular chains, addition of chloride salts is generally needed to offer Cl- ions for dissolution of aromatic polyamides. In this paper, poly-(benzimidazole-terephthalamide) which complexed with by-product HCl during polymerization (PABI-HCl) was prepared and imidazole compound as cosolvent was added into dimethylacetamide (DMAc) to dissolve PABI-HCl. Due to stronger affinity to protons, imidazole compound could in-situ complex with HCl of PABI-HCl and form imidazolium hydrochloride. Then imidazolium hydrochloride would ionize and produce much free Cl- ions which acted as stronger hydrogen-bond acceptor to disrupt interaction among macromolecular chains. As a result, solubility of PABI-HCl in DMAc was improved significantly in existence of small amount of imidazole compound. Moreover, DMAc-imidazole mixture was utlized for synthesis of different kinds of aramids and no precipitation was observed with progress of the reaction. So the mixture was suitable to be utlized as solvent for polymerization of aramid. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, crystal structure and anticancer activity of tetrakis(N-isopropylimidazolidine-2-selenone)platinum(II) chloride

NASA Astrophysics Data System (ADS)

Ahmad, Saeed; Altoum, Ali Osman S.; Vančo, Ján; Křikavová, Radka; Trávníček, Zdeněk; Dvořák, Zdeněk; Altaf, Muhammad; Sohail, Manzar; Isab, Anvarhusein A.

2018-01-01

A Platinum(II) complex of N-isopropylimidazolidine-2-selenone (i-PrImSe), [Pt(i-PrImSe)4]Cl2 (1) was prepared and characterized by elemental analysis, IR and NMR (1H, 13C, 77Se &195Pt) spectroscopy, and X-ray crystallography. The structure of 1 consists of [Pt(i-PrImSe)4]2+ complex ion and chloride counter ions. The platinum(II) atom adopts a distorted square planar geometry. The in vitro antitumor activity of 1 as well as cisplatin, was evaluated by MTT assay against human; ovarian carcinoma A2780 and its cisplatin-resistant subline A2780R, prostate cancer 22Rv1 and breast cancer MCF-7 cell lines. The title complex displayed the activity against the A2780 cells (IC50 = 30.8 μM) at the level comparable to cisplatin (IC50 = 26.8 μM). The interaction studies with sulfur-containing biomolecules revealed its ability to form a variety of intermediates and oxidized species with L-cysteine and reduced glutathione.

Lipophilicity-dependent ruthenium N-heterocyclic carbene complexes as potential anticancer agents.

PubMed

Lv, Gaochao; Guo, Liubin; Qiu, Ling; Yang, Hui; Wang, Tengfei; Liu, Hong; Lin, Jianguo

2015-04-28

Five Ru(II)-N-heterocyclic carbenes (NHC) (1-5) were synthesized by reacting the appropriately substituted imidazolium chlorides with Ag2O, forming the NHC-silver chloride in situ followed by transmetalation with dimeric p-cymene ruthenium(II) dichloride. All the complexes were characterized by NMR and ESI-MS, and complex 1 was also characterized by single-crystal X-ray diffraction. The IC50 values of these five complexes were determined by the MTT-based assay on four human cancer cell lines, SKOV-3 (ovarian), PC-3 (prostate), MDA-MB-231 (breast) and EC109 (esophagus). The cytotoxicities of these complexes changed from a moderate effect to a fine one, corresponding to the increasing lipophilicity order of the complex of 2 < 1 < 3 < 4 < 5 (0.91, 0.88, 1.36, 1.85 and 2.62 for 1–5 respectively). Complex 5 showed the most cytotoxicity with the IC50 values 10.3 ± 0.3 μM for SKOV-3, 2.9 ± 0.1 μM for PC-3, 8.2 ± 0.6 μM for MDA-MB-231, 6.4 ± 0.2 μM for EC109 cell lines. Due to the superior cytotoxicity of complex 5 against the PC-3 cell lines, further biological evaluations were carried out to elucidate its action mechanism. The morphologic changes and cell cycle analysis showed that complex 5 can inhibit PC-3 cell lines by inducing cell cycle arrest at the G2/M phase. The DNA binding experiments further demonstrate that complex 5 has a better binding ability for DNA (Kb = 2.2 × 10(6) M(-1)) than complexes 1-4 (3.8 × 10(5), 7.0 × 10(5), 5.7 × 10(5), and 1.9 × 10(5) respectively).

PVC: health implications and production trends.

PubMed Central

Karstadt, M

1976-01-01

Poly(vinyl chloride) (PVC) is a complex plastic system. Individual components of the PVC system, including residual vinyl chloride monomer (RVCM) and certain additives, may pose risks of harm to human health. There have been significant reductions in the RVCM content of PVC resin since 1974, reducing the cancer risk of workers in PVC fabrication plants and consumers of PVC products. A "no-effect" level for vinyl chloride monomer (VCM)-induced carcinogenesis has not been found to date; therefore, the significance of human exposure to low levels of RVCM remains to be determined. Exposure to PVC dust may cause pulmonary dysfunctions. Pulmonary and other possible health effects of PVC dust require further study. The PVC plastics system should be characterized as to interactions among its various components and as to interactions of the components and the PVC system as a whole with biological systems. Images FIGURE 1. FIGURE 2. PMID:799961

Study to establish cost predictions for the production of Redox chemicals

NASA Technical Reports Server (NTRS)

Ammann, P. R.; Loreth, M.; Harvey, W. W.

1982-01-01

The chromium and iron chloride chemicals are significant first costs for NASA Redox energy storage systems. This study was performed to determine the lowest cost at which chromium and iron chlorides could be obtained for a complex of redox energy storage systems. In addition, since the solutions gradually become intermixed during the course of operation of Redox units, it was an objective to evaluate schemes for regeneration of the operating solutions. Three processes were evaluated for the production of chromium and iron chlorides. As a basis for the preliminary plant design and economic evaluation, it was assumed that the plant would produce about 25,000 tons of contained chromium as CrCl3 and an equivalent molar quantity of FeCl2. Preliminary plant designs, including materials and energy balances and sizing of major equipment, were prepared, and capital and operating costs were estimated.

Sulfonato-imino copper(ii) complexes: fast and general Chan-Evans-Lam coupling of amines and anilines.

PubMed

Hardouin Duparc, V; Schaper, F

2017-10-14

Sulfonato-imine copper complexes with either chloride or triflate counteranions were prepared in a one-step reaction followed by anion-exchange. They are highly active in Chan-Evans-Lam couplings under mild conditions with a variety of amines or anilines, in particular with sterically hindered substrates. No optimization of reaction conditions other than time and/or temperature is required.

Preparation of a N-Heterocyclic Carbene Nickel(II) Complex: Synthetic Experiments in Current Organic and Organometallic Chemistry

ERIC Educational Resources Information Center

Ritleng, Vincent; Brenner, Eric; Chetcuti, Michael J.

2008-01-01

A four-part experiment that leads to the synthesis of a cyclopentadienyl chloro-nickel(II) complex bearing a N-heterocyclic carbene (NHC) ligand is presented. In the first part, the preparation of 1,3-bis-(2,4,6-trimethylphenyl)imidazolium chloride (IMes[middle dot]HCl) in a one-pot procedure by reaction of 2,4,6-trimethylaniline with…

Hydrothermal fluoride and chloride complexation of indium: an EXAFS study

NASA Astrophysics Data System (ADS)

Loges, Anselm; Testemale, Denis; Huotari, Simo; Honkanen, Ari-Pekka; Potapkin, Vasily; Wagner, Thomas

2017-04-01

Indium (In) is one of the geochemically lesser studied ore metals, and the factors that control the hydrothermal transport and deposition are largely unknown. It has no ore deposits of its own and is commonly mined as a by-product of Zn ores, and there are very few minerals that contain In as an essential structural component. Recently, industrial application of In in touch screen devices has drastically increased demand, which is projected to exceed supply from the current sources in the near future. Since the most relevant In sources are hydrothermal sphalerite ores and to a lesser extent hydrothermal greisen-type deposits in evolved granitic plutons, the aqueous geochemistry of In is of particular interest for understanding its ore forming processes. As a first step towards a comprehensive model for hydrothermal In solubility and speciation, we have studied In speciation in fluoride and chloride bearing solutions at 30-400˚ C and 500 bar using X-Ray Absorption Spectroscopy (XAS) measurements. The experiments were conducted in a unique hydrothermal autoclave setup at beamline BM30B-FAME at the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. Our results show that the complexation of In changes dramatically between 30 and 400˚ C. Below ca. 200˚ C, fluoride complexes are the most stable ones, but they break down at higher temperatures. Chloride complexes on the other hand become increasingly stable with increasing temperature. This behavior has interesting consequences for natural ore forming systems. In Cl-rich systems (e.g. massive sulfide ores formed in sea floor environments), cooling can be an effective precipitating mechanism. In F-rich systems, fluoride complexation can extend In mobility to low temperatures and In will only precipitate when F is effectively removed from the fluid, e.g. by mixing with a Ca-rich fluid and precipitation of fluorite (CaF2) as is commonly observed in skarn or greisen-type deposits. Due to In complexing with both F and Cl, depending on temperature, In distribution also has great potential as a fluid chemistry/temperature indicator in a wide range of different hydrothermal ore-forming systems.

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1982

1982-01-01

Presents laboratory procedures, classroom materials/activities, and demonstrations, including: vapor pressure of liquid mixtures and Raoult's law; preparation/analysis of transition metal complexes of ethylammonium chloride; atomic structure display using a ZX81 (includes complete program listing); "pop-up" models of molecules and ions;…

A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

PubMed

Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

2013-03-01

The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

Sodium and chloride levels in rainfall, mist. streamwater and groundwater at the Plynlimon catchments, mid-Wales: inferences on hydrological and chemical controls

NASA Astrophysics Data System (ADS)

Neal, C.; Kirchner, J. W.

Variations in sodium and chloride in atmospheric inputs (rainfall and mist), stream runoff and groundwater stores are documented for the upper Severn River (Afon Hafren and Afon Hore catchments), Plynlimon, mid-Wales. The results show five salient features.

1. Sodium and chloride concentrations are highly variable and highly correlated in rainfall and mist. The sodium-chloride relationship in rainfall has a slope close to the sodium/chloride ratio in sea-water, and an intercept that is not significantly different from zero. This indicates that sea-salt is the dominant source of both sodium and chloride in rainfall, which would be expected given the maritime nature of the metrology. For mist, there is also a straight line with near-zero intercept, but with a slightly higher gradient than the sea-salt ratio, presumably due to small additional sodium inputs from other sources.
2. There is an approximate input-output balance for both sodium and chloride, with the exception of one groundwater well, in which high chemical weathering results in an anomalous high Na/Cl ratio. Thus, atmospheric deposition is the dominant source of both sodium and chloride in groundwater and streamflow.
3. The fluctuations in sodium and chloride concentrations in the streams and groundwaters are strongly damped compared to those in the rain and the mist, reflecting the storage and mixing of waters in the subsurface.
4. On all timescales, from weeks to years, sodium fluctuations are more strongly damped than chloride fluctuations in streamflow. The additional damping of sodium is consistent with ion exchange buffering of sodium in the catchment soils.
5. Sodium and chloride concentrations are linearly correlated in the streams and groundwaters, but the slope is almost universally less than the sea-salt ratio and there is a non-zero intercept. The Na/Cl ratio in streamflow and groundwater is higher than the sea-salt ratio when salinity is low and lower than the sea-salt ratio when salinity is high. This pattern of behaviour is again consistent with ion exchange buffering of sodium in the catchment soils.

Shifts of microbial community structure in soils of a photovoltaic plant observed using tag-encoded pyrosequencing of 16S rRNA.

PubMed

Wu, Shijin; Li, Yuan; Wang, Penghua; Zhong, Li; Qiu, Lequan; Chen, Jianmeng

2016-04-01

The environmental risk of fluoride and chloride pollution is pronounced in soils adjacent to solar photovoltaic sites. The elevated levels of fluoride and chloride in these soils have had significant impacts on the population size and overall biological activity of the soil microbial communities. The microbial community also plays an essential role in remediation of these soils. Questions remain as to how the fluoride and chloride contamination and subsequent remediation at these sites have impacted the population structure of the soil microbial communities. We analyzed the microbial communities in soils collected from close to a solar photovoltaic enterprise by pyrosequencing of the 16S rRNA tag. In addition, we used multivariate statistics to identity the relationships shared between sequence diversity and heterogeneity in the soil environment. The overall microbial communities were surprisingly diverse, harboring a wide variety of taxa and sharing significant correlations with different degrees of fluoride and chloride contamination. The contaminated soils harbored abundant bacteria that were probably resistant to the high acidity, high fluoride and chloride concentration, and high osmotic pressure environment. The dominant genera were Sphingomonas, Subgroup_6_norank, Clostridium sensu stricto, Nitrospira, Rhizomicrobium, and Acidithiobacillus. The results of this study provide new information regarding a previously uncharacterized ecosystem and show the value of high-throughput sequencing in the study of complex ecosystems.

Understanding the microcrystal tests of three related phenethylamines: the ortho-metallated (±)-amphetamine formed with gold(III) chloride, and the tetrachloridoaurate(III) salts of (+)-methamphetamine and (±)-ephedrine.

PubMed

Wood, Matthew R; Lalancette, Roger A

2013-04-01

The ortho-metallation product of the reaction of (±)-amphetamine with gold(III) chloride, [D,L-2-(2-aminopropyl)phenyl-κ(2)N,C(1)]dichloridogold(III), [Au(C9H12N)Cl2], and the two salts resulting from crystallization of (+)-methamphetamine with gold(III) chloride, D-methyl(1-phenylpropan-2-yl)azanium tetrachloridoaurate(III), (C10H16N)[AuCl4], and of (±)-ephedrine with gold(III) chloride, D,L-(1-hydroxy-1-phenylpropan-2-yl)(methyl)azanium tetrachloridoaurate(III), (C10H16NO)[AuCl4], have different structures. The first makes a bidentate complex directly with a dichloridogold(III) group, forming a six-membered ring structure; the second and third each form a salt with [AuCl4](-) (each has two formula units in the asymmetric unit). The organic components are all members of the same class of stimulants that are prevalent in illicit drug use. These structures are important contributions to the understanding of the microcrystal tests for these drugs that have been employed for well over 100 years.

Effect of molybdenum ion implantation of the pitting corrosion of depleted uranium - 0.75 titanium alloy. (Reannouncement with new availability information). Final report

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

Lei, K.S.; Chang, F.; Levy, M.

1993-07-01

Pitting corrosion of molybdenum-ion-implanted, depleted uranium -0 75 Ti (DU -0 75 Ti) has been studied electrochemically in acidic, neutral, and alkaline solutions containing sodium chloride, and the results have been compared to those of the unimplanted DU -0 75 Ti. The data show that Mo implantation shifts the pitting potential of DU -0 75 Ti in the noble direction in acidic and alkaline solutions. In neutral 50 ppm Cl- solution, however, there is no beneficial effect of Mo implantation. Auger analysis studies show that before exposure to the solutions, all the molybdenum is in the oxide, which is approximatelymore » l000 A thick. After electrochemical scans in the acidic and alkaline chloride solutions, most of the Mo disappears from the oxide. However, no decrease in Mo concentration is found after exposure in neutral chloride solution. It is proposed that the implanted molybdenum dissolves in the acidic and alkaline solutions and forms simple or complex molybdates that inhibit pitting corrosion. The implanted molybdenum does not dissolve in the neutral chloride solution and inhibition does not occur.« less

Biochemical indicators of nephrotoxicity in blood serum of rats treated with novel 4-thiazolidinone derivatives or their complexes with polyethylene glycol-containing nanoscale polymeric carrier

PubMed

Kоbyli nska, L I; Havrylyuk, D Ya; Mitina, N E; Zaichenko, A S; Lesyk, R B; Zіme nkovsky, B S; Stoika, R S

2016-01-01

The aim of this study was to compare the effect of new synthetic 4-thiazolidinone derivatives (potential anticancer compounds denoted as 3882, 3288 and 3833) and doxorubicin (positive control) in free form and in their complexes with synthetic polyethylene glycol-containing nanoscale polymeric carrier on the biochemical indicators of nephrotoxicity in blood serum of rats. The concentration of total protein, urea, creatinine, glucose, ions of sodium, potassium, calcium, iron and chloride was measured. It was found that after injection of the investigated compounds, the concentration of sodium cations and chloride anions in blood serum was increased compared with control (untreated animals). Doxorubicin’s injection was accompanied by a decrease in the concentration of iron cations. The concentration of total protein, urea and creatinine decreased under the influence of the studied compounds. Complexation of these аntineoplastic substances with a synthetic polymeric nanocarrier lowered the concentration of the investigated metabolites substantially compared to the effect of these compounds in free form. The normalization of concentration of total protein, urea and creatinine in blood serum of rats treated with complexes of the studied compounds with the polymeric carrier comparing with increased concentration of these indicators at the introduction of such compounds in free form was found.

Comparative study of mono- and dinuclear complexes of late 3d-metal chlorides with N,N-dimethylformamide in the gas phase.

PubMed

Duchácková, Lucie; Roithová, Jana; Milko, Petr; Zabka, Jan; Tsierkezos, Nikos; Schröder, Detlef

2011-02-07

Mono- and binuclear complexes of N,N-dimethylformamide (DMF) with chlorides of the divalent, late 3d metals M = Co, Ni, Cu, and Zn are investigated by means of electrospray ionization (ESI). Specifically, ESI leads to monocations of the type [(DMF)(n)MCl](+) and [(DMF)(n)M(2)Cl(3)](+), of which the species with n = 2 and 3 were selected for in-depth studies. The latter include collision-induced dissociation experiments, gas-phase infrared spectroscopy, and calculations using density functional theory. The mononuclear complexes [(DMF)(n)MCl](+) almost exclusively lose neutral DMF upon collisional activation with the notable exception of the copper complex, for which also a reduction from Cu(II) to Cu(I) concomitant with the release of atomic chlorine is observed. For the dinuclear clusters, there exists a competition between loss of a DMF ligand and cluster degradation via loss of neutral MCl(2) with decreasing cluster stability from cobalt to zinc. For the specific case of [(DMF)(n)ZnCl](+) and [(DMF)(n)Zn(2)Cl(3)](+), ion-mobility mass spectrometry indicates the existence of two isomeric cluster ions in the case of [(DMF)(2)Zn(2)Cl(3)](+) which corroborates parallel theoretical predictions.

Iron Pentapyridyl Complexes as Molecular Water Oxidation Catalysts: Strong Influence of a Chloride Ligand and pH in Altering the Mechanism.

PubMed

Das, Biswanath; Orthaber, Andreas; Ott, Sascha; Thapper, Anders

2016-05-23

The development of molecular water oxidation catalysts based on earth-abundant, non-noble metals is essential for artificial photosynthesis research. Iron, which is the most abundant transition metal in the earth's crust, is a prospective candidate for this purpose. Herein, we report two iron complexes based on the polypyridyl ligand Py5OH (Py5OH=pyridine-2,6-diylbis [di(pyridin-2-yl)methanol]) that can catalyse water oxidation to produce O2 in Ru(III) -induced (at pH 8, highest turnover number (TON)=26.5; turnover frequency (TOF)=2.2 s(-1) ), Ce(IV) -induced (at pH≈1.5 highest TON=16; TOF=0.75 s(-1) ) and photo-induced (at pH 8, highest TON=43.5; TOF=0.6 s(-1) ) reactions. A chloride ligand in one of the iron complexes is shown to affect the activity strongly, improve stability and, thereby, the performance at pH 8 but it inhibits oxygen evolution at pH≈1.5. The observations are consistent with a change in mechanism for catalytic water oxidation with the Fe(Py5OH) complexes between acidic (Ce(IV) ) and near-neutral pH (Ru(III) ). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cooperativity and complexity in the binding of anions and cations to a tetratopic ion-pair host.

PubMed

Howe, Ethan N W; Bhadbhade, Mohan; Thordarson, Pall

2014-05-21

Cooperative interactions play a very important role in both natural and synthetic supramolecular systems. We report here on the cooperative binding properties of a tetratopic ion-pair host 1. This host combines two isophthalamide anion recognition sites with two unusual "half-crown/two carbonyl" cation recognition sites as revealed by the combination of single-crystal X-ray analysis of the free host and the 1:2 host:calcium cation complex, together with two-dimensional NMR and computational studies. By systematically comparing all of the binding data to several possible binding models and focusing on four different variants of the 1:2 binding model, it was in most cases possible to quantify these complex cooperative interactions. The data showed strong negative cooperativity (α = 0.01-0.05) of 1 toward chloride and acetate anions, while for cations the results were more variable. Interestingly, in the competitive (CDCl3/CD3OD (9:1, v/v)) solvent, the addition of calcium cations to the tetratopic ion-pair host 1 allosterically switched "on" chloride binding that is otherwise not present in this solvent system. The insight into the complexity of cooperative interactions revealed in this study of the tetratopic ion-pair host 1 can be used to design better cooperative supramolecular systems for information transfer and catalysis.

Novelmetal-organic photocatalysts: Synthesis, characterization and decomposition of organic dyes

NASA Astrophysics Data System (ADS)

Gopal Reddy, N. B.; Murali Krishna, P.; Kottam, Nagaraju

2015-02-01

An efficient method for the photocatalytic degradation of methylene blue in an aqueous medium was developed using metal-organic complexes. Two novel complexes were synthesized using, Schiff base ligand, N‧-[(E)-(4-ethylphenyl)methylidene]-4-hydroxybenzohydrazide (HL) and Ni(II) (Complex 1)/Co(II) (Complex 2) chloride respectively. These complexes were characterized using microanalysis, various spectral techniques. Spectral studies reveal that the complexes exhibit square planar geometry with ligand coordination through azomethine nitrogen and enolic oxygen. The effects of catalyst dosage, irradiation time and aqueous pH on the photocatalytic activity were studied systematically. The photocatalytic activity was found to be more efficient in the presence of Ni(II) complexes than the Co(II) complex. Possible mechanistic aspects were discussed.

Regeneration of anion exchange resins by catalyzed electrochemical reduction

DOEpatents

Gu, Baohua; Brown, Gilbert M.

2002-01-01

Anion exchange resins sorbed with perchlorate may be regenerated by a combination of chemical reduction of perchlorate to chloride using a reducing agent and an electrochemical reduction of the oxidized reducing agent. Transitional metals including Ti, Re, and V are preferred chemical reagents for the reduction of perchlorate to chloride. Complexing agents such as oxalate are used to prevent the precipitation of the oxidized Ti(IV) species, and ethyl alcohol may be added to accelerate the reduction kinetics of perchlorate. The regeneration may be performed by continuously recycling the regenerating solution through the resin bed and an electrochemical cell so that the secondary waste generation is minimized.

Presence of chemical additives and microbial inhibition capacity in grapefruit seed extracts used in apiculture.

PubMed

Spinosi, Valerio; Semprini, Primula; Langella, Vincenzo; Scortichini, Giampiero; Calvarese, Silvano

2007-01-01

American foulbrood, caused by Paenibacillus larvae subsp. larvae (White 1906) is one of the most serious diseases of honey bees, causing beekeepers and health workers to make difficult, complex decisions and leading to the development of 'organic' treatments, such as grapefruit seed extract, with minor residue problems in the end product. This study evaluates the chemical composition of grapefruit seed extracts using gas chromatography/mass spectrometry for the detection of benzethonium chloride, cetrimonium bromide and decyltrimethylammonium chloride. The results obtained suggest a close correlation between the microbial effect and the presence of chemical additives in the samples analysed.

Copper Complex in Poly(vinyl chloride) as a Nitric Oxide-Generating Catalyst for the Control of Nitrifying Bacterial Biofilms.

PubMed

Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

2015-10-14

In this study, catalytic generation of nitric oxide by a copper(II) complex embedded within a poly(vinyl chloride) matrix in the presence of nitrite (source of nitric oxide) and ascorbic acid (reducing agent) was shown to effectively control the formation and dispersion of nitrifying bacteria biofilms. Amperometric measurements indicated increased and prolonged generation of nitric oxide with the addition of the copper complex when compared to that with nitrite and ascorbic acid alone. The effectiveness of the copper complex-nitrite-ascorbic acid system for biofilm control was quantified using protein analysis, which showed enhanced biofilm suppression when the copper complex was used in comparison to that with nitrite and ascorbic acid treatment alone. Confocal laser scanning microscopy (CLSM) and LIVE/DEAD staining revealed a reduction in cell surface coverage without a loss of viability with the copper complex and up to 5 mM of nitrite and ascorbic acid, suggesting that the nitric oxide generated from the system inhibits proliferation of the cells on surfaces. Induction of nitric oxide production by the copper complex system also triggered the dispersal of pre-established biofilms. However, the addition of a high concentration of nitrite and ascorbic acid to a pre-established biofilm induced bacterial membrane damage and strongly decreased the metabolic activity of planktonic and biofilm cells, as revealed by CLSM with LIVE/DEAD staining and intracellular adenosine triphosphate measurements, respectively. This study highlights the utility of the catalytic generation of nitric oxide for the long-term suppression and removal of nitrifying bacterial biofilms.

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

Giattino, L.R.; Irwin, L.J.

Recently, reserve batteries utilizing other electrochemical systems have gained acceptance in missiles, especially for those of longer than a five-minute mission time, and in others of increasing complexity and power requirements. Recent developments at GTE have proven the feasibility of using the lithium thionyl chloride electrochemistry in these latter applications.

The unexpected discovery of the Mg(HMDS) 2 /MgCl 2 complex as a magnesium electrolyte for rechargeable magnesium batteries

DOE PAGES

Liao, Chen; Sa, Niya; Key, Baris; ...

2015-02-02

We developed a unique class of non-Grignard, aluminum-free magnesium electrolytes based on a simple mixture of magnesium compounds: magnesium hexamethyldisilazide (Mg(HMDS) 2) and magnesium chloride (MgCl 2).

Investigation of corrosion caused by constituents of refinery wastewater effluent used as circulating cooling water.

PubMed

Zhang, Zhongzhi; Song, Shaofu; Huang, Jie; Ji, Lin; Wu, Fangyun

2003-01-01

The corrosion rate of steel plate using single-factor, multifactor, and complex water systems was investigated via refinery wastewater effluents used as circulating cooling water. The results show that the primary corrosion factors of steel depend on the characteristics of the ions, the formation of the oxidized coating, the diffusion of dissolved oxygen, and other complex factors, although ions such as chloride, calcium, and carbonate play an important role. The corrosion rate of carbon steel exhibits two trends: The corrosion rate is high at low conductivity, increases to a maximum, and then decreases and becomes stable with increasing conductivity, as is the case with chloride, sulfate, nitrate and calcium ions. On the other hand, the corrosion rate is highest at low conductivity and then decreases and becomes stable with increasing conductivity, as is the case with carbonate, silicate, and sodium nitrate ions. Research results indicate that the anticorrosive ability is minimal at low conductivity; but is excellent at high conductivity. Pretreatment of low-conductivity water using air flotation and clarification to decrease the concentrations of chloride, calcium, and carbonate ions to a suitable level to satisfy the anticorrosion requirements is required. However, it is not necessary to significantly reduce the salt concentration or conductivity of the water by osmosis or ion exchange to obtain an anticorrosion effect when reusing wastewater effluents as circulating cooling water.

Highly microporous carbons derived from a complex of glutamic acid and zinc chloride for use in supercapacitors

NASA Astrophysics Data System (ADS)

Dong, Xiao-Ling; Lu, An-Hui; He, Bin; Li, Wen-Cui

2016-09-01

The selection of carbon precursor is an important factor when designing carbon materials. In this study, a complex derived from L-glutamic acid and zinc chloride was used to prepare highly microporous carbons via facile pyrolysis. L-glutamic acid, a new carbon precursor with nitrogen functionality, coordinated with zinc chloride resulted in a homogeneous distribution of Zn2+ on the molecular level. During pyrolysis, the evaporation of the in situ formed zinc species creates an abundance of micropores together with the inert gases. The obtained carbons exhibit high specific surface area (SBET: 1203 m2 g-1) and a rich nitrogen content (4.52 wt%). In excess of 89% of the pore volume consists of micropores with pore size ranging from 0.5 to 1.2 nm. These carbons have been shown to be suitable for use as supercapacitor electrodes, and have been tested in 6 M KOH where a capacitance of 217 F g-1 was achieved at a current density of 0.5 A g-1. A long cycling life of 30 000 cycles was achieved at a current density of 1 A g-1, with only a 9% loss in capacity. The leakage current through a two-electrode device was measured as 2.3 μA per mg of electrode and the self-discharge characteristics were minimal.

N-Heterocyclic Carbene Complexes in Dehalogenation Reactions

NASA Astrophysics Data System (ADS)

Mas-Marzá, Elena; Page, Michael J.; Whittlesey, Michael K.

Catalytic dehalogenation represents an underdeveloped transformation in M-NHC chemistry with a small number of reports detailing the reactivity of Co, Ru, Ni and Pd catalysts. In situ generated nickel and palladium NHC complexes catalyse the hydrodechlorination of aryl chlorides. Lower coordinate Ni complexes are proposed to operate in the hydrodefluorination of mono- and poly-fluorinated substrates. The single example of Ru-NHC catalysed hydrodefluorination of fully and partially fluorinated aromatic substrates is characterised by an unusual regioselectivity. The highly regioselective dehydrohalogenation of relatively unreactive alkyl halide substrates is achieved with a cobalt NHC catalyst.

Electronic spectra and photophysics of platinum(II) complexes with alpha-diimine ligands - Solid-state effects. I - Monomers and ligand pi dimers

NASA Technical Reports Server (NTRS)

Miskowski, Vincent M.; Houlding, Virginia H.

1989-01-01

Two types of emission behavior for Pt(II) complexes containing alpha-diimine ligands have been observed in dilute solution. If the complex also has weak field ligands such as chloride, ligand field (d-d) excited states become the lowest energy excited states. If only strong field ligands are present, a diimine 3(pi-pi/asterisk/) state becomes the lowest. In none of the cases studied did metal-to-ligand charge transfer excited state lie lowest.

Widespread legacy brine contamination from oil production reduces survival of chorus frog larvae

USGS Publications Warehouse

Hossack, Blake R.; Puglis, Holly J.; Battaglin, William A.; Anderson, Chauncey; Honeycutt, Richard; Smalling, Kelly

2017-01-01

Advances in drilling techniques have facilitated a rapid increase in hydrocarbon extraction from energy shales, including the Williston Basin in central North America. This area overlaps with the Prairie Pothole Region, a region densely populated with wetlands that provide numerous ecosystem services. Historical (legacy) disposal practices often released saline co-produced waters (brines) with high chloride concentrations, affecting wetland water quality directly or persisting in sediments. Despite the potential threat of brine contamination to aquatic habitats, there has been little research into its ecological effects. We capitalized on a gradient of legacy brine-contaminated wetlands in northeast Montana to conduct laboratory experiments to assess variation in survival of larval Boreal Chorus Frogs (Pseudacris maculata) reared on sediments from 3 local wetlands and a control source. To help provide environmental context for the experiment, we also measured chloride concentrations in 6 brine-contaminated wetlands in our study area, including the 2 contaminated sites used for sediment exposures. Survival of frog larvae during 46- and 55-day experiments differed by up to 88% among sediment sources (Site Model) and was negatively correlated with potential chloride exposure (Chloride Model). Five of the 6 contaminated wetlands exceeded the U.S. EPA acute benchmark for chloride in freshwater (860 mg/L) and all exceeded the chronic benchmark (230 mg/L). However, the Wetland Site model explained more variation in survival than the Chloride Model, suggesting that chloride concentration alone does not fully reflect the threat of contamination to aquatic species. Because the profiles of brine-contaminated sediments are complex, further surveys and experiments are needed across a broad range of conditions, especially where restoration or remediation actions have reduced brine-contamination. Information provided by this study can help quantify potential ecological threats and help land managers prioritize conservation strategies as part of responsible and sustainable energy development.

Assessment of urinary thiodiglycolic acid exposure in school-aged children in the vicinity of a petrochemical complex in central Taiwan

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

Huang, Po-Chin, E-mail: pchuang@nhri.org.tw

Background: School-aged children living in the vicinity of vinyl chloride (VCM)/polyvinyl chloride (PVC) factories may have an increased risk of exposure to hazardous air pollutants. Objectives: We aimed to evaluate the urinary thiodiglycolic acid (TDGA) level, as TDGA is a major metabolite of VCM, for students at elementary schools near a petrochemical complex in central Taiwan. Methods: We recruited 343 students from 5 elementary schools based on distance to the VCM/PVC factory. First-morning urine and blood samples were obtained from our subjects from October 2013 to September 2014. Urine samples were analyzed for urinary creatinine and TDGA using LC/MS–MS. Hepatitismore » virus infection were assessed using blood samples. We determined their vitamin consumption, resident location, parent’s employment, and other demographic or lifestyle characteristics using a questionnaire. Results: Median urinary TDGA levels for 316 students at 5 elementary schools from the closest (<.9 km) to the farthest (∼8.6 km) with respect to the petrochemical complex were 147.6, 95.5, 115.5, 86.8, and 17.3 μg/g creatinine, respectively. After adjusting for age, gender, hepatitis virus infection, vitamin B consumption, passive smoking, and home to source distance, we found that urinary TDGA levels for the closest students was significantly higher than those at other schools. Further, median urinary TDGA levels for students during school time were 4.1-fold higher than those during summer vacation. Conclusions: After adjusting for confounders, urinary TDGA levels for the school-aged children decreased with increasing distances between the elementary schools and the petrochemical complex. - Highlights: • We conducted a bio-monitoring survey of students nearby a petrochemical complex. • We measured thiodiglycolic acid (TDGA) as a biomarker of vinyl chloride monomer. • Increased urinary TDGA levels in students nearby a VCM factory was found. • Significantly lower urinary TDGA levels for students on summer vacation was found. • Spatial variation of urinary TGDA in students was found after adjustment.« less

Modeling of multiple equilibria in the self-aggregation of di-n-decyldimethylammonium chloride/octaethylene glycol monododecyl ether/cyclodextrin ternary systems.

PubMed

Leclercq, Loïc; Lubart, Quentin; Aubry, Jean-Marie; Nardello-Rataj, Véronique

2013-05-28

The surface tension equations of binary surfactant mixtures (di-n-decyldimethylammonium chloride and octaethylene glycol monododecyl ether) are established by combining the Szyszkowski equation of surfactant solutions, the ideal or nonideal mixing theory, and the phase separation model. For surfactant mixtures, the surface tension at the air-water interface is calculated using nonideal theory due to synergism between the two adsorbed surfactant types. The incorporation of cyclodextrin complexation model to the surface tension equations gives a robust model for the description of the surface tension isotherms of binary, ternary, and more complex systems involving numerous inclusion complexes. The surface tension data obtained experimentally shows excellent agreement with the theoretical model below and above the formation of micelles. The strong synergistic effect observed between the two surfactants is disrupted by the presence of CDs, leading to ideal behavior of ternary systems. Indeed, depending on the nature of the cyclodextrin (i.e., α, β, or γ), which allows a tuning of the cavity size, the binding constants with the surfactants are modified as well as the surface properties due to strong modification of equilibria involved in the ternary mixture.

Indirect spectrophotometric determination of arbutin, whitening agent through oxidation by periodate and complexation with ferric chloride

NASA Astrophysics Data System (ADS)

Barsoom, B. N.; Abdelsamad, A. M. E.; Adib, N. M.

2006-07-01

A simple and accurate spectrophotometric method for the determination of arbutin (glycosylated hydroquinone) is described. It is based on the oxidation of arbutin by periodate in presence of iodate. Excess periodate causes liberation of iodine at pH 8.0. The unreacted periodate is determined by measurement of the liberated iodine spectrophotometrically in the wavelength range (300-500 nm). A calibration curve was constructed for more accurate results and the correlation coefficient of linear regression analysis was -0.9778. The precision of this method was better than 6.17% R.S.D. ( n = 3). Regression analysis of Bear-Lambert plot shows good correlation in the concentration range 25-125 ug/ml. The identification limit was determined to be 25 ug/ml a detailed study of the reaction conditions was carried out, including effect of changing pH, time, temperature and volume of periodate. Analyzing pure and authentic samples containing arbutin tested the validity of the proposed method which has an average percent recovery of 100.86%. An alternative method is also proposed which involves a complexation reaction between arbutin and ferric chloride solution. The produced complex which is yellowish-green in color was determined spectophotometrically.

Forced-flow chromatographic determination of calcium and magnesium with continuous spectrophotometric detection

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

Arguello, M.D.

1977-12-01

Modifications to the forced-flow chromatograph include a flow-through pH monitor to continuously monitor the pH of the final effluent and an active low-pass filter to eliminate noise in the spectrophotometric detector. All separations are performed using partially sulfonated XAD-2 as the ion exchanger. Elution of calcium and magnesium is accomplished using ammonium chloride and ethylenediammonium chloride solutions. Calcium and magnesium are detected by means of Arsenazo I and PAR-ZnEDTA color-forming reagents. Other metal ions are detected by means of PAR and Chromazurol S color-forming reagents. Calcium and magnesium distribution coefficients on partially sulfonated XAD-2 as functions of ammonium chloride andmore » ethylenediammonium chloride concentration are given together with distribution coefficients of other metal ions. Methods for the selective elution of interfering metal ions prior to the elution of calcium and magnesium are described. Beryllium and aluminum are selectively eluted with sulfosalicylic acid. Those elements forming anionic chloride complexes are selectively eluted with HCl-acetone. Nickel is selectively eluted with HCl-acetone-dimethylglyoxime. Synthetic samples containing calcium and magnesium, both alone and in combination with alkali metals, strontium, barium, beryllium, aluminum, transition metals, and rare earths, are analyzed. Hard water samples are analyzed for calcium and magnesium and the results compared to those obtained by EDTA titration, atomic absorption spectroscopy, and plasma emission spectroscopy. Several clinical serum samples are analyzed for calcium and magnesium and the results compared to those obtained by atomic absorption spectroscopy.« less

Palladium-catalyzed coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates: a general method for the preparation of primary arylamines.

PubMed

Vo, Giang D; Hartwig, John F

2009-08-12

We report that the complex generated from Pd[P(o-tol)(3)](2) and the alkylbisphosphine CyPF-t-Bu is a highly active and selective catalyst for the coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates. The couplings of ammonia with this catalyst conducted with a solution of ammonia in dioxane form primary arylamines from a variety of aryl electrophiles in high yields. Catalyst loadings as low as 0.1 mol % were sufficient for reactions of many aryl chlorides and bromides. In the presence of this catalyst, aryl sulfonates also coupled with ammonia for the first time in high yields. A comparison of reactions in the presence of this catalyst versus those in the presence of existing copper and palladium systems revealed a complementary, if not broader, substrate scope. The utility of this method to generate amides, imides, and carbamates is illustrated by a one-pot synthesis of a small library of these carbonyl compounds from aryl bromides and chlorides, ammonia, and acid chlorides or anhydrides. Mechanistic studies show that reactions conducted with the combination of Pd[P(o-tol)(3)](2) and CyPF-t-Bu as catalyst occur with faster rates and higher yields than those conducted with CyPF-t-Bu and palladiun(II) as catalyst precursors because of the low concentration of active catalyst that is generated from the combination of palladium(II), ammonia, and base.

Lipophilic Polycation Vehicles Display High Plasmid DNA Delivery to Multiple Cell Types.

PubMed

Wu, Yaoying; Smith, Adam E; Reineke, Theresa M

2017-08-16

A class of cationic poly(alkylamidoamine)s (PAAAs) containing lipophilic methylene linkers were designed and examined as in vitro plasmid DNA (pDNA) delivery agents. The PAAAs were synthesized via step-growth polymerization between a diamine monomer and each of four different diacid chloride monomers with varying methylene linker lengths, including glutaryl chloride, adipoyl chloride, pimeloyl chloride, and suberoyl chloride, which served to systematically increase the lipophilicity of the polymers. The synthesized polymers successfully complexed with pDNA in reduced serum medium at N/P ratios of 5 and greater, resulting in polyplexes with hydrodynamic diameters of approximately 1 μm. These polyplexes were tested for in vitro transgene expression and cytotoxicity using HDFa (human dermal fibroblast), HeLa (human cervical carcinoma), HMEC (human mammary epithelial), and HUVEC (human umbilical vein endothelial) cells. Interestingly, select PAAA polyplex formulations were found to be more effective than Lipofectamine 2000 at promoting transgene expression (GFP) while maintaining comparable or higher cell viability. Transgene expression was highest in HeLa cells (∼90% for most formulations) and lowest in HDFa cells (up to ∼20%) as measured by GFP fluorescence. In addition, the cytotoxicity of PAAA polyplex formulations was significantly increased as the molecular weight, N/P ratio, and methylene linker length were increased. The PAAA vehicles developed herein provide a new delivery vehicle design strategy of displaying attributes of both polycations and lipids, which show promise as a tunable scaffold for refining the structure-activity-toxicity profiles for future genome editing studies.

A Simple Qualitative Analysis Scheme for Several Environmentally Important Elements

ERIC Educational Resources Information Center

Lambert, Jack L.; Meloan, Clifton E.

1977-01-01

Describes a scheme that uses precipitation, gas evolution, complex ion formation, and flame tests to analyze for the following ions: Hg(I), Hg(II), Sb(III), Cr(III), Pb(II), Sr(II), Cu(II), Cd(II), As(III), chloride, nitrate, and sulfate. (MLH)

Electrolytic conditioning of a magnesium aluminum chloride complex for reversible magnesium deposition

DOE PAGES

Barile, Christopher J.; Barile, Elizabeth C.; Zavadil, Kevin R.; ...

2014-12-04

We describe in this report the electrochemistry of Mg deposition and dissolution from the magnesium aluminum chloride complex (MACC). The results define the requirements for reversible Mg deposition and definitively establish that voltammetric cycling of the electrolyte significantly alters its composition and performance. Elemental analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy (SEM-EDS) results demonstrate that irreversible Mg and Al deposits form during early cycles. Electrospray ionization-mass spectrometry (ESI-MS) data show that inhibitory oligomers develop in THF-based solutions. These oligomers form via the well-established mechanism of a cationic ring-opening polymerization of THF during the initial synthesis of the MACC andmore » under resting conditions. In contrast, MACC solutions in 1,2-dimethoxyethane (DME), an acyclic solvent, do not evolve as dramatically at open circuit potential. Furthermore, we propose a mechanism describing how the conditioning process of the MACC in THF improves its performance by both tuning the Mg:Al stoichiometry and eliminating oligomers.« less

Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

PubMed

Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

2016-09-05

The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Carbon Dioxide Transformation in Imidazolium Salts: Hydroaminomethylation Catalyzed by Ru-Complexes.

PubMed

Ali, Meher; Gual, Aitor; Ebeling, Gunter; Dupont, Jairton

2016-08-23

The catalytic species generated by dissolving Ru3 (CO)12 in the ionic liquids 1-n-butyl-3-methyl-imidazolium chloride or 1-n-butyl-2,3-dimethyl-imidazolium chloride are efficient multifunctional catalysts for: (a) reverse water-gas shift, (b) hydroformylation of alkenes, and (c) reductive amination of aldehydes. Thus the reaction of alkenes with primary or secondary amines (alkene/amine, 1:1) under CO2 /H2 (1:1) affords the hydroaminomethylations products in high alkene conversions (up to 99 %) and selectivities (up to 96 %). The reaction proceeds under relatively mild reaction conditions (120 °C, 60 bar=6 MPa) and affords selectively secondary and tertiary amines. The presence of amine strongly reduces the alkene hydrogenation competitive pathway usually observed in the hydroformylation of terminal alkenes by Ru complexes. The catalytic system is also highly active for the reductive amination of aldehydes and ketones yielding amines in high yields (>90 %). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Absorption spectra analysis of hydrated uranium(III) complex chlorides

NASA Astrophysics Data System (ADS)

Karbowiak, M.; Gajek, Z.; Drożdżyński, J.

2000-11-01

Absorption spectra of powdered samples of hydrated uranium(III) complex chlorides of the formulas NH 4UCl 4 · 4H 2O and CsUCl 4 · 3H 2O have been recorded at 4.2 K in the 4000-26 000 cm -1 range. The analysis of the spectra enabled the determination of crystal-field parameters and assignment of 83 and 77 crystal-field levels for the tetrahydrate and trihydrate, respectively. The energies of the levels were computed by applying a simplified angular overlap model as well as a semiempirical Hamiltonian representing the combined atomic and crystal-field interactions. Ab initio calculations have enabled the application of a simplified parameterization and the determination of the starting values of the AOM parameters. The received results have proved that the AOM approach can quite well predict both the structure of the ground multiplet and the positions of the crystal-field levels in the 17 000-25 000 cm -1 range, usually obscured by strong f-d bands.

A chloride-anion insensitive colorimetric chemosensor for trinitrobenzene and picric acid.

PubMed

Kim, Dae-Sik; Lynch, Vincent M; Nielsen, Kent A; Johnsen, Carsten; Jeppesen, Jan O; Sessler, Jonathan L

2009-09-01

A new receptor, the bisTTF-calix[2]thiophene[2]pyrrole derivative 3, has been prepared from the Lewis acid-catalyzed condensation of 2,5-bis(1-hydroxymethylethyl)thiopheno-TTF and pyrrole. This new system is found to form complexes with the electron-deficient guests, trinitrobenzene (TNB) and picric acid (PA), which serve as models for nitroaromatic explosives. The binding phenomenon, which has been studied in organic solution using proton nuclear magnetic resonance and absorption spectroscopies, results in an easy-to-visualize color change in chloroform that is independent of the presence of chloride anion, a known interferant for an earlier tetrakisTTF-calix[4]pyrrole TNB chemosensor. Support for the proposed binding mode comes from a preliminary solid state structure of the complex formed from TNB, namely TNB subset3. A color change is also observed when dichloromethane solutions of chemosensor 3 are added to solvent-free samples of TNB, PA, and 2,4,6-trinitrotoluene supported on silica gel.

cis,cis,cis-(Acetato-κ(2) O,O')bis-[1,2-bis-(diphenyl-phosphan-yl)ethane-κ(2) P,P']ruthenium(II) 0.75-trifluoro-methane-sulfonate 0.25-chloride.

PubMed

Figueira, João; Rodrigues, João; Valkonen, Arto

2013-04-01

In the title Ru(II) carboxyl-ate compound, [Ru(C2H3O2)(C26H24P2)2](CF3O3S)0.75Cl0.25, the distorted tris-bidentate octa-hedral stereochemistry about the Ru(II) atom in the complex cation comprises four P-atom donors from two 1,2-bis-(diphenyl-phosphan-yl)ethane ligands [Ru-P = 2.2881 (13)-2.3791 (13) Å] and two O-atom donors from the acetate ligand [Ru-O = 2.191 (3) and 2.202 (3) Å]. The disordered counter-anions are located on the same site in the structure in a 3:1 ratio, the expanded formula comprising four complex cations, three trifluoro-methane-sulfonate anions and one chloride anion, with two such formula units in the unit cell.

Preparation of bio-deep eutectic solvent triggered cephalopod shaped silver chloride-DNA hybrid material having antibacterial and bactericidal activity.

PubMed

Bhatt, Jitkumar; Mondal, Dibyendu; Bhojani, Gopal; Chatterjee, Shruti; Prasad, Kamalesh

2015-11-01

2.5% w/w DNA (Salmon testes) was solubilized in a bio-deep eutectic solvent [(bio-DES), obtained by the complexation of choline chloride and ethylene glycol at 1:2 molar ratio] containing 1% w/w of silver chloride (AgCl) to yield a AgCl decorated DNA based hybrid material. Concentration dependent formation of AgCl crystals in the DES was observed and upon interaction with DNA it gave formation of a cephalopod shaped hybrid material. DNA was found to maintain its chemical and structural stability in the material. Further, AgCl microstructures were found to have orderly self assembled on the DNA helices indicating the electrostatic interaction between Ag(+) and phosphate side chain of DNA as a driving force for the formation of the material with ordered microstructural distribution of AgCl. Furthermore, the functionalized material exhibited excellent antibacterial and bactericidal activity against both Gram negative and Gram positive pathogenic bacteria. Copyright © 2015 Elsevier B.V. All rights reserved.

A designed inhibitor of a CLC antiporter blocks function through a unique binding mode

PubMed Central

Howery, Andrew E.; Elvington, Shelley; Abraham, Sherwin J.; Choi, Kee-Hyun; Phillips, Sabrina; Ryan, Christopher M.; Sanford, R. Lea; Simpson-Dworschak, Sierra; Almqvist, Jonas; Tran, Kevin; Chew, Thomas A.; Zachariae, Ulrich; Andersen, Olaf S.; Whitelegge, Julian; Matulef, Kimberly; Du Bois, Justin; Maduke, Merritt C.

2012-01-01

SUMMARY The lack of small-molecule inhibitors for anion-selective transporters and channels has impeded our understanding of the complex mechanisms that underlie ion passage. The ubiquitous CLC “Chloride Channel” family represents a unique target for biophysical and biochemical studies because its distinctive protein fold supports both passive chloride channels and secondary-active chloride-proton transporters. Here, we describe the synthesis and characterization of the first specific small-molecule inhibitor directed against a CLC antiporter (ClC-ec1). This compound, 4,4′-octanamidostilbene-2,2′-disulfonate (OADS), inhibits ClC-ec1 with low micromolar affinity and has no specific effect on a CLC channel (ClC-1). Inhibition of ClC-ec1 occurs by binding to two distinct intracellular sites. The location of these sites and the lipid-dependence of inhibition suggest potential mechanisms of action. The discovery of this compound will empower research to elucidate differences between antiporter and channel mechanisms and to develop treatments for CLC-mediated disorders. PMID:23177200

Di-μ3-chlorido-tetra-μ2-chlorido-dichloridobis(dimethyl­formamide-κO)hexa­kis­(1H-imidazole-κN 3)tetra­cadmium

PubMed Central

Zhu, Run-Qiang

2011-01-01

The centrosymmetric mol­ecule of the title complex, [Cd4Cl8(C3H4N2)6(C3H7NO)2], contains four CdII atoms, six imidazole, two dimethyl­formamide and eight chloride ligands. The structure shows a novel chloride-bridged tetra­nuclear cadmium quasi-cubane cluster. The coordination geometry of all CdII atoms is distorted octa­hedral, with the two metal atoms in the asymmetric unit in different coordination environments. One of the Cd2+ ions is coordinated by five Cl− ions and by one N atom from an imidazole ligand, while the second is coordinated by three chloride ligands, two N atoms from two imidazole ligands and one O atom from a dimethyl­formamide mol­ecule. Inter­molecular N—H⋯Cl hydrogen bonds link the mol­ecules into a two-dimensional polymeric structure parallel to the ab plane. PMID:22058708

Evaluation of diatomea algae Thalassiosira weissflogii sensitivity to chloride mercury and methylmercury by chlorophyll fluorescence analysis

NASA Astrophysics Data System (ADS)

Graevskaya, E. E.; Antal, T. K.; Matorin, D. N.; Voronova, E. N.; Pogosyan, S. I.; Rubin, A. B.

2003-05-01

Measurement of chlorophyll fluorescence has been shown to be a rapid, non-invasive, and reliable method to assess photosynthetic performance in a changing environment. In our study, the pulseamplitude-modulation (PAM) - fluorometric method was used to evaluate the sensitivity to chloride mercury and methylmercury chloride of diatomea microalgae Thalassiosira weissflogii. We found that 10^{-6} and 10^{-7} M MeHg led to a slow decrease in the PS II activity following for prolonged lag phase, whereas the algae was not sensitive to the same concentrations of HgCl2. However observed PS II inactivation by methylmercury was not complete and about 10 percents ofthe cells kept the high level of PS II activity as it was shown by microfluorometric analysis. These cells could determine adaptation of algae to methylmercury effect. Both toxicants decreased the rate of PS II reparation, as well as increased a heat pathway of excitation dissipation in PS II antennae complex.

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides.

PubMed

Lennon, David; Winfield, John M

2017-01-28

Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

Aerospace applications of sodium batteries using novel cathode materials

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.; Di Stefano, S.; Bankston, C. P.

1989-01-01

Preliminary fundamental investigations aimed at evaluating sodium metal chloride systems for future aerospace applications are described. Since the sodium metal chloride systems are relatively new, the approach has been to characterize their fundamental properties in order to understand their limitations. To this end, a series of fundamental electrochemical investigations have been carried out, the results of which are reported here. The metal chloride cathodes show high exchange current densities which corroborate their good reversibility in a battery application. The reduction mechanisms appear to be complex and involve multielectron transfer steps and intermediates. Such intermediates in the reaction mechanism have already been identified in the case of FeCl2. Similar mechanisms may be operative in the case of NiCl2. CuCl2, however, exhibits a second relaxation loop in the impedance plot at low frequencies and also a sloping discharge curve, unlike FeCl2 and NiCl2, which may indicate the existence of monovalent copper in the reduction mechanism.

A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration.

PubMed

Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C; Lee, Dong-Heon; Mondal, Biplab; Narducci Sarjeant, Amy A; del Rio, Diego; Pau, Monita Y M; Solomon, Edward I; Karlin, Kenneth D

2009-11-01

Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)-(*NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO(-))-Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO(2) (-)) complex and 0.5 mol equiv O(2). In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper-nitrosyl and copper-peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.

EXAFS characterisation of metal bonding in highly luminescent, UV stable, water-soluble and biocompatible lanthanide complexes

NASA Astrophysics Data System (ADS)

Kalyakina, A.; Utochnikova, V.; Trigub, A.; Zubavichus, Y.; Kuzmina, N.; Bräse, S.

2016-05-01

The combination of X-ray diffraction with EXAFS was employed to assess the coordination environment of lanthanide complexes in solutions. This method is based on the assumption that the local structure of lanthanide complexes in solution combines elements of the crystal structure of the complex in the solid state (single- or polycrystalline) and the elements of the local structure of a lanthanide salt, completely dissociated in the solvent (usually chlorides). The success of this approach is demonstrated with the lanthanide (III) 2,3,4,5,6-pentafluorobenzoate complexes, where the local structure in aqueous and methanol solutions were estimated. Moreover, the dissociation degree of the complexes in aqueous and methanol solutions was evaluated.

Shiga-Like Toxin 2 of Enterohemorrhagic Escherichia Coli (EHEC): Genetic Organization and Effects of Toxin in a Murine Model of EHEC Infection

DTIC Science & Technology

1990-04-27

centrifugation. Cells were resuspended in 3.5 ml of 4 M guanidinium isothiocyanate, 20 mM sodium acetate pH 5.2, 0.1 mM DTT, and 0.5% N- lauryl sarcosine. The... sulfate , and 0.4 M sodium chloride. The mixture was heated to 80°C for 5 minutes and then at 37°C for 2 hours to permit the annealing of the...complex was then mixed with 200 /tl of 0.25 M sodium chloride, 30 mM sodium acetate pH 4.5, and 1 mM zinc sulfate , followed by 10 units of SI

Humane studies of octopuses get a boost

NASA Astrophysics Data System (ADS)

Staaf, Danna

2018-04-01

Because of their complex brains, cephalopods enjoy the same protections as vertebrate animals in laboratory experiments in the European Union, New Zealand, and some Australian states. As a result, researchers have to use anesthesia in cephalopod studies that can cause pain. Most use either ethanol or magnesium chloride for this purpose because they immobilize cephalopods quickly and the animals soon recover without lasting effects. But until now it was unclear whether these compounds actually take away pain or just paralyze the animals. Now, a new study in three species suggests that both ethanol and magnesium chloride suppress pain signals in cephalopods, reassuring researchers they are compliant with the law and treating their subjects humanely.

Catalytic and inhibiting effect of amino acids on the porphyrin metallation reactions

NASA Astrophysics Data System (ADS)

Mamardashvili, Galina M.; Zhdanova, Daria Yu.; Mamardashvili, Nugzar Zh.; Koifman, Oskar I.; Dehaen, Wim

In the present work, using the interaction of tetra-(4-sulfophenyl)porphyrin with copper(II) chloride as an example, it has been shown how different amino acid additives (glycine, valine, leucine and tryptophan) catalyze or inhibit the formation of Cu-porphyrin as a function of the chemical environment (borate buffer (pH7.4), DMSO) and the concentration of the additive. It has been demonstrated that the type of amino acid affects the complexation reaction rate. Possible mechanisms of metalloporphyrin formation and the ways of their acceleration are discussed. Ways in which different amino acid additives catalyze or inhibit the interaction of tetra-(4-sulfophenyl)porphyrin with copper(II) chloride are examined.

Numerical investigation of road salt impact on an urban wellfield.

PubMed

Bester, M L; Frind, E O; Molson, J W; Rudolph, D L

2006-01-01

The impact of road salt on a wellfield in a complex glacial moraine aquifer system is studied by numerical simulation. The moraine underlies an extensive urban and industrial landscape, which draws its water supply from >20 wellfields, several of which are approaching or have exceeded the drinking water limit for chloride. The study investigates the mechanisms of road salt infiltration, storage, and transport in the subsurface and assesses the effectiveness of mitigation measures designed to reduce the impact. The three-dimensional transport model accounts for increases in salt loading, as well as growth of the urbanized area and road network over the past 50 years. The simulations, which focus on one impacted wellfield, show chloride plumes originating mainly at arterial roads and migrating through aquitard windows into the water supply aquifers. The results suggest that the aquifer system contains a large and heterogeneously distributed mass of chloride and that concentrations in the aquifer can be substantially higher than the concentrations in the well water. Future impact scenarios indicate that although the system responds rapidly to reductions in salt loading, the residual chloride mass may take decades to flush out, even if road salting were discontinued. The implications with respect to urban wellfields in typical snow-belt areas are discussed.

Solvation of actinide salts in water using a polarizable continuum model.

PubMed

Kumar, Narendra; Seminario, Jorge M

2015-01-29

In order to determine how actinide atoms are dressed when solvated in water, density functional theory calculations have been carried out to study the equilibrium structure of uranium plutonium and thorium salts (UO2(2+), PuO2(2+), Pu(4+), and Th(4+)) both in vacuum as well as in solution represented by a conductor-like polarizable continuum model. This information is of paramount importance for the development of sensitive nanosensors. Both UO2(2+) and PuO2(2+) ions show coordination number of 4-5 with counterions replacing one or two water molecules from the first coordination shell. On the other hand, Pu(4+), has a coordination number of 8 both when completely solvated and also in the presence of chloride and nitrate ions with counterions replacing water molecules in the first shell. Nitrates were found to bind more strongly to Pu(IV) than chloride anions. In the case of the Th(IV) ion, the coordination number was found to be 9 or 10 in the presence of chlorides. Moreover, the Pu(IV) ion shows greater affinity for chlorides than the Th(IV) ion. Adding dispersion and ZPE corrections to the binding energy does not alter the trends in relative stability of several conformers because of error cancelations. All structures and energetics of these complexes are reported.

Neural Modulation of the Immune Response through the Benzodiazepine/GABA Receptor Chloride Ionophore Complex

DTIC Science & Technology

1988-08-30

dose of Alprazolam (a triaobenzodiazepine with high affinty for "central" but not "peripheral" benzodiazepine receptbr). These results suggest that...1987), provide additional support for the hypothesis that the "supramolecular complex" (in the CNS) regulates NK cell activity. 3). Effect of Alprazolam ...this study the effects of alprazolam (a triazolobenzodiazepine with high affinity for "central" but not "peripheral" benzodiazepine receptors) on

Potentiometric/turbidometric titration of antiperspirant actives.

PubMed

Johnston, Clifford T; Hem, Stanley L; Guenin, Eric; Mattai, Jairajh; Afflito, John

2003-01-01

A titration procedure that simultaneously monitors the pH and turbidity of an antiperspirant solution during neutralization with sodium hydroxide was developed to characterize antiperspirant actives. Aluminum chloride, aluminum chlorohydrate (ACH), and aluminum zirconium glycine complex (AZG) gave distinctive pH/turbidity profiles. The activated forms of aluminum chlorohydrate (ACH') and aluminum zirconium glycine complex (AZG') produced more turbidity than the non-activated forms. On an equimolar basis, AZG' produced more turbidity than any of the antiperspirant actives tested.

Feasibility of using sodium chloride as a tracer for the characterization of the distribution of matter in complex multi-compartment 3D bioreactors for stem cell culture.

PubMed

Gerlach, Jörg C; Witaschek, Tom; Strobel, Catrin; Brayfield, Candace A; Bornemann, Reinhard; Catapano, Gerardo; Zeilinger, Katrin

2010-06-01

The experimental characterization of the distribution of matter in complex multi-compartment three-dimensional membrane bioreactors for human cell culture is complicated by tracer interactions with the membranes and other bioreactor constituents. This is due to the fact that membranes with a high specific surface area often feature a hydrophobic chemical backbone that may adsorb tracers often used to this purpose, such as proteins and dyes. Membrane selectivity, and its worsening caused by protein adsorption, may also hinder tracer transfer across neighboring compartments, thus preventing effective characterization of the distribution of matter in the whole bioreactor. Tracer experiments with sodium chloride (NaCl) may overcome some of these limitations and be effectively used to characterize the distribution of matter in complex 3D multi-compartments membrane bioreactors for stem cell culture. NaCl freely permeates most used membranes, it does not adsorb on uncharged membranes, and its concentration may be accurately measured in terms of solution conductivity. In this preliminary study, the feasibility of complex multi-compartment membrane bioreactors was investigated with a NaCl concentration pulse challenge to characterize how their distribution of matter changes when they are operated under different conditions. In particular, bioreactors consisting of three different membrane types stacked on top of one another to form a 3D network were characterized under different feed conditions.

Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment.

PubMed

Rampazzi, Vincent; Roger, Julien; Amardeil, Régine; Penouilh, Marie-José; Richard, Philippe; Fleurat-Lessard, Paul; Hierso, Jean-Cyrille

2016-11-07

A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis(5-methyl-2-furyl)phosphino]-3,3'-di-tert-butylferrocene (5-r), and rac-1,1'-bis(diphenylphosphino)-3,3'-bis[(tri-iso-propylsilyl)oxy]ferrocene (6-r) were used to form dinuclear gold complexes. Coordination of tert-butylated ferrocenyl phosphines generated aurophilic interactions in the corresponding dinuclear gold complexes, contrary to gold(I) complexes reported with 1,1'-bis(diphenylphosphino)ferrocene. The structurally related tetraphosphine 1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene (11) also gave access to mononuclear, dinuclear, and the original trinuclear gold chloride aurophilic complexes in which 14e - to 16e - gold centers coexist. In such complexes, nonbonded ("through-space") 31 P- 31 P' nuclear spin couplings were evidenced by high-resolution NMR. In these interactions nuclear spin information is transferred between the lone-pair electron of an uncoordinated phosphorus P and a phosphorus P' that is involved in a σ covalent bond Au-P'. The dinuclear aurophilic complex displayed a concerted shuttling of its [ClAu···AuCl] fragment between the four phosphorus donors of the tetraphosphine ligand. Thus, an aurophilic Au···Au bond, which is assumed to be a weak energy interaction, can be conserved within a dynamic shuttling process at high temperature involving an intramolecular coordination-decoordination process of digold(I) at phosphorus atoms.

Development and evaluation of in situ gel of pregabalin

PubMed Central

Madan, Jyotsana R; Adokar, Bhushan R; Dua, Kamal

2015-01-01

Aim and Background: Pregabalin (PRG), an analog of gamma-aminobutyric acid, reduces the release of many neurotransmitters, including glutamate, and noradrenaline. It is used for the treatment of epilepsy; simple and complex partial convulsion. The present research work aims to ensure a high drug absorption by retarding the advancement of PRG formulation through the gastrointestinal tract. The work aims to design a controlled release PRG formulation which is administered as liquid and further gels in the stomach and floats in gastric juice. Materials and Methods: In situ gelling formulations were prepared using sodium alginate, calcium chloride, sodium citrate, hydroxypropyl methylcellulose (HPMC) K100M, and sodium bicarbonate. The prepared formulations were evaluated for solution viscosity, drug content, in vitro gelling studies, gel strength, and in vitro drug release. The final formulation was optimized using a 32 full factorial design. Results: The formulation containing 2.5% w/v sodium alginate and 0.2% w/v calcium chloride were considered optimum since it showed minimum floating lag time (18 s), optimum viscosity (287.3 cps), and gel strength (4087.17 dyne/cm2). The optimized formulation follows Korsmeyer-Peppas kinetic model with n value 0.3767 representing Fickian diffusion mechanism of drug release. Conclusion: Floating in situ gelling system of PRG can be formulated using sodium alginate as a gelling polymer and calcium chloride as a complexing agent to control the drug release for about 12 h for the treatment of epilepsy. PMID:26682193

Redox-switchable copper(I) metallogel: a metal-organic material for selective and naked-eye sensing of picric acid.

PubMed

Sarkar, Sougata; Dutta, Soumen; Chakrabarti, Susmita; Bairi, Partha; Pal, Tarasankar

2014-05-14

Thiourea (TU), a commercially available laboratory chemical, has been discovered to introduce metallogelation when reacted with copper(II) chloride in aqueous medium. The chemistry involves the reduction of Cu(II) to Cu(I) with concomitant oxidation of thiourea to dithiobisformamidinium dichloride. The gel formation is triggered through metal-ligand complexation, i.e., Cu(I)-TU coordination and extensive hydrogen bonding interactions involving thiourea, the disulfide product, water, and chloride ions. Entangled network morphology of the gel selectively develops in water, maybe for its superior hydrogen-bonding ability, as accounted from Kamlet-Taft solvent parameters. Complete and systematic chemical analyses demonstrate the importance of both Cu(I) and chloride ions as the key ingredients in the metal-organic coordination gel framework. The gel is highly fluorescent. Again, exclusive presence of Cu(I) metal centers in the gel structure makes the gel redox-responsive and therefore it shows reversible gel-sol phase transition. However, the reversibility does not cause any morphological change in the gel phase. The gel practically exhibits its multiresponsive nature and therefore the influences of different probable interfering parameters (pH, selective metal ions and anions, selective complexing agents, etc.) have been studied mechanistically and the results might be promising for different applications. Finally, the gel material shows a highly selective visual response to a commonly used nitroexplosive, picric acid among a set of 19 congeners and the preferred selectivity has been mechanistically interpreted with density functional theory-based calculations.

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

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

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

DOE PAGES

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; ...

2017-10-24

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+, UO 2Cl +, and UO 2Cl 2°. UO 2Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species showmore » fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2Cl 4 2- and UO 2Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2Cl 2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2Cl 2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.« less

A spectroscopic study of uranyl speciation in chloride-bearing solutions at temperatures up to 250 °C

NASA Astrophysics Data System (ADS)

Migdisov, A. A.; Boukhalfa, H.; Timofeev, A.; Runde, W.; Roback, R.; Williams-Jones, A. E.

2018-02-01

The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO22+, UO2Cl+, and UO2Cl2°. UO2Cl3- is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO2Cl42- and UO2Cl53- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T > 150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO2Cl2°. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO22+ + Cl- = UO2Cl+ are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO22+ + 2Cl- = UO2Cl2° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.

The structure and stability of aqueous rare-earth elements in hydrothermal fluids: New results on neodymium(III) aqua and chloroaqua complexes in aqueous solutions to 500 °C and 520 MPa

USGS Publications Warehouse

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

2009-01-01

X-ray absorption spectroscopy (XAS) measurements were made at the Nd L3-edge on neodymium(III) aqua and chloroaqua complexes in low pH aqueous solutions from 25 to 500????C and up to 520??MPa. Analysis of the extended X-ray absorption fine structure of the XAS spectra measured from a 0.07??m Nd/0.16??m HNO3 aqueous solution reveals a contraction of the Nd-O distance of the Nd3+ aqua ion at a uniform rate of ~ 0.013????/100????C and a uniform reduction of the number of coordinated H2O molecules from 10.0 ?? 0.9 to 7.4 ?? 0.9 over the range from 25 to 500????C and up to 370??MPa. The rate of reduction of the first-shell water molecules with temperature for Nd3+ (26%) is intermediate between the rate for the Gd3+ aqua ion (22% from 25 to 500????C) and the rates for the Eu3+ (29% from 25 to 400????C) and the Yb3+ aqua ions (42% from 25 to 500????C) indicating an intermediate stability of the Nd3+ aqua ion consistent with the tetrad effect. Nd L3-edge XAS measurements of 0.05??m NdCl3 aqueous solution at 25 to 500????C and up to 520??MPa show that stepwise inner-sphere complexes most likely of the type Nd(H2O)?? - nCln+3 - n occur in the solution at elevated temperatures, where ?? ??? 9 at 150????C decreasing to ~ 6 at 500????C and the number of chloride ions (n) of the chloroaqua complexes increases uniformly with temperature from 1.2 ?? 0.2 to 2.0 ?? 0.2 in the solution upon increase of temperature from 150 to 500????C. Conversely, the number of H2O ligands of Nd(H2O)?? - nCln+3 - n complexes is uniformly reduced with temperature from 7.5 ?? 0.8 to 3.7 ?? 0.3 in the aqueous solution, in the same temperature range. These data show greater stability of neodymium(III) than gadolinium(III) and ytterbium(III) chloride complexes in low pH aqueous solutions at elevated temperatures. Our data suggest a greater stability of aqueous light REE than that of heavy REE chloride complexes in low pH fluids at elevated temperatures consistent with REE analysis of fluids from deep-sea hydrothermal vents. ?? 2008 Elsevier B.V.

Effects of Small Molecule Calcium-Activated Chloride Channel Inhibitors on Structure and Function of Accessory Cholera Enterotoxin (Ace) of Vibrio cholerae

PubMed Central

Chatterjee, Tanaya; Sheikh, Irshad Ali; Chakravarty, Devlina; Chakrabarti, Pinak; Sarkar, Paramita; Saha, Tultul; Chakrabarti, Manoj K.; Hoque, Kazi Mirajul

2015-01-01

Cholera pathogenesis occurs due to synergistic pro-secretory effects of several toxins, such as cholera toxin (CTX) and Accessory cholera enterotoxin (Ace) secreted by Vibrio cholerae strains. Ace activates chloride channels stimulating chloride/bicarbonate transport that augments fluid secretion resulting in diarrhea. These channels have been targeted for drug development. However, lesser attention has been paid to the interaction of chloride channel modulators with bacterial toxins. Here we report the modulation of the structure/function of recombinant Ace by small molecule calcium-activated chloride channel (CaCC) inhibitors, namely CaCCinh-A01, digallic acid (DGA) and tannic acid. Biophysical studies indicate that the unfolding (induced by urea) free energy increases upon binding CaCCinh-A01 and DGA, compared to native Ace, whereas binding of tannic acid destabilizes the protein. Far-UV CD experiments revealed that the α-helical content of Ace-CaCCinh-A01 and Ace-DGA complexes increased relative to Ace. In contrast, binding to tannic acid had the opposite effect, indicating the loss of protein secondary structure. The modulation of Ace structure induced by CaCC inhibitors was also analyzed using docking and molecular dynamics (MD) simulation. Functional studies, performed using mouse ileal loops and Ussing chamber experiments, corroborate biophysical data, all pointing to the fact that tannic acid destabilizes Ace, inhibiting its function, whereas DGA stabilizes the toxin with enhanced fluid accumulation in mouse ileal loop. The efficacy of tannic acid in mouse model suggests that the targeted modulation of Ace structure may be of therapeutic benefit for gastrointestinal disorders. PMID:26540279

Allylic aminations with hindered secondary amine nucleophiles catalyzed by heterobimetallic Pd-Ti complexes.

PubMed

Walker, Whitney K; Anderson, Diana L; Stokes, Ryjul W; Smith, Stacey J; Michaelis, David J

2015-02-06

Phosphinoamide-scaffolded heterobimetallic palladium-titanium complexes are highly effective catalysts for allylic aminations of allylic chlorides with hindered secondary amine nucleophiles. Three titanium-containing ligands are shown to assemble active catalysts in situ and enable catalysis at room temperature. A variety of sterically bulky secondary amines are efficiently allylated in high yields with as little as 1 mol % palladium catalyst. Piperidine and pyrrolidine products are also efficiently generated via intramolecular aminations with hindered amine nucleophiles.

A Bimetallic Aluminium(Salphen) Complex for the Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide.

PubMed

Wu, Xiao; North, Michael

2017-01-10

A bimetallic aluminium(salphen) complex is reported as a sustainable, efficient and inexpensive catalyst for the synthesis of cyclic carbonates from epoxides and carbon dioxide. In the presence of this complex and tetrabutylammonium bromide, terminal and internal epoxides reacted at 50 °C and 10 bar carbon dioxide pressure to afford their corresponding cyclic carbonates in yields of 50-94 % and 30-71 % for terminal and internal cyclic carbonates, respectively. Mechanistic studies using deuterated epoxides and an analogous monometallic aluminium(salphen) chloride complex support a mechanism for catalysis by the bimetallic complex, which involves intramolecular cooperative catalysis between the two aluminium centres. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A general access to organogold(iii) complexes by oxidative addition of diazonium salts.

PubMed

Huang, Long; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

2016-05-11

At room temperature under mild photochemical conditions, namely irradiation with a simple blue light LED, gold(i) chloro complexes of both phosphane and carbene ligands in combination with aryldiazonium salts afford arylgold(iii) complexes. With chelating P,N-ligands cationic six- or five-membered chelate complexes were isolated in the form of salts with weakly coordinating counter anions that were brought in from the diazonium salt. With monodentate P ligands or N-heterocyclic carbene ligands and diazonium chlorides neutral arylgold(iii) dichloro complexes were obtained. The coordination geometry was determined by X-ray crystal structure analyses of representative compounds, a cis arrangement of the aryl and the phosphane ligand at the square planar gold(iii) center is observed.

Lithium Ion Recognition with Nanofluidic Diodes through Host-Guest Complexation in Confined Geometries.

PubMed

Ali, Mubarak; Ahmed, Ishtiaq; Ramirez, Patricio; Nasir, Saima; Mafe, Salvador; Niemeyer, Christof M; Ensinger, Wolfgang

2018-05-15

The lithium ion recognition is receiving significant attention because of its application in pharmaceuticals, lubricants and, especially, in energy technology. We present a nanofluidic device for specific lithium ion recognition via host-guest complexation in a confined environment. A lithium-selective receptor molecule, the aminoethyl-benzo-12-crown-4 (BC12C4-NH 2 ), is designed and functionalized on single conical nanopores in polyethylene terephthalate (PET) membranes. The native carboxylic acid groups on the pore walls are covalently linked with the crown ether moieties and the process is monitored from the changes in the current-voltage ( I- V) curves. The B12-crown-4 moieties are known to specifically bind with lithium ions and when the modified pore is exposed to different alkali metal chloride solutions separately, significant changes in the ion current and rectification are only observed for lithium chloride. This fact suggests the generation of positively charged B12C4-Li + complexes on the pore surface. Furthermore, the nanofluidic diode is able to recognize the lithium ion even in the presence of high concentrations of potassium ions in the external electrolyte solution. Thus, this nanodevice suggests a strategy to miniaturize nanofluidic porous systems for efficient recognition, extraction, and separation of lithium from raw materials.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions.

PubMed

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan R

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions.

Uranium Biominerals Precipitated by an Environmental Isolate of Serratia under Anaerobic Conditions

PubMed Central

Newsome, Laura; Morris, Katherine; Lloyd, Jonathan. R.

2015-01-01

Stimulating the microbially-mediated precipitation of uranium biominerals may be used to treat groundwater contamination at nuclear sites. The majority of studies to date have focussed on the reductive precipitation of uranium as U(IV) by U(VI)- and Fe(III)-reducing bacteria such as Geobacter and Shewanella species, although other mechanisms of uranium removal from solution can occur, including the precipitation of uranyl phosphates via bacterial phosphatase activity. Here we present the results of uranium biomineralisation experiments using an isolate of Serratia obtained from a sediment sample representative of the Sellafield nuclear site, UK. When supplied with glycerol phosphate, this Serratia strain was able to precipitate 1 mM of soluble U(VI) as uranyl phosphate minerals from the autunite group, under anaerobic and fermentative conditions. Under phosphate-limited anaerobic conditions and with glycerol as the electron donor, non-growing Serratia cells could precipitate 0.5 mM of uranium supplied as soluble U(VI), via reduction to nano-crystalline U(IV) uraninite. Some evidence for the reduction of solid phase uranyl(VI) phosphate was also observed. This study highlights the potential for Serratia and related species to play a role in the bioremediation of uranium contamination, via a range of different metabolic pathways, dependent on culturing or in situ conditions. PMID:26132209

Detection of hexamethonium-perchlorate association complexes using NACE-MS.

PubMed

Groom, Carl A; Hawari, Jalal

2007-02-01

Perchlorate (ClO(4) (+)) and other chlorine oxide anions were observed to complex weakly with hexamethonium (1,6-bis-(trimethylammonium)-hexane) in both aqueous and polar nonaqueous solvents. The resultant positively charged complexes were resolved by NACE using 2-propanol/acetone electrolytes prior to mass spectrometric detection using an Agilent(3D)CE system coupled to a Bruker Esquire 3000+ quadrupole IT mass detector. Using electrokinetic injection, the method detection limit for perchlorate in nonaqueous media was 10 microg/L. The isotope patterns due to the presence of (35)Cl and (37)Cl in complex mass spectra allowed for unambiguous identification of perchlorate, chlorate (ClO(3) (+)), chlorite (ClO(2) (+)), and chloride (Cl(+)) in photoreaction samples.

Synthesis, spectral characterization and catalytic activity of Co(II) complexes of drugs: crystal structure of Co(II)-trimethoprim complex.

PubMed

Madhupriya, Selvaraj; Elango, Kuppanagounder P

2014-01-24

New Co(II) complexes with drugs such as trimethoprim (TMP), cimetidine (CTD), niacinamide (NAM) and ofloxacin (OFL) as ligands were synthesized. The complexes were characterized by analytical analysis, various spectral techniques such as FT-IR, UV-Vis, magnetic measurements and molar conductivity. The magnetic susceptibility results coupled with the electronic spectra suggested a tetrahedral geometry for the complexes. The coordination mode of trimethoprim ligand and geometry of the complex were confirmed by single crystal X-ray studies. In this complex the metal ion possesses a tetrahedral geometry with two nitrogen atom from two TMP ligands and two chloride ions coordinated to it. The catalytic activity of the complexes in aryl-aryl coupling reaction was screened and the results indicated that among the four complexes [Co(OFL)Cl(H2O)] exhibited excellent catalytic activity. Copyright © 2013 Elsevier B.V. All rights reserved.

In Vivo Recording of Neural and Behavioral Correlates of Anesthesia Induction, Reversal, and Euthanasia in Cephalopod Molluscs.

PubMed

Butler-Struben, Hanna M; Brophy, Samantha M; Johnson, Nasira A; Crook, Robyn J

2018-01-01

Cephalopod molluscs are among the most behaviorally and neurologically complex invertebrates. As they are now included in research animal welfare regulations in many countries, humane and effective anesthesia is required during invasive procedures. However, currently there is no evidence that agents believed to act as anesthetics produce effects beyond immobility. In this study we demonstrate, for the first time, that two of the most commonly used agents in cephalopod general anesthesia, magnesium chloride and ethanol, are capable of producing strong and reversible blockade of afferent and efferent neural signal; thus they are genuine anesthetics, rather than simply sedating agents that render animals immobile but not insensible. Additionally, we demonstrate that injected magnesium chloride and lidocaine are effective local anesthetic agents. This represents a considerable advance for cephalopod welfare. Using a reversible, minimally invasive recording procedure, we measured activity in the pallial nerve of cuttlefish ( Sepia bandensis ) and octopus ( Abdopus aculeatus, Octopus bocki ), during induction and reversal for five putative general anesthetic and two local anesthetic agents. We describe the temporal relationship between loss of behavioral responses (immobility), loss of efferent neural signal (loss of "consciousness") and loss of afferent neural signal (anesthesia) for general anesthesia, and loss of afferent signal for local anesthesia. Both ethanol and magnesium chloride were effective as bath-applied general anesthetics, causing immobility, complete loss of behavioral responsiveness and complete loss of afferent and efferent neural signal. Cold seawater, diethyl ether, and MS-222 (tricaine) were ineffective. Subcutaneous injection of either lidocaine or magnesium chloride blocked behavioral and neural responses to pinch in the injected area, and we conclude that both are effective local anesthetic agents for cephalopods. Lastly, we demonstrate that a standard euthanasia protocol-immersion in isotonic magnesium chloride followed by surgical decerebration-produced no behavioral response and no neural activity during surgical euthanasia. Based on these data, we conclude that both magnesium chloride and ethanol can function as general anesthetic agents, and lidocaine and magnesium chloride can function as local anesthetic agents for cephalopod molluscs.

In Vivo Recording of Neural and Behavioral Correlates of Anesthesia Induction, Reversal, and Euthanasia in Cephalopod Molluscs

PubMed Central

Butler-Struben, Hanna M.; Brophy, Samantha M.; Johnson, Nasira A.; Crook, Robyn J.

2018-01-01

Cephalopod molluscs are among the most behaviorally and neurologically complex invertebrates. As they are now included in research animal welfare regulations in many countries, humane and effective anesthesia is required during invasive procedures. However, currently there is no evidence that agents believed to act as anesthetics produce effects beyond immobility. In this study we demonstrate, for the first time, that two of the most commonly used agents in cephalopod general anesthesia, magnesium chloride and ethanol, are capable of producing strong and reversible blockade of afferent and efferent neural signal; thus they are genuine anesthetics, rather than simply sedating agents that render animals immobile but not insensible. Additionally, we demonstrate that injected magnesium chloride and lidocaine are effective local anesthetic agents. This represents a considerable advance for cephalopod welfare. Using a reversible, minimally invasive recording procedure, we measured activity in the pallial nerve of cuttlefish (Sepia bandensis) and octopus (Abdopus aculeatus, Octopus bocki), during induction and reversal for five putative general anesthetic and two local anesthetic agents. We describe the temporal relationship between loss of behavioral responses (immobility), loss of efferent neural signal (loss of “consciousness”) and loss of afferent neural signal (anesthesia) for general anesthesia, and loss of afferent signal for local anesthesia. Both ethanol and magnesium chloride were effective as bath-applied general anesthetics, causing immobility, complete loss of behavioral responsiveness and complete loss of afferent and efferent neural signal. Cold seawater, diethyl ether, and MS-222 (tricaine) were ineffective. Subcutaneous injection of either lidocaine or magnesium chloride blocked behavioral and neural responses to pinch in the injected area, and we conclude that both are effective local anesthetic agents for cephalopods. Lastly, we demonstrate that a standard euthanasia protocol—immersion in isotonic magnesium chloride followed by surgical decerebration—produced no behavioral response and no neural activity during surgical euthanasia. Based on these data, we conclude that both magnesium chloride and ethanol can function as general anesthetic agents, and lidocaine and magnesium chloride can function as local anesthetic agents for cephalopod molluscs. PMID:29515454

From well-defined Pt(II) surface species to the controlled growth of silica supported Pt nanoparticles.

PubMed

Laurent, Pierre; Veyre, Laurent; Thieuleux, Chloé; Donet, Sébastien; Copéret, Christophe

2013-01-07

Silica-supported Pt nanoparticles were prepared from well-defined surface platinum(II) surface species, obtained by grafting of well-defined Pt(II) molecular precursors with specific ligands (Cl, Me, N(SiMe(3))(2), OSi(OtBu)(3)) onto silica partially dehydroxylated at 200 and 700 °C yielding well-defined platinum(II) surface species. This approach allowed for testing the effect of Pt density and ligands on nanoparticle size. Higher grafting densities are achieved on silica partially dehydroxylated at 200 °C due to its initially higher surface silanol density. Surface species have been synthesized from symmetrical and dissymmetrical complexes, namely (COD)Pt(Me)(2), (COD)Pt(OSi(OtBu)(3))(2), (COD)Pt(Me)(OSi(OtBu)(3)), (COD)Pt(Me)(N(SiMe(3))(2)), (COD)Pt(Cl)(N(SiMe(3))(2)) and (COD)Pt(N(SiMe(3))(2))(OSi(OtBu)(3)) yielding mono-grafted complexes of general formula (COD)Pt(R)(OSi≡) according to elemental analyses, diffuse reflectance infrared fourier transform (DRIFT) and carbon-13 solid-state nuclear magnetic resonance (NMR) spectroscopies. While the dimethyl-complex shows low reactivity towards grafting, bis-siloxy and dissymmetric complexes demonstrate better reactivity yielding platinum loadings up to 7.4 wt%. Upon grafting amido complexes, the surface passivation yielding Me(3)SiOSi≡ surface species is demonstrated. Nanoparticles have been synthesized from these well-defined surface species by reduction under H(2) at 300 °C, under static or flow conditions. This process yields nanoparticles with sizes ranging from 2 to 3.3 nm and narrow size dispersion from 0.5 to 1.2 nm. Interestingly, the chloride complex yields large nanoparticles from 5 to 40 nm demonstrating the strong influence of chloride over the nanoparticles growth.

2-Acylpyrroles as mono-anionic O,N-chelating ligands in silicon coordination chemistry.

PubMed

Kämpfe, Alexander; Brendler, Erica; Kroke, Edwin; Wagler, Jörg

2014-07-21

Kryptopyrrole (2,4-dimethyl-3-ethylpyrrole) was acylated with, for example, benzoyl chloride to afford 2-benzoyl-3,5-dimethyl-4-ethylpyrrole (L(1)H). With SiCl4 this ligand reacts under liberation of HCl and formation of the complex L(1)2SiCl2. In related reactions with HSiCl3 or H2SiCl2, the same chlorosilicon complex is formed under liberation of HCl and H2 or liberation of H2, respectively. The chlorine atoms of L(1)2SiCl2 can be replaced by fluoride and triflate using ZnF2 and Me3Si-OTf, respectively. The use of a supporting base (triethylamine) is required for the complexation of phenyltrichlorosilane and diphenyldichlorosilane. The complexes L(1)2SiCl2, L(1)2SiF2, L(1)2Si(OTf)2, L(1)2SiPhCl, and L(1)2SiPh2 exhibit various configurations of the octahedral silicon coordination spheres (i.e. cis or trans configuration of the monodentate substituents, different orientations of the bidentate chelating ligands relative to each other). Furthermore, cationic silicon complexes L(1)3Si(+) and L(1) SiPh(+) were synthesized by chloride abstraction with GaCl3. In contrast, reaction of L(1)2SiCl2 with a third equivalent of L(1)H in the presence of excess triethylamine produced a charge-neutral hexacoordinate Si complex with a new tetradentate chelating ligand which formed by Si-templated C-C coupling of two ligands L(1). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of phosphinoferrocene amides and thioamides from carbamoyl chlorides and the structural chemistry of Group 11 metal complexes with these mixed-donor ligands.

PubMed

Fernandes, Tiago A; Solařová, Hana; Císařová, Ivana; Uhlík, Filip; Štícha, Martin; Štěpnička, Petr

2015-02-21

The reaction of in situ generated 1'-(diphenylphosphino)-1-lithioferrocene with carbamoyl chlorides, ClC(E)NMe2, affords the corresponding (thio)amides, Ph2PfcC(E)NMe2 (E = O (), S (); fc = ferrocene-1,1'-diyl). These compounds as well as their analogues, Ph2PfcC(O)NHMe () and Ph2PfcC(O)NH2 (), prepared from 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) were studied as ligands for the Group 11 metal ions. In the reactions with [Cu(MeCN)4][BF4], the amides give rise to bis-chelate complexes of the type [Cu(L-κ(2)O,P)2][BF4]. Similar products, [Ag(L-κ(2)O,P)2]ClO4, are obtained from silver(i) perchlorate and , or . In contrast, the reaction of AgClO4 with produces a unique molecular dimer [Ag()(ClO4-κO)]2, where the metal centres are bridged by the sulfur atoms of the P,S-chelating thioamides. The reactions of with [AuCl(tht)] (tht = tetrahydrothiophene) afford the expected gold(i)-phosphine complexes, [AuCl(L-κP)], containing uncoordinated (thio)amide moieties. Hemilabile coordination of the phosphinoamide ligands in complexes with the soft Group 11 metal ions is established by the crystal structure of a solvento complex, [Cu(-κ(2)O,P)(-κP)(CHCl3-κCl)][BF4], which was isolated serendipitously during an attempted crystallisation of [Cu(-κ(2)O,P)2][BF4]. All of the compounds are characterised by spectroscopic methods, and the structures of several representatives of both the free phosphinoamides and their complexes are determined by X-ray diffraction analysis and further studied by DFT calculations and cyclic voltammetry.

Flexible Acyclic Polyol-Chloride Anion Complexes and Their Characterization by Photoelectron Spectroscopy and Variable Temperature Binding Constant Determinations

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

Shokri, Alireza; Wang, Xue B.; Wang, Yangping

2016-03-17

Flexible acyclic alcohols with 1–5 hydroxyl groups were bound to chloride anion and these complexes were interrogated by negative ion photoelectron spectroscopy and companion density functional theory computations. The resulting vertical detachment energies are reproduced on average to 0.10 eV by M06-2X/aug-cc-pVTZ predictions and range from 4.45 – 5.96 eV. These values are 0.84 – 2.35 eV larger than the adiabatic detachment energy of Cl– as a result of the larger hydrogen bond networks in the bigger polyols. Adiabatic detachment energies of the alcohol–Cl– clusters are more difficult to determine both experimentally and computationally. This is due to the largemore » geometry changes that occur upon photodetachment and the large bond dissociation energy of H–Cl which enables the resulting chlorine atom to abstract a hydrogen from any of the methylene (CH2) or methine (CH) positions. Both ionic and non-ionic hydrogen bonds (i.e., OH•••Cl– and OH•••OH•••Cl–) form in the larger polyols complexes, and are found to be energetically comparable. Subtle structural differences, consequently can lead to the formation of different types of hydrogen bonds and maximizing the ionic ones is not always preferred. Solution equilibrium binding constants between the alcohols and tetrrabuylammonium chloride (TBACl) in acetonitrile at -24.2, 22.0, and 53.6 °C were also determined. The free energies of association are nearly identical for all of the substrates (i.e., ΔG° = -2.8 ± 0.7 kcal mol–1). Compensating enthalpy and entropy values reveal, contrary to expectation and the intrinsic gas-phase preferences, that the bigger systems with more hydroxyl groups are entropically favored and enthalpically disfavored relative to the smaller species. This suggests that more solvent molecules are released upon binding TBACl to alcohols with more hydroxyl groups and is consistent with the measured negative heat capacities. These quantities increase with molecular complexity of the substrate, however, contrary to common interpretation of these values.« less

Zinc composite anode for batteries with solid electrolyte

NASA Astrophysics Data System (ADS)

Tedjar, F.; Melki, T.; Zerroual, L.

A new negative composite anode for batteries with a solid electrolyte is studied. Using a complex of zinc ammonium chloride mixed with zinc metal powder, the advantage of the Zn/Zn 2+ electrode ( e = -760 mV) is kept while the energy density and the shelf-life of the battery are increased.

Production and short-term of synthetic seeds from encapsulated begonia

USDA-ARS?s Scientific Manuscript database

Synthetic seeds were formed from in vitro grown Begonia (cvs ‘Sweetheart Mix’ and ‘Baby Wing White’) shoot tips using 3% sodium alginate in Murashige and Skoog (1962) medium (MS) salt solution as the gel matrix and 100 mM calcium chloride for complexation. Synthetic seed formation was achieved by re...

Alginate encapsulation of Begonia microshoots for short-term storage and distribution

USDA-ARS?s Scientific Manuscript database

Synthetic seeds were formed from in vitro grown Begonia cultivars (Sweetheart Mix and BabyWing White) shoot tips using 3% sodium alginate in Murashige and Skoog medium (MS) salt solution as the gel matrix and 100 mM calcium chloride for complexation. Synthetic seed formation was achieved by releasin...

40 CFR Appendix A to Part 414 - Non-Complexed Metal-Bearing Waste Streams and Cyanide-Bearing Waste Streams

Code of Federal Regulations, 2010 CFR

2010-07-01

... Mercaptan/Ethanol + Hydrogen sulfide Methanol/H.P. Synthesis from natural gas via synthetic gas Oxo Alcohols... + Ammonia n-Propyl alcohol/Hydrogenation of propionaldehyde, Oxo process SAN resin/Suspension polymerization... methanol Acetaldehyde/Oxidation of ethylene with cupric chloride catalyst Acetic acid/Catalytic oxidation...

Utilization of the wastes of vital activity

NASA Technical Reports Server (NTRS)

Gusarov, B. G.; Drigo, Y. A.; Novikov, V. M.; Samsonov, N. M.; Farafonov, N. S.; Chizhov, S. V.; Yazdovskiy, V. I.

1979-01-01

The recycling of wastes from the biological complex for use in life-support systems is discussed. Topics include laboratory equipment, heat treatment of waste materials, mineralization of waste products, methods for production of ammonium hydroxide and nitric acid, the extraction of sodium chloride from mineralized products, and the recovery of nutrient substances for plants from urine.

Inhibition of GABA-gated chloride channels by 12,14-dichlorodehydroabietic acid in mammalian brain

PubMed Central

Nicholson, Russell A; Lees, George; Zheng, Jian; Verdon, Bernard

1999-01-01

12,14-dichlorodehydroabietic acid (12,14-Cl2DHA) reduced GABA-stimulated uptake of 36Cl− into mouse brain synaptoneurosomes suggesting inhibition of mammalian GABAA receptor function. 12,14-Cl2DHA did not affect the binding of [3H]-muscimol to brain membranes but displaced specifically bound [3H]-EBOB. The inhibitory effect on [3H]-EBOB binding was not reversible. 12,14-Cl2DHA reduced the availability of [3H]-EBOB binding sites (Bmax) without changing the KD of the radioligand for remaining sites. 12,14-Cl2DHA did not affect the rate of association of [3H]-EBOB with its chloride channel receptor, but increased the initial rate of [3H]-EBOB dissociation. 12,14-Cl2DHA enhanced the incidence of EPSCs when rapidly applied to cultured rat cortical neurones. Longer exposures produced block of IPSCs with marked increases in the frequency of EPSCs and min EPSCs. 12,14-Cl2DHA also irreversibly suppressed chloride currents evoked by pulses of exogenous GABA in these cells. Ultimately, 12,14-Cl2DHA inhibited all synaptic traffic and action currents in current clamped cells indicating that, in contrast to picrotoxinin (which causes paroxysmal bursting), it is not fully selective for the GABAA receptor-chloride channel complex. The depolarizing block seen with 12,14-Cl2DHA in amphotericin-perforated preparations implicates loss of Ca2+ buffering in the polarity change and this may account for inhibition of spontaneous action potentials. Our investigation demonstrates that 12,14-Cl2DHA blocks GABA-dependent chloride entry in mammalian brain and operates as a non-competitive insurmountable GABAA antagonist. The mechanism likely involves either irreversible binding of 12,14-Cl2DHA to the trioxabicyclooctane recognition site or a site that is allosterically coupled to it. We cannot exclude, however, the possibility that 12,14-Cl2DHA causes localized proteolysis or more extensive conformational change within a critical subunit of the chloride channel. PMID:10204999

Attachment of chloride anion to sugars: mechanistic investigation and discovery of a new dopant for efficient sugar ionization/detection in mass spectrometers.

PubMed

Boutegrabet, Lemia; Kanawati, Basem; Gebefügi, Istvan; Peyron, Dominique; Cayot, Philippe; Gougeon, Régis D; Schmitt-Kopplin, Philippe

2012-10-08

A new method for efficient ionization of sugars in the negative-ion mode of electrospray mass spectrometry is presented. Instead of using strongly hydrophobic dopants such as dichloromethane or chloroform, efficient ionization of sugars has been achieved by using aqueous HCl solution for the first time. This methodology makes it possible to use hydrophilic dopants, which are more appropriate for chromatographic separation techniques with efficient sugar ionization and detection in mass spectrometry. The interaction between chloride anions and monosaccharides (glucose and galactose) was studied by DFT in the gas phase and by implementing the polarizable continuum model (PCM) for calculations in solution at the high B3LYP/6-31+G(d,p)//B3LYP/6-311+G(2d,p) level of theory. In all optimized geometries of identified [M+Cl](-) anions, a non-covalent interaction exists. Differences were revealed between monodentate and bidentate complex anions, with the latter having noticeably higher binding energies. The calculated affinity of glucose and galactose toward the chloride anion in the gas phase and their chloride anion binding energies in solution are in excellent agreement with glucose and galactose [M+Cl](-) experimental intensity profiles that are represented as a function of the chloride ion concentration. Density functional calculations of gas-phase affinities toward chloride anion were also performed for the studied disaccharides sucrose and gentiobiose. All calculations are in excellent agreement with the experimental data. An example is introduced wherein HCl was used to effectively ionize sugars and form chlorinated adduct anions to detect sugars and glycosylated metabolites (anthocyanins) in real biological systems (Vitis vinifera grape extracts and wines), whereas they would not have been easily detectable under standard infusion electrospray mass spectrometry conditions as deprotonated species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microscopic diffusion in hydrated encysted eggs of brine shrimp

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

Mamontov, Eugene

We have studied microscopic diffusion of water in fully hydrated encysted eggs of brine shrimp (Artemia). We utilized quasielastic neutron scattering. Dry eggs of brine shrimp were rehydrated using (1) water without additives, (2) eutectic mixture of water and dimethyl sulfoxide, and (3) a concentrated aqueous solution of lithium chloride. Despite the complexity of the hydrated multicellular organism, measurable microscopic diffusivity of water is rather well defined. Pure hydration water in eggs exhibits freezing temperature depression, whereas hydration water in eggs mixed with dimethyl sulfoxide or lithium chloride does not crystallize at all. The characteristic size of the voids occupiedmore » by water or aqueous solvents in hydrated brine shrimp eggs is between 2 and 10 nm. Those voids are accessible to co-solvents such as dimethyl sulfoxide and lithium chloride. There is no evidence of intracellular water in the hydrated eggs. The lack of intracellular water in the fully hydrated (but still under arrested development) state must be linked to the unique resilience against adverse environmental factors documented not only for the anhydrous, but also hydrated encysted eggs of brine shrimp.« less

Understanding Anionic "Ligandless" Palladium Species in the Mizoroki-Heck Reaction.

PubMed

Schroeter, Felix; Strassner, Thomas

2018-05-07

The anionic complex [NBu 4 ][Pd(DMSO)Cl 3 ], as a "ligandless" system, was shown to be an active catalyst in the Mizoroki-Heck coupling of aryl chlorides in the absence of strongly σ-donating ligands. To investigate the experimentally observed influence of halides and the amount of water on the catalytic activity, we employed a combination of experiments and theoretical calculations. The presence of water was shown to be critical for the formation of the active palladium(0) species by oxidation of in situ generated tributylamine. Oxidative addition to an anionic palladium(0) species was found to be the rate-determining step of the catalytic cycle. For the ensuing steps, both neutral and anionic pathways were considered. It was shown that, in the absence of strongly σ-donating neutral ligands, chloride ions stabilize the catalytic intermediates. Therefore, an anionic pathway is preferred, which explains the need for tetrabutylammonium chloride as an additive. The study of the influence of bromide ions on the catalytic activity revealed that the strongly exergonic displacement of the neutral substrates by bromide ions lowers the catalytic activity.

Microscopic diffusion in hydrated encysted eggs of brine shrimp

DOE PAGES

Mamontov, Eugene

2017-05-24

We have studied microscopic diffusion of water in fully hydrated encysted eggs of brine shrimp (Artemia). We utilized quasielastic neutron scattering. Dry eggs of brine shrimp were rehydrated using (1) water without additives, (2) eutectic mixture of water and dimethyl sulfoxide, and (3) a concentrated aqueous solution of lithium chloride. Despite the complexity of the hydrated multicellular organism, measurable microscopic diffusivity of water is rather well defined. Pure hydration water in eggs exhibits freezing temperature depression, whereas hydration water in eggs mixed with dimethyl sulfoxide or lithium chloride does not crystallize at all. The characteristic size of the voids occupiedmore » by water or aqueous solvents in hydrated brine shrimp eggs is between 2 and 10 nm. Those voids are accessible to co-solvents such as dimethyl sulfoxide and lithium chloride. There is no evidence of intracellular water in the hydrated eggs. The lack of intracellular water in the fully hydrated (but still under arrested development) state must be linked to the unique resilience against adverse environmental factors documented not only for the anhydrous, but also hydrated encysted eggs of brine shrimp.« less

The effect of crack width on the service life of reinforced concrete structures

NASA Astrophysics Data System (ADS)

Van Hung, Nguyen; Viet Hung, Vu; Viet, Tran Bao

2018-04-01

Reinforced concrete has become a widely used construction material around the world. Nowadays, the assessment of deterioration and life expectancy of reinforced concrete structure is very important and necessary as concrete is a complex material with brittle failure. Under the effect of load and over time, cracks occur in the structure, significantly reducing its performance and durability. Therefore, a number of models for predicting the penetration of chloride ions into the concrete were proposed to assess the durability of the structure. In the study performed by T B Viet (2016) [1], the author proposed a new theoretical model, especially considering the effects of macro and micro cracking on the diffusion coefficient of chloride ion in the cracked concrete. The following experimental results, in term of electrical indication of concrete’s ability to resist chloride ion penetration, are used to calculate the lifespan of a reinforced concrete structure according to Dura Crete approach [8] with different crack widths to evaluate the accuracy and reliability of the above model in the range of concrete compressive strength of 30-70MPa.

[Immunobiological blood parameters in rabbits after addition to the diet suspensions of chlorella, sodium sulfate, citrate and chromium chloride].

PubMed

Lesyk, Ia V; Fedoruk, R S; Dolaĭchuk, O P

2013-01-01

We studied the content of glycoproteins and their individual carbohydrate components, the phagocyte activity of neutrophils, phagocyte index, phagocyte number lizotsym and bactericidal activity of the serum concentration of circulating immune complexes and middle mass molecules in the blood of rabbits following administration into the diet chlorella suspension, sodium sulfate, chromium citrate and chromium chloride. The studies were conducted on rabbits weighing 3.7-3.9 kg with altered diet from the first day of life to 118 days old. Rabbits were divided into five groups: the control one and four experimental groups. We found that in the blood of rabbits of experimental groups recieved sodium sulphate, chromium chloride and chromium citrate, the content of glycoprotein's and their carbohydrate components was significantly higher during the 118 days of the study compared with the control group. Feeding rabbits with mineral supplements likely reflected the differences compared with the control parameters of nonspecific resistance in the blood for the study period, which was more pronounced in the first two months of life.

(1)H NMR-based DS determination of barley starch sulfates prepared in 1-allyl-3-methylimidazolium chloride.

PubMed

Kärkkäinen, Johanna; Wik, Tiia-Riikka; Niemelä, Matti; Lappalainen, Katja; Joensuu, Päivi; Lajunen, Marja

2016-01-20

The use of natural resources in a development of products and materials is currently increasing. Starch is one of the investigated resources due to its bioavailability, biodegradability, safety and affordability. In this study, native barley starch was sulfated using a SO3-pyridine complex. The reaction was carried out for the first time using 1-allyl-3-methylimidazolium chloride ionic liquid, an excellent solvent for the starch modification. Reaction conditions (temperature, time and amount of the reagent) were studied using an experimental design. Starch sulfates with the degree of substitution (DS) 1.37 were obtained when the reaction was carried out at 40 °C for 75 min with 4:1 molar ratio of SO3-pyridine complex:anhydroglucose unit. The determination of DS was based on (1)H NMR instead of elemental analysis, which showed overestimated DS values in this study. Starch sulfates were analyzed with FTIR and HPLC, which showed that products contained small and large sulfated molecules. Copyright © 2015 Elsevier Ltd. All rights reserved.

Peroxidative oxidation of halides catalysed by myeloperoxidase. Effect of fluoride on halide oxidation.

PubMed

Zgliczyński, J M; Stelmaszyńska, T; Olszowska, E; Krawczyk, A; Kwasnowska, E; Wróbel, J T

1983-01-01

It was found that all halides can compete with cyanide for binding with myeloperoxidase. The lower is the pH, the higher is the affinity of halides. The apparent dissociation constants (Kd) of myeloperoxidase-cyanide complex were determined in the presence of F-, Cl-, Br- and I- in the pH range of 4 to 7. In slightly acidic pH (4 - 6) fluoride and chloride exhibit a higher affinity towards the enzyme than bromide and iodide. Taking into account competition between cyanide and halides for binding with myeloperoxidase the dissociation constants of halide-myeloperoxidase complexes were calculated. All halides except fluoride can be oxidized by H2O2 in the presence of myeloperoxidase. However, since fluoride can bind with myeloperoxidase, it can competitively inhibit the oxidation of other halides. Fluoride was a competitive inhibitor with respect to other halides as well as to H2O2. Inhibition constants (Ki) for fluoride as a competitive inhibitor with respect to H2O2 increased from iodide oxidation through bromide to chloride oxidation.

Chemical mechanism of the Gram stain and synthesis of a new electron-opaque marker for electron microscopy which replaces the iodine mordant of the stain.

PubMed Central

Davies, J A; Anderson, G K; Beveridge, T J; Clark, H C

1983-01-01

Crystal violet (hexamethyl-para-rosaniline chloride) interacts with aqueous KI-I2 during the Gram stain via a simple metathetical anion exchange to produce a chemical precipitate. There is an apparent 1:1 stoichiometry between anion (I-) and cation (hexamethyl-para-rosaniline+) during the reaction and, since the small chloride anion is replaced by the bulkier iodide, the complex formed becomes insoluble in water. It is this same precipitate which forms in the cellular substance of bacteria (both gram-positive and gram-negative types) and which initiates the Gram reaction. Potassium trichloro(eta 2-ethylene)-platinum(II), as an electronopaque marker for electron microscopy, was chemically synthesized, and it produced an anion in aqueous solution which was compatible with crystal violet for the Gram stain. It interacted with crystal violet in a similar manner as iodide to produce an insoluble complex which was chemically and physically analogous to the dye-iodide precipitate. This platinum anion therefore allows the Gram staining mechanism to be followed by electron microscopy. Images PMID:6195147

Complex effect of lignocellulosic biomass pretreatment with 1-butyl-3-methylimidazolium chloride ionic liquid on various aspects of ethanol and fumaric acid production by immobilized cells within SSF.

PubMed

Dotsenko, Anna S; Dotsenko, Gleb S; Senko, Olga V; Stepanov, Nikolay A; Lyagin, Ilya V; Efremenko, Elena N; Gusakov, Alexander V; Zorov, Ivan N; Rubtsova, Ekaterina A

2018-02-01

The pretreatment of softwood and hardwood samples (spruce and hornbeam wood) with 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) was undertaken for further simultaneous enzymatic saccharification of renewable non-food lignocellulosic biomass and microbial fermentation of obtained sugars to ethanol and fumaric acid. A multienzyme cocktail based on cellulases and yeast or fungus cells producing ethanol and fumaric acid were the main objects of [Bmim]Cl influence studies. A complex effect of lignocellulosic biomass pretreatment with [Bmim]Cl on various aspects of the process (both action of cellulases and microbial conversion of hydrolysates to target products) was revealed. Positive effects of the pretreatment with [Bmim]Cl included decreasing the lignin content in the biomass, and increasing the effectiveness of enzymatic hydrolysis and microbial transformation of pretreated biomass. Immobilized cells of both yeasts and fungi possessed improved productive characteristics in the biotransformation of biomass pretreated with [Bmim]Cl to ethanol and fumaric acid. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis and characterization of N-(2-hydroxy)propyl-3-trimethyl ammonium chitosan chloride for potential application in gene delivery.

PubMed

Xiao, Bo; Wan, Ying; Wang, Xiaoyu; Zha, Qichen; Liu, Haoming; Qiu, Zhiye; Zhang, Shengmin

2012-03-01

A series of N-(2-hydroxy)propyl-3-trimethyl ammonium chitosan chloride (HTCC) samples with various degrees of quaternization ranging from 12.4 to 43.7% was synthesized. The structures and properties of HTCC were investigated by FT-IR, (1)H NMR, conductometric titration and XRD analysis. It was found that HTCC had a more amorphous structure than chitosan. HTCC samples showed significantly lower cytotoxicity than polyethyleneimine in HepG2 and HeLa cell lines. The samples spontaneously formed complexes with pGL3 luciferase plasmid. These complexes had desirable particle sizes (160-300 nm) and zeta potentials (10.8-18.7 mV) when the weight ratios of HTCC to plasmid altered in the range of 3:1-20:1. In vitro gene transfection results indicated that HTCC had significantly high transfection efficiency compared with chitosan for delivering pGL3 luciferase plasmid to HeLa cells. The results suggest that HTCC could be a promising non-viral vector for safe and efficient DNA delivery. Copyright © 2011 Elsevier B.V. All rights reserved.

alpha,beta-poly(asparthylhydrazide)-glycidyltrimethylammonium chloride copolymers (PAHy-GTA): novel polymers with potential for DNA delivery.

PubMed

Pedone, E; Cavallaro, G; Richardson, S C; Duncan, R; Giammona, G

2001-11-09

Hydrophilic polycations form complexes when mixed with plasmids. Following functionalisation with glycidyltrimethylammonium chloride (GTA) alpha,beta-poly(asparthylhydrazide) (PAHy), a water-soluble synthetic macromolecule, becomes polycationic and potentially useful for systemic gene delivery. Initially the biocompatibility of PAHy and PAHy-GTA derivatives with different degrees of positive charge substitution were studied and it was shown that PAHy-GTA was neither haemolytic nor cytotoxicity up to 1 mg/ml. After intravenous injection (125)I-labelled PAHy-GTA derivative containing 46 mol% (PAHy-GTA(b)) of trimethylammonium groups did not accumulate in the liver (4.1+/-0.9% of the recovered dose after 1 h) but was subjected to renal excretion (45+/-21% of the recovered dose was in the kidneys after 1 h). PAHy-GTA formed complexes with DNA (gel retardation) and they protected against degradation by DNase II. Finally the ability of the PAHy-GTA(b) derivative to mediate the transfection of HepG2 cells using the marker gene beta-galactosidase was studied. The optimum plasmid/polymer mass ratio was examined in comparison to LipofectACE, Lipofectin and polyethylenimine.

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

Kasschau, M.R.; Skaggs, M.M.; Chen, E.C.M.

Stress has been reported to accelerate protein catabolism in man and animals and as a result one can expect to observe changes in certain amino acids pools of these organisms. In the present study, the Gulf Coast sea anemone, Bunodosoma cavernata, was used as the test animal and free amino acid levels of whole animals were measured following stressed conditions. Sea anemones were chosen as the test animals since they are sessile and, due to the nature of their morphology, they have few mechanisms by which they can escape environmental stress. The animals were exposed to sublethal concentrations of mercuricmore » chloride and cadmium chloride and the organic amines, aniline, diethanol amine (DEA), and ethylene diamine (EDA). Chloride salts of mercury and cadmium were chosen rather than other anions since chloride is the most abundant anion in seawater. These two particular metals were chosen as challenge compounds due to their high toxicity in aquatic systems. The three organic amines were chosen for their relatively high water solubility and low vapor pressure in an aqueous solution, thus insuring that the toxic compound is retained in the test solution. Since organic amines are used extensively in the Gulf Coast industrial complex, there is a high probability of these compounds contaminating the marine environment. Results indicate that the reaction of B. cavernata to stress from organic amines is similar to the response to heavy metals, only more extensive.« less

Palladium-Catalyzed Coupling of Ammonia with Aryl Chlorides, Bromides, Iodides and Sulfonates: A General Method for the Preparation of Primary Arylamines

PubMed Central

Vo, Giang D.

2010-01-01

We report that the complex generated from Pd[P(o-tol)3]2 and the alkylbisphosphine CyPF-t-Bu is a highly active and selective catalyst for the coupling of ammonia with aryl chlorides, bromides, iodides, and sulfonates. The couplings of ammonia with this catalyst conducted with a solution of ammonia in dioxane form primary arylamines from a variety of aryl electrophiles in high yields. Catalyst loadings as low as 0.1 mol % were sufficient for reactions of many aryl chlorides and bromides. In the presence of this catalyst, aryl sulfonates also coupled with ammonia for the first time in high yields. A comparison of reactions in the presence of this catalyst versus those in the presence of existing copper and palladium systems revealed a complementary, if not broader substrate scope. The utility of this method to generate amides, imides and carbamates is illustrated by a one-pot synthesis of a small library of these carbonyl compounds from aryl bromides and chlorides. Mechanistic studies show that Pd[P(o-tol)3]2 and CyPF-t-Bu generate a more active and general catalyst than that generated from CyPF-t-Bu and palladiun(II) precursors because of the low concentration of active catalyst that is generated from the combination of palladium(II), ammonia and base. PMID:19591470

Molecular organization and dynamics of micellar phase of polyelectrolyte-surfactant complexes: ESR spin probe study

NASA Astrophysics Data System (ADS)

Wasserman, A. M.; Kasaikin, V. A.; Zakharova, Yu. A.; Aliev, I. I.; Baranovsky, V. Yu.; Doseva, V.; Yasina, L. L.

2002-04-01

Molecular dynamics and organization of the micellar phase of complexes of linear polyelectrolytes with ionogenic and non-ionogenic surfactants was studied by the ESR spin probe method. Complexes of polyacrylic acid (PAA) and sodium polystyrenesulfonate (PSS) with alkyltrimethylammonium bromides (ATAB), as well as complexes of poly- N, N'-dimethyldiallylammonium chloride (PDACL) with sodium dodecylsulfate (SDS) were studied. The micellar phase of such complexes is highly organized molecular system, molecular ordering of which near the polymeric chain is much higher than in the 'center' of the micelle, it depends on the polymer-detergent interaction, flexibility of polymeric chain and length of carbonic part of the detergent molecule. Complexes of polymethacrylic acid (PMAA) with non-ionic detergent (dodecyl-substituted polyethyleneglycol), show that the local mobility of surfactant in such complexes is significantly lower than in 'free' micelles and depends on the number of micellar particles participating in formation of complexes.

Comparative solution equilibrium studies on pentamethylcyclopentadienyl rhodium complexes of 2,2'-bipyridine and ethylenediamine and their interaction with human serum albumin.

PubMed

Enyedy, Éva A; Mészáros, János P; Dömötör, Orsolya; Hackl, Carmen M; Roller, Alexander; Keppler, Bernhard K; Kandioller, Wolfgang

2015-11-01

Complex formation equilibrium processes of the (N,N) donor containing 2,2'-bipyridine (bpy) and ethylenediamine (en) with (η(5)-pentamethylcyclopentadienyl)rhodium(III) were investigated in aqueous solution via pH-potentiometry, (1)H NMR spectroscopy, and UV-vis spectrophotometry in the absence and presence of chloride ions. The structure of [RhCp*(en)Cl]ClO4 (Cp*, pentamethylcyclopentadienyl) was also studied by single-crystal X-ray diffraction. pKa values of 8.56 and 9.58 were determined for [RhCp*(bpy)(H2O)](2+) and [RhCp*(en)(H2O)](2+), respectively resulting in the formation of negligible amount of mixed hydroxido complexes at pH 7.4. Stability and the H2O/Cl(-) co-ligand exchange constants of bpy and en complexes considerably exceed those of the bidentate O-donor deferiprone. The strong affinity of the bpy and en complexes to chloride ions most probably contributes to their low antiproliferative effect. Interactions between human serum albumin (HSA) and [RhCp*(H2O)3](2+), its complexes formed with deferiprone, bpy and en were also monitored by (1)H NMR spectroscopy, ultrafiltration/UV-vis and spectrofluorometry. Numerous binding sites (≥ 8) are available for [RhCp*(H2O)3](2+); and the interaction takes place most probably via covalent bonds through the imidazole nitrogen of His. According to the various fluorescence studies [RhCp*(H2O)3](2+) binds on sites I and II, and coordination of surface side chain donor atoms of the protein is also feasible. The binding of the bpy and en complex is weaker and slower compared to that of [RhCp*(H2O)3](2+), and formation of ternary HSA-RhCp*-ligand adducts was proved. In the case of the deferiprone complex, the RhCp* fragment is cleaved off when HSA is loaded with low equivalents of the compound.

The Eye Drop Preservative Benzalkonium Chloride Potently Induces Mitochondrial Dysfunction and Preferentially Affects LHON Mutant Cells.

PubMed

Datta, Sandipan; Baudouin, Christophe; Brignole-Baudouin, Francoise; Denoyer, Alexandre; Cortopassi, Gino A

2017-04-01

Benzalkonium chloride (BAK) is the most commonly used eye drop preservative. Benzalkonium chloride has been associated with toxic effects such as "dry eye" and trabecular meshwork degeneration, but the underlying biochemical mechanism of ocular toxicity by BAK is unclear. In this study, we propose a mechanistic basis for BAK's adverse effects. Mitochondrial O2 consumption rates of human corneal epithelial primary cells (HCEP), osteosarcoma cybrid cells carrying healthy (control) or Leber hereditary optic neuropathy (LHON) mutant mtDNA [11778(G>A)], were measured before and after acute treatment with BAK. Mitochondrial adenosine triphosphate (ATP) synthesis and cell viability were also measured in the BAK-treated control: LHON mutant and human-derived trabecular meshwork cells (HTM3). Benzalkonium chloride inhibited mitochondrial ATP (IC50, 5.3 μM) and O2 consumption (IC50, 10.9 μM) in a concentration-dependent manner, by directly targeting mitochondrial complex I. At its pharmaceutical concentrations (107-667 μM), BAK inhibited mitochondrial function >90%. In addition, BAK elicited concentration-dependent cytotoxicity to cybrid cells (IC50, 22.8 μM) and induced apoptosis in HTM3 cells at similar concentrations. Furthermore, we show that BAK directly inhibits mitochondrial O2 consumption in HCEP cells (IC50, 3.8 μM) at 50-fold lower concentrations than used in eye drops, and that cells bearing mitochondrial blindness (LHON) mutations are further sensitized to BAK's mitotoxic effect. Benzalkonium chloride inhibits mitochondria of human corneal epithelial cells and cells bearing LHON mutations at pharmacologically relevant concentrations, and we suggest this is the basis of BAK's ocular toxicity. Prescribing BAK-containing eye drops should be avoided in patients with mitochondrial deficiency, including LHON patients, LHON carriers, and possibly primary open-angle glaucoma patients.

The Eye Drop Preservative Benzalkonium Chloride Potently Induces Mitochondrial Dysfunction and Preferentially Affects LHON Mutant Cells

PubMed Central

Datta, Sandipan; Baudouin, Christophe; Brignole-Baudouin, Francoise; Denoyer, Alexandre; Cortopassi, Gino A.

2017-01-01

Purpose Benzalkonium chloride (BAK) is the most commonly used eye drop preservative. Benzalkonium chloride has been associated with toxic effects such as “dry eye” and trabecular meshwork degeneration, but the underlying biochemical mechanism of ocular toxicity by BAK is unclear. In this study, we propose a mechanistic basis for BAK's adverse effects. Method Mitochondrial O2 consumption rates of human corneal epithelial primary cells (HCEP), osteosarcoma cybrid cells carrying healthy (control) or Leber hereditary optic neuropathy (LHON) mutant mtDNA [11778(G>A)], were measured before and after acute treatment with BAK. Mitochondrial adenosine triphosphate (ATP) synthesis and cell viability were also measured in the BAK-treated control: LHON mutant and human-derived trabecular meshwork cells (HTM3). Results Benzalkonium chloride inhibited mitochondrial ATP (IC50, 5.3 μM) and O2 consumption (IC50, 10.9 μM) in a concentration-dependent manner, by directly targeting mitochondrial complex I. At its pharmaceutical concentrations (107–667 μM), BAK inhibited mitochondrial function >90%. In addition, BAK elicited concentration-dependent cytotoxicity to cybrid cells (IC50, 22.8 μM) and induced apoptosis in HTM3 cells at similar concentrations. Furthermore, we show that BAK directly inhibits mitochondrial O2 consumption in HCEP cells (IC50, 3.8 μM) at 50-fold lower concentrations than used in eye drops, and that cells bearing mitochondrial blindness (LHON) mutations are further sensitized to BAK's mitotoxic effect. Conclusions Benzalkonium chloride inhibits mitochondria of human corneal epithelial cells and cells bearing LHON mutations at pharmacologically relevant concentrations, and we suggest this is the basis of BAK's ocular toxicity. Prescribing BAK-containing eye drops should be avoided in patients with mitochondrial deficiency, including LHON patients, LHON carriers, and possibly primary open-angle glaucoma patients. PMID:28444329

Role of sulfate, chloride, and nitrate anions on the degradation of fluoroquinolone antibiotics by photoelectro-Fenton.

PubMed

Villegas-Guzman, Paola; Hofer, Florian; Silva-Agredo, Javier; Torres-Palma, Ricardo A

2017-12-01

Taking ciprofloxacin (CIP) as a fluoroquinolone antibiotic model, this work explores the role of common anions (sulfate, nitrate, and chloride) during the application of photoelectro-Fenton (PEF) at natural pH to degrade this type of compound in water. The system was composed of an IrO 2 anode, Ti, or gas diffusion electrode (GDE) as cathode, Fe 2+ , and UV (254 nm). To determine the implications of these anions, the degradation pathway and efficiency of the PEF sub-processes (UV photolysis, anodic oxidation, and electro-Fenton at natural pH) were studied in the individual presence of the anions. The results highlight that degradation routes and kinetics are strongly dependent on electrolytes. When chloride and nitrate ions were present, indirect electro-chemical oxidation was identified by electro-generated HOCl and nitrogenated oxidative species, respectively. Additionally, direct photolysis and direct oxidation at the anode surface were identified as degradation routes. As a consequence of the different pathways, six primary CIP by-products were identified. Therefore, a scheme was proposed representing the pathways involved in the degradation of CIP when submitted to PEF in water with chloride, nitrate, and sulfate ions, showing the complexity of this process. Promoted by individual and synergistic actions of this process, the PEF system leads to a complete elimination of CIP with total removal of antibiotic activity against Staphylococcus aureus and Escherichia coli, and significant mineralization. Finally, the role of the anions was tested in seawater containing CIP, in which the positive contributions of the anions were partially suppressed by its OH radical scavenger action. The findings are of interest for the understanding of the degradation of antibiotics via the PEF process in different matrices containing sulfate, nitrate, and chloride ions.

The transport dynamics of chloride and sodium in a ladder fen during a continuous wastewater polishing experiment

NASA Astrophysics Data System (ADS)

McCarter, Colin P. R.; Price, Jonathan S.

2017-06-01

Ladder fen peatlands have excellent potential for wastewater polishing as they naturally contain both open water (pools) and subsurface (peat) treatment landforms; however, there is a poor understanding of solute transport in ladder fens with and without the increased hydrological load imposed by wastewater discharge. To better understand solute transport in ladder fens under wastewater polishing conditions a continuous solute (NaCl) tracer experiment (38 m3 day-1 of water, chloride - 47.2 mg L-1, and sodium - 25.3 mg L-1) was conducted during the summer of 2014 (day of year 192-243) in a small ladder fen in the James Bay Lowland. The transmissivity distribution and effective porosity (average 0.5) of the peat ribs were determined through repeated bail tests and the drainable porosity of 18 peat cores at -100 mb, respectively. Water samples were taken at least every 7 days to capture the solute (sodium and chloride) plumes. Both solute plumes never reached the site outflow (∼250 m downgradient) and displayed complex plume morphology, typically following the patterns of higher hydraulic conductivity within the upper 0.1 m of the saturated peat, rather than the microtopography. Based on the 50% breakthrough isotherms, sodium and chloride were transported at an average solute velocity of 1.9 and 1.1 m day-1, respectively (average linear groundwater velocity = 2.1 m day-1); thus, the solutes were retarded by a factor of 2.1 and 1.2 for sodium and chloride, respectively. Due to the inherent retardation of solutes into inactive pores and relatively high solute residence times, this study demonstrates the potential for wastewater polishing in ladder fens.

Effect of media composition on bioavailability and toxicity of silver and silver nanoparticles in fish intestinal cells (RTgutGC).

PubMed

Minghetti, Matteo; Schirmer, Kristin

2016-12-01

To understand conditions affecting bioavailability and toxicity of citrate-coated silver nanoparticles (cit-AgNP) and dissolved silver at the luminal enterocyte interface, we exposed rainbow trout (Oncorhynchus mykiss) gut cells (RTgutGC) in media of contrasting composition: two amino acid-containing media, one of which was supplemented with proteins, as can be expected during digestion; and two protein and amino acid-free media contrasting low and high chloride content, as can be expected in the lumen of fish adapting to freshwater or seawater, respectively. Dose-response curves were generated measuring cell metabolic activity, membrane and lysosome integrity over a period of 72 hours. Then, nontoxic doses were applied and total silver accumulation, metallothionein and glutathione reductase mRNA levels were determined. The presence of proteins stabilized cit-AgNP keeping them in suspension. Conversely, in protein-free media, cit-AgNP agglomerated and settled, resulting in higher cellular accumulation of silver and toxicity. Chloride concentrations in exposure media modulated the toxicity of AgNO 3 but not of cit-AgNP. Moreover, while amino acid-containing media are protective against AgNO 3 , likely due to the formation of thiolate complexes, they are only partially protective against cit-AgNP. Viability assays indicated that lysosomes are targets of cit-AgNP, supporting the hypothesis that cit-AgNP exert toxicity intracellularly. Metallothionein, a sensor of metal bioavailability, was induced by cit-AgNP in high chloride medium but not in low chloride medium, indicating that chloride might have a role in mobilizing silver from intercellular vesicles. Overall, this study shows that AgNP bioavailability and toxicity in the intestine is linked to its luminal content.

Nonequilibrium 2-Hydroxyoctadecanoic Acid Monolayers: Effect of Electrolytes

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

Lendrum, Conrad D.; Ingham, Bridget; Lin, Binhua

2012-02-06

2-Hydroxyacids display complex monolayer phase behavior due to the additional hydrogen bonding afforded by the presence of the second hydroxy group. The placement of this group at the position {alpha} to the carboxylic acid functionality also introduces the possibility of chelation, a utility important in crystallization including biomineralization. Biomineralization, like many biological processes, is inherently a nonequilibrium process. The nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid was investigated on each of pure water, calcium chloride, sodium bicarbonate and calcium carbonate crystallizing subphases as a precursor study to a model calcium carbonate biomineralizing system, each at a pH of {approx}6. Themore » role of the bicarbonate co-ion in manipulating the monolayer structure was determined by comparison with monolayer phase behavior on a sodium chloride subphase. Monolayer phase behavior was probed using surface pressure/area isotherms, surface potential, Brewster angle microscopy, and synchrotron-based grazing incidence X-ray diffraction and X-ray reflectivity. Complex phase behavior was observed for all but the sodium chloride subphase with hydrogen bonding, electrostatic and steric effects defining the symmetry of the monolayer. On a pure water subphase hydrogen bonding dominates with three phases coexisting at low pressures. Introduction of calcium ions into the aqueous subphase ensures strong cation binding to the surfactant head groups through chelation. The monolayer becomes very unstable in the presence of bicarbonate ions within the subphase due to short-range hydrogen bonding interactions between the monolayer and bicarbonate ions facilitated by the sodium cation enhancing surfactant solubility. The combined effects of electrostatics and hydrogen bonding are observed on the calcium carbonate crystallizing subphase.« less

Synthesis, characterization and spectroscopic properties of the hydrazodye and new hydrazodye-metal complexes

NASA Astrophysics Data System (ADS)

Bouhdada, M.; EL Amane, M.

2017-12-01

The hydrazodye (L) [disodium (7-hydroxyl-8-phenylazo-1,3-naphthalenedisulfonate)] is prepared and characterized by infrared 1H,13C, NMR and UV-visible spectra. The spectral data of the ligand (L) existing predominantly in the hydrazones form. Reaction of the hydrazodye (L) with Cd2+, Ni2+, Cu2+ and Zn2+ chloride gave two series of metal complexes with general formula [ML2 (OH2)2]2Cl and [ML2 (caf)2]2Cl. Their complexes were identified by FTIR, UV-visible spectra, 1H, 13C, NMR, EPR, XRD and molar conductance. The molar conductance reveals that the new series of metal complexes are non-electrolytes. The postulated octahedral structure of the obtained complexes is also proposed on spectroscopic data analysis.

Synthesis, characterization and antibacterial activity of a new calcium complex using sodium 2-mercaptobenzothiazole and 1, 10-phenanthroline as ligands

NASA Astrophysics Data System (ADS)

Gulab, Hussain; Shah, Zarbad; Mahmood, Mazhar; Shah, Syed Raza; Ali, Sajid; Iqbal, Muhammad; Khan, Muhammad Naeem; Flörke, Ulrich; Khan, Shahid Ali

2018-02-01

A new Ca-complex (Ca (H2 O)4 (C12 H8 N2)2)(C7 H4 N S2)2 has been synthesized by the reaction of calcium chloride, sodium 2-mercaptobenzothiazole and 1,10-phenanthroline. The complex was characterized by using X-ray crystallography and FT-IR spectroscopy. The complex was tested against different bacterial strains i.e. Staphylococcus aureus, Escherichia coli, Acinetobacter baumanni, Providencia stuartii and Pseudomonas aeruginosa. The complex was found to exhibit remarkable anti-bacterial activity against Pseudomonas aeruginosa with an inhibition zone of 25 mm and good anti-bacterial activity against Acinetobacter baumanni with a zone of inhibition of 16 mm comparable to the Levofloxacin standard (zone of inhibition of 25 mm).

Synthesis and evaluation of gadolinium complexes based on PAMAM as MRI contrast agents.

PubMed

Yan, Guo-Ping; Hu, Bin; Liu, Mai-Li; Li, Li-Yun

2005-03-01

Diethylenetriaminepentaacetic acid (DTPA) and pyridoxamine (PM) were incorporated into the amine groups on the surface of ammonia-core poly(amidoamine) dendrimers (PAMAM, Generation 2.0-5.0) to obtain dendritic ligands. These dendritic ligands were reacted with gadolinium chloride to yield the corresponding dendritic gadolinium (Gd) complexes. The dendritic ligands and their gadolinium complexes were characterized by(1)HNMR, IR, UV and elemental analysis. Relaxivity studies showed that the dendritic gadolinium complexes possessed higher relaxation effectiveness compared with the clinically used Gd-DTPA. After administration of the dendritic gadolinium complexes (0.09 mmol kg(-1) ) to rats, magnetic resonance imaging of the liver indicated that the dendritic gadolinium complexes containing pyridoxamine groups enhanced the contrast of the MR images of the liver, provided prolonged intravascular duration and produced highly contrasted visualization of blood vessels.

Utility of positron annihilation lifetime technique for the assessment of spectroscopic data of some charge-transfer complexes derived from N-(1-Naphthyl)ethylenediamine dihydrochloride

NASA Astrophysics Data System (ADS)

Refat, Moamen S.; Adam, Abdel Majid A.; Sharshar, T.; Saad, Hosam A.; Eldaroti, Hala H.

2014-03-01

In this work, structural, thermal, morphological, pharmacological screening and positron annihilation lifetime measurements were performed on the interactions between a N-(1-Naphthyl)ethylenediamine dihydrochloride (NEDA·2HCl) donor and three types of acceptors to characterize these CT complexes. The three types of acceptors include π-acceptors (quinol and picric acid), σ-acceptors (iodine) and vacant orbital acceptors (tin(IV) tetrachloride and zinc chloride). The positron annihilation lifetime parameters were found to be dependent on the structure, electronic configuration, the power of acceptors and molecular weight of the CT complexes. The positron annihilation lifetime spectroscopy can be used as a probe for the formation of charge-transfer (CT) complexes.

Complexes possessing rare "tertiary" sulfonamide nitrogen-to-metal bonds of normal length: fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes with hydrophilic sulfonamide ligands.

PubMed

Abhayawardhana, Pramuditha L; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

2014-01-21

Tertiary sulfonamide nitrogen-to-metal bonds of normal length are very rare. We recently discovered such a bond in one class of fac-[Re(CO)3(N(SO2R)(CH2Z)2)](n) complexes (Z = 2-pyridyl) with N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). fac-[M(CO)3(N(SO2R)(CH2Z)2)](n) agents (M = (186/188)Re, (99m)Tc) could find use as radiopharmaceutical bioconjugates when R is a targeting moiety. However, the planar, electron-withdrawing 2-pyridyl groups of N(SO2R)dpa destabilize the ligand to base and create relatively rigid chelate rings, raising the possibility that the rare M-N(sulfonamide) bond is an artifact of a restricted geometry. Also, the hydrophobic 2-pyridyl groups could cause undesirable accumulation in the liver, limiting future use in radiopharmaceuticals. Our goal is to identify a robust, hydrophilic, and flexible N(CH2Z)2 chelate framework. New C2-symmetric ligands, N(SO2R)(CH2Z)2 with (Z = CH2NH2; R = Me, dmb, or tol), were prepared by treating N(H)dien(Boc)2, a protected diethylenetriamine (N(H)dien) derivative, with methanesulfonyl chloride (MeSO2Cl), 3,5-dimethylbenzenesulfonyl chloride (dmbSO2Cl), and 4-methylbenzenesulfonyl chloride (tolSO2Cl). Treatment of fac-[Re(CO)3(H2O)3](+) with these ligands, designated as N(SO2R)dien, afforded new fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes. Comparing the fac-[Re(CO)3(N(SO2Me)dien)]PF6 and fac-[Re(CO)3(N(SO2Me)dpa)]PF6 complexes, we find that the Re(I)-N(sulfonamide) bonds are normal in length and statistically identical and that the methyl (13)C NMR signal has an unusually upfield shift compared to that in the free ligand. We attribute this unusual upfield shift to the fact that the sulfonamide N undergoes an sp(2)-to-sp(3) rehybridization upon coordination to Re(I) in both complexes. Thus, the sulfonamide N of N(SO2R)dien ligands is a good donor, even though the chelate rings are conformationally flexible. Addition of the strongly basic and potentially monodentate ligand, 4-dimethylaminopyridine, did not affect the fac-[Re(CO)3(N(SO2tol)dien)]PF6 complex, even after several weeks. This complex is also stable to heat in aqueous solution. These results indicate that N(SO2R)dien ligands form fac-[Re(CO)3(N(SO2R)dien)]PF6 complexes sufficiently robust to be utilized for radiopharmaceutical development.

Phosphate removal by refined aspen wood fiber treated with carboxymethyl cellulose and ferrous chloride

Treesearch

Thomas L. Eberhardt; Soo-Hong Min; James S. Han

2006-01-01

Biomass-based filtration media are of interest as an economical means to remove pollutants and nutrients found in stormwater runoff. Refined aspen wood fiber samples treated with iron salt solutions demonstrated limited capacities to remove (ortho)phosphate from test solutions. To provide additional sites for iron complex formation, and thereby impart a greater...

Hexadecyl ammonium chloride amylose inclusion complex to emulsify cedarwood oil and treat wood against termites and wood-decay fungi

USDA-ARS?s Scientific Manuscript database

Cedarwood oil (CWO) has a wide range of bioactivities, including insect repellency and toxicity as well as conferring resistance against termites and wood-rot fungi. In previous pressure treatment work, ethanol was used as the diluent/carrier for CWO. However, it is preferable to use a water-based ...

Autocatalytic Patterning with Silver Using Tin(II) Chloride Sensitizer

ERIC Educational Resources Information Center

Mbindyo, Jeremiah K. N.; Anna, Laura J.; Fell, B. Andrew; Patton, David A.

2011-01-01

A silver mirror can be deposited on many types of surfaces from the reduction of the silver-diammine complex by a reducing sugar as proposed by Kemp in this "Journal". Three extensions of Kemp's demonstration that highlight the role of SnCl[subscript 2] sensitizer in the deposition of a silver mirror on surfaces are presented. The demonstration…

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.

Hypervalent iodine-promoted α-fluorination of acetophenone derivatives with a triethylamine·HF complex.

PubMed

Kitamura, Tsugio; Muta, Kensuke; Muta, Kazutaka

2014-06-20

The direct fluorination reaction of acetophenone using iodosylarenes and TEA·5HF was conducted under mild conditions except for use of a HF reagent. The fluorination reaction was applied to acetophenone derivatives, acetonaphthones, benzyl phenyl ketone, propiophenone, butyrophenone, 1-indanone, and phenacyl chloride, giving selectively the corresponding α-fluoroketone derivatives in good yields.

Room Temperature Synthesis of Highly Monodisperse and Sers-Active Glucose-Reduced Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Boitor, R. A.; Tódor, I. Sz.; Leopold, L. F.; Leopold, N.

2015-07-01

A novel method of synthesizing gold nanoparticles was developed through which glucose-coated nanospheres of high monodispersity were synthesized at room temperature. More than 85% of the nanoparticles showed a mean diameter of 8-9 nm. The nanoparticles were characterized through TEM, UV-Vis absorption spectroscopy, dynamic light scattering (DLS), and Zeta potential measurements and were found to be highly stable in colloidal form over time with a surface potential of -38.7 mV. The nanoparticles also showed a great Raman enhancing factor when they were tested as a surface-enhanced Raman scattering (SERS) substrate on various analytes such as rhodamine 6G, crystal violet chloride, cresyl violet chloride, rose bengal, and the Cu(II) 4-(2-pyridylazo)resorcinol complex at micromolar concentrations.

Silver in geological fluids from in situ X-ray absorption spectroscopy and first-principles molecular dynamics

NASA Astrophysics Data System (ADS)

Pokrovski, Gleb S.; Roux, Jacques; Ferlat, Guillaume; Jonchiere, Romain; Seitsonen, Ari P.; Vuilleumier, Rodolphe; Hazemann, Jean-Louis

2013-04-01

The molecular structure and stability of species formed by silver in aqueous saline solutions typical of hydrothermal settings were quantified using in situ X-ray absorption spectroscopy (XAS) measurements, quantum-chemical modeling of near-edge absorption spectra (XANES) and extended fine structure spectra (EXAFS), and first-principles molecular dynamics (FPMD). Results show that in nitrate-bearing acidic solutions to at least 200 °C, silver speciation is dominated by the hydrated Ag+ cation surrounded by 4-6 water molecules in its nearest coordination shell with mean Ag-O distances of 2.32 ± 0.02 Å. In NaCl-bearing acidic aqueous solutions of total Cl concentration from 0.7 to 5.9 mol/kg H2O (m) at temperatures from 200 to 450 °C and pressures to 750 bar, the dominant species are the di-chloride complex AgCl2- with Ag-Cl distances of 2.40 ± 0.02 Å and Cl-Ag-Cl angle of 160 ± 10°, and the tri-chloride complex AgCl32- of a triangular structure and mean Ag-Cl distances of 2.60 ± 0.05 Å. With increasing temperature, the contribution of the tri-chloride species decreases from ˜50% of total dissolved Ag in the most concentrated solution (5.9m Cl) at 200 °C to less than 10-20% at supercritical temperatures for all investigated solutions, so that AgCl2- becomes by far the dominant Ag-bearing species at conditions typical of hydrothermal-magmatic fluids. Both di- and tri-chloride species exhibit outer-sphere interactions with the solvent as shown by the detection, using FPMD modeling, of H2O, Cl-, and Na+ at distances of 3-4 Å from the silver atom. The species fractions derived from XAS and FPMD analyses, and total AgCl(s) solubilities, measured in situ in this work from the absorption edge height of XAS spectra, are in accord with thermodynamic predictions using the stability constants of AgCl2- and AgCl32- from Akinfiev and Zotov (2001) and Zotov et al. (1995), respectively, which are based on extensive previous AgCl(s) solubility measurements. These data are thus recommended for chemical equilibrium calculations in mineral-fluid systems above 200 °C. In contrast, our data disagree with SUPCRT-based datasets for Ag-Cl species, which predict large fractions of high-order chloride species, AgCl32- and AgCl43- in high-temperature saline fluids. Comparisons of the structural and stability data of Ag-Cl species derived in this study with those of their Au and Cu analogs suggest that molecular-level differences amongst the chloride complexes such as geometry, dipole moment, distances, and resulting outer-sphere interactions with the solvent may account, at least partly, for the observed partitioning of Au, Ag and Cu in vapor-brine and fluid-melt systems. In hydrothermal environments dominated by fluid-rock interactions, the contrasting affinity of these metals for sulfur ligands and the differences both in chemistry and stability of their main solid phases (Ag sulfides, Cu-Fe sulfides, and native Au) largely control the concentration and distribution of these metals in their economic deposits.

An update of hydrologic conditions and distribution of selected constituents in water, eastern Snake River Plain aquifer and perched groundwater zones, Idaho National Laboratory, Idaho, emphasis 2009–11

USGS Publications Warehouse

Davis, Linda C.; Bartholomay, Roy C.; Rattray, Gordon W.

2013-01-01

Since 1952, wastewater discharged to infiltration ponds (also called percolation ponds) and disposal wells at the Idaho National Laboratory (INL) has affected water quality in the eastern Snake River Plain (ESRP) aquifer and perched groundwater zones underlying the INL. The U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, maintains groundwater monitoring networks at the INL to determine hydrologic trends, and to delineate the movement of radiochemical and chemical wastes in the aquifer and in perched groundwater zones. This report presents an analysis of water-level and water-quality data collected from aquifer, multilevel monitoring system (MLMS), and perched groundwater wells in the USGS groundwater monitoring networks during 2009–11. Water in the ESRP aquifer primarily moves through fractures and interflow zones in basalt, generally flows southwestward, and eventually discharges at springs along the Snake River. The aquifer primarily is recharged from infiltration of irrigation water, infiltration of streamflow, groundwater inflow from adjoining mountain drainage basins, and infiltration of precipitation. From March–May 2009 to March–May 2011, water levels in wells generally declined in the northern part of the INL. Water levels generally rose in the central and eastern parts of the INL. Detectable concentrations of radiochemical constituents in water samples from aquifer wells or MLMS equipped wells in the ESRP aquifer at the INL generally decreased or remained constant during 2009–11. Decreases in concentrations were attributed to radioactive decay, changes in waste-disposal methods, and dilution from recharge and underflow. In 2011, concentrations of tritium in groundwater from 50 of 127 aquifer wells were greater than or equal to the reporting level and ranged from 200±60 to 7,000±260 picocuries per liter. Tritium concentrations from one or more discrete zones from four wells equipped with MLMS were greater than or equal to reporting levels in water samples collected at various depths. Tritium concentrations in water from wells completed in shallow perched groundwater at the Advanced Test Reactor Complex (ATR Complex) were less than the reporting levels. Tritium concentrations in deep perched groundwater at the ATR Complex equaled or exceeded the reporting level in 12 wells during at least one sampling event during 2009–11 at the ATR Complex. Concentrations of strontium-90 in water from 20 of 76 aquifer wells sampled during April or October 2011 exceeded the reporting level. Strontium-90 was not detected within the ESRP aquifer beneath the ATR Complex. During at least one sampling event during 2009–11, concentrations of strontium-90 in water from 10 wells completed in deep perched groundwater at the ATR Complex equaled or exceeded the reporting levels. During 2009–11, concentrations of plutonium-238, and plutonium-239, -240 (undivided), and americium-241 were less than the reporting level in water samples from all aquifer wells and in all wells equipped with MLMS. Concentrations of cesium-137 were equal to or slightly above the reporting level in 8 aquifer wells and from 2 wells equipped with MLMS. The concentration of chromium in water from one well south of the ATR Complex was 97 micrograms per liter (μg/L) in April 2011, just less than the maximum contaminant level (MCL) of 100 μg/L. Concentrations of chromium in water samples from 69 other wells sampled ranged from 0.8 μg/L to 25 μg/L. During 2009–11, dissolved chromium was detected in water from 15 wells completed in perched groundwater at the ATR Complex. In 2011, concentrations of sodium in water from most wells in the southern part of the INL were greater than the background concentration of 10 milligrams per liter (mg/L); the highest concentrations were at or near the Idaho Nuclear Engineering and Technology Center (INTEC). After the newpercolation ponds were put into service in 2002 southwest of the INTEC, concentrations of sodium in water samples from the Rifle Range well rose steadily until 2008, when the concentrations generally began decreasing. The increases and decreases were attributed to disposal variability in the new percolation ponds. Concentrations of sodium in most wells equipped with MLMS generally were consistent with depth. During 2011, dissolved sodium concentrations in water from 17 wells completed in deep perched groundwater at the ATR Complex ranged from 6 to 146 mg/L. In 2011, concentrations of chloride in most water samples from aquifer wells south of the INTEC and at the Central Facilities Area exceeded the background concentrations of 15 mg/L, but were less than the secondary MCL of 250 mg/L. Chloride concentrations in water from wells south of the INTEC have generally increased because of increased chloride disposal to the old percolation ponds since 1984 when discharge of wastewater to the INTEC disposal well was discontinued. After the new percolation ponds were put into service in 2002 southwest of the INTEC, concentrations of chloride in water samples from one well rose steadily until 2008 then began decreasing. Chloride concentrations in water from all but one well completed in the ESRP aquifer at or near the ATR Complex were less than background and ranged between 10 and 14 mg/L during 2011, similar to concentrations detected during the 2006–08 reporting period. During 2011, chloride concentrations in water from two aquifer wells at the Radioactive Waste Management Complex (RWMC) were slightly greater than concentrations detected during the 2006–08 reporting period. The vertical distribution of chloride concentrations in wells equipped with MLMS were generally consistent within zones during 2009–11 and ranged from about 8 to 20 mg/L. During April 2011, dissolved chloride concentrations in shallow perched groundwater at the ATR Complex ranged from 7 to 13 mg/L in water from three wells. Dissolved chloride concentrations in deep perched groundwater at the ATR Complex during 2011 ranged from 4 to 54 mg/L. In 2011, sulfate concentrations in water samples from 11 aquifer wells in the south-central part of the INL equaled or exceeded the background concentration of sulfate and ranged from 40 to 167 mg/L. The greater-than-background concentrations in water from these wells probably resulted from sulfate disposal at the ATR Complex infiltration ponds or the old INTEC percolation ponds. In 2011, sulfate concentrations in water samples from two wells near the RWMC were greater than background levels and could have resulted from well construction techniques and (or) waste disposal at the RWMC. The vertical distribution of sulfate concentrations in three wells near the southern boundary of the INL was generally consistent with depth, and ranged between 19 and 25 mg/L. The maximum dissolved sulfate concentration in shallow perched groundwater near the ATR Complex was 400 mg/L in well CWP 1 in April 2011. During 2009–11, the maximum concentration of dissolved sulfate in deep perched groundwater at the ATR Complex was 1,550 mg/L in a well located west of the chemical-waste pond. In 2011, concentrations of nitrate in water from most wells at and near the INTEC exceeded the regional background concentrations of 1 mg/L and ranged from 1.6 to 5.95 mg/L. Concentrations of nitrate in wells south of INTEC and farther away from the influence of disposal areas and the Big Lost River show a general decrease in nitrate concentrations through time. During 2009–11, water samples from 30 wells were collected and analyzed for volatile organic compounds (VOCs). Six VOCs were detected. At least one and up to five VOCs were detected in water samples from 10 wells. The primary VOCs detected include carbon tetrachloride, chloroform, tetrachloroethylene, 1,1,1-trichloroethane, and trichloroethylene. In 2011, concentrations for all VOCs were less than their respective MCL for drinking water, except carbon tetrachloride in water from two wells. During 2009–11, variability and bias were evaluated from 56 replicate and 16 blank quality-assurance samples. Results from replicate analyses were investigated to evaluate sample variability. Constituents with acceptable reproducibility were stable isotope ratios, major ions, nutrients, and VOCs. All radiochemical constituents and trace metals had acceptable reproducibility except for gross beta-particle radioactivity, aluminum, antimony, and cobalt. Bias from sample contamination was evaluated from equipment, field, container, and source-solution blanks. No detectable constituent concentrations were reported for equipment blanks of the thief samplers and sampling pipes or for the source-solution and field blanks. Equipment blanks of bailers had detectable concentrations of strontium-90, sodium, chloride, and sulfate, and the container blank had a detectable concentration of dichloromethane.

Influence of Structure, Charge, and Concentration on the Pectin-Calcium-Surfactant Complexes.

PubMed

Joshi, Nidhi; Rawat, Kamla; Bohidar, H B

2016-05-12

Polymer-surfactant complex formation of pectin with different types of surfactants, cationic (cetyltrimethylammonium bromide, CTAB and dodecyl trimethylammonium bromide, DTAB), anionic (sodium dodecyl sulfate, SDS), and neutral (Triton X-100, TX-100), was investigated at room temperature in the presence and absence of cross-linker calcium chloride using light scattering, zeta potential, rheology, and UV-vis spectroscopic measurements where the surfactant concentration was maintained below their critical micellar concentration (CMC). Results indicated that the interaction of cationic surfactant with pectin in the presence and absence of calcium chloride was much stronger compared to anionic and neutral surfactants. The neutral surfactant showed identifiable interaction despite the absence of any charged headgroup, while anionic surfactant showed feeble or very weak interaction with the polymer. The pectin-CTAB or DTAB complex formation was attributed to associative electrostatic and hydrophobic interactions. On comparison between the cationic surfactants, it was found that CTAB interacts strongly with pectin because of its long hydrocarbon chain. The morphology of complexes formed exhibited random coil structures while at higher concentration of surfactant, rod-like or extended random coil structures were noticed. Thus, functional characteristics of the complex could be tuned by varying the type of surfactant (charge and structure) and its concentration. The differential network rigidity (pectin-CTAB versus pectin-DTAB gels) obtained from rheology measurements showed that addition of a very small amount of surfactant (concentration ≪ CMC) was required for enhancing network strength, while the presence of a large amount of surfactant resulted in the formation of fragile gels. No gel formation occurred when the surfactant concentration was close to their CMC values. Considering the importance of pectin in food and pharmaceutical industry, this study is relevant.

Constants for mercury binding by organic matter isolates from the Florida Everglades

USGS Publications Warehouse

Benoit, J.M.; Mason, R.P.; Gilmour, C.C.; Aiken, G.R.

2001-01-01

Dissolved organic matter (DOM) has been implicated as an important complexing agent for Hg that can affect its mobility and bioavailability in aquatic ecosystems. However, binding constants for natural Hg-DOM complexes are not well known. We employed a competitive ligand approach to estimate conditional stability constants for Hg complexes with DOM isolates collected from Florida Everglades surface waters. The isolates examined were the hydrophobic fraction of DOM from a eutrophic, sulfidic site (F1-HPoA) and the hydrophilic fraction from an oligotrophic, low-sulfide site (2BS-HPiA). Our experimental determinations utilized overall octanol-water partitioning coefficients (Dow) for 203Hg at 0.01 M chloride and across pH and DOM concentration gradients. Use of this radioisotope allowed rapid determinations of Hg concentrations in both water and octanol phases without problems of matrix interference. Conditional stability constants (1 = 0.06, 23??C) were log K??? = 11.8 for F1-HPoA and log K' = 10.6 for 2BS-HPiA. These are similar to previously published stability constants for Hg binding to low-molecular-weight thiols. Further, F1-HPoA showed a pH-dependent decline in Dow that was consistent with models of Hg complexation with thiol groups as the dominant Hg binding sites in DOM. These experiments demonstrate that the DOM isolates are stronger ligands for Hg than chloride ion or ethylenediamine-tetraacetic acid. Speciation calculations indicate that at the DOM concentrations frequently measured in Everglades, 20 to 40 ??M, significant complexation of Hg by DOM would be expected in aerobic (sulfide-free) surface waters. Copyright ?? 2001 Elsevier Science Ltd.

Unusual 2:3:2 complex of DABCO mono-betaine with HCl and H 2O studied by X-ray diffraction, DFT calculations and spectroscopic methods

NASA Astrophysics Data System (ADS)

Barczyński, P.; Dega-Szafran, Z.; Katrusiak, A.; Perdoch, W.; Szafran, M.

2009-12-01

DABCO mono-betaine (1,4-diazabicyclo[2.2.2]octane-1-acetate) forms a complex with HCl and water in the ratio 2:3:2. The crystals are triclinic, space group P1¯. Two non-equivalent molecules of protonated DABCO mono-betaines form a homoconjugated cation through the short and asymmetric O·H·O hydrogen bond of 2.470(3) Å. Two chloride anions are involved in the N-H···Cl hydrogen bonds of 3.049(2) and 3.023(3) Å. The third chloride anion is solvated by the water molecules. The molecules of bis(1,4-diazoniumbicyclo[2.2.2]octane-1-acetate) trihydrochloride dihydrate are linked into comb-like chains by the hydrogen bond formed between water molecules of the neighboring complexes; the O(W)-H···O(W) distance is 2.920(5) Å. FTIR spectrum shows several broad bands attributed to the νO-H, νN-H and νO·H·O vibrations. The structure of three bis(1,4-diazoniumbicyclo[2.2.2]octane-1-acetate) hydrochlorides are optimized at the B3LYP/6-31G(d,p) level of theory and a theoretical IR spectrum is calculated. The values of p Ka of DABCO, DABCO mono- and di-betaines are determined by the potentiometric titration of their hydrohalides.

Raman spectroscopy of gold chloro-hydroxy speciation in fluids at ambient temperature and pressure: a re-evaluation of the effects of pH and chloride concentration

NASA Astrophysics Data System (ADS)

Murphy, P. J.; LaGrange, M. S.

1998-11-01

Previous work on gold chloride and hydroxide speciation in fluids has shown differences in opinion as to the relative importance of gold (I) and gold (III) species, as well as for the Raman peak assignments for the various species. In addition, previous experimental work has not been consistent with theoretical predictions either of the number or of the frequencies of the peaks in the Raman spectrum. In order to re-evaluate the effect of pH on Raman spectra and speciation, solutions containing gold (III) chloride were analysed by Raman spectroscopy at ambient temperature and pressure, over a range of pH from 1 to 11. Total gold concentrations were from 0.001 to 0.02 M, with total chloride concentrations of 0.004-0.5 M. The spectra obtained are consistent with the hydrolysis sequence of square-planar Au(III) complex ions [AuCl x(OH) 4-x] -, where x = 0-4. The Au-Cl stretching peaks obtained were 348/325 Rcm -1 for [AuCl 4] -, 348/335/325 Rcm -1 for [AuCl 3(OH)] -, 337/355 Rcm -1 for [AuCl 2(OH) 2] -, and 355 Rcm -1 for [AuCl(OH) 3] -. [Au(OH) 4] - probably occurred, alongside [AuCl(OH) 3] - at pH values above 11. A dark purplish-grey precipitate (Au(I)OH) formed at high pH values. No evidence for Au(I) species was found. The spectra are more consistent with theory than previous data and show the predicted number of peaks for Au-Cl and Au-OH stretches for each species. However, the peak frequencies do not fit precisely with the predictions of Tossell (1996), particularly for Au-OH stretches. Hydrolysis of the simple chloride species occurs at lower pH values than found previously, and both gold and chloride concentration were found to affect the pH ranges of stability for the various chloro-hydroxy species. Decreasing gold concentration resulted in hydrolysis occurring at lower pH values. This is especially important in the absence of excess chloride (ΣCl = 4ΣAu). Substantial hydrolysis occurred below pH = 4 for 0.02 M Au /0.08 M Cl -, and below pH = 2 for 0.001 M Au / 0.004 M Cl -. Addition of excess chloride (as NaCl) increases the pH of hydrolysis at a given gold concentration.

Inhibition of caudal fin regeneration in Corydoras aeneus by lithium chloride.

PubMed

Zarnescu, Otilia; Stavri, Simona; Moldovan, Lucia

2013-03-01

In the present study we examined the effects of lithium chloride on the Corydoras aeneus caudal fin regeneration. After caudal fin amputation, the fish were exposed 3h daily to 35 mM lithium chloride for 9 days. The effects of lithium chloride treatment were evaluated by analyzing the caudal fin structure at 3, 6 and 9 days after amputation. Comparison of normal and LiCl treated fish clearly shows that regeneration of amputated caudal fins was inhibited or delayed after lithium treatment. By the third day after amputation (dpa) either no epidermal cap or blastema ever formed or the epidermal cap had an abnormal morphology in lithium treated fish. By the 3 and 6 dpa no lepidotrichial matrix deposition was observed in the lithium treated fish compared to control fish. Unlike the control fish that completely regenerate their caudal fins after 9 dpa and have fully mineralized lepidotrichia, lithium treated fish have small blastema. In some treated fish, small amounts of new lepidotrichial matrix were observed at this time, in some fin rays. Ultrastructural observations have shown differences between control and lithium treated fish. Thus, in the lithium treated fish we observed expanded intercellular spaces between epidermal cells and many apoptotic cells. Results of this study suggest the use of this model in elucidating the molecular mechanisms that are responsible for regeneration of complex structures such as fish fins. Copyright © 2013 Elsevier Ltd. All rights reserved.

Iron clad wetlands: Soil iron-sulfur buffering determines coastal wetland response to salt water incursion

NASA Astrophysics Data System (ADS)

Schoepfer, Valerie A.; Bernhardt, Emily S.; Burgin, Amy J.

2014-12-01

Coastal freshwater wetland chemistry is rapidly changing due to increased frequency of salt water incursion, a consequence of global change. Seasonal salt water incursion introduces sulfate, which microbially reduces to sulfide. Sulfide binds with reduced iron, producing iron sulfide (FeS), recognizable in wetland soils by its characteristic black color. The objective of this study is to document iron and sulfate reduction rates, as well as product formation (acid volatile sulfide (AVS) and chromium reducible sulfide (CRS)) in a coastal freshwater wetland undergoing seasonal salt water incursion. Understanding iron and sulfur cycling, as well as their reduction products, allows us to calculate the degree of sulfidization (DOS), from which we can estimate how long soil iron will buffer against chemical effects of sea level rise. We show that soil chloride, a direct indicator of the degree of incursion, best predicted iron and sulfate reduction rates. Correlations between soil chloride and iron or sulfur reduction rates were strongest in the surface layer (0-3 cm), indicative of surface water incursion, rather than groundwater intrusion at our site. The interaction between soil moisture and extractable chloride was significantly related to increased AVS, whereas increased soil chloride was a stronger predictor of CRS. The current DOS in this coastal plains wetland is very low, resulting from high soil iron content and relatively small degree of salt water incursion. However, with time and continuous salt water exposure, iron will bind with incoming sulfur, creating FeS complexes, and DOS will increase.

Episodic fluid flow in the Nankai accretionary complex: Timescale, geochemistry, flow rates, and fluid budget

USGS Publications Warehouse

Saffer, D.M.; Bekins, B.A.

1998-01-01

Down-hole geochemical anomalies encountered in active accretionary systems can be used to constrain the timing, rates, and localization of fluid flow. Here we combine a coupled flow and solute transport model with a kinetic model for smectite dehydration to better understand and quantify fluid flow in the Nankai accretionary complex offshore of Japan. Compaction of sediments and clay dehydration provide fluid sources which drive the model flow system. We explicitly include the consolidation rate of underthrust sediments in our calculations to evaluate the impact that variations in this unknown quantity have on pressure and chloride distribution. Sensitivity analysis of steady state pressure solutions constrains bulk and flow conduit permeabilities. Steady state simulations with 30% smectite in the incoming sedimentary sequence result in minimum chloride concentrations at site 808 of 550 mM, but measured chlorinity is as low as 447 mM. We simulate the transient effects of hydrofracture or a strain event by assuming an instantaneous permeability increase of 3-4 orders of magnitude along a flow conduit (in this case the de??collement), using steady state results as initial conditions. Transient results with an increase in de??collement permeability from 10-16 m2 to 10-13 m2 and 20% smectite reproduce the observed chloride profile at site 808 after 80-160 kyr. Modeled chloride concentrations are highly sensitive to the consolidation rate of underthrust sediments, such that rapid compaction of underthrust material leads to increased freshening. Pressures within the de??collement during transient simulations rise rapidly to a significant fraction of lithostatic and remain high for at least 160 kyr, providing a mechanism for maintaining high permeability. Flow rates at the deformation front for transient simulations are in good agreement with direct measurements, but steady state flow rates are 2-3 orders of magnitude smaller than observed. Fluid budget calculations indicate that nearly 71% of the incoming water in the sediments leaves the accretionary wedge via diffuse flow out the seafloor, 0-5% escapes by focused flow along the de??collement, and roughly 1% is subducted. Copyright 1998 by the American Geophysical Union.

The Role of Chloride Complexation on Anaerobic and Aerobic Mercury Bioavailability

NASA Astrophysics Data System (ADS)

Stenzler, B.; Ruuskanen, M.; Hinz, A.; Poulain, A.

2016-12-01

In the absence of dissolved organic matter, chloride and sulphide are the dominant complexing agents affecting mercury (Hg) speciation in the environment. Bioreporters are good tools in evaluating bioavailable species of Hg. However, signal production for current Hg bioreporters requires oxygen, namely for lux and gfp gene encoded proteins, resulting in a paucity of data in anaerobic bioavailability of Hg species where it is methylated to toxic CH3Hg+. We developed and optimized a whole-cell Hg bioreporter using Escherichia coli 5α capable of functioning in aerobic and anaerobic conditions by transforming a vector containing the gene fusion between the regulatory circuitry of the mer-operon and a flavin mononucleotide-based fluorescent protein. The bioreporter exhibited no physiological limitations with respect to signal production over a chloride gradient ranging from 0 to 0.7 M. The bioreporter had a detection limit of 1 nM Hg(II) however we used 5nM Hg(II) as the optimal working concentration for Hg speciation assays. We report that HgCl42- is highly bioavailable under anoxic conditions in contrast to what was observed under oxic conditions where Hg was not bioavailable. HgCl3- was not bioavailable regardless of the presence of oxygen which we attributed to either coordination polymers consisting of [HgCl3-]x chains on the cell surface or molecular mimicry of HgCl42- onto anaerobically expressed periplasmic binding proteins specific for divalent polyatomic anions shuttling Hg to the inner membrane. In the presence of HgCl42- in saline media and Hg(OH)2 in non-saline media the addition of 2.5 and 5 μM Zn, respectively, completely inhibited uptake of neutral and negatively charged Hg species regardless of the presence of oxygen. The presence of S2- inhibited Hg uptake regardless of the presence or absence of chloride. Our experiments also suggest that ligand exchange occurred faster between S2- and Cl- than between S2- and OH-. The unexpected bioavailability of HgCl42- indicates the possibility of a novel mechanism for Hg uptake in marine environments while the bioavailability of HgS species is dependent on equilibration time and salinity.

A novel in vitro metabolomics approach for neurotoxicity testing, proof of principle for methyl mercury chloride and caffeine.

PubMed

van Vliet, Erwin; Morath, Siegfried; Eskes, Chantra; Linge, Jens; Rappsilber, Juri; Honegger, Paul; Hartung, Thomas; Coecke, Sandra

2008-01-01

There is a need for more efficient methods giving insight into the complex mechanisms of neurotoxicity. Testing strategies including in vitro methods have been proposed to comply with this requirement. With the present study we aimed to develop a novel in vitro approach which mimics in vivo complexity, detects neurotoxicity comprehensively, and provides mechanistic insight. For this purpose we combined rat primary re-aggregating brain cell cultures with a mass spectrometry (MS)-based metabolomics approach. For the proof of principle we treated developing re-aggregating brain cell cultures for 48 h with the neurotoxicant methyl mercury chloride (0.1-100 microM) and the brain stimulant caffeine (1-100 microM) and acquired cellular metabolic profiles. To detect toxicant-induced metabolic alterations the profiles were analysed using commercial software which revealed patterns in the multi-parametric dataset by principal component analyses (PCA), and recognised the most significantly altered metabolites. PCA revealed concentration-dependent cluster formations for methyl mercury chloride (0.1-1 microM), and treatment-dependent cluster formations for caffeine (1-100 microM) at sub-cytotoxic concentrations. Four relevant metabolites responsible for the concentration-dependent alterations following methyl mercury chloride treatment could be identified using MS-MS fragmentation analysis. These were gamma-aminobutyric acid, choline, glutamine, creatine and spermine. Their respective mass ion intensities demonstrated metabolic alterations in line with the literature and suggest that the metabolites could be biomarkers for mechanisms of neurotoxicity or neuroprotection. In addition, we evaluated whether the approach could identify neurotoxic potential by testing eight compounds which have target organ toxicity in the liver, kidney or brain at sub-cytotoxic concentrations. PCA revealed cluster formations largely dependent on target organ toxicity indicating possible potential for the development of a neurotoxicity prediction model. With such results it could be useful to perform a validation study to determine the reliability, relevance and applicability of this approach to neurotoxicity screening. Thus, for the first time we show the benefits and utility of in vitro metabolomics to comprehensively detect neurotoxicity and to discover new biomarkers.

Solvent dynamical control of ultrafast ground state electron transfer: implications for Class II-III mixed valency.

PubMed

Lear, Benjamin J; Glover, Starla D; Salsman, J Catherine; Londergan, Casey H; Kubiak, Clifford P

2007-10-24

We relate the solvent and temperature dependence of the rates of intramolecular electron transfer (ET) of mixed valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L = pyridyl ligand and BL = pyrazine. Complexes were reduced chemically or electrochemically to obtain the mixed valence anions in seven solvents: acetonitrile, methylene chloride, dimethylformamide, tetrahydrofuran, dimethylsulfoxide, chloroform, and hexamethylphosphoramide. Rate constants for intramolecular ET were estimated by simulating the observed degree of nu(CO) IR band shape coalescence in the mixed valence state. Correlations between rate constants for ET and solvent properties including static dielectric constant, optical dielectric constant, the quantity 1/epsilonop - 1/epsilonS, microscopic solvent polarity, viscosity, cardinal rotational moments of inertia, and solvent relaxation times were examined. In the temperature study, the complexes displayed a sharp increase in the ket as the freezing points of the solvents methylene chloride and acetonitrile were approached. The solvent phase transition causes a localized-to-delocalized transition in the mixed valence ions and an acceleration in the rate of ET. This is explained in terms of decoupling the slower solvent motions involved in the frequency factor nuN which increases the value of nuN. The observed solvent and temperature dependence of the ket for these complexes is used in order to formulate a new definition for Robin-Day class II-III mixed valence compounds. Specifically, it is proposed that class II-III compounds are those for which thermodynamic properties of the solvent exert no control over ket, but the dynamic properties of the solvent still influence ket.

Corrosion Prediction with Parallel Finite Element Modeling for Coupled Hygro-Chemo Transport into Concrete under Chloride-Rich Environment

PubMed Central

Na, Okpin; Cai, Xiao-Chuan; Xi, Yunping

2017-01-01

The prediction of the chloride-induced corrosion is very important because of the durable life of concrete structure. To simulate more realistic durability performance of concrete structures, complex scientific methods and more accurate material models are needed. In order to predict the robust results of corrosion initiation time and to describe the thin layer from concrete surface to reinforcement, a large number of fine meshes are also used. The purpose of this study is to suggest more realistic physical model regarding coupled hygro-chemo transport and to implement the model with parallel finite element algorithm. Furthermore, microclimate model with environmental humidity and seasonal temperature is adopted. As a result, the prediction model of chloride diffusion under unsaturated condition was developed with parallel algorithms and was applied to the existing bridge to validate the model with multi-boundary condition. As the number of processors increased, the computational time decreased until the number of processors became optimized. Then, the computational time increased because the communication time between the processors increased. The framework of present model can be extended to simulate the multi-species de-icing salts ingress into non-saturated concrete structures in future work. PMID:28772714

The effect of metal salts on the decomposition of sweet sorghum bagasse in flow-through liquid hot water.

PubMed

Yu, Qiang; Zhuang, Xinshu; Yuan, Zhenhong; Qi, Wei; Wang, Qiong; Tan, Xuesong

2011-02-01

The impact of the metal salts NaCl, KCl, CaCl(2), MgCl(2), FeCl(3), FeCl(2), and CuCl(2), particularly the latter, on the decomposition of hemicellulose and lignin from sweet sorghum bagasse in liquid hot water pretreatment processing was studied in an attempt to enhance the recovery of sugars. Transition metal chlorides significantly enhanced the hemicellulose removal compared to the alkaline earth metal chlorides and alkaline metal chlorides, contributing to the formation of a saccharide-metal cation intermediate complex. FeCl(2) greatly increased xylose degradation and about 60% xylan was converted into non-saccharide products. In contrast, an excellent total and monomeric xylose recovery was obtained after the CuCl(2) pretreatment. Most of the lignin was deposited on the surface of the residual solid with droplet morphologies after this pretreatment, and about 20% was degraded into monomeric products. The total recovery of sugars from sweet sorghum bagasse with 0.1% CuCl(2) solution pretreatment and 48 h enzymatic digestibility, reached 90.4%, which is superior to the recovery using hot water pretreatment only. Copyright © 2010 Elsevier Ltd. All rights reserved.

Determining the Effect of Environmental Conditions on Iron Corrosion by Atomic Absorption

ERIC Educational Resources Information Center

Malel, Esteban; Shalev, Deborah E.

2013-01-01

Iron corrosion is a complex process that occurs when iron is exposed to oxygen and humidity and is exacerbated by the presence of chloride ions. The deterioration of iron structures or other components can be costly to society and is usually evaluated by following the properties of the corroding material. Here, the iron ions released into solution…

Hydrolysis and coordination behavior of ferrocenyl-phosphonodithiolate: Synthesis and structure of Cu 4[FcP(OCH 3)( μ-S)( μ3-S)] 4 [Fc = Fe( η5-C 5H 4)( η5-C 5H 5)

NASA Astrophysics Data System (ADS)

Liu, Shu-Lei; Wang, Xi-Ying; Duan, Taike; Leung, Wa-Hung; Zhang, Qian-Feng

2010-02-01

Treatment of the dimeric [FcP(S)( μ-S)] 2 [Fc = Fe( η5-C 5H 4)( η5-C 5H 5)] with the organic base Et 3N in methylene chloride solution resulted in the isolation of a multi-component compound [Et 3NH] 2[(FcPO 2S) 2CH 2][FcPS(OH) 2] 2·CH 2Cl 2 ( 1·CH 2Cl 2). The formation of the [(FcPO 2S) 2CH 2] 2- anion was due to the dechlorination of methylene chloride, it consists of two [FcPO 2S] 2- units bridging by a methylene group. Reaction of Na[FcP(OCH 3)S 2] with equal equivalent of [Cu(MeCN) 4][ClO 4] in methanol afforded a sole tetranuclear copper(I) complex Cu 4[FcP(OCH 3)( μ-S)( μ3-S)] 4 ( 2). The neutral complex 2 consists of a crystallographically centrosymmetric tetramer containing four CuS 3 arrays each of which has one μ-sulfur and two μ3-sulfur bridges.

Rapid Fabrication of Cell-Laden Alginate Hydrogel 3D Structures by Micro Dip-Coating.

PubMed

Ghanizadeh Tabriz, Atabak; Mills, Christopher G; Mullins, John J; Davies, Jamie A; Shu, Wenmiao

2017-01-01

Development of a simple, straightforward 3D fabrication method to culture cells in 3D, without relying on any complex fabrication methods, remains a challenge. In this paper, we describe a new technique that allows fabrication of scalable 3D cell-laden hydrogel structures easily, without complex machinery: the technique can be done using only apparatus already available in a typical cell biology laboratory. The fabrication method involves micro dip-coating of cell-laden hydrogels covering the surface of a metal bar, into the cross-linking reagents calcium chloride or barium chloride to form hollow tubular structures. This method can be used to form single layers with thickness ranging from 126 to 220 µm or multilayered tubular structures. This fabrication method uses alginate hydrogel as the primary biomaterial and a secondary biomaterial can be added depending on the desired application. We demonstrate the feasibility of this method, with survival rate over 75% immediately after fabrication and normal responsiveness of cells within these tubular structures using mouse dermal embryonic fibroblast cells and human embryonic kidney 293 cells containing a tetracycline-responsive, red fluorescent protein (tHEK cells).

Cholic acid modified N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride for superoxide dismutase delivery.

PubMed

Cheng, Ye; Cai, Huanxin; Yin, Baoru; Yao, Ping

2013-09-15

A series of novel amphiphilic chitosan derivatives, cholic acid modified N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (HTCC-CA) with different quaternization degrees and cholic acid substitutions were synthesized in this study. HTCC-CA is biocompatible and forms particles in aqueous solution. The binding with superoxide dismutase (SOD) at pH 6.8 destroys the original aggregates of HTCC-CA and produces smaller SOD/HTCC-CA complex nanoparticles via electrostatic and hydrophobic interactions. The SOD loading efficiency and loading capacity of HTCC-CA can reach to more than 90% and 45%, respectively. Confocal laser scanning microscopy observation and flow cytometry analysis reveal that SOD/HTCC-CA complex nanoparticles greatly enhance the cellular internalization of the loaded SOD. The SOD activities and malonaldehyde concentrations in the serum and organs of the rats, administrated intravenously with free SOD, free HTCC-CA, and SOD/HTCC-CA nanoparticles, were assayed to evaluate the antioxidant efficiency in vivo. The results demonstrate that free HTCC-CA is effective to scavenge superoxide radicals in the blood circulation and SOD/HTCC-CA nanoparticles have better antioxidant efficiency than free SOD as well as free HTCC-CA. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrochemical preparation of nanostructured lanthanum using lanthanum chloride as a precursor in 1-butyl-3-methylimidazolium dicyanamide ionic liquid.

PubMed

Zhang, Q B; Yang, C; Hua, Y X; Li, Y; Dong, P

2015-02-14

Nanostructured lanthanum was electrochemically prepared on a platinum (Pt) substrate in the room temperature ionic liquid 1-butyl-3-methylimidazolium dicyanamide (BMI-DCA) containing anhydrous LaCl3 at 333 K. The electrochemical reduction behavior of La(iii) was investigated using cyclic voltammetry and chronoamperometry techniques. Cyclic voltammogram revealed that the reduction of La(iii) in BMI-DCA involved an irreversible process controlled by diffusion. Chronoamperometric transient analysis confirmed the diffusion controlled electrodeposition process with the diffusion coefficient of La(iii) species in the range of 10(-10) cm(2) s(-1). The strong complexing capability of DCA(-) anions facilitated the displacement of chloride ligands and induced the solubility of LaCl3. The subsequent coordination of La(iii) and DCA(-) anions forming [La(DCA)4](-) complex anions was monitored by designing amperometric titration experiments. Potentiostatically deposited La-deposits with different nanostructures were characterized by SEM, XRD and XPS analyses. The electrodeposition potential was found to play an important role in controlling the nucleation and growth kinetics of the nanocrystal during the electrodeposition process. Depending on the deposition potential, metallic lanthanum with either nanoparticles or nanoporous structures was obtained.

Molecular biology of hereditary diabetes insipidus.

PubMed

Fujiwara, T Mary; Bichet, Daniel G

2005-10-01

The identification, characterization, and mutational analysis of three different genes-the arginine vasopressin gene (AVP), the arginine vasopressin receptor 2 gene (AVPR2), and the vasopressin-sensitive water channel gene (aquaporin 2 [AQP2])-provide the basis for understanding of three different hereditary forms of "pure" diabetes insipidus: Neurohypophyseal diabetes insipidus, X-linked nephrogenic diabetes insipidus (NDI), and non-X-linked NDI, respectively. It is clinically useful to distinguish two types of hereditary NDI: A "pure" type characterized by loss of water only and a complex type characterized by loss of water and ions. Patients who have congenital NDI and bear mutations in the AVPR2 or AQP2 genes have a "pure" NDI phenotype with loss of water but normal conservation of sodium, potassium, chloride, and calcium. Patients who bear inactivating mutations in genes (SLC12A1, KCNJ1, CLCNKB, CLCNKA and CLCNKB in combination, or BSND) that encode the membrane proteins of the thick ascending limb of the loop of Henle have a complex polyuro-polydipsic syndrome with loss of water, sodium, chloride, calcium, magnesium, and potassium. These advances provide diagnostic and clinical tools for physicians who care for these patients.

Toxicity Identification and Evaluation for the Effluent from Wastewater Treatment Plant in Industrial Complex using D.magna

NASA Astrophysics Data System (ADS)

Lee, S.; Keum, H.; Chun Sang, H.

2015-12-01

In recent years, the interests on the impacts of industrial wastewater on aquatic ecosystem have increased with concern about ecosystem protection and human health. Whole effluent toxicity tests are used to monitor toxicity by unknown toxic chemicals as well as conventional pollutants from industrial effluent discharges. This study describes the application of TIE (toxicity identification evaluation) procedures to an acutely toxic effluent from a wastewater treatment plant in industrial complex which was toxic to Daphnia magna. In TIE phase I (characterization step), the toxic effects by heavy metals, organic compounds, oxidants, volatile organic compounds, suspended solids and ammonia were screened and revealed that the source of toxicity is far from these toxicants group. Chemical analysis (TIE phase II) on TDS showed that the concentration of chloride ion (6,900 mg/L) was substantially higher than that predicted from EC50 for D. magna. In confirmation step (TIE phase III), chloride ion was demonstrated to be main toxicant in this effluent by the spiking approach, species sensitivity approach and deletion approach. Calcium, potassium, magnesium, sodium, fluorine, sulfate ion concentration (450, 100, 80, 5,300, 0.66, 2,200mg/L) was not shown toxicity from D. magna. Finally, we concluded that chloride was the most contributing toxicant in the waste water treatment plant. Further research activities are needed for technical support of toxicity identification and evaluation on the various types of wastewater treatment plant discharge in Korea. Keywords : TIE, D. magna, Industrial waste water Acknowledgement This research was supported by a grant (15IFIP-B089908-02) from Plant Research Program funded by Ministry of Land, Infrastructure and Transport of Korean government

KLHL3 regulates paracellular chloride transport in the kidney by ubiquitination of claudin-8

PubMed Central

Gong, Yongfeng; Wang, Jinzhi; Yang, Jing; Gonzales, Ernie; Perez, Ronaldo; Hou, Jianghui

2015-01-01

A rare Mendelian syndrome—pseudohypoaldosteronism type II (PHA-II)—features hypertension, hyperkalemia, and metabolic acidosis. Genetic linkage studies and exome sequencing have identified four genes—with no lysine kinase 1 (wnk1), wnk4, Kelch-like 3 (KLHL3), and Cullin 3 (Cul3)—mutations of which all caused PHA-II phenotypes. The previous hypothesis was that the KLHL3–Cul3 ubiquitin complex acted on the wnk4–wnk1 kinase complex to regulate Na+/Cl− cotransporter (NCC) mediated salt reabsorption in the distal tubules of the kidney. Here, we report the identification of claudin-8 as a previously unidentified physiologic target for KLHL3 and provide an alternative explanation for the collecting duct’s role in PHA-II. Using a tissue-specific KO approach, we have found that deletion of claudin-8 in the collecting duct of mouse kidney caused hypotension, hypokalemia, and metabolic alkalosis, an exact mirror image of PHA-II. Mechanistically, the phenotypes in claudin-8 KO animals were caused by disruption of the claudin-8 interaction with claudin-4, the paracellular chloride channel, and delocalization of claudin-4 from the tight junction. In mouse collecting duct cells, knockdown of KLHL3 profoundly increased the paracellular chloride permeability. Mechanistically, KLHL3 was directly bound to claudin-8, and this binding led to the ubiquitination and degradation of claudin-8. The dominant PHA-II mutation in KLHL3 impaired claudin-8 binding, ubiquitination, and degradation. These findings have attested to the concept that the paracellular pathway is physiologically regulated through the ubiquitination pathway, and its deregulation may lead to diseases of electrolyte and blood pressure imbalances. PMID:25831548

Reactivity of the Ni-->B dative sigma-bond in the nickel boratrane compounds [kappa4-B(mimBut)3]NiX (X=Cl, OAc, NCS, N3): synthesis of a series of B-functionalized tris(2-mercapto-1-tert-butylimidazolyl)borato complexes, [YTmBut)]NiZ.

PubMed

Pang, Keliang; Tanski, Joseph M; Parkin, Gerard

2008-02-28

The nickel boratrane complexes [kappa4-B(mimBut))3]Ni(kappa1-OAc), [kappa4-B(mimBut)3]NiNCS and [kappa4-B(mimBut)3]NiN3 are obtained via metathesis of the chloride ligand of [kappa4-B(mimBut)3]NiCl with TlOAc, KSCN and NaN3, respectively; the Ni-->B bond in these complexes is a site of reactivity, thereby providing a means of synthesizing nickel complexes that feature B-functionalized tris(mercaptoimidazolyl)borate derivatives, [YTmBut]NiZ.

Inhibition of GABA-gated chloride channels by 12,14-dichlorodehydroabietic acid in mammalian brain.

PubMed

Nicholson, R A; Lees, G; Zheng, J; Verdon, B

1999-03-01

1. 12,14-dichlorodehydroabietic acid (12,14-Cl2DHA) reduced GABA-stimulated uptake of 36Cl- into mouse brain synaptoneurosomes suggesting inhibition of mammalian GABA(A) receptor function. 2. 12,14-Cl2DHA did not affect the binding of [3H]-muscimol to brain membranes but displaced specifically bound [3H]-EBOB. The inhibitory effect on [3H]-EBOB binding was not reversible. 12,14-Cl2DHA reduced the availability of [3H]-EBOB binding sites (Bmax) without changing the KD of the radioligand for remaining sites. 12,14-Cl2DHA did not affect the rate of association of [3H]-EBOB with its chloride channel receptor, but increased the initial rate of [3H]-EBOB dissociation. 3. 12,14-Cl2DHA enhanced the incidence of EPSCs when rapidly applied to cultured rat cortical neurones. Longer exposures produced block of IPSCs with marked increases in the frequency of EPSCs and min EPSCs. 12,14-Cl2DHA also irreversibly suppressed chloride currents evoked by pulses of exogenous GABA in these cells. 4. Ultimately, 12,14-Cl2DHA inhibited all synaptic traffic and action currents in current clamped cells indicating that, in contrast to picrotoxinin (which causes paroxysmal bursting), it is not fully selective for the GABA(A) receptor-chloride channel complex. 5. The depolarizing block seen with 12,14-Cl2DHA in amphotericin-perforated preparations implicates loss of Ca2+ buffering in the polarity change and this may account for inhibition of spontaneous action potentials. 6. Our investigation demonstrates that 12,14-Cl2DHA blocks GABA-dependent chloride entry in mammalian brain and operates as a non-competitive insurmountable GABA(A) antagonist. The mechanism likely involves either irreversible binding of 12,14-Cl2DHA to the trioxabicyclooctane recognition site or a site that is allosterically coupled to it. We cannot exclude, however, the possibility that 12,14-Cl2DHA causes localized proteolysis or more extensive conformational change within a critical subunit of the chloride channel.

Biochar composites with nano zerovalent iron and eggshell powder for nitrate removal from aqueous solution with coexisting chloride ions.

PubMed

Ahmad, Munir; Ahmad, Mahtab; Usman, Adel R A; Al-Faraj, Abdullah S; Abduljabbar, Adel S; Al-Wabel, Mohammad I

2017-09-18

Biochar (BC) was produced from date palm tree leaves and its composites were prepared with nano zerovalent iron (nZVI-BC) and hen eggshell powder (EP-BC). The produced BC and its composites were characterized by SEM, XRD, BET, and FTIR for surface structural, mineralogical, and chemical groups and tested for their efficiency for nitrate removal from aqueous solutions in the presence and absence of chloride ions. The incidence of graphene and nano zerovalent iron (Fe 0 ) in the nZVI-BC composite was confirmed by XRD. The nZVI-BC composite possessed highest surface area (220.92 m 2  g -1 ), carbon (80.55%), nitrogen (3.78%), and hydrogen (11.09%) contents compared to other materials. Nitrate sorption data was fitted well to the Langmuir (R 2  = 0.93-0.98) and Freundlich (R 2  = 0.90-0.99) isotherms. The sorption kinetics was adequately explained by the pseudo-second-order, power function, and Elovich models. The nZVI-BC composite showed highest Langmuir predicted sorption capacity (148.10 mg g -1 ) followed by EP-BC composite (72.77 mg g -1 ). In addition to the high surface area, the higher nitrate removal capacity of nZVI-BC composite could be attributed to the combination of two processes, i.e., chemisorption (outer-sphere complexation) and reduction of nitrate to ammonia or nitrogen by Fe 0 . The appearance of Fe-O stretching and N-H bonds in post-sorption FTIR spectra of nZVI-BC composite suggested the occurrence of redox reaction and formation of Fe compound with N, such as ferric nitrate (Fe(NO 3 ) 3 ·9H 2 O). Coexistence of chloride ions negatively influenced the nitrate sorption. The decrease in nitrate sorption with increasing chloride ion concentration was observed, which could be due to the competition of free active sites on the sorbents between nitrate and chloride ions. The nZVI-BC composite exhibited higher nitrate removal efficiency compared to other materials even in the presence of highest concentration (100 mg L -1 ) of coexisting chloride ion.

Co-doped sodium chloride crystals exposed to different irradiation temperature

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

Ortiz-Morales, A.; Cruz-Zaragoza, E.; Furetta, C.

2013-07-03

Monocrystals of NaCl:XCl{sub 2}:MnCl{sub 2}(X = Ca,Cd) at four different concentrations have been analyzed. The crystals were exposed to different irradiation temperature, such as at room temperature (RT), solid water (SW), dry ice (DI) and liquid nitrogen (LN). The samples were irradiated with photon from {sup 60}Co irradiators. The co-doped sodium chloride crystals show a complex structure of glow curves that can be related to different distribution of traps. The linearity response was analyzed with the F(D) index. The F(D) value was less than unity indicating a sub-linear response was obtained from the TL response on the function of themore » dose. The glow curves were deconvoluted by using the CGCD program based on the first, second and general order kinetics.« less

Nitrate reduction by zerovalent iron: effects of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate.

PubMed

Su, Chunming; Puls, Robert W

2004-05-01

Recent studies have shown that zerovalent iron (Fe0) may potentially be used as a chemical medium in permeable reactive barriers (PRBs) for groundwater nitrate remediation; however, the effects of commonly found organic and inorganic ligands in soil and sediments on nitrate reduction by Fe0 have not been well understood. A 25.0 mL nitrate solution of 20.0 mg of N L(-1) (1.43 mM nitrate) was reacted with 1.00 g of Peerless Fe0 at 200 rpm on a rotational shaker at 23 degrees C for up to 120 h in the presence of each of the organic acids (3.0 mM formic, 1.5 mM oxalic, and 1.0 mM citric acids) and inorganic acids (3.0 mM HCl, 1.5 mM H2SO4, 3.0 mM H3BO3, and 1.5 mM H3PO4). These acids provided an initial dissociable H+ concentration of 3.0 mM available for nitrate reduction reactions under conditions of final pH < 9.3. Nitrate reduction rates (pseudo-first-order) increased in the order: H3PO4 < citric acid < H3BO3 < oxalic acid < H2SO4 < formic acid < HCl, ranging from 0.00278 to 0.0913 h(-1), corresponding to surface area normalized rates ranging from 0.126 to 4.15 h(-1) m(-2) mL. Correlation analysis showed a negative linear relationship between the nitrate reduction rates for the ligands and the conditional stability constants for the soluble complexes of the ligands with Fe2+ (R2 = 0.701) or Fe3+ (R2 = 0.918) ions. This sequence of reactivity corresponds also to surface adsorption and complexation of the three organic ligands to iron oxides, which increase in the order formate < oxalate < citrate. The results are also consistent with the sequence of strength of surface complexation of the inorganic ligands to iron oxides, which increases in the order: chloride < sulfate < borate < phosphate. The blockage of reactive sites on the surface of Fe0 and its corrosion products by specific adsorption of the inner-sphere complex forming ligands (oxalate, citrate, sulfate, borate, and phosphate) may be responsible for the decreased nitrate reduction by Fe0 relative to the chloride system.

mer, fac, and Bidentate Coordination of an Alkyl-POP Ligand in the Chemistry of Nonclassical Osmium Hydrides.

PubMed

Esteruelas, Miguel A; García-Yebra, Cristina; Martín, Jaime; Oñate, Enrique

2017-01-03

Nonclassical and classical osmium polyhydrides containing the diphosphine 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant(P i Pr 2 ) 2 ), coordinated in κ 3 -mer, κ 3 -fac, and κ 2 -P,P fashions, have been isolated during the cyclic formation of H 2 by means of the sequential addition of H + and H - or H - and H + to the classical trihydride OsH 3 Cl{xant(P i Pr 2 ) 2 } (1). This complex adds H + to form the compressed dihydride dihydrogen complex [OsCl(H···H)(η 2 -H 2 ){xant(P i Pr 2 ) 2 }] + (2). Under argon, cation 2 loses H 2 and the resulting unsaturated fragment dimerizes to give [(Os(H···H){xant(P i Pr 2 ) 2 }) 2 (μ-Cl) 2 ] 2+ (3). During the transformation the phosphine changes its coordination mode from mer to fac. The benzofuran counterpart of 1, OsH 3 Cl{dbf(P i Pr 2 ) 2 } (4; dbf(P i Pr 2 ) 2 = 4,6-bis(diisopropylphosphino)dibenzofuran), also adds H + to afford the benzofuran counterpart of 2, [OsCl(H···H)(η 2 -H 2 ){xant(P i Pr 2 ) 2 }] + (5), which in contrast to the latter is stable and does not dimerize. Acetonitrile breaks the chloride bridge of 3 to form the dihydrogen [OsCl(η 2 -H 2 )(CH 3 CN){xant(P i Pr 2 ) 2 }] + (6), regenerating the mer coordination of the diphosphine. The hydride ion also breaks the chloride bridge of 3. The addition of KH to 3 leads to 1, closing a cycle for the formation of H 2 . Complex 1 reacts with a second hydride ion to give OsH 4 {xant(P i Pr 2 ) 2 } (7) as consequence of the displacement of the chloride. Similarly to the latter, the oxygen atom of the mer-coordinated diphosphine of 7 has a tendency to be displaced by the hydride ion. Thus, the addition of KH to 7 yields [OsH 5 {xant(P i Pr 2 ) 2 }] - (8), containing a κ 2 -P,P-diphosphine. Complex 8 is easily protonated to afford OsH 6 {xant(P i Pr 2 ) 2 } (9), which releases H 2 to regenerate 7, closing a second cycle for the formation of molecular hydrogen.

Short Communication: Evaluation of antimicrobial activities of Harmine, Harmaline, Nicotine and their complexes.

PubMed

Salman, Saad; Idrees, Fariha; Pervaiz, Sadia; Shah, Fahad Hassan; Badshah, Sareer; Abdullah; Usman, Mohammad; Halimi, Sm Ashhad; Idrees, Jawaria

2016-07-01

Harmine, Harmaline, Nicotine and its various complexes synthesized have been characterized by physical, spectral and analytical methods and curtained for in-vitro antimicrobial activity against different bacterial and fungal species at two different concentrations i.e.100μ/100µl and 200μ/100µl dose level respectively. Analysis showed that Nicotine, Zinc-Nico, Cd-Nico, Hg-Nico, Ni-Nico, Cu-Nico, Co-Nico, Harmine, and Harmaline having conc. of 100ug/ 100ul had antibacterial activity on zero, 5, 4, 10, zero, 5, 7, zero, zero strain of bacteria having an average of zero (SD=0.0000), 15.2000 (SD=1.30384), 18.2500 (SD=3.30404), 20.2000 (SD=1.39841), zero (SD=0.0000), 14.6000 (SD=0.89443), 15.8571 (SD=1.34519), zero (SD=0.0000), zero (SD=0.0000) respectively. Zinc (II) chloride, Cadmium (II) Iodide, Mercury (II) chloride, Nickel (II) chloride, Copper (II) chloride, Cobalt (II) chloride, Mercury (II) chloride, Mercury (II) harmine, Mercury (II) harmaline at 100ug/100ul is valid for 7, 8, 9, 2, 7, 8, 9, 10, 8 strains of bacteria with an average of 7.1429 (SD=1.06904), 10.0000 (SD=5.01427), 14.8889 (SD=6.00925), 6.0000 (SD=0.0000), 8.5714 (SD=4.27618), 8.2500 (SD=0.88641), 14.8889 (SD=6.00925), 18.6000 (SD=2.45855), 18.5000 (SD=1.85164) respectively. The above given compounds at the conc. of 200 μ/100ul is valid for 10, 9, 10, 8, 8, 10, 10, 10, 10 strains of bacteria with an average of 8.1 (SD=1.66333), 11.7778 (SD=5.28625), 16.1000 (SD=6.36745), 6.5000 (SD=0.92582), 9.7500 (SD=4.43203), 9.9000 (SD=2.76687), 16.1000 (SD=6.36745), 22.0000 (SD=2.44949), 20.4000 (SD=2.75681) respectively. The above given compounds at conc. of 200 μ/100ul showed antibacterial action on 3, 8, 8, 10, 3, 9, 8, zero, 3 strains of bacteria with an average of 14(SD=0.000), 16.8750 (SD=1.35620), 18.2500 (SD=3.45378), 22.7000 (SD=1.82878), 14.3333 (SD=0.57735), 16.7778 (SD=1.71594), zero (SD=0.000), 12.0000 (SD=1.00000) respectively. Hence according to the average value of the zone of inhibition, maximum antibacterial activity at 100-200ug/100ul is of Hg-Nico and Mercury salt; Mercury (II) harmine having an average of 20.2000 (SD=1.39841)-22.7000 (SD=1.82878) and 18.6000 (SD=2.45855)-22.0000 (SD=2.44949). Minimum antibacterial activity at 100-200ug/100ul is Nicotine100, Nicotine-Nico100, Harmine 100,Harmaline 100, Harmine 200 having zero average (SD=0.000).

Self-assembly of silver nanoparticles as high active surface-enhanced Raman scattering substrate for rapid and trace analysis of uranyl(VI) ions

NASA Astrophysics Data System (ADS)

Wang, Shaofei; Jiang, Jiaolai; Wu, Haoxi; Jia, Jianping; Shao, Lang; Tang, Hao; Ren, Yiming; Chu, Mingfu; Wang, Xiaolin

2017-06-01

A facile surface-enhanced Raman scattering (SERS) substrate based on the self-assembly of silver nanoparticles on the modified silicon wafer was obtained, and for the first time, an advanced SERS analysis method basing on this as-prepared substrate was established for high sensitive and rapid detection of uranyl ions. Due to the weakened bond strength of Odbnd Udbnd O resulting from two kinds of adsorption of uranyl species (;strong; and ;weak; adsorption) on the substrate, the ν1 symmetric stretch vibration frequency of Odbnd Udbnd O shifted from 871 cm- 1 (normal Raman) to 720 cm- 1 and 826 cm- 1 (SERS) along with significant Raman enhancement. Effects of the hydrolysis of uranyl ions on SERS were also investigated, and the SERS band at 826 cm- 1 was first used to approximately define the constitution of uranyl species at trace quantity level. Besides, the SERS intensity was proportional to the variable concentrations of uranyl nitrate ranging from 10- 7 to 10- 3 mol L- 1 with an excellent linear relation (R2 = 0.998), and the detection limit was 10- 7 mol L- 1. Furthermore, the related SERS approach involves low-cost substrate fabrication, rapid and trace analysis simultaneously, and shows great potential applications for the field assays of uranyl ions in the nuclear fuel cycle and environmental monitoring.

The application of visible absorption spectroscopy to the analysis of uranium in aqueous solutions

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

Colletti, Lisa Michelle; Copping, Roy; Garduno, Katherine

Through assay analysis into an excess of 1 M H 2SO 4 at fixed temperature a technique has been developed for uranium concentration analysis by visible absorption spectroscopy over an assay concentration range of 1.8 – 13.4 mgU/g. Once implemented for a particular spectrophotometer and set of spectroscopic cells this technique promises to provide more rapid results than a classical method such as Davies-Gray (DG) titration analysis. While not as accurate and precise as the DG method, a comparative analysis study reveals that the spectroscopic method can analyze for uranium in well characterized uranyl(VI) solution samples to within 0.3% ofmore » the DG results. For unknown uranium solutions in which sample purity is less well defined agreement between the developed spectroscopic method and DG analysis is within 0.5%. The technique can also be used to detect the presence of impurities that impact the colorimetric analysis, as confirmed through the analysis of ruthenium contamination. Finally, extending the technique to other assay solution, 1 M HNO 3, HCl and Na 2CO 3, has also been shown to be viable. As a result, of the four aqueous media the carbonate solution yields the largest molar absorptivity value at the most intensely absorbing band, with the least impact of temperature.« less

The application of visible absorption spectroscopy to the analysis of uranium in aqueous solutions

DOE PAGES

Colletti, Lisa Michelle; Copping, Roy; Garduno, Katherine; ...

2017-07-18

Through assay analysis into an excess of 1 M H 2SO 4 at fixed temperature a technique has been developed for uranium concentration analysis by visible absorption spectroscopy over an assay concentration range of 1.8 – 13.4 mgU/g. Once implemented for a particular spectrophotometer and set of spectroscopic cells this technique promises to provide more rapid results than a classical method such as Davies-Gray (DG) titration analysis. While not as accurate and precise as the DG method, a comparative analysis study reveals that the spectroscopic method can analyze for uranium in well characterized uranyl(VI) solution samples to within 0.3% ofmore » the DG results. For unknown uranium solutions in which sample purity is less well defined agreement between the developed spectroscopic method and DG analysis is within 0.5%. The technique can also be used to detect the presence of impurities that impact the colorimetric analysis, as confirmed through the analysis of ruthenium contamination. Finally, extending the technique to other assay solution, 1 M HNO 3, HCl and Na 2CO 3, has also been shown to be viable. As a result, of the four aqueous media the carbonate solution yields the largest molar absorptivity value at the most intensely absorbing band, with the least impact of temperature.« less

Synthesis, molecular structure and magnetic properties of a rhenium(IV) compound with catechol

NASA Astrophysics Data System (ADS)

Cuevas, A.; Geis, L.; Pintos, V.; Chiozzone, R.; Sanchíz, J.; Hummert, M.; Schumann, H.; Kremer, C.

2009-03-01

A novel Re(IV) complex containing catechol as ligand has been prepared and characterized. The crystal structure of (HNEt 3)(NBu 4)[ReCl 4(cat)]·H 2cat was determined. The rhenium ion presents a distorted octahedral geometry, being bonded to a bidentate catecholate group and four chloride anions. The magnetic properties of the complex were studied, a /2 D/ (the energy gap between ±3/2 and ±1/2 Kramers doublets) value of 190(10) cm -1. This is the largest /2 D/ value reported for Re(IV) up to now.

Chemo-enzymatic synthesis of a glycosylated peptide containing a complex N-glycan based on unprotected oligosaccharides by using DMT-MM and Endo-M.

PubMed

Tomabechi, Yusuke; Katoh, Toshihiko; Kunishima, Munetaka; Inazu, Toshiyuki; Yamamoto, Kenji

2017-08-01

For chemo-enzymatic synthesis of a glycosylated peptide, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) was used for the synthesis of a N-acetylglucosaminyl peptide and a pseudoglycopeptide by solid-phase peptide synthesis without the requirement of protecting groups on the carbohydrate. We also performed transglycosylation of an N-glycan to the N-acetylglucosaminyl peptide using endo-β-N-acetylglucosaminidase from Mucor hiemalis (Endo-M) to synthesize a glycopeptide containing a complex N-glycan.

Controlled synthesis of racemic indenyl rare-earth metal complexes via the cooperation between the intramolecular coordination of donor atoms and a bridge.

PubMed

Zhou, Shuangliu; Wu, Zhangshuan; Zhou, Lingmin; Wang, Shaowu; Zhang, Lijun; Zhu, Xiancui; Wei, Yun; Zhai, Jinhua; Wu, Jie

2013-06-03

The reactions of Me2Si(C9H6CH2CH2-DG)2 (DG = NMe2 (1), CH2NMe2 (2), OMe (3), and N(CH2CH2)2O (4)) with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 in toluene afforded a series of racemic divalent rare-earth metal complexes: {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2-DG)2}RE (DG = NMe2, RE = Yb (6) and Eu (7); DG = CH2NMe2, RE = Yb (8), Eu (9), and Sm (10); DG = OMe, RE = Yb (11) and Eu (12); DG = N(CH2CH2)2O, RE = Yb (13) and Eu (14)). Similarly, the racemic divalent rare-earth metal complexes {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2CH2NMe2)(C9H5CH2CH2OMe)}RE (RE = Yb (15) and Eu (16)) were also obtained. The reaction of Me2Si(C9H5CH2CH2OMe)2Li2 with NdCl3 gave a racemic dimeric neodymium chloride {η(5):η(1):η(5)-Me2Si(C9H5CH2CH2OMe)2NdCl}2 (17), whereas the reaction of Me2Si(C9H5CH2CH2NMe2)2Li2 with SmCl3 afforded a racemic dinuclear samarium chloride bridged by lithium chloride {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2NMe2)2SmCl}2(μ-LiCl) (18). Further reaction of complex 18 with LiCH2SiMe3 provided an unexpected rare-earth metal alkyl complex {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm (19) through the activation of an sp(3) C-H bond α-adjacent to the nitrogen atom. Complexes 19 and {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Y (20) were also obtained by one-pot reactions of Me2Si(C9H5CH2CH2NMe2)2Li2 with RECl3 followed by treatment with LiCH2SiMe3. All compounds were fully characterized by spectroscopic methods and elemental analysis. Complexes 6-10 and 14-20 were further characterized by single-crystal X-ray diffraction analysis. All of the prepared rare-earth metal complexes were racemic, suggesting that racemic organo rare-earth metal complexes could be controllably synthesized by the cooperation between a bridge and the intramolecular coordination of donor atoms.

Synthesis and amino acids complexation of tripodal hexasubstituted benzene chiral receptors

NASA Astrophysics Data System (ADS)

Choksakulporn, Saowanaporn; Punkvang, Auradee; Sritana-anant, Yongsak

2015-02-01

The parent 1,3,5-triacetyl-2,4,6-trihydroxybenzene was prepared in up to 91% yield using a one-pot, one step reaction catalyzed by aluminum chloride. Its alkylations with 1,5-dibromopentane generated a symmetric tripodal hexasubstituted benzene precursor in the alternated conformer predicted by a theoretical calculation. Subsequent substitutions and reductions provided the corresponding tris-amine in 59% yield. Aminations of the tripodal precursor with (R)-(+)-1-phenylethylamine obtained a chiral tris-amine ligand in 44% yield. 1H NMR titrations of this ligand with each of three L-amino acid derivatives as guest molecules confirmed the presence of their complexes, in which the complex with alanine derivative displayed the strongest interactions with the ligand. Job plots suggested that all complexes composed of 1:2 ratios of the ligand and these guests. Theoretical calculations additionally revealed the structures and the associated binding parameters of the complexes.

Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

DOE R&D Accomplishments Database

Cram, D. J.

1980-01-15

Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

Arrested 1,2-hydrogen migration from silicon to nickel upon oxidation of a three-coordinate Ni(I) silyl complex.

PubMed

Iluc, Vlad M; Hillhouse, Gregory L

2010-09-01

Reaction of the dimeric Ni(I) chloride complex [(dtbpe)NiCl](2) (1) with dimesitylsilyl potassium affords the three-coordinate Ni(I) silyl complex (dtbpe)Ni(SiHMes(2)) (2). Alternatively, 2 can be prepared by an oxidative-addition reaction of Mes(2)Si(H)OTf (Tf = CF(3)SO(3)) with the nickel(0) complex [(dtbpe)Ni](2)(mu-C(6)H(6)) (3), with (dtbpe)Ni(OTf) (4) formed as an easily separable byproduct. The one-electron oxidation of 2 by ferrocenium affords diamagnetic [(dtbpe)Ni(mu-H)SiMes(2)][BAr(F)(4)] (5), a Ni(II) complex formed by partial 1,2-H migration from silicon to nickel and featuring an unusual 3-center, 2-electron bonding motif between Ni, Si, and the bridging H. Complex 5 was also obtained from Mes(2)SiH(2) activation by the neopentyl complex salt [(dtbpe)Ni(CH(2)CMe(3))][BAr(F)(4)] (6) with elimination of neopentane.

Synthesis, spectroscopic characterization, thermal studies, catalytic epoxidation and biological activity of chromium and molybdenum hexacarbonyl bound to a novel N 2O 2 Schiff base

NASA Astrophysics Data System (ADS)

Abdel Aziz, Ayman A.

2010-08-01

Complexes of M(CO) 6 (M = Cr and Mo) with novel Schiff base N,N'-bis(salicylidene)4,5-dichloro-1,2-phenylenediamine (H 2L) were prepared in benzene in two different conditions: (i) under reduced pressure resulting the dicarbonyl precursors [Cr(CO) 2(H 2L)] and [Mo(CO) 2(L)] and (ii) in air resulting the oxo complex [Cr(O)(L)] and the dioxo complex [Mo(O) 2(L)]. The complexes were characterized by elemental analysis, IR, 1H NMR, mass spectrometry, and magnetic measurement. Thermal behaviors of the complexes were also studied by using thermogravimetric analysis (TGA). The catalytic activity of the novel complexes in the epoxidation of cyclooctene, cyclohexene, 1-octene and 1-hexene with tert-butyl-hydroperoxide (TBHP) in methylene chloride was investigated. The antimicrobial activities of the ligand and their complexes have been screened against various strains of bacteria and fungi and the results have been compared with some known antibiotics.

Review of Laboratory Program on Degradation Mechanisms in Soil of Wastewater From Nitroguanidine Manufacture

DTIC Science & Technology

1987-03-01

in./hr) (3). Nutrients (organic nitrogen, ammonia-nitrogen, nitrate/I nitrite-nitrogen, potassium , and phosphorus) in SFAAP soils are generally...A mixture con- taining equal portions of these was diluted with 0.085 percent potassium chloride. The 30 percent solution was filtered and the...01 L (d) Cyanamide - Spectrophotometric determination after complexation with pentacyanoamine ferrate reagent. Detection limit was approximately 100

Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: Synthesis, spectroscopic characterization and anticancer activity

NASA Astrophysics Data System (ADS)

El-Boraey, Hanaa A.

2012-11-01

Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N4] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate dx2-y2 ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC50 = 25.6 and 41 μM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line.

Synthesis, characterization and properties of copper(I) complexes with bis(diphenylphosphino)-ferrocene ancillary ligand

NASA Astrophysics Data System (ADS)

Liu, Xinfang; Zhang, Songlin; Ding, Yuqiang

2012-06-01

Three copper(I) complexes (2-4) containing dppf ancillary ligand (dppf = bis(diphenylphosphino)-ferrocene) were synthesized when chloride-bridged copper(I) complex 1 reacted with acetanilide and characterized by IR, element analysis and NMR spectrum. And the crystal structures of complexes 2 and 4 have been determined by X-ray diffraction method. Complex 2, an acetate-bridged copper(I) complex, was obtained under N2 atmosphere in un-dried solvent; the acetate ion came from the hydrolysis reaction of acetanilide due to residual water in solvent. Acetanilide was deprotonated and coordinated with the copper(I) centre to form a copper(I) amidate complex 3 when reacted in pre-dried solvent. In addition, a known complex 4, the oxidation product of dppf, was isolated from the same reaction system when reacted in air atmosphere. CV and TG experiments were carried out to check the electron transfer properties and thermal stabilities of complexes 2-3. Finally, the arylation reaction of complex 3 with iodobenzene was performed to study the reaction mechanism of copper(I) catalyzed Goldberg reaction.

Activation of renal ClC-K chloride channels depends on an intact N terminus of their accessory subunit barttin.

PubMed

Wojciechowski, Daniel; Thiemann, Stefan; Schaal, Christina; Rahtz, Alina; de la Roche, Jeanne; Begemann, Birgit; Becher, Toni; Fischer, Martin

2018-06-01

ClC-K channels belong to the CLC family of chloride channels and chloride/proton antiporters. They contribute to sodium chloride reabsorption in Henle's loop of the kidney and to potassium secretion into the endolymph by the stria vascularis of the inner ear. Their accessory subunit barttin stabilizes the ClC-K/barttin complex, promotes its insertion into the surface membrane, and turns the pore-forming subunits into a conductive state. Barttin mutations cause Bartter syndrome type IV, a salt-wasting nephropathy with sensorineural deafness. Here, studying ClC-K/barttin channels heterologously expressed in MDCK-II and HEK293T cells with confocal imaging and patch-clamp recordings, we demonstrate that the eight-amino-acids-long barttin N terminus is required for channel trafficking and activation. Deletion of the complete N terminus (Δ2-8 barttin) retained barttin and human hClC-Ka channels in intracellular compartments. Partial N-terminal deletions did not compromise subcellular hClC-Ka trafficking but drastically reduced current amplitudes. Sequence deletions encompassing Thr-6, Phe-7, or Arg-8 in barttin completely failed to activate hClC-Ka. Analyses of protein expression and whole-cell current noise revealed that inactive channels reside in the plasma membrane. Substituting the deleted N terminus with a polyalanine sequence was insufficient for recovering chloride currents, and single amino acid substitutions highlighted that the correct sequence is required for proper function. Fast and slow gate activation curves obtained from rat V166E rClC-K1/barttin channels indicated that mutant barttin fails to constitutively open the slow gate. Increasing expression of barttin over that of ClC-K partially recovered this insufficiency, indicating that N-terminal modifications of barttin alter both binding affinities and gating properties. © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

The Sweat Metabolome of Screen-Positive Cystic Fibrosis Infants: Revealing Mechanisms beyond Impaired Chloride Transport

PubMed Central

2017-01-01

The sweat chloride test remains the gold standard for confirmatory diagnosis of cystic fibrosis (CF) in support of universal newborn screening programs. However, it provides ambiguous results for intermediate sweat chloride cases while not reflecting disease progression when classifying the complex CF disease spectrum given the pleiotropic effects of gene modifiers and environment. Herein we report the first characterization of the sweat metabolome from screen-positive CF infants and identify metabolites associated with disease status that complement sweat chloride testing. Pilocarpine-stimulated sweat specimens were collected independently from two CF clinics, including 50 unaffected infants (e.g., carriers) and 18 confirmed CF cases. Nontargeted metabolite profiling was performed using multisegment injection–capillary electrophoresis–mass spectrometry as a high throughput platform for analysis of polar/ionic metabolites in volume-restricted sweat samples. Amino acids, organic acids, amino acid derivatives, dipeptides, purine derivatives, and unknown exogenous compounds were identified in sweat when using high resolution tandem mass spectrometry, including metabolites associated with affected yet asymptomatic CF infants, such as asparagine and glutamine. Unexpectedly, a metabolite of pilocarpine, used to stimulate sweat secretion, pilocarpic acid, and a plasticizer metabolite from environmental exposure, mono(2-ethylhexyl)phthalic acid, were secreted in the sweat of CF infants at significantly lower concentrations relative to unaffected CF screen-positive controls. These results indicated a deficiency in human paraoxonase, an enzyme unrelated to mutations to the cystic fibrosis transmembrane conductance regulator (CFTR) and impaired chloride transport, which is a nonspecific arylesterase/lactonase known to mediate inflammation, bacterial biofilm formation, and recurrent lung infections in affected CF children later in life. This work sheds new light into the underlying mechanisms of CF pathophysiology as required for new advances in precision medicine of orphan diseases that benefit from early detection and intervention, including new molecular targets for therapeutic intervention. PMID:28852705

Photochemical oxidation of chloride ion by ozone in acid aqueous solution.

PubMed

Levanov, Alexander V; Isaykina, Oksana Ya; Amirova, Nazrin K; Antipenko, Ewald E; Lunin, Valerii V

2015-11-01

The experimental investigation of chloride ion oxidation under the action of ozone and ultraviolet radiation with wavelength 254 nm in the bulk of acid aqueous solution at pH 0-2 has been performed. Processes of chloride oxidation in these conditions are the same as the chemical reactions in the system O3 - OH - Cl(-)(aq). Despite its importance in the environment and for ozone-based water treatment, this reaction system has not been previously investigated in the bulk solution. The end products are chlorate ion ClO3(-) and molecular chlorine Cl2. The ions of trivalent iron have been shown to be catalysts of Cl(-) oxidation. The dependencies of the products formation rates on the concentrations of O3 and H(+) have been studied. The chemical mechanism of Cl(-) oxidation and Cl2 emission and ClO3(-) formation has been proposed. According to the mechanism, the dominant primary process of chloride oxidation represents the complex interaction with hydroxyl radical OH with the formation of Cl2(-) anion-radical intermediate. OH radical is generated on ozone photolysis in aqueous solution. The key subsequent processes are the reactions Cl2(-) + O3 → ClO + O2 + Cl(-) and ClO + H2O2 → HOCl + HO2. Until the present time, they have not been taken into consideration on mechanistic description and modelling of Cl(-) oxidation. The final products are formed via the reactions 2ClO → Cl2O2, Cl2O2 + H2O → 2H(+) + Cl(-) + ClO3(-) and HOCl + H(+) + Cl(-) ⇄ H2O + Cl2. Some portion of chloride is oxidized directly by O3 molecule with the formation of molecular chlorine in the end.

The Sweat Metabolome of Screen-Positive Cystic Fibrosis Infants: Revealing Mechanisms beyond Impaired Chloride Transport.

PubMed

Macedo, Adriana N; Mathiaparanam, Stellena; Brick, Lauren; Keenan, Katherine; Gonska, Tanja; Pedder, Linda; Hill, Stephen; Britz-McKibbin, Philip

2017-08-23

The sweat chloride test remains the gold standard for confirmatory diagnosis of cystic fibrosis (CF) in support of universal newborn screening programs. However, it provides ambiguous results for intermediate sweat chloride cases while not reflecting disease progression when classifying the complex CF disease spectrum given the pleiotropic effects of gene modifiers and environment. Herein we report the first characterization of the sweat metabolome from screen-positive CF infants and identify metabolites associated with disease status that complement sweat chloride testing. Pilocarpine-stimulated sweat specimens were collected independently from two CF clinics, including 50 unaffected infants (e.g., carriers) and 18 confirmed CF cases. Nontargeted metabolite profiling was performed using multisegment injection-capillary electrophoresis-mass spectrometry as a high throughput platform for analysis of polar/ionic metabolites in volume-restricted sweat samples. Amino acids, organic acids, amino acid derivatives, dipeptides, purine derivatives, and unknown exogenous compounds were identified in sweat when using high resolution tandem mass spectrometry, including metabolites associated with affected yet asymptomatic CF infants, such as asparagine and glutamine. Unexpectedly, a metabolite of pilocarpine, used to stimulate sweat secretion, pilocarpic acid, and a plasticizer metabolite from environmental exposure, mono(2-ethylhexyl)phthalic acid, were secreted in the sweat of CF infants at significantly lower concentrations relative to unaffected CF screen-positive controls. These results indicated a deficiency in human paraoxonase, an enzyme unrelated to mutations to the cystic fibrosis transmembrane conductance regulator (CFTR) and impaired chloride transport, which is a nonspecific arylesterase/lactonase known to mediate inflammation, bacterial biofilm formation, and recurrent lung infections in affected CF children later in life. This work sheds new light into the underlying mechanisms of CF pathophysiology as required for new advances in precision medicine of orphan diseases that benefit from early detection and intervention, including new molecular targets for therapeutic intervention.

Effects of chloride, sulfate and natural organic matter (NOM) on the accumulation and release of trace-level inorganic contaminants from corroding iron.

PubMed

Peng, Ching-Yu; Ferguson, John F; Korshin, Gregory V

2013-09-15

This study examined effects of varying levels of anions (chloride and sulfate) and natural organic matter (NOM) on iron release from and accumulation of inorganic contaminants in corrosion scales formed on iron coupons exposed to drinking water. Changes of concentrations of sulfate and chloride were observed to affect iron release and, in lesser extent, the retention of representative inorganic contaminants (vanadium, chromium, nickel, copper, zinc, arsenic, cadmium, lead and uranium); but, effects of NOM were more pronounced. DOC concentration of 1 mg/L caused iron release to increase, with average soluble and total iron concentrations being four and two times, respectively, higher than those in the absence of NOM. In the presence of NOM, the retention of inorganic contaminants by corrosion scales was reduced. This was especially prominent for lead, vanadium, chromium and copper whose retention by the scales decreased from >80% in the absence of NOM to <30% in its presence. Some of the contaminants, notably copper, chromium, zinc and nickel retained on the surface of iron coupons in the presence of DOC largely retained their mobility and were released readily when ambient water chemistry changed. Vanadium, arsenic, cadmium, lead and uranium retained by the scales were largely unsusceptible to changes of NOM and chloride levels. Modeling indicated that the observed effects were associated with the formation of metal-NOM complexes and effects of NOM on the sorption of the inorganic contaminants on solid phases that are typical for iron corrosion in drinking water. Copyright © 2013 Elsevier Ltd. All rights reserved.

Physiologically based pharmacokinetic modeling using microsoft excel and visual basic for applications.

PubMed

Marino, Dale J

2005-01-01

Abstract Physiologically based pharmacokinetic (PBPK) models are mathematical descriptions depicting the relationship between external exposure and internal dose. These models have found great utility for interspecies extrapolation. However, specialized computer software packages, which are not widely distributed, have typically been used for model development and utilization. A few physiological models have been reported using more widely available software packages (e.g., Microsoft Excel), but these tend to include less complex processes and dose metrics. To ascertain the capability of Microsoft Excel and Visual Basis for Applications (VBA) for PBPK modeling, models for styrene, vinyl chloride, and methylene chloride were coded in Advanced Continuous Simulation Language (ACSL), Excel, and VBA, and simulation results were compared. For styrene, differences between ACSL and Excel or VBA compartment concentrations and rates of change were less than +/-7.5E-10 using the same numerical integration technique and time step. Differences using VBA fixed step or ACSL Gear's methods were generally <1.00E-03, although larger differences involving very small values were noted after exposure transitions. For vinyl chloride and methylene chloride, Excel and VBA PBPK model dose metrics differed by no more than -0.013% or -0.23%, respectively, from ACSL results. These differences are likely attributable to different step sizes rather than different numerical integration techniques. These results indicate that Microsoft Excel and VBA can be useful tools for utilizing PBPK models, and given the availability of these software programs, it is hoped that this effort will help facilitate the use and investigation of PBPK modeling.

Electrodeposition of copper composites from deep eutectic solvents based on choline chloride.

PubMed

Abbott, Andrew P; El Ttaib, Khalid; Frisch, Gero; McKenzie, Katy J; Ryder, Karl S

2009-06-07

Here we describe for the first time the electrolytic deposition of copper and copper composites from a solution of the metal chloride salt in either urea-choline chloride, or ethylene glycol-choline chloride based eutectics. We show that the deposition kinetics and thermodynamics are quite unlike those in aqueous solution under comparable conditions and that the copper ion complexation is also different. The mechanism of copper nucleation is studied using chronoamperometry and it is shown that progressive nucleation leads to a bright nano-structured deposit. In contrast, instantaneous nucleation, at lower concentrations of copper ions, leads to a dull deposit. This work also pioneers the use of the electrochemical quartz crystal microbalance (EQCM) to monitor both current efficiency and the inclusion of inert particulates into the copper coatings. This technique allows the first in situ quantification or particulate inclusion. It was found that the composition of composite material was strongly dependent on the amount of species suspended in solution. It was also shown that the majority of material was dragged onto the surface rather than settling on to it. The distribution of the composite material was found to be even throughout the coating. This technology is important because it facilitates deposition of bright copper coatings without co-ligands such as cyanide. The incorporation of micron-sized particulates into ionic liquids has resulted, in one case, in a decrease in viscosity. This observation is both unusual and surprising; we explain this here in terms of an increase in the free volume of the liquid and local solvent perturbation.

The calcium content of human erythrocytes

PubMed Central

Harrison, D. G.; Long, C.

1968-01-01

1. The calcium content of human erythrocytes, after removal of the buffy coat and washing free from plasma with isotonic sodium chloride, has been determined by atomic absorption spectrophotometry. The mean value found for normal subjects was 0·634 μg/ml. of packed erythrocytes (0·0158 μg-atom/ml.). The corresponding values for magnesium and zinc were 79·7 and 20·1 μg/ml., respectively. 2. The calcium is considered to be mostly and perhaps exclusively located in the erythrocyte membrane, since, after osmotic haemolysis, the same amount was found in the ghost cells as was present in the erythrocytes from which they were prepared. By contrast, magnesium and zinc, which are essentially intracellular, were lost to the extent of about 96 and 92%, respectively. 3. About 90% of the calcium was removed from erythrocytes by washing with isotonic sodium chloride containing 5 mM ethylenediaminetetraacetate (EDTA), or other complexing agents of high stability constant for calcium. A small fraction of the magnesium but none of the zinc was removed by this treatment. 4. Other complexing agents of lower stability constant removed somewhat less calcium from the erythrocytes. Citrate was totally ineffective. 5. The buffy coat had a high calcium content, but this could not be removed by washing with EDTA. 6. Calcium was also determined in trichloroacetic acid extracts of ghost cells after ashing and treatment with bis-(o-hydroxyphenylimino)-ethane and measuring the red complex spectrophotometrically. The values obtained confirmed the atomic absorption measurements. PMID:4972779

Anthocyanin Interactions with DNA: Intercalation, Topoisomerase I Inhibition and Oxidative Reactions

PubMed Central

Webb, Michael R.; Min, Kyungmi; Ebeler, Susan E.

2009-01-01

Anthocyanins and their aglycone anthocyanidins are pigmented flavonoids found in significant amounts in many commonly consumed foods. They exhibit a complex chemistry in aqueous solution, which makes it difficult to study their chemistry under physiological conditions. Here we used a gel electrophoresis assay employing supercoiled DNA plasmid to examine the ability of these compounds (1) to intercalate DNA, (2) to inhibit human topoisomerase I through both inhibition of plasmid relaxation activity (catalytic inhibition) and stabilization of the cleavable DNA-topoisomerase complex (poisoning), and (3) to inhibit or enhance oxidative single-strand DNA nicking. We found no evidence of DNA intercalation by anthocyan(id)ins in the physiological pH range for any of the compounds used in this study—cyanidin chloride, cyanidin 3-O-glucoside, cyanidin 3,5-O-diglucoside, malvidin 3-O-glucoside and luteolinidin chloride. The anthocyanins inhibited topoisomerase relaxation activity only at high concentrations (> 50 μM) and we could find no evidence of topoisomerase I cleavable complex stabilization by these compounds. However, we observed that all of the anthocyan(id)ins used in this study were capable of inducing significant oxidative DNA strand cleavage (nicking) in the presence of 1 mM DTT (dithiothreitol), while the free radical scavenger, DMSO, at concentrations typically used in similar studies, completely inhibited DNA nicking. Finally, we propose a mechanism to explain the anthocyan(id)in induced oxidative DNA cleavage observed under our experimental conditions. PMID:19924259

Reactivity of lithium n-butyl amidinates towards group 14 metal(II) chlorides providing series of hetero- and homoleptic tetrylenes.

PubMed

Chlupatý, Tomáš; Padělková, Zdeňka; Lyčka, Antonín; Brus, Jiří; Růžička, Aleš

2012-04-28

The new class of homo- and heteroleptic n-butyl-N,N'-disubstituted amidinato group 14 metal(II) complexes were prepared by salt elimination from starting lithium amidinates and metal(II) chlorides both in stoichiometric ratio 2:1 and 1:1, respectively. The target amidinates contain less bulky isopropyl or cyclohexyl as well as a sterically demanding aromatic substituent. Desired 1:1 Pb(II) complexes are not accessible by the described procedure. Ligand transfer from Pb to Sn is taking place if homoleptic Pb(II) compounds are reacted with SnCl(2). Prepared tetrylenes were characterized by (1)H, (13)C, (119)Sn and (207)Pb NMR spectroscopy in C(6)D(6) or THF-d(8). X-Ray diffraction studies of one heteroleptic Ge(II) monomeric where the coordination polyhedron of the three coordinated germanium atoms is a trigonal pyramid, two different dimeric structures of heteroleptic Sn(II) complexes, one amidine hydroiodide byproduct and the oxidation product of the heteroleptic chloro Sn(II) amidinate as a tetranuclear species with two Sn(IV) and two Sn(II) atoms in central Sn(2)O(2) planar ring were performed on appropriate single crystals. The dimer of one of the heteroleptic stannylenes reveals a new type of monomeric units connection, weak Sn-Cl contact and an interaction of the tin atom with delocalized N-C(C)-N system of the amidinato ligand of the second molecule. This journal is © The Royal Society of Chemistry 2012

46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

Code of Federal Regulations, 2010 CFR

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall... equipment that may come in contact with vinyl chloride liquid or vapor. (b) Valves, flanges, and pipe...

Complexes of Nitrocellulose with Cupric Chloride,

DTIC Science & Technology

1985-11-01

4 Z I Vm 04 N-C-11 0soa -~~~ ii a Lid US 1 U C. U . i .ci OC S 0V- C C C 0 d i 0 41 v . 0i C u -s4 0- C .4 ~ tw aM 0i u U-JU I CU- w4 05 a.- ow US...la formation *d’un complexe et de la fraction pond&rale de CC par rapport A la NC, X , dltermin~ s au point de saturation. Le PCC est caractfristique de...59 s - 1. 3.5 Effect of X on the Rate of Complex Formation The variation of the ratio (ki/kf) with X is shown in Fig. 4 for sample 11 at C - 59 s

Luminescence of europium (III) complexes for visualization

NASA Astrophysics Data System (ADS)

Kolontaeva, Olga A.; Pozharov, Mikhail V.; Korolovich, Vladimir F.; Khokhlova, Anastasia R.; Kirdyanova, Anna N.; Burmistrova, Natalia A.; Zakharova, Tamara V.; Goryacheva, Irina Y.

2016-04-01

With the purpose to develop bright non-toxic luminescent label for theranostic application we have studied complexation of lanthanide dipicolinates (2,6-pyridinedicarboxylates) by sodium alginate and effect of thermal exposure of synthesized micro-capsules on their luminescent properties. Synthesized micro-capsules are stable in acidic medium but dissolve at pH ~ 4 due to transformation of cationic europium dipicolinate complex to anionic. Luminescence studies have shown that emission spectra of europium(III)-alginate complexes (both chloride and dipicolinate) contain two intensive bands characteristic to Eu3+ ion (5D0 --> 7F1 (590 nm) and 5D0 --> 7F1 (612 nm)). We have also found that at 160ºC europium(III)- alginate micro-capsules decompose to black, soot-like substance, therefore, their thermal treatment must be performed in closed environment (i.e., sealed ampoules).

Deportment of PGE and semimetals in the Volspruit deposit: the most ultramafic PGE horizon of the Bushveld Complex

NASA Astrophysics Data System (ADS)

Tanner, D.; McDonald, I.; Harmer, R. E. J.; Hughes, H. S. R.; Muir, D. D.

2017-12-01

The Volspruit deposit is a zone of disseminated magmatic sulphides carrying Ni-PGE (platinum-group element) mineralization in the Northern Limb of the Bushveld Complex, South Africa. It is one of the few known PGE prospects hosted by the lower ultramafic portion of a layered intrusion and the only known example in the Bushveld Complex. Volspruit therefore provides a unique insight into the processes governing mineralisation early in the Bushveld magmatic system. This study presents a detailed analysis from the northern portion of the Volspruit orebody combining mineralogical and textural observations with sulphide mineral trace element compositions. Electron microscopy reveals a diverse assemblage of Pt-, Pd- and Rh- dominant platinum-group minerals (PGM), electrum, Ag tellurides, Pb-chlorides, Pb-sulphides, U-oxide and monazite. Laser ablation ICP-MS has demonstrated that the Volspruit base metal sulphides have elevated PGE tenors but a range of S/Se values 1414-19319 - greater than other magmatic sulphide deposits in the northern Bushveld. The S/Se values are typical of crustal S and in agreement with previous S isotope data. These data imply a magma with initially high tenor sulphide liquid experienced local contamination from sedimentary S, leading to reduced tenors and elevated S/Se in sulphides coupled with a propensity of Pb- and Zn-bearing minerals (e.g., Pb-sulphide, Pb-chloride and sphalerite) in association with archetypal orthomagmatic sulphide assemblages. Our data demonstrate that assimilation of sedimentary rocks can modify sulphide melt evolution through the addition of metals such as Pb and Zn, not just contamination by sulphur. The Volspruit deposit illustrates the complexity of multi-stage processes governing mineralisation in the ultramafic portions of layered mafic intrusions.

Assessment of urinary thiodiglycolic acid exposure in school-aged children in the vicinity of a petrochemical complex in central Taiwan.

PubMed

Huang, Po-Chin; Liu, Li-Hsuan; Shie, Ruei-Hao; Tsai, Chih-Hsin; Liang, Wei-Yen; Wang, Chih-Wen; Tsai, Cheng-Hsien; Chiang, Hung-Che; Chan, Chang-Chuan

2016-10-01

School-aged children living in the vicinity of vinyl chloride (VCM)/polyvinyl chloride (PVC) factories may have an increased risk of exposure to hazardous air pollutants. We aimed to evaluate the urinary thiodiglycolic acid (TDGA) level, as TDGA is a major metabolite of VCM, for students at elementary schools near a petrochemical complex in central Taiwan. We recruited 343 students from 5 elementary schools based on distance to the VCM/PVC factory. First-morning urine and blood samples were obtained from our subjects from October 2013 to September 2014. Urine samples were analyzed for urinary creatinine and TDGA using LC/MS-MS. Hepatitis virus infection were assessed using blood samples. We determined their vitamin consumption, resident location, parent's employment, and other demographic or lifestyle characteristics using a questionnaire. Median urinary TDGA levels for 316 students at 5 elementary schools from the closest (<.9km) to the farthest (∼8.6km) with respect to the petrochemical complex were 147.6, 95.5, 115.5, 86.8, and 17.3μg/g creatinine, respectively. After adjusting for age, gender, hepatitis virus infection, vitamin B consumption, passive smoking, and home to source distance, we found that urinary TDGA levels for the closest students was significantly higher than those at other schools. Further, median urinary TDGA levels for students during school time were 4.1-fold higher than those during summer vacation. After adjusting for confounders, urinary TDGA levels for the school-aged children decreased with increasing distances between the elementary schools and the petrochemical complex. Copyright © 2015 Elsevier Inc. All rights reserved.

Method and Apparatus for Preventing Biofouling of Surfaces

DTIC Science & Technology

2011-06-14

ammonium compounds that are suitable for this purpose include benzalkonium chloride , benzethonium chloride , methylbenzethonium chloride , cetalkonium... chloride , cetylpyridinium chloride , cetrimonium, cetrimide, dofanium chloride , tetraethylammonium bromide, didecyldimethylammonium chloride and domiphen...upon layers of impermeable nano-particles cause diffusing molecules to follow a tortuous, 8 slow path that results in a huge reduction in

Method of processing aluminous ores

DOEpatents

Loutfy, Raouf O.; Keller, Rudolf; Yao, Neng-Ping

1981-01-01

A method of producing aluminum chloride from aluminous materials containing compounds of iron, titanium and silicon comprising reacting the aluminous materials with carbon and a chlorine-containing gas at a temperature of about 900.degree. K. to form a gaseous mixture containing chlorides of aluminum, iron, titanium and silicon and oxides of carbon; cooling the gaseous mixture to a temperature of about 400.degree. K. or lower to condense the aluminum chlorides and iron chlorides while titanium chloride and silicon chloride remain in the gas phase to effect a separation thereof; heating the mixture of iron chlorides and aluminum chlorides to a temperature of about 800.degree. K. to form gaseous aluminum chlorides and iron chlorides; passing the heated gases into intimate contact with aluminum sulfide to precipitate solid iron sulfide and to form additional gaseous aluminum chlorides; and separating the gaseous aluminum chloride from the solid iron sulfide.

Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

NASA Astrophysics Data System (ADS)

Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

2008-09-01

The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate ( I), bromo-(2-formylpyridinethiosemicarbazono)copper ( II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate ( III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I III at a concentration of 10-5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

Synthesis, characterization and molecular modeling of some transition metal complexes of Schiff base derived from 5-aminouracil and 2-benzoyl pyridine

NASA Astrophysics Data System (ADS)

Abdel-Monem, Yasser K.; Abouel-Enein, Saeyda A.; El-Seady, Safa M.

2018-01-01

Multidentate Schiff base (H2L) ligand results from condensation of 5-aminouracil and 2-benzoyl pyridine and its metal chloride (Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Fe(III), Cr(III), Ru(III), Zr(IV) and Hf(IV)) complexes were prepared. The structural features of the ligand and its metal complexes were confirmed by elemental analyses, spectroscopic methods (IR, UV-Vis, 1H NMR, mass), magnetic moment measurements and thermal studies. The data refer to the ligand coordinates with metal ions in a neutral form and shows different modes of chelation toward the metal atom. All complexes have octahedral skeleton structure, tetrahedrally Mn(II), Ni(II), trigonalbipyramidal Co(II) and square planner Pd(II). Thermal decomposition of complexes as well as the interaction of different types of solvent of crystallization are assigned by thermogravimetric analysis. Molecular modeling of prepared complexes were investigated to study the expected anticancer activities of the prepared complexes. All metal complexes have no interaction except the complexes of Pd(II), Fe(III) and Mn(II).

Blood tolerant laccase by directed evolution.

PubMed

Mate, Diana M; Gonzalez-Perez, David; Falk, Magnus; Kittl, Roman; Pita, Marcos; De Lacey, Antonio L; Ludwig, Roland; Shleev, Sergey; Alcalde, Miguel

2013-02-21

High-redox potential laccases are powerful biocatalysts with a wide range of applications in biotechnology. We have converted a thermostable laccase from a white-rot fungus into a blood tolerant laccase. Adapting the fitness of this laccase to the specific composition of human blood (above neutral pH, high chloride concentration) required several generations of directed evolution in a surrogate complex blood medium. Our evolved laccase was tested in both human plasma and blood, displaying catalytic activity while retaining a high redox potential at the T1 copper site. Mutations introduced in the second coordination sphere of the T1 site shifted the pH activity profile and drastically reduced the inhibitory effect of chloride. This proof of concept that laccases can be adapted to function in extreme conditions opens an array of opportunities for implantable nanobiodevices, chemical syntheses, and detoxification. Copyright © 2013 Elsevier Ltd. All rights reserved.

Methylmercury chloride damage to the adult rat hippocampus cannot be detected by proton magnetic resonance spectroscopy

PubMed Central

Lu, Zhiyan; Wu, Jinwei; Cheng, Guangyuan; Tian, Jianying; Lu, Zeqing; Bi, Yongyi

2014-01-01

Previous studies have found that methylmercury can damage hippocampal neurons and accordingly cause cognitive dysfunction. However, a non-invasive, safe and accurate detection method for detecting hippocampal injury has yet to be developed. This study aimed to detect methylmercury-induced damage on hippocampal tissue using proton magnetic resonance spectroscopy. Rats were given a subcutaneous injection of 4 and 2 mg/kg methylmercury into the neck for 50 consecutive days. Water maze and pathology tests confirmed that cognitive function had been impaired and that the ultrastructure of hippocampal tissue was altered after injection. The results of proton magnetic resonance spectroscopy revealed that the nitrogen-acetyl aspartate/creatine, choline complex/creatine and myoinositol/creatine ratio in rat hippocampal tissue were unchanged. Therefore, proton magnetic resonance spectroscopy can not be used to determine structural damage in the adult rat hippocampus caused by methylmercury chloride. PMID:25368649

Pseudosymmetric fac-di-aqua-trichlorido[(di-methyl-phosphor-yl)methanaminium-κO]manganese(II).

PubMed

Reiss, Guido J

2013-05-01

In the title compound, [Mn(C3H11NOP)Cl3(H2O)2], the Mn(II) metal center has a distorted o-cta-hedral geometry, coordinated by the three chloride ligands showing a facial arrangement. Two water mol-ecules and the O-coordinated dpmaH cation [dpmaH = (di-methyl-phosphor-yl)methanaminium] complete the coordination sphere. Each complex mol-ecule is connected to its neighbours by O-H⋯Cl and N-H⋯Cl hydrogen bonds. Two of the chloride ligands and the two water ligands form a hydrogen-bonded polymeric sheet in the ab plane. Furthermore, these planes are connected to adjacent planes by hydrogen bonds from the aminium function of cationic dpmaH ligand. A pseudo-mirror plane perpendicular to the b axis in the chiral space group P21 is observed together with inversion twinning [ratio = 0.864 (5):0.136 (5)].

Changes in tissue glutathione and mercury concentrations in rats following mercuric chloride injection through the hepatic portal vein

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

Chey, Sin Wun; Keong, Wong Ming; Min, Sin Yoke

The kidney is known as a primary target organ for mercury deposition. However, it is also known as an important organ for the elimination of the absorbed mercury. Tanaka and her collaborators showed that inorganic mercury when injected through caudal vein is transported to the kidney as mercury-GSH complex. If that is so, liver which contains the highest level of tissue GSH than any other organs in normal animals would appear to be a prime site for the complexion of mercury ions with GSH before they are released and transported to the kidney. In view of this, it is ofmore » interest to establish the interrelative changes of the amounts of GSH and mercury in between liver and kidney at the earlier time intervals after a direct injection of a low dosage of mercuric chloride (HgCl{sub 2}) into the hepatic portal vein.« less

The neutron structure of urate oxidase resolves a long-standing mechanistic conundrum and reveals unexpected changes in protonation.

PubMed

Oksanen, Esko; Blakeley, Matthew P; El-Hajji, Mohamed; Ryde, Ulf; Budayova-Spano, Monika

2014-01-01

Urate oxidase transforms uric acid to 5-hydroxyisourate without the help of cofactors, but the catalytic mechanism has remained enigmatic, as the protonation state of the substrate could not be reliably deduced. We have determined the neutron structure of urate oxidase, providing unique information on the proton positions. A neutron crystal structure inhibited by a chloride anion at 2.3 Å resolution shows that the substrate is in fact 8-hydroxyxanthine, the enol tautomer of urate. We have also determined the neutron structure of the complex with the inhibitor 8-azaxanthine at 1.9 Å resolution, showing the protonation states of the K10-T57-H256 catalytic triad. Together with X-ray data and quantum chemical calculations, these structures allow us to identify the site of the initial substrate protonation and elucidate why the enzyme is inhibited by a chloride anion.

Data Presentation Report, Army Spill Sites, South Plants Manufacturing Complex. Version 3.2. Phase I

DTIC Science & Technology

1988-09-01

M d C ’, pC c0 a, on 4. 10 C *0 o * ... 44 4. 14. 0 4 A. 0 tfl Vf M m Al 4, 1 Vam 77ey cS b. C tM 0 ’a .4 1 c 0 *ý 0 n 3* z aE~ c - aa42a 6%-E. a m...0 do I0 aa lp 4A - S CE 00 .1 .2.. .1.2 in .3 .2 .3 V)L 10. a MCA 6* . 6 6 mm 41 41 a 0 0 In 0 .0 4 a to0 ,C v I0 IP EEG %C.3 .3.3 .3.2 . C~~~- on 00...CLC2AThiodiglycol Thiodiglycol ( TDC ) TDGCL jAGET PRIO CHRQ D= Isopropylmethylphosphonic Isopropylmethylphosphonate IMPA acid ANIONS /IONCHROM Chloride Chloride CL

Development of a Database of Thermochemical Parameters for Use with the SOLGASMIX Computer Program

DTIC Science & Technology

1988-07-01

TITANIUM CHLORIDE (TICL4) CL4Wl(CR) TUNGSTEN CHLORIDE (WCL4) CL4Wl(G) TUNGSTEN CHLORIDE (WCL4) CL4ZR1(CR) ZIRCONIUM CHLORIDE ( ZRCL4 ) CL4ZR1(G) ZIRCONIUM...CHLORIDE ( ZRCL4 ) % % % CL5MO1(CR) MOLYBDENUM CHLORIDE (MOCL5) CL5MO1(CR,L) MOLYBDENUM CHLORIDE (MOCL5) CL5MO1(G) MOLYBDENUM CHLORIDE (MOCL5) CL5MOI(L

ELUTION OF URANIUM FROM RESIN

DOEpatents

McLEan, D.C.

1959-03-10

A method is described for eluting uranium from anion exchange resins so as to decrease vanadium and iron contamination and permit recycle of the major portion of the eluats after recovery of the uranium. Diminution of vanadium and iron contamination of the major portion of the uranium is accomplished by treating the anion exchange resin, which is saturated with uranium complex by adsorption from a sulfuric acid leach liquor from an ore bearing uranium, vanadium and iron, with one column volume of eluant prepared by passing chlorine into ammonium hydroxide until the chloride content is about 1 N and the pH is about 1. The resin is then eluted with 8 to 9 column volumes of 0.9 N ammonium chloride--0.1 N hydrochloric acid solution. The eluants are collected separately and treated with ammonia to precipitate ammonium diuranate which is filtered therefrom. The uranium salt from the first eluant is contaminated with the major portion of ths vanadium and iron and is reworked, while the uranium recovered from the second eluant is relatively free of the undesirable vanadium and irons. The filtrate from the first eluant portion is discarded. The filtrate from the second eluant portion may be recycled after adding hydrochloric acid to increase the chloride ion concentration and adjust the pH to about 1.

Atmospheric corrosion performance of different steels in early exposure in the coastal area region West Java, Indonesia

NASA Astrophysics Data System (ADS)

Nuraini, Lutviasari; Prifiharni, Siska; Priyotomo, Gadang; Sundjono, Gunawan, Hadi; Purawiardi, Ibrahim

2018-05-01

The performance of carbon steel, galvanized steel and aluminium after one month exposed in the atmospheric coastal area, which is in Limbangan and Karangsong Beach, West Java, Indonesia was evaluated. The corrosion rate was determined by weight loss method and the morphology of the steel after exposed was observed by Scanning Electron Microscopy(SEM)/Energy Dispersive X-Ray Analysis(EDX). The site was monitored to determine the chloride content in the marine atmosphere. Then, the corrosion products formed at carbon steel were characterized by X-Ray diffraction (XRD). The result showed the aggressively corrosion in Karangsong beach, indicated from the corrosion rate of carbon steel, galvanized steel and aluminium were 38.514 mpy; 4.7860 mpy and 0.5181 mpy, respectively. While in Limbangan Beach the corrosion rate of specimen carbon steel, galvanized steel and aluminium were 3.339; 0.219 and 0.166 mpy, respectively. The chloride content was found to be the main factor that influences in the atmospheric corrosion process in this area. Chloride content accumulated in Karangsong and Limbangan was 497 mg/m2.day and 117 mg/m2.day, respectively. The XRD Analysis on each carbon steel led to the characterization of a complex mixture of iron oxides phases.

Characterization of homoionic Fe 2+-type montmorillonite: Potential chemical species of iron contaminant

NASA Astrophysics Data System (ADS)

Kozai, Naofumi; Inada, Koichi; Adachi, Yoshifusa; Kawamura, Sachi; Kashimoto, Yusuke; Kozaki, Tamotsu; Sato, Seichi; Ohnuki, Toshihiko; Sakai, Takuro; Sato, Takahiro; Oikawa, Masakazu; Esaka, Fumitaka; Mitamura, Hisayoshi

2007-08-01

Fe 2+-montmorillonite with Fe 2+ ions occupying cation exchange sites is an ideal transformation product in bentonite buffer material. In our previous study on preparation and characterization of Fe 2+-montmorillonite, the montmorillonite sample that adsorbed Fe 2+ ions on almost all of the cation exchange sites was prepared using a FeCl 2 solution under an inert gas condition [N. Kozai, Y. Adachi, S. Kawamura, K. Inada, T. Kozaki, S. Sato, H. Ohashi, T. Ohnuki, T. Banba, J. Nucl. Sci. Technol. 38 (2001) 1141]. In view of the unstable nature of iron(II) chemical species, this study attempted to determine the potential contaminant iron chemical species in the sample. Nondestructive elemental analysis revealed that a small amount of chloride ions remained dispersed throughout the clay particles. The chloride ion retention may be due to the adsorption of FeCl + ion pairs in the initial FeCl 2 solution and the subsequent containment of the Cl - ions that are dissociated from the FeCl + ion pairs during excess salt removal treatment. Two explanations are advanced for the second process: the slow release of the remaining Cl - ions from the collapsed interlayer of the montmorillonite, and the transformation of a minor fraction of the remaining FeCl + ion pairs to iron(III) hydroxide chloride complexes having low solubility.

CALCIUM CHLORIDE PLANT LOOKING EAST. CALCIUM CHLORIDE BUILDING IN CENTER, ...

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

CALCIUM CHLORIDE PLANT LOOKING EAST. CALCIUM CHLORIDE BUILDING IN CENTER, CALCIUM CHLORIDE STORAGE BUILDING ON RIGHT WITH SA (SODA ASH) BUILDING IN RIGHT BACKGROUND. - Solvay Process Company, Calcium Chloride Plant, Between Willis & Milton Avenues, Solvay, Onondaga County, NY

Bicarbonate secretion and chloride absorption by rabbit cortical collecting ducts. Role of chloride/bicarbonate exchange.

PubMed Central

Star, R A; Burg, M B; Knepper, M A

1985-01-01

Cortical collecting ducts (CCD) from rabbits treated with deoxycorticosterone (DOC) actively secrete bicarbonate at high rates. To investigate the mechanism of bicarbonate secretion, we measured bicarbonate and chloride transport in CCD from rabbits treated with DOC for 9-24 d. Removal of chloride (replaced with gluconate) from both perfusate and bath inhibited bicarbonate secretion without changing transepithelial voltage. Removal of chloride only from the bath increased bicarbonate secretion, while removal of chloride only from the perfusate inhibited secretion. In contrast to the effect of removing chloride, removal of sodium from both the perfusate and bath (replacement with N-methyl-D-glucamine) did not change the rate of bicarbonate secretion. The rate of bicarbonate secretion equaled the rate of chloride absorption in tubules bathed with 0.1 mM ouabain to inhibit any cation-dependent chloride transport. Under these conditions, chloride absorption occurred against an electrochemical gradient. Removal of bicarbonate from both the perfusate and bath inhibited chloride absorption. Removal of bicarbonate only from the bath inhibited chloride absorption, while removal of bicarbonate from the lumen stimulated chloride absorption. We conclude that CCD from DOC-treated rabbits actively secrete bicarbonate and actively absorb chloride by an electroneutral mechanism involving 1:1 chloride/bicarbonate exchange. The process is independent of sodium. PMID:3930570

Superoxide scavenging activity of pirfenidone-iron complex

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

Mitani, Yoshihiro; Sato, Keizo; Muramoto, Yosuke

Pirfenidone (PFD) is focused on a new anti-fibrotic drug, which can minimize lung fibrosis etc. We evaluated the superoxide (O{sub 2}{sup {center_dot}}{sup -}) scavenging activities of PFD and the PFD-iron complex by electron spin resonance (ESR) spectroscopy, luminol-dependent chemiluminescence assay, and cytochrome c reduction assay. Firstly, we confirmed that the PFD-iron complex was formed by mixing iron chloride with threefold molar PFD, and the complex was stable in distillated water and ethanol. Secondary, the PFD-iron complex reduced the amount of O{sub 2}{sup {center_dot}}{sup -} produced by xanthine oxidase/hypoxanthine without inhibiting the enzyme activity. Thirdly, it also reduced the amount ofmore » O{sub 2}{sup {center_dot}}{sup -} released from phorbor ester-stimulated human neutrophils. PFD alone showed few such effects. These results suggest the possibility that the O{sub 2}{sup {center_dot}}{sup -} scavenging effect of the PFD-iron complex contributes to the anti-fibrotic action of PFD used for treating idiopathic pulmonary fibrosis.« less

Chloride sensing by WNK1 kinase involves inhibition of autophosphorylation

PubMed Central

Piala, Alexander T.; Moon, Thomas M.; Akella, Radha; He, Haixia; Cobb, Melanie H.; Goldsmith, Elizabeth J.

2014-01-01

WNK1 [with no lysine (K)] is a serine-threonine kinase associated with a form of familial hypertension. WNK1 is at the top of a kinase cascade leading to phosphorylation of several cotransporters, in particular those transporting sodium, potassium, and chloride (NKCC), sodium and chloride (NCC), and potassium and chloride (KCC). The responsiveness of NKCC, NCC, and KCC to changes in extracellular chloride parallels their phosphorylation state, provoking the proposal that these transporters are controlled by a chloride-sensitive protein kinase. Here, we found that chloride stabilizes the inactive conformation of WNK1, preventing kinase autophosphorylation and activation. Crystallographic studies of inactive WNK1 in the presence of chloride revealed that chloride binds directly to the catalytic site, providing a basis for the unique position of the catalytic lysine. Mutagenesis of the chloride binding site rendered the kinase less sensitive to inhibition of autophosphorylation by chloride, validating the binding site. Thus, these data suggest that WNK1 functions as a chloride sensor through direct binding of a regulatory chloride ion to the active site, which inhibits autophosphorylation. PMID:24803536

Reversibly bound chloride in the atrial natriuretic peptide receptor hormone-binding domain: possible allosteric regulation and a conserved structural motif for the chloride-binding site.

PubMed

Ogawa, Haruo; Qiu, Yue; Philo, John S; Arakawa, Tsutomu; Ogata, Craig M; Misono, Kunio S

2010-03-01

The binding of atrial natriuretic peptide (ANP) to its receptor requires chloride, and it is chloride concentration dependent. The extracellular domain (ECD) of the ANP receptor (ANPR) contains a chloride near the ANP-binding site, suggesting a possible regulatory role. The bound chloride, however, is completely buried in the polypeptide fold, and its functional role has remained unclear. Here, we have confirmed that chloride is necessary for ANP binding to the recombinant ECD or the full-length ANPR expressed in CHO cells. ECD without chloride (ECD(-)) did not bind ANP. Its binding activity was fully restored by bromide or chloride addition. A new X-ray structure of the bromide-bound ECD is essentially identical to that of the chloride-bound ECD. Furthermore, bromide atoms are localized at the same positions as chloride atoms both in the apo and in the ANP-bound structures, indicating exchangeable and reversible halide binding. Far-UV CD and thermal unfolding data show that ECD(-) largely retains the native structure. Sedimentation equilibrium in the absence of chloride shows that ECD(-) forms a strongly associated dimer, possibly preventing the structural rearrangement of the two monomers that is necessary for ANP binding. The primary and tertiary structures of the chloride-binding site in ANPR are highly conserved among receptor-guanylate cyclases and metabotropic glutamate receptors. The chloride-dependent ANP binding, reversible chloride binding, and the highly conserved chloride-binding site motif suggest a regulatory role for the receptor bound chloride. Chloride-dependent regulation of ANPR may operate in the kidney, modulating ANP-induced natriuresis.

Reversibly Bound Chloride in the Atrial Natriuretic Peptide Receptor Hormone Binding Domain: Possible Allosteric Regulation and a Conserved Structural Motif for the Chloride-binding Site

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

Ogawa, H.; Qiu, Y; Philo, J

2010-01-01

The binding of atrial natriuretic peptide (ANP) to its receptor requires chloride, and it is chloride concentration dependent. The extracellular domain (ECD) of the ANP receptor (ANPR) contains a chloride near the ANP-binding site, suggesting a possible regulatory role. The bound chloride, however, is completely buried in the polypeptide fold, and its functional role has remained unclear. Here, we have confirmed that chloride is necessary for ANP binding to the recombinant ECD or the full-length ANPR expressed in CHO cells. ECD without chloride (ECD(-)) did not bind ANP. Its binding activity was fully restored by bromide or chloride addition. Amore » new X-ray structure of the bromide-bound ECD is essentially identical to that of the chloride-bound ECD. Furthermore, bromide atoms are localized at the same positions as chloride atoms both in the apo and in the ANP-bound structures, indicating exchangeable and reversible halide binding. Far-UV CD and thermal unfolding data show that ECD(-) largely retains the native structure. Sedimentation equilibrium in the absence of chloride shows that ECD(-) forms a strongly associated dimer, possibly preventing the structural rearrangement of the two monomers that is necessary for ANP binding. The primary and tertiary structures of the chloride-binding site in ANPR are highly conserved among receptor-guanylate cyclases and metabotropic glutamate receptors. The chloride-dependent ANP binding, reversible chloride binding, and the highly conserved chloride-binding site motif suggest a regulatory role for the receptor bound chloride. Chloride-dependent regulation of ANPR may operate in the kidney, modulating ANP-induced natriuresis.« less

Reversibly bound chloride in the atrial natriuretic peptide receptor hormone-binding domain: Possible allosteric regulation and a conserved structural motif for the chloride-binding site

PubMed Central

Ogawa, Haruo; Qiu, Yue; Philo, John S; Arakawa, Tsutomu; Ogata, Craig M; Misono, Kunio S

2010-01-01

The binding of atrial natriuretic peptide (ANP) to its receptor requires chloride, and it is chloride concentration dependent. The extracellular domain (ECD) of the ANP receptor (ANPR) contains a chloride near the ANP-binding site, suggesting a possible regulatory role. The bound chloride, however, is completely buried in the polypeptide fold, and its functional role has remained unclear. Here, we have confirmed that chloride is necessary for ANP binding to the recombinant ECD or the full-length ANPR expressed in CHO cells. ECD without chloride (ECD(−)) did not bind ANP. Its binding activity was fully restored by bromide or chloride addition. A new X-ray structure of the bromide-bound ECD is essentially identical to that of the chloride-bound ECD. Furthermore, bromide atoms are localized at the same positions as chloride atoms both in the apo and in the ANP-bound structures, indicating exchangeable and reversible halide binding. Far-UV CD and thermal unfolding data show that ECD(−) largely retains the native structure. Sedimentation equilibrium in the absence of chloride shows that ECD(−) forms a strongly associated dimer, possibly preventing the structural rearrangement of the two monomers that is necessary for ANP binding. The primary and tertiary structures of the chloride-binding site in ANPR are highly conserved among receptor-guanylate cyclases and metabotropic glutamate receptors. The chloride-dependent ANP binding, reversible chloride binding, and the highly conserved chloride-binding site motif suggest a regulatory role for the receptor bound chloride. Chloride-dependent regulation of ANPR may operate in the kidney, modulating ANP-induced natriuresis. PMID:20066666

Corrosion of Steel in a Black Mangrove Environment

DTIC Science & Technology

1982-10-01

neceaaary and Identify by block number) Black Mangrove Environment Chloride Salts Corrosion Iron- Tannin Complex Steel Tannic Acid Tropic Test Center...identified to be as follows: rain water falling through the mangrove canopy picks up salts and tannins from the black mangroves. The salts...attack steel, forming water-soluble ferric ions. The tannins react DD , JAN 73 •*/J EDITION OF » MOV 65 IS OBSOLETE UNCLASSIFIED SECURITY

METHOD OF IMPROVING CORROSION RESISTANCE OF ZIRCONIUM

DOEpatents

Shannon, D.W.

1961-03-28

An improved intermediate rinse for zirconium counteracts an anomalous deposit that often results in crevices and outof-the-way places when ordinary water is used to rinse away a strong fluoride etching solution designed to promote passivation of the metal. The intermediate rinse, which is used after the etching solution and before the water, is characterized by a complexing agent for fluoride ions such as aluminum or zirconium nitrates or chlorides.

Hexadecyl ammonium chloride amylose inclusion complex to emulsify cedarwood oil and treat wood against termites and wood-decay fungi

Treesearch

F.J. Eller; W.T. Hay; G.T. Kirker; M.E. Mankowski; G.W. Sellling

2018-01-01

Cedarwood oil (CWO) has a wide range of bioactivities, including insect repellency and toxicity, as well as conferring resistance against termites and wood-decay fungi. In previous work examining pressure treatment of wood, ethanol was used as the diluent/carrier for CWO. However, it is preferable to use a water-based carrier for environmental, safety and cost...

Synthesis of 3-Methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-One: How to Avoid O-Acylation

ERIC Educational Resources Information Center

Kurteva, Vanya B.; Petrova, Maria A.

2015-01-01

In this laboratory experiment, students synthesize 3-methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-one by selective C-acylation of 3-methyl-1-phenyl-1H-pyrazol-5-one. Calcium hydroxide is used to push the tautomeric equilibrium toward the enol form, to protect the hydroxyl functionality as a complex, to trap the liberated hydrogen chloride, and to…

Formation of an Oxidant-Sensible Pd(II) Coordination Compound and Its [superscript 1]H NMR Specific Characterization: A Preparative and Analytical Challenge in Current Coordination Chemistry

ERIC Educational Resources Information Center

Abraham, Maria L.; Oppel, Iris M.

2014-01-01

A three-part experiment that leads to the synthesis of palladium(II) complex starting from a C[subscript 3]-symmetric triaminoguanidinium-based ligand is presented. In the first part, the preparation of tris-benzylidenetriaminoguanidinium chloride ([H[subscript 6]Br[subscript 3]L]Cl) by an acidic catalyzed 3-fold imine formation reaction of…

Effects of bulk colloidal stability on adsorption layers of poly(diallyldimethylammonium chloride)/sodium dodecyl sulfate at the air-water interface studied by neutron reflectometry.

PubMed

Campbell, Richard A; Yanez Arteta, Marianna; Angus-Smyth, Anna; Nylander, Tommy; Varga, Imre

2011-12-29

We show for the oppositely charged system poly(diallyldimethylammonium chloride)/sodium dodecyl sulfate that the cliff edge peak in its surface tension isotherm results from the comprehensive precipitation of bulk complexes into sediment, leaving a supernatant that is virtually transparent and a depleted adsorption layer at the air/water interface. The aggregation and settling processes take about 3 days to reach completion and occur at bulk compositions around charge neutrality of the complexes which lack long-term colloidal stability. We demonstrate excellent quantitative agreement between the measured surface tension values and a peak calculated from the surface excess of surfactant in the precipitation region measured by neutron reflectometry, using the approximation that there is no polymer left in the liquid phase. The nonequilibrium nature of the system is emphasized by the production of very different interfacial properties from equivalent aged samples that are handled differently. We go on to outline our perspective on the "true equilibrium" state of this intriguing system and conclude with a comment on its practical relevance given that the interfacial properties can be so readily influenced by the handling of kinetically trapped bulk aggregates. © 2011 American Chemical Society

CALCIUM CHLORIDE PLANT LOOKING EAST. CALCIUM CHLORIDE BUILDING ON LEFT, ...

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

CALCIUM CHLORIDE PLANT LOOKING EAST. CALCIUM CHLORIDE BUILDING ON LEFT, CALCIUM CHLORIDE STORAGE BUILDING ON RIGHT OF CENTER WITH TOP OF SA (SODA ASH) BUILDING IN RIGHT BACKGROUND. - Solvay Process Company, Calcium Chloride Plant, Between Willis & Milton Avenues, Solvay, Onondaga County, NY

Dioxin formation from waste incineration.

PubMed

Shibamoto, Takayuki; Yasuhara, Akio; Katami, Takeo

2007-01-01

There has been great concern about dioxins-polychlorinated dibenzo dioxins (PCDDs), polychlorinated dibenzo furans (PCDFs), and polychlorinated biphenyls (PCBs)-causing contamination in the environment because the adverse effects of these chemicals on human health have been known for many years. Possible dioxin-contamination has received much attention recently not only by environmental scientists but also by the public, because dioxins are known to be formed during the combustion of industrial and domestic wastes and to escape into the environment via exhaust gases from incinerators. Consequently, there is a pressing need to investigate the formation mechanisms or reaction pathways of these chlorinated chemicals to be able to devise ways to reduce their environmental contamination. A well-controlled small-scale incinerator was used for the experiments in the core references of this review. These articles report the investigation of dioxin formation from the combustion of various waste-simulated samples, including different kinds of paper, various kinds of wood, fallen leaves, food samples, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), polyvinylidene chloride, polyethylene tetraphthalate (PET), and various kinds of plastic products. These samples were also incinerated with inorganic chlorides (NaCl, KCl, CuCI2, MgCl2, MnCl2, FeCl2, CoCl2, fly ash, and seawater) or organic chlorides (PVC, chlordane, and pentachlorophenol) to investigate the role of chlorine content and/or the presence of different metals in dioxin formation. Some samples, such as newspapers, were burned after they were impregnated with NaCl or PVC, as well as being cocombusted with chlorides. The roles of incineration conditions, including chamber temperatures, O2 concentrations, and CO concentrations, in dioxin formation were also investigated. Dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases from a controlled small-scale incinerator, where experimental waste samples were burned, were analyzed by gas chromatography/mass spectrometry. Formation of total PCDFs was much higher than that of PCDDs in all samples. The total PCDFs comprised 70%-90% of the total dioxin formed. The amount of total PCDFs formed ranged from 0.78 ng/g (newspaper) to 8,490ng/g (PVC burned in high CO concentration). The amount of total PCDDs formed ranged from 0.02ng/g (newspaper) to 430ng/g (PVC). Coplanar PCBs were found at the lowest level of the dioxins formed. Their formation levels ranged from 0ng/g (newspaper) to 77.6ng/g (PVC). It is obvious that the samples with either inorganic or organic chlorides produced much more dioxins than the sample without chlorides when incinerated under similar conditions. It is not clear how inorganic and organic chloride contribute differently to dioxin formation. Among the metals examined, copper seems to have higher activity toward dioxin formation than other metals. It acted not only as a catalyst but also as a transmitter of heterogeneous chlorine. The toxicity equivalence quantity (TEQ) values generally correlated with the amount of chlorine content in the samples and the amount of dioxin formed in exhaust gases from an incinerator. When the same sample was incinerated at different temperatures, however, the sample burned at low temperature yielded a higher TEQ value than did the sample burned at high temperature. The samples that did not contain chlorine or were not combusted with chlorides exhibited low TEQ values. In contrast, samples with high chlorine content, such as PVC (51.3%), gave high TEQ values. Combustion temperatures may play an important role in dioxin formation in exhaust gases from the incineration of waste materials. However, no significant relationship between dioxin formation and chamber temperatures was reported in the core articles. However, It is obvious that dioxin formation occurred at temperatures above 450'C and was reduced significantly at temperatures above 850 degrees C. The reaction occurring in an incinerator is extremely complex, and there are many factors in addition to combustion temperature influencing dioxin formation. Even though it is possible to hypothesize reasonable formation mechanisms of dioxins produced in exhaust gases according to the results obtained from experiments in classical chemistry, the reactions involved in an incinerator are extremely complex and heterogeneous. More detailed investigation of the many individual factors influencing dioxin formation is needed to find ways to reduce their formation in individual and municipal incinerators.

Effects of Cations on Corrosion of Inconel 625 in Molten Chloride Salts

NASA Astrophysics Data System (ADS)

Zhu, Ming; Ma, Hongfang; Wang, Mingjing; Wang, Zhihua; Sharif, Adel

2016-04-01

Hot corrosion of Inconel 625 in sodium chloride, potassium chloride, magnesium chloride, calcium chloride and their mixtures with different compositions is conducted at 900°C to investigate the effects of cations in chloride salts on corrosion behavior of the alloy. XRD, SEM/EDS were used to analyze the compositions, phases, and morphologies of the corrosion products. The results showed that Inconel 625 suffers more severe corrosion in alkaline earth metal chloride molten salts than alkaline metal chloride molten salts. For corrosion in mixture salts, the corrosion rate increased with increasing alkaline earth metal chloride salt content in the mixture. Cations in the chloride molten salts mainly affect the thermal and chemical properties of the salts such as vapor pressure and hydroscopicities, which can affect the basicity of the molten salt. Corrosion of Inconel 625 in alkaline earth metal chloride salts is accelerated with increasing basicity.

Experimente ueber den Einflusse von Metaboliten und Antimetaboliten am Modell von Trichomonas Vaginalis. V. Mitteilung: Beziehungen der Vitamin-B-Kemplexe zu Trichomonas Vaginalis (Experiments on the Influence of Metabolites and Antimetabolites on the Model of Trichomonas Vaginalis. V. Communication: Relationship between Vitamin-B-Complexes and Trichomonas Vaginalis),

DTIC Science & Technology

vitamin B1 clear evidence of any influence upon Trichomonas growth could not be obtained. Choline favours the growth of Trichomonas vaginalis . In...0.20 mg/ml onward liponic acid had inhibiting effect upon Trichomonas . Carnitine chloride favoured the growth of Trichomonas vaginalis . (Modified author abstract)...The present study was concerned with the relationship between the vitamins of the B-complex and Trichomonas . From the results obtained in studies on

Dichlorido{[2-(diphenyl­phosphino)phenyl­imino­meth­yl]ferrocene-κ2 N,P}palladium(II) dichloro­methane hemi­solvate

PubMed Central

Liu, Huanyu; Shen, Dongsheng

2009-01-01

There are two independent PdII complex mol­ecules in the asymmetric unit of the title compound, [PdCl2{Fe(C5H5)(C24H19NP)}]·0.5CH2Cl2. One ferrocenyl ring of one complex mol­ecule is disordered over two sites with half-occupancy for each component. Both PdII cations adopt a distorted square-planar coordination geometry with a bidentate [2-(diphenyl­phosphino)phenyl­imino­meth­yl]ferrocene ligand and two chloride anions. PMID:21581545

NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions.

PubMed

Adam, Rosa; Alberico, Elisabetta; Baumann, Wolfgang; Drexler, Hans-Joachim; Jackstell, Ralf; Junge, Henrik; Beller, Matthias

2016-03-24

A series of seven novel N(Im)N(H)P-type pincer imidazolylphosphine ruthenium complexes has been synthesized and fully characterized. The use of hydrogenation of benzonitrile as a benchmark test identified [RuHCl(CO)(N(Im)N(H) P(tBu))] as the most active catalyst. With its stable Ru-BH4 analogue, in which chloride is replaced by BH4, a broad range of (hetero)aromatic and aliphatic nitriles, including industrially interesting adiponitrile, has been hydrogenated under mild and base-free conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution.

PubMed

See, Kimberly A; Liu, Yao-Min; Ha, Yeyoung; Barile, Christopher J; Gewirth, Andrew A

2017-10-18

Magnesium batteries offer an opportunity to use naturally abundant Mg and achieve large volumetric capacities reaching over four times that of conventional Li-based intercalation anodes. High volumetric capacity is enabled by the use of a Mg metal anode in which charge is stored via electrodeposition and stripping processes, however, electrolytes that support efficient Mg electrodeposition and stripping are few and are often prepared from highly reactive compounds. One interesting electrolyte solution that supports Mg deposition and stripping without the use of highly reactive reagents is the magnesium aluminum chloride complex (MACC) electrolyte. The MACC exhibits high Coulombic efficiencies and low deposition overpotentials following an electrolytic conditioning protocol that stabilizes species necessary for such behavior. Here, we discuss the effect of the MgCl 2 and AlCl 3 concentrations on the deposition overpotential, current density, and the conditioning process. Higher concentrations of MACC exhibit enhanced Mg electrodeposition current density and much faster conditioning. An increase in the salt concentrations causes a shift in the complex equilibria involving both cations. The conditioning process is strongly dependent on the concentration suggesting that the electrolyte is activated through a change in speciation of electrolyte complexes and is not simply due to the annihilation of electrolyte impurities. Additionally, the presence of the [Mg 2 (μ-Cl) 3 ·6THF] + in the electrolyte solution is again confirmed through careful analysis of experimental Raman spectra coupled with simulation and direct observation of the complex in sonic spray ionization mass spectrometry. Importantly, we suggest that the ∼210 cm -1 mode commonly observed in the Raman spectra of many Mg electrolytes is indicative of the C 3v symmetric [Mg 2 (μ-Cl) 3 ·6THF] + . The 210 cm -1 mode is present in many electrolytes containing MgCl 2 , so its assignment is of broad interest to the Mg electrolyte community.

40 CFR Table 2 to Subpart Ggg of... - Partially Soluble HAP

Code of Federal Regulations, 2012 CFR

2012-07-01

... Trichloroethylene Chloroethane (ethyl chloride) Trimethylpentane Vinyl acetate Xylene (p) Vinyl chloride N-hexane... Methylene chloride Allyl chloride N,N-dimethylaniline Benzene Propionaldehyde Benzyl chloride Propylene...

40 CFR Table 2 to Subpart Ggg of... - Partially Soluble HAP

Code of Federal Regulations, 2011 CFR

2011-07-01

... Trichloroethylene Chloroethane (ethyl chloride) Trimethylpentane Vinyl acetate Xylene (p) Vinyl chloride N-hexane... Methylene chloride Allyl chloride N,N-dimethylaniline Benzene Propionaldehyde Benzyl chloride Propylene...

40 CFR Table 2 to Subpart Ggg of... - Partially Soluble HAP

Code of Federal Regulations, 2010 CFR

2010-07-01

... Trichloroethylene Chloroethane (ethyl chloride) Trimethylpentane Vinyl acetate Xylene (p) Vinyl chloride N-hexane... Methylene chloride Allyl chloride N,N-dimethylaniline Benzene Propionaldehyde Benzyl chloride Propylene...

46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

Code of Federal Regulations, 2011 CFR

2011-10-01

... 46 Shipping 5 2011-10-01 2011-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34 Section 151.50-34 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall...

Exploring DNA binding and nucleolytic activity of few 4-aminoantipyrine based amino acid Schiff base complexes: A comparative approach

NASA Astrophysics Data System (ADS)

Raman, N.; Sakthivel, A.; Pravin, N.

A series of novel Co(II), Cu(II), Ni(II) and Zn(II) complexes were synthesized from Schiff base(s), obtained by the condensation of 4-aminoantipyrine with furfural and amino acid (glycine(L1)/alanine(L2)/valine(L3)) and respective metal(II) chloride. Their structural features and other properties were explored from the analytical and spectral methods. The binding behaviors of the complexes to calf thymus DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. The intrinsic binding constants for the above synthesized complexes are found to be in the order of 102 to 105 indicating that most of the synthesized complexes are good intercalators. The binding constant values (Kb) clearly indicate that valine Schiff-base complexes have more intercalating ability than alanine and glycine Schiff-base complexes. The results indicate that the complexes bind to DNA through intercalation and act as efficient cleaving agents. The in vitro antibacterial and antifungal assay indicates that these complexes are good antimicrobial agents against various pathogens. The IC50 values of [Ni(L1)2] and [Zn(L1)2] complexes imply that these complexes have preferable ability to scavenge hydroxyl radical.

Organotrichlorogermane synthesis by the reaction of elemental germanium, tetrachlorogermane and organic chloride via dichlorogermylene intermediate.

PubMed

Okamoto, Masaki; Asano, Takuya; Suzuki, Eiichi

2004-08-07

Organotrichlorogermanes were synthesized by the reaction of elemental germanium, tetrachlorogermane and organic chlorides, methyl, propyl, isopropyl and allyl chlorides. Dichlorogermylene formed by the reaction of elemental germanium with tetrachlorogermane was the reaction intermediate, which was inserted into the carbon-chlorine bond of the organic chloride to give organotrichlorogermane. When isopropyl or allyl chloride was used as an organic chloride, organotrichlorogermane was formed also in the absence of tetrachlorogermane. These chlorides were converted to hydrogen chloride, which subsequently reacted with elemental germanium to give the dichlorogermylene intermediate. The reaction of elemental germanium, tetrachlorogermane and organic chlorides provides a simple and easy method for synthesizing organotrichlorogermanes, and all the raw materials are easily available.

Characterization of ternary bivalent metal complexes with bis(2-hydroxyethyl)iminotris(hydroxymethy)methane (Bis?Tris) and the comparison of five crystal structures of Bis?Tris complexes*1

NASA Astrophysics Data System (ADS)

Inomata, Yoshie; Gochou, Yoshihiro; Nogami, Masanobu; Howell, F. Scott; Takeuchi, Toshio

2004-09-01

Eleven bivalent metal complexes with bis(2-hydroxyethyl)iminotris(hydroxymethy)methane (Bis-Tris:hihm): [M(hihm)(H 2O)]SO 4· nH 2O (M: Co, Ni, Cu, Zn), [MCl(hihm)]Cl· nH 2O (M: Co, Ni, Cu), and [M(HCOO)(hihm)](HCOO) (M: Co, Ni, Cu, Zn) have been prepared and characterized by using their infrared absorption and powder diffuse reflection spectra, magnetic susceptibility, thermal analysis and powder X-ray diffraction analysis. The crystal structures of [Ni(hihm)(H 2O)]SO 4·H 2O ( 2), [Cu(hihm)(H 2O)]SO 4 ( 3), [NiCl(hihm)]Cl·H 2O ( 6), [CuCl(hihm)]Cl ( 7) and [Co(HCOO)(hihm)](HCOO) ( 8) have been determined by single crystal X-ray diffraction analysis. The crystals of [Ni(hihm)(H 2O)]SO 4·H 2O ( 2) and [Cu(hihm)(H 2O)]SO 4 ( 3) are each orthorhombic with the space group P2 12 12 1 and Pna2 1. For both complexes, the metal atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and a water molecule. [NiCl(hihm)]Cl·H 2O ( 6) is monoclinic with the space group P2 1/ n. For complex ( 6), the nickel atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and a chloride ion. [CuCl(hihm)]Cl ( 7) is orthorhombic with the space group P2 12 12 1. Although in this copper(II) complex the copper atom is ligated by six atoms, it is more reasonable to think that the copper atom is in a trigonal bipyramidal geometry coordinated with five atoms: three hydroxyl oxygen atoms, a nitrogen atom and a chloride ion if the bond distances and angles surrounding the copper atom are taken into consideration. [Co(HCOO)(hihm)](HCOO) ( 8) is monoclinic with the space group P2 1. In cobalt(II) complex ( 8), the cobalt atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and an oxygen atom of a formate ion. The structure of complex ( 8) is the same as the structure of [NiCl(hihm)]Cl·H 2O ( 6) except for the formate ion coordinating instead of the chloride ion. [M(hihm)(H 2O)]SO 4·H 2O (M: Co, Zn) ( 1, 4), [CoCl(hihm)]Cl·H 2O ( 5) and [M(HCOO)(hihm)](HCOO) (M: Ni, Cu, Zn) ( 9- 11) seem to have the same structures as the structures of [Ni(hihm)(H 2O)]SO 4·H 2O ( 2), [NiCl(hihm)]Cl·H 2O ( 6) and [Co(HCOO)(hihm)](HCOO) ( 8), respectively, judging by the results of IR and powder diffuse reflection spectra and powder X-ray diffraction analysis. Bis-Tris has coordinated to the metal atoms as a pentadentate ligand in all complexes of which the structures have been determined by single crystal X-ray diffraction analysis in this work.

40 CFR 415.670 - Applicability; description of the zinc chloride production subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... chloride production subcategory. 415.670 Section 415.670 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Zinc Chloride Production Subcategory § 415.670 Applicability; description of the zinc chloride... chloride. ...

Removal of chloride from MSWI fly ash.

PubMed

Chen, Wei-Sheng; Chang, Fang-Chih; Shen, Yun-Hwei; Tsai, Min-Shing; Ko, Chun-Han

2012-10-30

The high levels of alkali chloride and soluble metal salts present in MSWI fly ash is worth noting for their impact on the environment. In addition, the recycling or reuse of fly ash has become an issue because of limited landfill space. The chloride content in fly ash limits its application as basis for construction materials. Water-soluble chlorides such as potassium chloride (KCl), sodium chloride (NaCl), and calcium chloride hydrate (CaCl(2) · 2H(2)O) in fly ash are easily washed away. However, calcium chloride hydroxide (Ca(OH)Cl) might not be easy to leach away at room temperature. The roasting and washing-flushing processes were applied to remove chloride content in this study. Additionally, air and CO(2) were introduced into the washing process to neutralize the hazardous nature of chlorides. In comparison with the water flushing process, the roasting process is more efficient in reducing the process of solid-liquid separation and drying for the reuse of Cl-removed fly ash particles. In several roasting experiments, the removal of chloride content from fly ash at 1050°C for 3h showed the best results (83% chloride removal efficiency). At a solid to liquid ratio of 1:10 the water-flushing process can almost totally remove water-soluble chloride (97% chloride removal efficiency). Analyses of mineralogical change also prove the efficiency of the fly ash roasting and washing mechanisms for chloride removal. Copyright © 2012 Elsevier B.V. All rights reserved.

Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder

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

Feng, Chao; Easter, Quinn T.; Blum, Suzanne A.

Employment of fluorophore-tagged alkyl and aryl iodides permitted detection of persistent surface intermediates during their direct insertion to commercially available zinc powder. The sensitivity of this subensemble microscopy technique enabled structure–reactivity studies in the formation of intermediates that are present in quantities sufficiently low as to have been undetected previously by traditional ensemble analytical techniques. In these surface intermediates we transformed them using lithium chloride, which lead to the assignment of the mechanistic role of lithium chloride as changing the rate-determining step in the reaction by lowering the barrier for solubilization of these otherwise persistent surface organometallic intermediates. The temperaturemore » dependence/qualitative barrier of the direct insertion step was determined independently from the solubilization step and from the barrier for the overall reaction. Detection of these zinc surface intermediates at the single-molecule level, i.e., of individual surface organometallic species, has been achieved for the first time. Energy dispersive X-ray spectroscopy (EDS) measurements of the elemental composition of the surface of the zinc powder determined that lithium chloride does not clean the surface of the oxides; instead, pretreatment of the surface with TMSCl effects partial removal of surface oxides after the 2 h pretreatment time previously reported in the empirically optimized synthetic procedure. The current limitations of this microscopy approach are also determined and discussed with respect to the addition of solid reagents during in operando imaging. Characterization of the resulting soluble fluorophore-tagged organozinc/LiCl complex by 1H NMR spectroscopy, mass spectrometry, and fluorescence spectroscopy provided insight into its solution dynamics and chemical exchange processes.« less

Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder

DOE PAGES

Feng, Chao; Easter, Quinn T.; Blum, Suzanne A.

2017-02-03

Employment of fluorophore-tagged alkyl and aryl iodides permitted detection of persistent surface intermediates during their direct insertion to commercially available zinc powder. The sensitivity of this subensemble microscopy technique enabled structure–reactivity studies in the formation of intermediates that are present in quantities sufficiently low as to have been undetected previously by traditional ensemble analytical techniques. In these surface intermediates we transformed them using lithium chloride, which lead to the assignment of the mechanistic role of lithium chloride as changing the rate-determining step in the reaction by lowering the barrier for solubilization of these otherwise persistent surface organometallic intermediates. The temperaturemore » dependence/qualitative barrier of the direct insertion step was determined independently from the solubilization step and from the barrier for the overall reaction. Detection of these zinc surface intermediates at the single-molecule level, i.e., of individual surface organometallic species, has been achieved for the first time. Energy dispersive X-ray spectroscopy (EDS) measurements of the elemental composition of the surface of the zinc powder determined that lithium chloride does not clean the surface of the oxides; instead, pretreatment of the surface with TMSCl effects partial removal of surface oxides after the 2 h pretreatment time previously reported in the empirically optimized synthetic procedure. The current limitations of this microscopy approach are also determined and discussed with respect to the addition of solid reagents during in operando imaging. Characterization of the resulting soluble fluorophore-tagged organozinc/LiCl complex by 1H NMR spectroscopy, mass spectrometry, and fluorescence spectroscopy provided insight into its solution dynamics and chemical exchange processes.« less

Quantitative DFT modeling of product concentration in organometallic reactions: Cu-mediated pentafluoroethylation of benzoic acid chlorides as a case study.

PubMed

Jover, Jesús

2017-11-08

DFT calculations are widely used for computing properties, reaction mechanisms and energy profiles in organometallic reactions. A qualitative agreement between the experimental and the calculated results seems to usually be enough to validate a computational methodology but recent advances in computation indicate that a nearly quantitative agreement should be possible if an appropriate DFT study is carried out. Final percent product concentrations, often reported as yields, are by far the most commonly reported properties in experimental metal-mediated synthesis studies but reported DFT studies have not focused on predicting absolute product amounts. The recently reported stoichiometric pentafluoroethylation of benzoic acid chlorides (R-C 6 H 4 COCl) with [(phen)Cu(PPh 3 )C 2 F 5 ] (phen = 1,10-phenanthroline, PPh 3 = triphenylphosphine) has been used as a case study to check whether the experimental product concentrations can be reproduced by any of the most popular DFT approaches with high enough accuracy. To this end, the Gibbs energy profile for the pentafluoroethylation of benzoic acid chloride has been computed using 14 different DFT methods. These computed Gibbs energy profiles have been employed to build kinetic models predicting the final product concentration in solution. The best results are obtained with the D3-dispersion corrected B3LYP functional, which has been successfully used afterwards to model the reaction outcomes of other simple (R = o-Me, p-Me, p-Cl, p-F, etc.) benzoic acid chlorides. The product concentrations of more complex reaction networks in which more than one position of the substrate may be activated by the copper catalyst (R = o-Br and p-I) are also predicted appropriately.

Dielectric and electrical studies of PVC-PPy blends in dilute solution of THF

NASA Astrophysics Data System (ADS)

Sharma, Deepika; Tripathi, Deepti

2018-05-01

An influence of adding Polypyrrole (PPy) which is an intrinsically conducting polymer (ICP), on the dielectric dispersion behavior of Polyvinyl chloride (PVC) in dilute solution of Tetrahydrofuran (THF) at low frequency is reported. The blends of PVC with PPy forms colloidal suspension in THF. The dielectric dispersion study of PVC-PPy blends in THF has been carried out in the frequency range of 20 Hz to 2 MHz at temperature of 303K. The effect of increasing PPy concentration on dielectric and electrical parameters such as complex dielectric function [ɛ*(ω)], loss tangent [tan δ], complex electric modulus [M*(ω)], ac conductivity [σac], and complex impedance [Z*(ω)] of PVC - PPy blends in THF solution were studied. The electrode polarization and ionic conduction appears to have dominant influence on the complex dielectric constant in the low frequency region. The relaxation time values corresponding to these two phenomena are also reported.

Selective synthesis of a series of isostructural MIICuI heterobimetallic complexes spontaneously assembled by an unsymmetrical naphthyridine-based ligand.

PubMed

Nicolay, Amélie; Tilley, T Don

2018-05-31

Metal-metal cooperation is integral to the function of many enzymes and materials, and model complexes hold enormous potential for providing insights into the capabilities of analogous multimetallic cores. However, the selective synthesis of heterobimetallic complexes still presents a significant challenge, especially for systems that hold the metals in close proximity and feature open or reactive coordination sites for both metals. To address this issue, a rigid, naphthyridine-based dinucleating ligand featuring distinct binding environments was synthesized. This ligand enables the selective synthesis of a series of MIICuI bimetallic complexes (M = Mn, Fe, Co, Ni, Cu, Zn), in which each metal center exclusively occupies its preferred binding pocket, from simple chloride salts. The precision of this selectivity is evident from cyclic voltammetry, ESI-MS and anomalous X-ray diffraction measurements. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Smart responsive phosphorescent materials for data recording and security protection.

PubMed

Sun, Huibin; Liu, Shujuan; Lin, Wenpeng; Zhang, Kenneth Yin; Lv, Wen; Huang, Xiao; Huo, Fengwei; Yang, Huiran; Jenkins, Gareth; Zhao, Qiang; Huang, Wei

2014-04-07

Smart luminescent materials that are responsive to external stimuli have received considerable interest. Here we report ionic iridium (III) complexes simultaneously exhibiting mechanochromic, vapochromic and electrochromic phosphorescence. These complexes share the same phosphorescent iridium (III) cation with a N-H moiety in the N^N ligand and contain different anions, including hexafluorophosphate, tetrafluoroborate, iodide, bromide and chloride. The anionic counterions cause a variation in the emission colours of the complexes from yellow to green by forming hydrogen bonds with the N-H proton. The electronic effect of the N-H moiety is sensitive towards mechanical grinding, solvent vapour and electric field, resulting in mechanochromic, vapochromic and electrochromic phosphorescence. On the basis of these findings, we construct a data-recording device and demonstrate data encryption and decryption via fluorescence lifetime imaging and time-gated luminescence imaging techniques. Our results suggest that rationally designed phosphorescent complexes may be promising candidates for advanced data recording and security protection.

Infrared Spectroscopy of NaCl(CH3OH)n Complexes in Helium Nanodroplets.

PubMed

Sadoon, Ahmed M; Sarma, Gautam; Cunningham, Ethan M; Tandy, Jon; Hanson-Heine, Magnus W D; Besley, Nicholas A; Yang, Shengfu; Ellis, Andrew M

2016-10-10

Infrared (IR) spectra of complexes between NaCl and methanol have been recorded for the first time. These complexes were formed in liquid helium nanodroplets by consecutive pick-up of NaCl and CH 3 OH molecules. For the smallest NaCl(CH 3 OH) n , complexes where n = 1-3, the IR data suggest that the lowest-energy isomer is the primary product in each case. The predominant contribution to the binding comes from ionic hydrogen bonds between the OH in each methanol molecule and the chloride ion in the NaCl, as established by the large red shift of the OH stretching bands compared with the isolated CH 3 OH molecule. For n ≥ 4, there is a dramatic shift from discrete vibrational bands to very broad absorption envelopes, suggesting a profound change in the structural landscape and, in particular, access to multiple low-energy isomers.

21 CFR 184.1297 - Ferric chloride.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ferric chloride. 184.1297 Section 184.1297 Food and... Substances Affirmed as GRAS § 184.1297 Ferric chloride. (a) Ferric chloride (iron (III) chloride, FeC13, CAS Reg. No. 7705-08-0) may be prepared from iron and chlorine or from ferric oxide and hydrogen chloride...

Sodium and potassium content and their ratio in meatballs in tomato sauce produced with lower amounts of sodium

NASA Astrophysics Data System (ADS)

Lilić, S.; Nikolić, D.; Pejkovski, Z.; Velebit, B.; Lakićević, B.; Korićanac, V.; Vranić, D.

2017-09-01

The goal of this study was to examine the possibility of partial replacement of sodium chloride with potassium chloride and ammonium chloride, with the target of achieving less sodium content in meatballs and tomato sauce as well as achieving a better Na:K ratio. The trial consisted of five groups. In the control group of meatballs and sauce, only sodium chloride was added. In group 1, half of the sodium chloride was replaced with potassium chloride related to control group while in group 2 one third of the sodium chloride was replaced with potassium chloride. In group 3, one third of the sodium chloride was replaced with ammonium chloride, and in group 4, sodium chloride was reduced to half the amount in the control group, and 1 g (0.25%) of ammonium chloride was also added. All products were acceptable according to sensory analyses. The largest reductions of sodium content were 44.64%, achieved in meatballs from group 1 and 50.62% in tomato sauce from group 4 in relation to meatballs and tomato sauce from control group. The highest Na:K ratio was calculated in meatballs and tomato sauce from control group, 2.88 and 4.39, respectively. The best Na:K ratio was in meatballs and tomato sauce from group 1, 0.60 and 0.92, respectively, in which half of sodium chloride was replaced with potassium chloride. However, in meatballs and tomato sauce from group 4, with only half the amount of sodium chloride related to control group, the Na:K ratio was worse because in these products, potassium chloride was not added.

Influence of complexation with chloride on the responses of a lux-marked bacteria bioassay to cadmium, copper, lead, and mercury

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

Sarin, C.; Hall, J.M.; Cotter-Howells, J.

2000-02-01

The toxicity of a heavy metal in solution to a microorganism depends not only on its concentration but also on pH and the concentrations of any aqueous complexing ligands in the microorganism's environment. This paper reports on the use of different inorganic resuscitation media and effect of the chloride ion, Cl{sup {minus}}, on the bioluminescence response of a bacterial biosensor, Escherichia coli HB101 (pUCD607), to four metals: Cd, Cu, Hg, and Pb. The toxicity tests were conducted at pH 4, using 0.1 M KNO{sub 3} as resuscitation medium and adding KCl to investigate effect of Cl{sup {minus}} concentration. The speciesmore » distributions of metals as a function of Cl{sup {minus}} concentration were calculated using GeoChem-PC. Resuscitation in 0.1 M KCl gave significantly higher light output than that in 0.1 M KNO{sub 3}, demonstrating that Cl{sup {minus}} ions increased the toxicity of Hg, apparently because of the formation of HgCl{sub 3}{sup {minus}}, and increased the toxicity of Pb because of PbCl{sup +} formation. The toxicity of Cu decreased at high Cl{sup {minus}} concentrations as free Cu{sup 2+} decreased, in accordance with the free ion model. Concentrations of Cl{sup {minus}} had no significant effect on the toxicity of Cd. This study clearly demonstrates that the chloro-complexes of some heavy metals can be toxic and, for Pb and Hg, more toxic than the free ion.« less

Verification of chloride adsorption effect of mortar with salt adsorbent

NASA Astrophysics Data System (ADS)

Hoshina, T.; Nakajima, N.; Sudo, H.; Date, S.

2017-11-01

In order to investigate the chloride adsorption effect of mortar mixed with chloride adsorbent, electrophoresis test using mortar specimen and immersion dry repeated test were conducted to evaluate chloride adsorption effect. As a result, it was confirmed that soluble salt content that causes corrosion of rebar in the specimen was reduced by the chloride adsorbent and corrosion inhibiting effect of the rebar was also obtained. It was also confirmed that by increasing dosage of the chloride adsorbent, the chloride adsorbing effect becomes larger as well..

A self-organized ensemble of fluorescent 3-hydroxyflavone-Al (III) complex as sensor for fluoride and acetate ions.

PubMed

Sathish, Sai; Narayan, Govindh; Rao, Nageswara; Janardhana, Chelli

2007-01-01

Aluminum chloride addition results in a self-organized TURN-ON fluorescence of 3-hydroxyflavone (3HF) by a complexation reaction in MeOH and subsequent ligand exchange reaction with fluoride or acetate ions causes a fluorescence TURN-OFF of this complex, delivering a quantitative estimation route for fluoride and acetate ions. The ternary complex of 3HF with Al (III), a hard acid provides for a sensitive signalling system for fluoride ion, a hard base in the concentration range from 6 muM to 50 mM by a concerted co-ordination of fluoride ion involving an intermediate mechanistic pathway, while the complex is sensitive to acetate addition between 0-68 muM. The ligand exchange reaction of Al (3HF)(2) complex by fluoride or acetate ion, without interference from other common anions, has been investigated by UV-visible and fluorescence spetroscopies. The structure of the in-situ intermediate isolated at higher Al (3HF)(2) complex and acetate concentrations was inferred from the FT-IR spectrum and ESI-MS of the sample.

Molecular and thermodynamic mechanisms of the chloride-dependent human angiotensin-I-converting enzyme (ACE).

PubMed

Yates, Christopher J; Masuyer, Geoffrey; Schwager, Sylva L U; Akif, Mohd; Sturrock, Edward D; Acharya, K Ravi

2014-01-17

Somatic angiotensin-converting enzyme (sACE), a key regulator of blood pressure and electrolyte fluid homeostasis, cleaves the vasoactive angiotensin-I, bradykinin, and a number of other physiologically relevant peptides. sACE consists of two homologous and catalytically active N- and C-domains, which display marked differences in substrate specificities and chloride activation. A series of single substitution mutants were generated and evaluated under varying chloride concentrations using isothermal titration calorimetry. The x-ray crystal structures of the mutants provided details on the chloride-dependent interactions with ACE. Chloride binding in the chloride 1 pocket of C-domain ACE was found to affect positioning of residues from the active site. Analysis of the chloride 2 pocket R522Q and R522K mutations revealed the key interactions with the catalytic site that are stabilized via chloride coordination of Arg(522). Substrate interactions in the S2 subsite were shown to affect chloride affinity in the chloride 2 pocket. The Glu(403)-Lys(118) salt bridge in C-domain ACE was shown to stabilize the hinge-bending region and reduce chloride affinity by constraining the chloride 2 pocket. This work demonstrated that substrate composition to the C-terminal side of the scissile bond as well as interactions of larger substrates in the S2 subsite moderate chloride affinity in the chloride 2 pocket of the ACE C-domain, providing a rationale for the substrate-selective nature of chloride dependence in ACE and how this varies between the N- and C-domains.

Molecular and Thermodynamic Mechanisms of the Chloride-dependent Human Angiotensin-I-converting Enzyme (ACE)*

PubMed Central

Yates, Christopher J.; Masuyer, Geoffrey; Schwager, Sylva L. U.; Akif, Mohd; Sturrock, Edward D.; Acharya, K. Ravi

2014-01-01

Somatic angiotensin-converting enzyme (sACE), a key regulator of blood pressure and electrolyte fluid homeostasis, cleaves the vasoactive angiotensin-I, bradykinin, and a number of other physiologically relevant peptides. sACE consists of two homologous and catalytically active N- and C-domains, which display marked differences in substrate specificities and chloride activation. A series of single substitution mutants were generated and evaluated under varying chloride concentrations using isothermal titration calorimetry. The x-ray crystal structures of the mutants provided details on the chloride-dependent interactions with ACE. Chloride binding in the chloride 1 pocket of C-domain ACE was found to affect positioning of residues from the active site. Analysis of the chloride 2 pocket R522Q and R522K mutations revealed the key interactions with the catalytic site that are stabilized via chloride coordination of Arg522. Substrate interactions in the S2 subsite were shown to affect chloride affinity in the chloride 2 pocket. The Glu403-Lys118 salt bridge in C-domain ACE was shown to stabilize the hinge-bending region and reduce chloride affinity by constraining the chloride 2 pocket. This work demonstrated that substrate composition to the C-terminal side of the scissile bond as well as interactions of larger substrates in the S2 subsite moderate chloride affinity in the chloride 2 pocket of the ACE C-domain, providing a rationale for the substrate-selective nature of chloride dependence in ACE and how this varies between the N- and C-domains. PMID:24297181

Ultrastructure Processing of Advanced Materials.

DTIC Science & Technology

1992-11-01

alkoxide) involving the sodium and the other metal [e.g., NaZr 2(OR)9]. The use of anhydrous ammonia usually solves this problem. MCIX + xNH 3 + xROH - M...the formation of pentacoordinate silicic acid complexes with hydroxide and fluoride ions, as well as neutral adducts with hydrogen fluoride, ammonia ...stable than that for any other small neutral adduct such as water, ammonia , and hydrogen chloride. Elimination of water is much easier by internal

Synthesis of Synthetic Hydrocarbons Via Alpha Olefins.

DTIC Science & Technology

1985-05-01

THF complex, 0OC; (e) Pyridinium chlorochromate , dry CH2 CL29 room temperature; b (f) methyltriphenylphosphonium bromide, dimethyl sulfoxide, room...vigorously stirred solution of pyridinium chlorochromate (27.91 g, 0.13 mol) in dry methylene chloride (175 mL) was added all at once a solution of l... pyridinium chlorochroniate. 3 Our four-step synthesis of l-decene-2-1 3 C from 1-bromooctane is outlined in the Scheme. This synthetic sequence provides the

PROCESS OF PREPARING ZIRCONIUM OXYCHLORIDE

DOEpatents

Wilhelm, H.A.; Andrews, M.L.

1960-06-28

A process is given for preparing zirconyl chloride by mixing solid zirconyl chloride octahydrate and solid zirconium tetrachloride at room temperature whereby both chlorides are converted to zirconyl chloride trinydrate and hydrogen chloride is formed and volatilized by the reaction heat.

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

Akatsuchi, Y.

Mice were x irradiated by whole-body single doses of 700 r (lethal dose). The administration of phenylephrine chloride, naphazoline, tetrahydrozoline chloride, and noradrenaline gave considerable protection against the lethal effect, when an optimal dose of each agent was given. Cocaine chloride, histamine chloride, or adrenaline chloride gave moderate protection. No protective effect was seen after the administration of ephedrine chloride or diphenhydramine. (Abstr. Japan Med., 2, No. 1, Jan. 1962)

Prospects of development of highly mineralized high-temperature resources of the Tarumovskoye geothermal field

NASA Astrophysics Data System (ADS)

Alkhasov, A. B.; Alkhasova, D. A.; Ramazanov, A. Sh.; Kasparova, M. A.

2016-06-01

The promising nature of integrated processing of high-temperature geothermal brines of the Tarumovskoye geothermal field is shown. Thermal energy of a geothermal brine can be converted to the electric power at a binary geothermal power plant (GPP) based on low-boiling working substance. The thermodynamic Rankine cycles are considered which are implemented in the GPP secondary loop at different evaporation temperatures of the working substance―isobutane. Among them, the most efficient cycle from the standpoint of attaining a maximum power is the supercritical one which is close to the so-called triangular cycle with an evaporation pressure of p e = 5.0 MPa. The used low-temperature brine is supplied from the GPP to a chemical plant, where main chemical components (lithium carbonate, burnt magnesia, calcium carbonate, and sodium chloride) are extracted from it according to the developed technology of comprehensive utilization of geothermal brines of chloride-sodium type. The waste water is delivered to the geotechnological complex and other consumers. For producing valuable inorganic materials, the electric power generated at the GPP is used. Owing to this, the total self-sufficiency of production and independence from external conditions is achieved. The advantages of the proposed geotechnological complex are the full utilization of the heat potential and the extraction of main chemical components of multiparameter geothermal resources. In this case, there is no need for reverse pumping, which eliminates the significant capital costs for building injection wells and a pumping station and the operating costs for their service. A characteristic of the modern state of the field and estimated figures of the integrated processing of high-temperature brines of well no. 6 are given, from which it follows that the proposed technology has a high efficiency. The comprehensive development of the field resources will make it possible to improve the economic structure of the region and fully meet the needs of Russia in lithium carbonate and sodium chloride.

In Vitro Evaluation of Mitochondrial Function and Estrogen Signaling in Cell Lines Exposed to the Antiseptic Cetylpyridinium Chloride

PubMed Central

Datta, Sandipan; He, Guochun; Tomilov, Alexey; Sahdeo, Sunil; Denison, Michael S.

2017-01-01

Background: Quaternary ammonium salts (QUATS), such as cetylpyridinium chloride (CPC) and benzalkonium chloride (BAK), are frequently used in antiseptic formulations, including toothpastes, mouthwashes, lozenges, throat and nasal sprays, and as biocides. Although in a recent ruling, the U.S. Food and Drug Administration (FDA) banned CPC from certain products and requested more data on BAK’s efficacy and safety profile, QUATS, in general, and CPC and BAK, in particular, continue to be used in personal health care, food, and pharmaceutical and cleaning industries. Objectives: We aimed to assess CPC's effects on mitochondrial toxicity and endocrine disruption in vitro. Method: Mitochondrial O2 consumption and adenosine triphosphate (ATP) synthesis rates of osteosarcoma cybrid cells were measured before and after CPC and BAK treatment. Antiestrogenic effects of the compounds were measured by a luciferase-based assay using recombinant human breast carcinoma cells (VM7Luc4E2, ERalpha-positive). Results: CPC inhibited both mitochondrial O2 consumption [half maximal inhibitory concentration (IC50): 3.8μM] and ATP synthesis (IC50: 0.9μM), and additional findings supported inhibition of mitochondrial complex 1 as the underlying mechanism for these effects. In addition, CPC showed concentration-dependent antiestrogenic activity half maximal effective concentration [(EC50): 4.5μM)]. BAK, another antimicrobial QUATS that is structurally similar to CPC, and the pesticide rotenone, a known complex 1 inhibitor, also showed mitochondrial inhibitory and antiestrogenic effects. In all three cases, there was overlap of the antiestrogenic activity with the mitochondrial inhibitory activity. Conclusions: Mitochondrial inhibition in vitro occurred at a CPC concentration that may be relevant to human exposures. The antiestrogenic activity of CPC, BAK, rotenone, and triclosan may be related to their mitochondrial inhibitory activity. Our findings support the need for additional research on the mitochondrial inhibitory and antiestrogenic effects of QUATS, including CPC and BAK. https://doi.org/10.1289/EHP1404 PMID:28885978

Structure and thermodynamic stability of UTa 3 O 10 , a U( v )-bearing compound

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

Guo, Xiaofeng; Lipp, Christian; Tiferet, Eitan

Heating a mixture of uranyl(VI) nitrate and tantalum(V) oxide in the molar ratio of 2 : 3 to 1400 °C resulted in the formation of a new compound, UTa 3O 10. The honey colored to yellow brown crystals of UTa 3O 10 crystallize in an orthorhombic structure with the space group Fddd (no. 70), lattice parameters a = 7.3947(1), b = 12.7599(2), c = 15.8156(2) Å, and Z = 8. Vertex sharing [TaO 6] 7- octahedra of two crystallographically distinct Ta cations form a three dimensional tantalate framework. Within this framework, six membered rings of [TaO 6] 7- octahedra aremore » formed within the (001) plane. The center of these rings is occupied by the uranyl cations [UO 2] +, with an oxidation state of +5 for uranium. The pentavalence of U and Ta was confirmed by X-ray photoelectron spectroscopy and X-ray adsorption spectroscopy. The enthalpy of formation of UTa 3O 10 from Ta 2O 5, β-U 3O 7, and U 3O 8 has been determined to be 13.1 ± 18.1 kJ mol -1 using high temperature oxide melt solution calorimetry with sodium molybdate as the solvent at 700 °C. The close to zero enthalpy of formation of UTa 3O 10 can be explained by closely balanced structural stabilizing and destabilizing factors, which may also apply to other UM 3O 10 compounds.« less

A mixed valence zinc dithiolene system with spectator metal and reactor ligands.

PubMed

Ratvasky, Stephen C; Mogesa, Benjamin; van Stipdonk, Michael J; Basu, Partha

2016-08-16

Neutral complexes of zinc with N,N'-diisopropylpiperazine-2,3-dithione ( i Pr 2 Dt 0 ) and N,N'-dimethylpiperazine-2,3-dithione (Me 2 Dt 0 ) with chloride or maleonitriledithiolate (mnt 2- ) as coligands have been synthesized and characterized. The molecular structures of these zinc complexes have been determined using single crystal X-ray diffractometry. Complexes recrystallize in monoclinic P type systems with zinc adopting a distorted tetrahedral geometry. Two zinc complexes with mixed-valent dithiolene ligands exhibit ligand-to-ligand charge transfer bands. Optimized geometries, molecular vibrations and electronic structures of charge-transfer complexes were calculated using density functional theory (B3LYP/6-311G+(d,p) level). Redox orbitals are shown to be almost exclusively ligand in nature, with a HOMO based heavily on the electron-rich maleonitriledithiolate ligand, and a LUMO comprised mostly of the electron-deficient dithione ligand. Charge transfer is thus believed to proceed from dithiolate HOMO to dithione LUMO, showing ligand-to-ligand redox interplay across a d 10 metal.

Preparation and evaluation of Lu-177 phytate Complex for Radiosynovectomy

PubMed Central

Yousefnia, Hassan; Jalilian, Amir Reza; Zolghadri, Samaneh

2014-01-01

Lu-177 of 2.6-3 GBq/mg specific activity was obtained by irradiation of natural Lu2O3 sample with thermal neutron flux of 4 × 1013 n/cm/s. The product was converted into chloride form which was further used for labeling of Lu-177 phytate complex successfully with high radiochemical purity (>99.9%, instant thin layer chromatography, MeOH: H2O: Acetic acid, 4:4:2, as mobile phase). The complex stability and viscosity were checked in the final solution up to 7 days. The prepared complex solution (100 μCi/100 μl) was injected intra-articularly to the male rat knee joint. Leakage of radioactivity from the injection site and its distribution in organs were investigated up to 7 days. Approximately, all injected dose has remained in injection site 7 days after injection. The complex was proved to be a feasible agent for cavital radiotherapy in oncology and rheumatology. PMID:25191108

Growth, structural, optical, thermal and dielectric properties of lanthanum chloride—thiourea—L tartaric acid coordinated complex

NASA Astrophysics Data System (ADS)

Slathia, Goldy; Bamzai, K. K.

2017-11-01

Lanthanum chloride—thiourea—l tartaric acid coordinated complex was grown in the form of single crystal by slow evaporation of supersaturated solutions at room temperature. This coordinated complex crystallizes in orthorhombic crystal system having space group P nma. The crystallinity and purity was tested by powder x-ray diffraction. Fourier transform infra red and Raman spectroscopy analysis provide the evidences on structure and mode of coordination. The scanning electron microscopy (SEM) analysis shows the morphology evolution as brought by the increase in composition of lanthanum chloride. The band transitions due to C=O and C=S chromophores remain active in grown complexes and are recorded in the UV-vis optical spectrum. The thermal effects such as dehydration, melting and decomposition were observed by the thermogravimetric and differential thermo analytical (TGA/DTA) analysis. Electrical properties were studied by dielectric analysis in frequency range 100-30 MHz at various temperatures. Increase in values of dielectric constant was observed with change in lanthanum concentration in the coordinated complex.

A pH-independent DNA nanodevice for quantifying chloride transport in organelles of living cells.

PubMed

Saha, Sonali; Prakash, Ved; Halder, Saheli; Chakraborty, Kasturi; Krishnan, Yamuna

2015-07-01

The concentration of chloride ions in the cytoplasm and subcellular organelles of living cells spans a wide range (5-130 mM), and is tightly regulated by intracellular chloride channels or transporters. Chloride-sensitive protein reporters have been used to study the role of these chloride regulators, but they are limited to a small range of chloride concentrations and are pH-sensitive. Here, we show that a DNA nanodevice can precisely measure the activity and location of subcellular chloride channels and transporters in living cells in a pH-independent manner. The DNA nanodevice, called Clensor, is composed of sensing, normalizing and targeting modules, and is designed to localize within organelles along the endolysosomal pathway. It allows fluorescent, ratiometric sensing of chloride ions across the entire physiological regime. We used Clensor to quantitate the resting chloride concentration in the lumen of acidic organelles in Drosophila melanogaster. We showed that lumenal lysosomal chloride, which is implicated in various lysosomal storage diseases, is regulated by the intracellular chloride transporter DmClC-b.

A pH-independent DNA nanodevice for quantifying chloride transport in organelles of living cells

NASA Astrophysics Data System (ADS)

Saha, Sonali; Prakash, Ved; Halder, Saheli; Chakraborty, Kasturi; Krishnan, Yamuna

2015-07-01

The concentration of chloride ions in the cytoplasm and subcellular organelles of living cells spans a wide range (5-130 mM), and is tightly regulated by intracellular chloride channels or transporters. Chloride-sensitive protein reporters have been used to study the role of these chloride regulators, but they are limited to a small range of chloride concentrations and are pH-sensitive. Here, we show that a DNA nanodevice can precisely measure the activity and location of subcellular chloride channels and transporters in living cells in a pH-independent manner. The DNA nanodevice, called Clensor, is composed of sensing, normalizing and targeting modules, and is designed to localize within organelles along the endolysosomal pathway. It allows fluorescent, ratiometric sensing of chloride ions across the entire physiological regime. We used Clensor to quantitate the resting chloride concentration in the lumen of acidic organelles in Drosophila melanogaster. We showed that lumenal lysosomal chloride, which is implicated in various lysosomal storage diseases, is regulated by the intracellular chloride transporter DmClC-b.

Mapping the spatial distribution of chloride deposition across Australia

NASA Astrophysics Data System (ADS)

Davies, P. J.; Crosbie, R. S.

2018-06-01

The high solubility and conservative behaviour of chloride make it ideal for use as an environmental tracer of water and salt movement through the hydrologic cycle. For such use the spatial distribution of chloride deposition in rainfall at a suitable scale must be known. A number of authors have used point data acquired from field studies of chloride deposition around Australia to construct relationships to characterise chloride deposition as a function of distance from the coast; these relationships have allowed chloride deposition to be interpolated in different regions around Australia. In this paper we took this a step further and developed a chloride deposition map for all of Australia which includes a quantification of uncertainty. A previously developed four parameter model of chloride deposition as a function of distance from the coast for Australia was used as the basis for producing a continental scale chloride deposition map. Each of the four model parameters were made spatially variable by creating parameter surfaces that were interpolated using a pilot point regularisation approach within a parameter estimation software. The observations of chloride deposition were drawn from a literature review that identified 291 point measurements of chloride deposition over a period of 80 years spread unevenly across all Australian States and Territories. A best estimate chloride deposition map was developed from the resulting surfaces on a 0.05 degree grid. The uncertainty in the chloride deposition map was quantified as the 5th and 95th percentile of 1000 calibrated models produced via Null Space Monte Carlo analysis and the spatial variability of chloride deposition across the continent was consistent with landscape morphology. The temporal variability in chloride deposition on a decadal scale was investigated in the Murray-Darling Basin, this highlighted the need for long-term monitoring of chloride deposition if the uncertainty of the continental scale map is to be reduced. Use of the derived chloride deposition map was demonstrated for a probabilistic estimation of groundwater recharge for the southeast of South Australia using the chloride mass balance method.

42 CFR 84.250 - Vinyl chloride respirators; description.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 1 2010-10-01 2010-10-01 false Vinyl chloride respirators; description. 84.250... Respirators § 84.250 Vinyl chloride respirators; description. Vinyl chloride respirators, including all... escape from vinyl chloride atmospheres containing adequate oxygen to support life, are described...

Hydrocracking with molten zinc chloride catalyst containing 2-12% ferrous chloride

DOEpatents

Zielke, Clyde W.; Bagshaw, Gary H.

1981-01-01

In a process for hydrocracking heavy aromatic polynuclear carbonaceous feedstocks to produce hydrocarbon fuels boiling below about 475.degree. C. by contacting the feedstocks with hydrogen in the presence of a molten zinc chloride catalyst and thereafter separating at least a major portion of the hydrocarbon fuels from the spent molten zinc chloride catalyst, an improvement comprising: adjusting the FeCl.sub.2 content of the molten zinc chloride to from about 2 to about 12 mol percent based on the mixture of ferrous chloride and molten zinc chloride.

PLUTONIUM RECOVERY FROM NEUTRON-BOMBARDED URANIUM FUEL

DOEpatents

Moore, R.H.

1962-04-10

A process of recovering plutonium from neutronbombarded uranium fuel by dissolving the fuel in equimolar aluminum chloride-potassium chloride; heating the mass to above 700 deg C for decomposition of plutonium tetrachloride to the trichloride; extracting the plutonium trichloride into a molten salt containing from 40 to 60 mole % of lithium chloride, from 15 to 40 mole % of sodium chloride, and from 0 to 40 mole % of potassium chloride or calcium chloride; and separating the layer of equimolar chlorides containing the uranium from the layer formed of the plutonium-containing salt is described. (AEC)

Understanding the interacted mechanism between carbonation and chloride aerosol attack in ordinary Portland cement concrete

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

Liu, Jun; Qiu, Qiwen; Chen, Xiaochi

An experimental study is carried out with the aim to understand the interacted mechanism between carbonation and chloride aerosol attack in ordinary Portland cement (OPC) concrete. Effects of carbonation on the chloride profile, the chloride binding capacity and the chloride diffusion coefficient are evaluated. Besides, effect of chloride aerosol attack on the carbonation rate is investigated. Concrete specimens with three water-to-cement ratios (0.38, 0.47 and 0.53) are fabricated in this work. Tested results demonstrate that carbonation remarkably affects the chloride profile, reduces the chloride binding capacity, and also accelerates the rate of chloride ion diffusion of concrete. Besides, the presencemore » of chloride aerosol can lead to lower the carbonation depth and increase the pH value of carbonated concrete. Microscopic properties such as morphology, porosity, and pore size distribution for the contaminated concretes are explored by scanning electron microscope and mercury intrusion porosimetry, which provide strong evidence to these research findings.« less

Atmospheric chloride: Its implication for foliar uptake and damage

NASA Astrophysics Data System (ADS)

McWilliams, E. L.; Sealy, R. L.

Atmospheric chloride is inversely related to distance from the Texas coast; r2 = 0.86. Levels of atmospheric chloride are higher in the early summer than in the winter because of salt storms. Leaf chloride l'evels of Tillandsia usneoides L. (Spanish moss) reflect the atmospheric chloride levels; r2 = 0.78. The importance of considering the effect of atmospheric chloride on leaf damage to horticultural crops is discussed.

The central role of chloride in the metabolic acid-base changes in canine parvoviral enteritis.

PubMed

Burchell, Richard K; Schoeman, Johan P; Leisewitz, Andrew L

2014-04-01

The acid-base disturbances in canine parvoviral (CPV) enteritis are not well described. In addition, the mechanisms causing these perturbations have not been fully elucidated. The purpose of the present study was to assess acid-base changes in puppies suffering from CPV enteritis, using a modified strong ion model (SIM). The hypothesis of the study was that severe acid-base disturbances would be present and that the SIM would provide insights into pathological mechanisms, which have not been fully appreciated by the Henderson-Hasselbalch model. The study analysed retrospective data, obtained from 42 puppies with confirmed CPV enteritis and 10 healthy control dogs. The CPV-enteritis group had been allocated a clinical score, to allow classification of the data according to clinical severity. The effects of changes in free water, chloride, l-lactate, albumin and phosphate were calculated, using a modification of the base excess algorithm. When the data were summated for each patient, and correlated to each individual component, the most important contributor to the metabolic acid-base changes, according to the SIM, was chloride (P<0.001). Severely-affected animals tended to demonstrate hypochloraemic alkalosis, whereas mildly-affected puppies had a hyperchloraemic acidosis (P=0.007). In conclusion, the acid-base disturbances in CPV enteritis are multifactorial and complex, with the SIM providing information in terms of the origin of these changes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fluorescent and colorimetric molecular recognition probe for hydrogen bond acceptors.

PubMed

Pike, Sarah J; Hunter, Christopher A

2017-11-22

The association constants for formation of 1 : 1 complexes between a H-bond donor, 1-naphthol, and a diverse range of charged and neutral H-bond acceptors have been measured using UV/vis absorption and fluorescence emission titrations. The performance of 1-naphthol as a dual colorimetric and fluorescent molecular recognition probe for determining the H-bond acceptor (HBA) parameters of charged and neutral solutes has been investigated in three solvents. The data were employed to establish self-consistent H-bond acceptor parameters (β) for benzoate, azide, chloride, thiocyanate anions, a series of phosphine oxides, phosphate ester, sulfoxide and a tertiary amide. The results demonstrate both the transferability of H-bond parameters between different solvents and the utility of the naphthol-based dual molecular recognition probe to exploit orthogonal spectroscopic techniques to determine the HBA properties of neutral and charged solutes. The benzoate anion is the strongest HBA studied with a β parameter of 15.4, and the neutral tertiary amide is the weakest H-bond acceptor investigated with a β parameter of 8.5. The H-bond acceptor strength of the azide anion is higher than that of chloride (12.8 and 12.2 respectively), and the thiocyanate anion has a β value of 10.8 and thus is a significantly weaker H-bond acceptor than both the azide and chloride anions.

Chloride leaching and solvent extraction of cadmium, cobalt and nickel from spent nickel-cadmium, batteries using Cyanex 923 and 272

NASA Astrophysics Data System (ADS)

Reddy, B. Ramachandra; Priya, D. Neela

Studies are conducted on the leaching and solvent extraction separation of metals from chloride leach liquor of spent nickel-cadmium batteries with Cyanex 923 and 272 diluted in kerosene as the extractants. Dissolution of the metals increases with increase in acid concentration and time but decreases with the solids-to-liquid ratio. Complete dissolution of Cd, Co and Ni can be achieved with 1.5 M HCl at 85 °C for 8 h and a solids-to-liquid ratio of 4. Treatment of leach liquor for the separation of metals with Cyanex 923 shows that increase of extractant and chloride ion concentration increases the percentage extraction of cadmium. The plot of log[distribution coefficient] versus log[extractant]/[Cl -] is linear with a slope of 2, which indicates that the extraction follows a solvation mechanism with the extracted species as CdCl 2·2S (S, Cyanex 923). Moreover, Cyanex 923 enables a clear separation of Cd from Co and Ni. Extraction of cobalt with Cyanex 272 involves a cation-exchange mechanism with the formation of a 1:2 metal-to-ligand complex in the organic phase. Based on the distribution data, extractant concentration and equilibrium pH of the aqueous phase, a possible separation process is proposed for the recovery of cadmium, cobalt and nickel with >99% efficiency.

[Application of Brownian dynamics to the description of transmembrane ion flow as exemplified by the chloride channel of glycine receptor].

PubMed

Boronovskiĭ, S E; Nartsissov, Ia R

2009-01-01

Using the Brownian dynamics of the movement of hydrated ion in a viscous water solution, a mathematical model has been built, which describes the transport of charged particles through a single protein pore in a lipid membrane. The dependences of transmembrane ion currents on ion concentrations in solution have been obtained. It was shown that, if the geometry of a membrane pore is identical to that of the inner part of the glycine receptor channel and there is no ion selectivity, then the values of both chloride and sodium currents are not greater than 0.5 pA at the physiological concentrations of these ions. If local charge heterogeneity caused by charged amino acid residues of transmembrane protein segments is included into the model calculations, the chloride current increases to about 3.7 pA, which exceeds more than seven times the value for sodium ions under the conditions of the complex channel geometry in the range of physiological concentrations of ions in the solution. The model takes changes in the density of charge distribution both inside the channel and near the protein surface into account. The alteration of pore geometry can be also considered as a parameter at the researcher's option. Thus, the model appears as an effective tool for the description of transmembrane currents for other types of membrane channels.

Discrete-state representation of ion permeation coupled to fast gating in a model of ClC chloride channels: comparison to multi-ion continuous space Brownian dynamics simulations.

PubMed

Coalson, Rob D; Cheng, Mary Hongying

2010-01-28

A discrete-state model of chloride ion motion in a ClC chloride channel is constructed, following a previously developed multi-ion continuous space model of the same system (Cheng, M. H.; Mamonov, A. B.; Dukes, J. W.; Coalson, R. D. J. Phys. Chem. B 2007, 111, 5956) that included a simplistic representation of the fast gate in this channel. The reducibility of the many-body continuous space to the eight discrete-state model considered in the present work is examined in detail by performing three-dimensional Brownian dynamics simulations of each allowed state-to-state transition in order to extract the appropriate rate constant for this process, and then inserting the pairwise rate constants thereby obtained into an appropriate set of kinetic master equations. Experimental properties of interest, including the rate of Cl(-) ion permeation through the open channel and the average rate of closing of the fast gate as a function of bulk Cl(-) ion concentrations in the intracellular and extracellular electrolyte reservoirs are computed. Good agreement is found between the results obtained via the eight discrete-state model versus the multi-ion continuous space model, thereby encouraging continued development of the discrete-state model to include more complex behaviors observed experimentally in these channels.

21 CFR 522.1862 - Sterile pralidoxime chloride.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sterile pralidoxime chloride. 522.1862 Section 522....1862 Sterile pralidoxime chloride. (a) Chemical name. 2-Formyl-1-methylpyridinium chloride oxime. (b) Specifications. Sterile pralidoxime chloride is packaged in vials. Each vial contains 1 gram of sterile...

The adsorption of orthophosphate onto casein-iron precipitates.

PubMed

Mittal, Vikas A; Ellis, Ashling; Ye, Aiqian; Edwards, Patrick J B; Singh, Harjinder

2018-01-15

This study explored the interactions of orthophosphate with casein-iron precipitates. Casein-iron precipitates were formed by adding ferric chloride at ≥10mM to sodium caseinate solutions ranging in concentration from 1 to 3%(w/v). The addition of different concentrations of orthophosphate solution to the casein-iron precipitates resulted in gradual adsorption of the orthophosphate, causing re-dispersion of the casein-iron complexes. The interactions of added orthophosphate with iron in the presence and absence of caseins are postulated, and new mechanisms are proposed. The re-dispersed soluble complexes of casein-iron-orthophosphate generated using this process could be used as novel iron fortificants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Striking Confinement Effect: AuCl[subscript 4][superscript -] Binding to Amines in a Nanocage Cavity

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

Henao, Juan D.; Suh, Young-Woong; Lee, Jeong-Kyu

2009-02-23

Binding of AuCl{sub 4}{sup -} to amine groups tethered to the interior of a 2 nm siloxane nanocage was determined in solutions containing various concentrations of acid. The mode of binding was inferred from EXAFS and UV-vis spectra to be by ligand exchange of amine for chloride, which implies that the amines remain unprotonated. Cyclic voltammetry confirmed that the Au complexes bind to the nanocage interior and established a 1:1 relationship between bound Au complex and amine groups. The results suggested a 5-7 pH unit shift in the protonation constant of the interior amines relative to free amines in solution.

Lipofection: a highly efficient, lipid-mediated DNA-transfection procedure.

PubMed Central

Felgner, P L; Gadek, T R; Holm, M; Roman, R; Chan, H W; Wenz, M; Northrop, J P; Ringold, G M; Danielsen, M

1987-01-01

A DNA-transfection protocol has been developed that makes use of a synthetic cationic lipid, N-[1-(2,3-dioleyloxy)propyl]-N,N,N-trimethylammonium chloride (DOTMA). Small unilamellar liposomes containing DOTMA interact spontaneously with DNA to form lipid-DNA complexes with 100% entrapment of the DNA, DOTMA facilitates fusion of the complex with the plasma membrane of tissue culture cells, resulting in both uptake and expression of the DNA. The technique is simple, highly reproducible, and effective for both transient and stable expression of transfected DNA. Depending upon the cell line, lipofection is from 5- to greater than 100-fold more effective than either the calcium phosphate or the DEAE-dextran transfection technique. Images PMID:2823261

21 CFR 184.1622 - Potassium chloride.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Potassium chloride. 184.1622 Section 184.1622 Food... Specific Substances Affirmed as GRAS § 184.1622 Potassium chloride. (a) Potassium chloride (KCl, CAS Reg... levels not to exceed current good manufacturing practice. Potassium chloride may be used in infant...

21 CFR 184.1622 - Potassium chloride.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Potassium chloride. 184.1622 Section 184.1622 Food... Specific Substances Affirmed as GRAS § 184.1622 Potassium chloride. (a) Potassium chloride (KCl, CAS Reg... levels not to exceed current good manufacturing practice. Potassium chloride may be used in infant...

40 CFR 61.64 - Emission standard for polyvinyl chloride plants.

Code of Federal Regulations, 2010 CFR

2010-07-01

... chloride plants. 61.64 Section 61.64 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Standard for Vinyl Chloride § 61.64 Emission standard for polyvinyl chloride plants. An owner or operator of a polyvinyl chloride plant shall comply with the requirements of this section and § 61.65. (a...

21 CFR 173.375 - Cetylpyridinium chloride.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cetylpyridinium chloride. 173.375 Section 173.375... CONSUMPTION Specific Usage Additives § 173.375 Cetylpyridinium chloride. Cetylpyridinium chloride (CAS Reg. No....1666 of this chapter, at a concentration of 1.5 times that of cetylpyridinium chloride. (c) The...

Method for the abatement of hydrogen chloride

DOEpatents

Winston, S.J.; Thomas, T.R.

1975-11-14

A method is described for reducing the amount of hydrogen chloride contained in a gas stream by reacting the hydrogen chloride with ammonia in the gas phase so as to produce ammonium chloride. The combined gas stream is passed into a condensation and collection vessel, and a cyclonic flow is created in the combined gas stream as it passes through the vessel. The temperature of the gas stream is reduced in the vessel to below the condensation temperature of ammonium chloride in order to crystallize the ammonium chloride on the walls of the vessel. The cyclonic flow creates a turbulence which breaks off the larger particles of ammonium chloride which are, in turn, driven to the bottom of the vessel where the solid ammonium chloride can be removed from the vessel. The gas stream exiting from the condensation and collection vessel is further cleaned and additional ammonium chloride is removed by passing through additional filters.

Method for the abatement of hydrogen chloride

DOEpatents

Winston, Steven J.; Thomas, Thomas R.

1977-01-01

The present invention provides a method for reducing the amount of hydrogen chloride contained in a gas stream by reacting the hydrogen chloride with ammonia in the gas phase so as to produce ammonium chloride. The combined gas stream is passed into a condensation and collection vessel and a cyclonic flow is created in the combined gas stream as it passes through the vessel. The temperature of the gas stream is reduced in the vessel to below the condensation temperature of ammonium chloride in order to crystallize the ammonium chloride on the walls of the vessel. The cyclonic flow creates a turbulence which breaks off the larger particles of ammonium chloride which are, in turn, driven to the bottom of the vessel where the solid ammonium chloride can be removed from the vessel. The gas stream exiting from the condensation and collection vessel is further cleaned and additional ammonium chloride is removed by passing through additional filters.

Pore size distribution of OPC and SRPC mortars in presence of chlorides

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

Suryavanshi, A.K.; Scantlebury, J.D.; Lyon, S.B.

1995-07-01

The pore structure of chloride-free ordinary portland cement (OPC) and sulphate resistant portland cement (SRPC) mortars are compared with the corresponding mortars with NaCl and CaCl{sub 2} added during mixing. In both OPC and SRPC mortars the addition of chlorides reduced the total accessible pore volumes compared to the corresponding chloride-free mortars. Also, in the presence of chlorides, the number of coarse pores were increased. These changes in the pore structure are believed to be due to dense calcium silicate hydrate (C-S-H) gel morphology formed in the presence of chlorides. The SRPC showed greater changes in pore structures than themore » OPC with equivalent amounts of chlorides added. This may be due to the lower chloride binding capacity of the SRPC and hence the higher availability of free chlorides to modify the gel morphology.« less

Thiourea derivatives as chelating agents for bioconjugation of rhenium and technetium.

PubMed

Gomez, J D Castillo; Hagenbach, A; Gerling-Driessen, U I M; Koksch, B; Beindorff, N; Brenner, W; Abram, U

2017-10-31

Potential tetradentate thiocarbamoylbenzamidine derivatives H 4 L have been synthesized from the corresponding benzimidoyl chlorides and triglycine. They are suitable chelating agents for the oxidotechnetium(v) and oxidorhenium(v) cores and form stable, neutral [MO(HL)] complexes with an equatorial SN 3 coordination sphere and an additional, uncoordinated carboxylic group, which can be used for bioconjugation. Representatives of the rhenium and 99 Tc products have been isolated and analyzed with spectroscopic methods and X-ray diffraction. Bioconjugates of these complexes with angiotensin-II have been synthesized and structurally characterized. Analogous 99m Tc complexes have been produced and tested in vitro and in vivo. The experiments confirm a considerable stability for the [ 99m Tc(HL)] product as well as for its bioconjugate and recommend this class of compounds for further bioconjugation studies towards clinical applications.

Synthesis, spectroscopic, thermal and antimicrobial studies of neodymium(III) and samarium(III) complexes derived from tetradentate ligands containing N and S donor atoms

NASA Astrophysics Data System (ADS)

Ain, Qurratul; Pandey, S. K.; Pandey, O. P.; Sengupta, S. K.

2015-04-01

Trivalent lanthanide complexes of the type [Ln(L)Cl(H2O)2] (where Ln = Nd(III) or Sm(III) and LH2 = Schiff bases derived by the condensation of 3-(phenyl/substitutedphenyl)-4-amino-5-mercapto-1,2,4-triazole with diacetyl/benzil) have been synthesized by the reactions of anhydrous lanthanide(III) chloride with Schiff bases in methanol. The structures of the complexes have been proposed on the basis of elemental analysis, electrical conductance, magnetic moment, spectroscopic measurements (IR, 1H, 13C NMR and UV-vis spectra) and X-ray diffraction studies. The spectral data reveal that the Schiff base ligands behave as dibasic tetradentate chelating agents having coordination sites at two thiol sulfur atoms and two azomethine nitrogen atoms. The presence of coordinated water in metal complexes was confirmed by thermal and IR data of the complexes. All the Schiff bases and their metal complexes have also been screened for their antibacterial activity against Bacillus subtilis, Staphylococcus aureus and antifungal activities against Aspergillus niger, Curvularia pallescens and Colletotrichum capsici.

Development of 177Lu-phytate Complex for Radiosynovectomy

PubMed Central

Yousefnia, Hassan; Jalilian, Amir Reza; Bahrami-Samani, Ali; Mazidi, Mohammad; Ghannadi Maragheh, Mohammad; Abbasi-Davani, Fereydoun

2013-01-01

Objective(s): In this work a new possible agent for radiosynovectomy has been targeted for articular pain palliation. Materials and Methods: Lu-177 of 2.6-3 GBq/mg specific activity was obtained by irradiation of natural Lu2O3 sample with thermal neutron flux of 4 × 1013 n.cm-2.s-1. The product was converted into chloride form which was further used for labeling of 177Lu-phytate complex and checked using ITLC (MeOH: H2O: acetic acid, 4: 4: 2, as mobile phase). The complex stability and viscosity were checked in the final solution up to seven days. The prepared complex solution (100 µCi/100 µl) was injected intra-articularly to male rat knee joint. Leakage of radioactivity from injection site and its distribution in organs were investigated up to seven days. Results: The complex was successfully prepared with high radiochemical purity (>99.9 %). Approximately, the whole injected dose has remained in injection site seven days after injection. Conclusion: The complex was proved to be a feasible agent for cavital radiotherapy in oncology and rheumatology. PMID:23826493

Bis(2,2'-bipyridyl-κN,N')(carbonato-κO,O')cobalt(III) bromide trihydrate.

PubMed

Ma, Peng-Tao; Wang, Yu-Xia; Zhang, Guo-Qian; Li, Ming-Xue

2007-12-06

The title complex, [Co(CO(3))(C(10)H(8)N(2))(2)]Br·3H(2)O, is isostructural with the chloride analogue. The six-coordinated octahedral [Co(2,2'-bipy)(2)CO(3)](+) cation (2,2'-bipy is 2,2'-bipyrid-yl), bromide ion and water mol-ecules are linked together via O-H⋯Br and O-H⋯O hydrogen bonds, generating a one-dimensional chain.

In vivo and in vitro ivacaftor response in cystic fibrosis patients with residual CFTR function: N-of-1 studies.

PubMed

McGarry, Meghan E; Illek, Beate; Ly, Ngoc P; Zlock, Lorna; Olshansky, Sabrina; Moreno, Courtney; Finkbeiner, Walter E; Nielson, Dennis W

2017-04-01

Ivacaftor, a cystic fibrosis transmembrane conductance regulator (CFTR) potentiator, decreases sweat chloride concentration, and improves pulmonary function in 6% of cystic fibrosis (CF) patients with specific CFTR mutations. Ivacaftor increases chloride transport in many other CFTR mutations in non-human cells, if CFTR is in the epithelium. Some CF patients have CFTR in the epithelium with residual CFTR function. The effect of ivacaftor in these patients is unknown. This was a series of randomized, crossover N-of-1 trials of ivacaftor and placebo in CF patients ≥8 years old with potential residual CFTR function (intermediate sweat chloride concentration, pancreatic sufficient, or mild bronchiectasis on chest CT). Human nasal epithelium (HNE) was obtained via nasal brushing and cultured. Sweat chloride concentration change was the in vivo outcome. Chloride current change in HNE cultures with ivacaftor was the in vitro outcome. Three subjects had decreased sweat chloride concentration (-14.8 to -40.8 mmol/L, P < 0.01). Two subjects had unchanged sweat chloride concentration. Two subjects had increased sweat chloride concentration (+23.8 and +27.3 mmol/L, P < 0.001); both were heterozygous for A455E and pancreatic sufficient. Only subjects with decreased sweat chloride concentration had increased chloride current in HNE cultures. Some CF patients with residual CFTR function have decreased sweat chloride concentration with ivacaftor. Increased chloride current in HNE cultures among subjects with decreased sweat chloride concentrations may predict clinical response to ivacaftor. Ivacaftor can increase sweat chloride concentration in certain mutations with unclear clinical effect. Pediatr Pulmonol. 2017;52:472-479. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Sulfide-associated mineral assemblages in the Bushveld Complex, South Africa: platinum-group element enrichment by vapor refining by chloride-carbonate fluids

NASA Astrophysics Data System (ADS)

Kanitpanyacharoen, W.; Boudreau, A. E.

2013-02-01

The petrology of base metal sulfides and associated accessory minerals in rocks away from economically significant ore zones such as the Merensky Reef of the Bushveld Complex has previously received only scant attention, yet this information is critical in the evaluation of models for the formation of Bushveld-type platinum-group element (PGE) deposits. Trace sulfide minerals, primarily pyrite, pyrrhotite, pentlandite, and chalcopyrite are generally less than 100 microns in size, and occur as disseminated interstitial individual grains, as polyphase assemblages, and less commonly as inclusions in pyroxene, plagioclase, and olivine. Pyrite after pyrrhotite is commonly associated with low temperature greenschist alteration haloes around sulfide grains. Pyrrhotite hosted by Cr- and Ti-poor magnetite (Fe3O4) occurs in several samples from the Marginal to Lower Critical Zones below the platiniferous Merensky Reef. These grains occur with calcite that is in textural equilibrium with the igneous silicate minerals, occur with Cl-rich apatite, and are interpreted as resulting from high temperature sulfur loss during degassing of interstitial liquid. A quantitative model demonstrates how many of the first-order features of the Bushveld ore metal distribution could have developed by vapor refining of the crystal pile by chloride-carbonate-rich fluids during which sulfur and sulfide are continuously recycled, with sulfur moving from the interior of the crystal pile to the top during vapor degassing.

Cytotoxicity of Cyclometalated Platinum Complexes Based on Tridentate NCN and CNN-coordinating ligands: Remarkable Coordination Dependence

PubMed Central

Vezzu, Dileep A. k.; Lu, Qun; Chen, Yan-Hua; Huo, Shouquan

2014-01-01

A series of cyclometalated platinum complexes with diverse coordination patterns and geometries were screened for their anticancer activity. It was discovered that the NʌCʌN-coordinated platinum complex based on 1,3-di(pyridyl)benzene displayed much higher cytotoxicity against human lung cancer cells NCI-H522, HCC827, and NCI-H1299, and human prostate cancer cell RV1 than cisplatin. In a sharp contrast, the CʌNʌN-coordinated platinum complex based on 6-phenyl-2,2′-bipyridine was ineffective on these cancer cells. This remarkable difference in cytotoxicity displayed by NʌCʌN- and CʌNʌN-coordinated platinum complexes was related to the trans effect of the carbon donor in the cyclometalated platinum complexes, which played a crucial role in facilitating the dissociation of the chloride ligand to create an active binding site. The DNA binding was studied for the NʌCʌN-coordinated platinum complex using electrophoresis and emission titration. The cellular uptake observed by fluorescent microscope showed the complex is largely concentrated in the cytoplasm. The possible pathways for the cell apoptosis was studied by western blot analysis and the activation of PARP via caspase 7 was observed. PMID:24531534

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

NASA Astrophysics Data System (ADS)

Syaima, H.; Rahardjo, S. B.; Suciningrum, E.

2017-11-01

CuCl2·2H2O with diphenylamine formed a complex compound in 1:4-mole ratio of metal to the ligand in methanol. Its structural properties were investigated by employing metal content analysis by Atomic Absorption Spectroscopy (AAS), magnetic susceptibility, UV-vis and FTIR spectroscopy. The forming of the complex was indicated by shifting of UV-Vis spectra. The result of analysis Cu(II) in the complex showed empirical formula of the complex were Cu(diphenylamine)4Cl2(H2O)6. The electrical conductivity of complex showed the charge ratio of cation and anion = 2:1. Finally, the proposed formula of the complex was [Cu(diphenylamine)4]Cl2·6H2O. Based on infrared spectra, it was revealed that diphenylamine existed as monodentate bind to copper(II) through the functional group of N-H. The electronic spectral study of the complex showed three transition peaks on 861, 592, and 419 nm corresponding to the 2B1g → 2A1g, 2B1g → 2B2g dan 2B1g → 2Eg transitions. The complex was paramagnetic and indicated that ligands form square planar geometry around the Cu(II).

Influence of the current density on the electrochemical treatment of concentrated 1-butyl-3-methylimidazolium chloride solutions on diamond electrodes.

PubMed

Marcionilio, Suzana M L de Oliveira; Alves, Gisele M; E Silva, Rachel B Góes; Marques, Pablo J Lima; Maia, Poliana D; Neto, Brenno A D; Linares, José J

2016-10-01

This paper focuses on the influence of the current density treatment of a concentrated 1-butyl-3-methylimidazolium chloride (BMImCl) solution on an electrochemical reactor with a boron-doped diamond (BDD) anode. The decrease in the total organic carbon (TOC) and the BMImCl concentration demonstrate the capability of BDD in oxidizing ionic liquids (ILs) and further mineralizing (to CO2 and NO3 (-)) more rapidly at higher current densities in spite of the reduced current efficiency of the process. Moreover, the presence of Cl(-) led to the formation of oxychlorinated anions (mostly ClO3 (-) and ClO4 (-)) and, in combination with the ammonia generated in the cathode from the nitrate reduction, chloramines, more intensely at higher current density. Finally, the analysis of the intermediates formed revealed no apparent influence of the current density on the BMImCl degradation mechanism. The current density presents therefore a complex influence on the IL treatment process that is discussed throughout this paper.

Optically enhanced SnO{sub 2}/CdSe core/shell nanostructures grown by sol-gel spin coating method

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

Kumar, Vijay, E-mail: vijaynadda83@gmail.com; Goswami, Y. C.; Rajaram, P.

2015-08-28

Synthesis of SnO{sub 2}/CdSe metal oxide/ chalcogenide nanostructures on glass micro slides using ultrasonic sol-gel process followed by spin coating has been reported. Stannous chloride, cadmium chloride and selenium dioxide compounds were used for Sn, Cd and Se precursors respectively. Ethylene glycol was used as complexing agent. The samples were characterized by XRD, SEM, AFM and UV-spectrophotometer. All the peaks shown in diffractograms are identified for SnO{sub 2}. Peak broadening observed in core shell due to stress behavior of CdSe lattice. Scanning electron microscope and AFM exhibits the conversion of cluster in to nanorods structures forms. Atomic force microscope showsmore » the structures in nanorods form and a roughness reduced 1.5194 nm by the deposition of CdSe. Uv Visible spectra shows a new absorption edge in the visible region make them useful for optoelectronic applications.« less

Fundamental studies on the feasibility of deep eutectic solvents for the selective partition of glaucarubinone present in the roots of Simarouba glauca.

PubMed

Kholiya, Faisal; Bhatt, Nidhi; Rathod, Meena R; Meena, Ramavatar; Prasad, Kamalesh

2015-07-14

Several deep eutectic solvents prepared by the complexation of choline chloride as the hydrogen bond acceptor and hydrogen bond donors such as urea, thiourea, ethylene glycol, and glycerol were employed to partition glaucarubinone, an antimalarial compound present in roots of the plant, Simarouba glauca. Among all the solvents, the deep eutectic solvent consisting of the mixture of choline chloride and urea the most suitable to partition the antimalarial compound from the extract selectively. Analytical tools such as high-performance liquid chromatography and electrospray ionization mass spectrometry were used for characterizations, and glaucarubinone extracted from the roots of the plant by conventional solvent extraction method was used as a reference for comparison. The hydrogen and noncovalent bonds formed between glaucarubinone and the deep eutectic solvents could be responsible for the selective partition of the drug molecule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of water, sulfates and chloride on arsenopyrite surface

NASA Astrophysics Data System (ADS)

Silva, Juliana C. M.; dos Santos, Egon C.; de Oliveira, Aline; Heine, Thomas; De Abreu, Heitor A.; Duarte, Hélio A.

2018-03-01

Arsenopyrite is one of the sulfide minerals responsible for acid rock drainage (ARD) and is one of the most hazardous in regions affected by mining activities. This phenomenon involves complex reaction mechanism. Although it is intensely investigated, there is a lack of consensus concerning the reaction mechanisms and more information is still necessary. In this work, the adsorption of water, hydrochloric acid, and sulfuric acid on arsenopyrite (001) surface was investigated by means of Density Functional calculations and the results compared to other sulfides aiming to understand the mineral/water interface. The interaction of the chemical species with the (001) FeAsS surface is the first step to understand the intricate oxidation mechanism of arsenopyrite. Molecular water adsorption on (001) FeAsS is more favored than the adsorption of sulfate favoring the dissolution of sulfates and enhancing its oxidation. The estimated adsorption energies of water, sulfates and chloride on other sulfide minerals are compared with the estimated values for arsenopyrite and the chemical reactivity differences discussed in detail.

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

PubMed Central

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

2014-01-01

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

Magnetite-apatite-dolomitic rocks of Ust-Chulman (Aldan shield, Russia): Seligdar-type carbonatites?

NASA Astrophysics Data System (ADS)

Prokopyev, Ilya R.; Doroshkevich, Anna G.; Redina, Anna A.; Obukhov, Andrey V.

2018-04-01

The Ust-Chulman apatite ore body is situated within the Nimnyrskaya apatite zone at the Aldan shield in Russia. The latest data confirm the carbonatitic origin of the Seligdar apatite deposit (Prokopyev et al. in Ore Geol Rev 81:296-308, 2017). The results of our investigations demonstrate that the magnetite-apatite-dolomitic rocks of the Ust-Chulman are highly similar to Seligdar-type dolomitic carbonatites in terms of the mineralogy and the fluid regime of formation. The ilmenite and spinel mineral phases occur as solid solutions with magnetite, and support the magmatic origin of the Ust-Chulman ores. The chemical composition of REE- and SO3-bearing apatite crystals and, specifically, monazite-(Ce) mineralisation and the formation of Nb-rutile, late hydrothermal sulphate minerals (barite, anhydrite) and haematite are typical for carbonatite complexes. The fluid inclusions study revealed similarities to the evolutionary trend of the Seligdar carbonatites that included changes of the hydrothermal solutions from highly concentrated chloride to medium-low concentrated chloride-sulphate and oxidized carbonate-ferrous.

Detection and measurement of organic lampricide residues

USGS Publications Warehouse

Daniels, Stacy L.; Kempe, Lloyd L.; Billy, Thomas J.; Beeton, Alfred M.

1965-01-01

The selective lampricide, 3-trifluoromethyl-4-nitrophenol (TFM), and its synergist, 5,2'-dichloro-4'-nitrosalicylanilide (DCN), are separable from natural waters by anion exchange. The adsorbed compounds can then be recovered from the resin as concentrates by elution with selective solvent mixtures. Measurements of the amounts of lampricides in the final concentrates can be made colorimetrically at 395 mI? for TFM and at 530 mI? for the safranin complex of DCN. TFM has also been separated for quantitative determination from homogenates of whole fish. The fish is first macerated in a blender and then hydrolyzed in hot, 3 N hydrochloric acid. The amount of background color, due to certain components of the fish in the hydrolysate, is reduced by one or a combination of three methods: (1) a series of three extractions with ether, methylene chloride, and benzene; (2) cation exchange followed by methylene chloride extraction; or (3) ether extraction followed by anion exchange and subsequent desorption with amyl acetate-acetic acid.

Thermodynamic and structural effect of urea and guanidine chloride on the helical and on a hairpin fragment of GB1 from molecular simulations.

PubMed

Meloni, R; Tiana, G

2017-04-01

With the help of molecular-dynamics simulations, we studied the effect of urea and guanidine chloride on the thermodynamic and structural properties of the helical fragment of protein GB1, comparing them with those of its second beta hairpin. We showed that the helical fragment in different solvents populates an ensemble of states that is more complex than that of the hairpin, and thus the associated experimental observables (circular-dichroism spectra, secondary chemical shifts, m values), that we back-calculated from the simulations and compared with the actual data, are more difficult to interpret. We observed that in the case of both peptides, urea binds tightly to their backbone, while guanidine exerts its denaturing effect in a more subtle way, strongly affecting the electrostatic properties of the solution. This difference can have consequences in the way denaturation experiments are interpreted. Proteins 2017; 85:753-763. © 2016 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Pseudosymmetric fac-di­aqua­trichlorido[(di­methyl­phosphor­yl)methanaminium-κO]manganese(II)

PubMed Central

Reiss, Guido J.

2013-01-01

In the title compound, [Mn(C3H11NOP)Cl3(H2O)2], the MnII metal center has a distorted o­cta­hedral geometry, coordinated by the three chloride ligands showing a facial arrangement. Two water mol­ecules and the O-coordinated dpmaH cation [dpmaH = (di­methyl­phosphor­yl)methanaminium] complete the coordination sphere. Each complex mol­ecule is connected to its neighbours by O—H⋯Cl and N—H⋯Cl hydrogen bonds. Two of the chloride ligands and the two water ligands form a hydrogen-bonded polymeric sheet in the ab plane. Furthermore, these planes are connected to adjacent planes by hydrogen bonds from the aminium function of cationic dpmaH ligand. A pseudo-mirror plane perpendicular to the b axis in the chiral space group P21 is observed together with inversion twinning [ratio = 0.864 (5):0.136 (5)]. PMID:23723764

A Key concept in Magnesium Secondary Battery Electrolytes.

PubMed

Bertasi, Federico; Hettige, Chaminda; Sepehr, Fatemeh; Bogle, Xavier; Pagot, Gioele; Vezzù, Keti; Negro, Enrico; Paddison, Stephen J; Greenbaum, Steve G; Vittadello, Michele; Di Noto, Vito

2015-09-21

A critical roadblock toward practical Mg-based energy storage technologies is the lack of reversible electrolytes that are safe and electrochemically stable. Here, we report on high-performance electrolytes based on 1-ethyl-3-methylimidazolium chloride (EMImCl) doped with AlCl3 and highly amorphous δ-MgCl2 . The phase diagram of the electrolytes reveals the presence of four thermal transitions that strongly depend on salt content. High-level density functional theory (DFT)-based electronic structure calculations substantiate the structural and vibrational assignment of the coordination complexes. A 3D chloride-concatenated dynamic network model accounts for the outstanding redox behaviour and the electric and magnetic properties, providing insight into the conduction mechanism of the electrolytes. Mg anode cells assembled using the electrolytes were cyclically discharged at a high rate (35 mA g(-1) ), exhibiting an initial capacity of 80 mA h g(-1) and a steady-state voltage of 2.3 V. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on kinetics of adsorption of humic acid modified by ferric chloride on U(VI)

NASA Astrophysics Data System (ADS)

Zhang, Y. Y.; Lv, J. W.; Song, Y.; Dong, X. J.; Fang, Q.

2017-11-01

In order to reveal the adsorption mechanism of the ferric chloride modified humic acid on uranium, the influence of pH value and contact time of adsorption on uranium was studied through a series of batch experiments. Meanwhile, the adsorption kinetics was analyzed with pseudo-first order kinetic model and pseudo-second order kinetic model. The results show that adsorption is affected by the pH value of the solution and by contract time, and the best condition for adsorption on uranium is at pH=5 and the adsorption equilibrium time is about 80 min. Kinetics of HA-Fe adsorption on uranium accords with pseudo-second order kinetic model. The adsorption is mainly chemical adsorption, and complexes were produced by the reaction between uranium ions and the functional groups on the surface of HA-Fe, which can provide reference for further study of humic acid effecting on the migration of U(VI) in soil.

Electrodeposition mechanism and characterization of Ni-Cu alloy coatings from a eutectic-based ionic liquid

NASA Astrophysics Data System (ADS)

Wang, Shaohua; Guo, Xingwu; Yang, Haiyan; Dai, JiChun; Zhu, Rongyu; Gong, Jia; Peng, Liming; Ding, Wenjiang

2014-01-01

The electrodeposition mechanism, microstructures and corrosion resistances of Ni-Cu alloy coatings on Cu substrate were investigated in a choline chloride-urea (1:2 molar ratio) eutectic-based ionic liquid (1:2 ChCl-urea IL) containing nickel and copper chlorides. Cyclic voltammetry showed that the onset reduction potentials for Cu (∼-0.32 V) and for Ni (∼-0.47 V) were close to each other, indicating that Ni-Cu co-deposition could be easily achieved in the absence of complexing agent which was indispensable in aqueous plating electrolyte. Chronoamperometric investigations revealed that Ni-Cu deposits followed the three-dimensional instantaneous nucleation/growth mechanism, thus producing a solid solution. The compositions, microstructures and corrosion resistances of Ni-Cu alloy coatings were significantly dependent on the deposition current densities. Ni-Cu alloy coatings were α-Ni(Cu) solid solutions, and the coating containing ∼17.6 at.% Cu exhibited the best corrosion resistance because of its dense and crack-free structure.

3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate)

PubMed Central

Maestro, Armando; Llamas, Sara; Álvarez-Rodríguez, Jesús; Ortega, Francisco; Maroto-Valiente, Ángel

2016-01-01

Summary This work addresses the formation and the internal morphology of polyelectrolyte layers obtained by the layer-by-layer method. A multimodal characterization showed the absence of stratification of the films formed by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). Indeed the final organization might be regarded as three-dimensional solid-supported inter-polyelectrolyte films. The growth mechanism of the multilayers, followed using a quartz crystal microbalance, evidences two different growth trends, which show a dependency on the ionic strength due to its influence onto the polymer conformation. The hydration state does not modify the multilayer growth, but it contributes to the total adsorbed mass of the film. The water associated with the polyelectrolyte films leads to their swelling and plastification. The use of X-ray photoelectron spectroscopy has allowed for deeper insights on the internal structure and composition of the polyelectrolyte multilayers. PMID:26977377

3D solid supported inter-polyelectrolyte complexes obtained by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate).

PubMed

Guzmán, Eduardo; Maestro, Armando; Llamas, Sara; Álvarez-Rodríguez, Jesús; Ortega, Francisco; Maroto-Valiente, Ángel; Rubio, Ramón G

2016-01-01

This work addresses the formation and the internal morphology of polyelectrolyte layers obtained by the layer-by-layer method. A multimodal characterization showed the absence of stratification of the films formed by the alternate deposition of poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). Indeed the final organization might be regarded as three-dimensional solid-supported inter-polyelectrolyte films. The growth mechanism of the multilayers, followed using a quartz crystal microbalance, evidences two different growth trends, which show a dependency on the ionic strength due to its influence onto the polymer conformation. The hydration state does not modify the multilayer growth, but it contributes to the total adsorbed mass of the film. The water associated with the polyelectrolyte films leads to their swelling and plastification. The use of X-ray photoelectron spectroscopy has allowed for deeper insights on the internal structure and composition of the polyelectrolyte multilayers.

Interaction of triblock co-polymer micelles with phospholipid-bilayer: a spectroscopic investigation using a potential chloride channel blocker.

PubMed

Ganguly, Aniruddha; Ghosh, Soumen; Guchhait, Nikhil

2015-03-07

Interaction of a potential chloride channel blocker, 9-methyl anthroate (9-MA), has been studied with zwitterionic l-α-phosphatidylcholine (egg-PC) lipid vesicles, which ascertains the utility of the drug as an efficient molecular reporter for probing the microheterogeneous environment of lipid-bilayers. The effect of a non-ionic triblock co-polymer P123 on the stability of these drug-bound lipid-bilayers has also been investigated by means of steady state and time-resolved spectroscopic techniques exploiting the fluorescence properties of the drug. Experimental results reveal that the addition of P123 to the drug-bound lipid results in a preferential complexation of the drug with the Pluronic leaving the lipid vesicles aside, which has been attributed to a substantially stronger binding interaction of the drug with P123 than that with egg-PC. The result is of potential interest from a medical perspective owing to the context of excess drug desorption from bio-membranes.

Microbiological Leaching of Metallic Sulfides

PubMed Central

Razzell, W. E.; Trussell, P. C.

1963-01-01

The percentage of chalcopyrite leached in percolators by Thiobacillus ferrooxidans was dependent on the surface area of the ore but not on the amount. Typical examples of ore leaching, which demonstrate the role of the bacteria, are presented. In stationary fermentations, changes in KH2PO4 concentration above or below 0.1% decreased copper leaching as did reduction in the MgSO4·7H2O and increase in the (NH4)2SO4 concentration. Bacterial leaching of chalcopyrite was more effective than nonbiological leaching with ferric sulfate; ferric sulfate appeared to retard biological leaching, but this effect was likely caused by formation of an insoluble copper-iron complex. Ferrous sulfate and sodium chloride singly accentuated both bacterial and nonbiological leaching of chalcocite but jointly depressed bacterial action. Sodium chloride appeared to block bacterial iron oxidation without interfering with sulfide oxidation. Bacterial leaching of millerite, bornite, and chalcocite was greatest at pH 2.5. The economics of leaching a number of British Columbia ore bodies was discussed. PMID:16349627

Effects of copper source and concentration on in vitro phytate phosphorus hydrolysis by phytase.

PubMed

Pang, Yanfang; Applegate, Todd J

2006-03-08

Five copper (Cu) sources were studied at pH 2.5, 5.5, and 6.5 to determine how Cu affects phytate phosphorus (PP) hydrolysis by phytase at concentrations up to 500 mg/kg diet (60 min, 40-41 degrees C). Subsequently, Cu solubility with and without sodium phytate was measured. Adding Cu inhibited PP hydrolysis at pH 5.5 and pH 6.5 (P < 0.05). This inhibition was greater with higher concentrations of Cu. Tri-basic copper chloride and copper lysinate inhibited PP hydrolysis much less than copper sulfate pentahydrate, copper chloride, and copper citrate (P < 0.05). A strong negative relationship was observed between PP hydrolysis and soluble Cu at pH 5.5 (r = -0.76, P < 0.0001) and 6.5 (r = -0.54, P < 0.0001). In conclusion, pH, Cu concentration, and source influenced PP hydrolysis by phytase in vitro and were related to the amount of soluble Cu and the formation of insoluble copper-phytin complexes.

Regeneration of zinc chloride hydrocracking catalyst

DOEpatents

Zielke, Clyde W.

1979-01-01

Improved rate of recovery of zinc values from the solids which are carried over by the effluent vapors from the oxidative vapor phase regeneration of spent zinc chloride catalyst is achieved by treatment of the solids with both hydrogen chloride and calcium chloride to selectively and rapidly recover the zinc values as zinc chloride.

21 CFR 173.255 - Methylene chloride.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Methylene chloride. 173.255 Section 173.255 Food... Related Substances § 173.255 Methylene chloride. Methylene chloride may be present in food under the... label of the hops extract identifies the presence of the methylene chloride and provides for the use of...

21 CFR 184.1138 - Ammonium chloride.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ammonium chloride. 184.1138 Section 184.1138 Food... Specific Substances Affirmed as GRAS § 184.1138 Ammonium chloride. (a) Ammonium chloride (NH4Cl, CAS Reg. No. 12125-02-9) is produced by the reaction of sodium chloride and an ammonium salt in solution. The...

21 CFR 184.1622 - Potassium chloride.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Potassium chloride. 184.1622 Section 184.1622 Food... GRAS § 184.1622 Potassium chloride. (a) Potassium chloride (KCl, CAS Reg. No. 7447-40-7) is a white... manufacturing practice. Potassium chloride may be used in infant formula in accordance with section 412(g) of...

40 CFR 61.65 - Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 8 2010-07-01 2010-07-01 false Emission standard for ethylene... AIR POLLUTANTS National Emission Standard for Vinyl Chloride § 61.65 Emission standard for ethylene dichloride, vinyl chloride and polyvinyl chloride plants. An owner or operator of an ethylene dichloride...

Evaporation behavior of lithium, potassium, uranium and rare earth chlorides in pyroprocessing

NASA Astrophysics Data System (ADS)

Jang, Junhyuk; Kim, Tackjin; Park, Sungbin; Kim, Gha-Young; Kim, Sihyoung; Lee, Sungjai

2017-12-01

The evaporation behaviors of Li, K, U, and rare earth (RE) chlorides were examined for the cathode process in pyroprocessing. The evaporation temperatures of the chlorides were evaluated in vacuum by measuring the weight decrease. In addition, an evaporation test up to 1473 K of the cathode process using a surrogate mixture of uranium and chlorides was conducted. It was found that LiCl evaporated more readily than the other chlorides. The weight of LiCl was rapidly decreased at temperatures above 981 K, while that of KCl was decreased above 1035 K, indicating the evaporation. UCl3 evaporated at temperatures above 1103 K. RE chlorides showed a similar evaporation behavior, evaporating first at 1158 K then rapidly evaporating at temperatures above 1230 K. Thus, the order of evaporation with increasing temperature was found to be LiCl < KCl < UCl3 < RE chlorides, with different RE chlorides evaporating at similar temperature. The surrogate test confirmed the observed evaporation trend of the chlorides during the cathode process, and revealed that the contamination of uranium remains by the back-reaction of RE chlorides is negligible.

Transport and fate of chloride from road salt within a mixed urban and agricultural watershed in Illinois (USA): assessing the influence of chloride application rates

NASA Astrophysics Data System (ADS)

Ludwikowski, Jessica J.; Peterson, Eric W.

2018-06-01

In a typical winter season, approximately 471,000 tons of road salt are deposited along roadways in Illinois, USA. An estimated 45% of the deposited road salt will infiltrate through the soils and into shallow aquifers. Transported through shallow aquifers, chloride associated with the road salts has the potential to reside within groundwater for years based on the pathway, the geologic material, and the recharge rate of the aquifer system. Utilizing MODFLOW and MT3D, simulations employing various road-salt application rates were conducted to assess the net accumulation of chloride and the residence times of chloride in an agriculture-dominated watershed that originates in an urban area. A positive-linear relationship was observed between the application rate of chloride and both the maximum chloride concentration and total mass accumulated within the watershed. Simulated annual recharge rates along impacted surfaces ranged from 1,000 to 10,000 mg/L. After 60 years of application, simulated chloride concentrations in groundwater ranged from 197 to 1,900 mg/L. For all application rates, chloride concentrations within the groundwater rose at an annual rate of >3 mg/L. While concentrations increase throughout the system, the majority of chloride accumulation occurs near the roads and the urban areas. Model simulations reveal a positive relationship between application rate and residence time of chloride (1,123-1,288 days based on application rate). The models indicate that continued accumulation of chloride in shallow aquifers can be expected, and methods that apply less chloride effectively need to be examined.

Transport and fate of chloride from road salt within a mixed urban and agricultural watershed in Illinois (USA): assessing the influence of chloride application rates

NASA Astrophysics Data System (ADS)

Ludwikowski, Jessica J.; Peterson, Eric W.

2018-01-01

In a typical winter season, approximately 471,000 tons of road salt are deposited along roadways in Illinois, USA. An estimated 45% of the deposited road salt will infiltrate through the soils and into shallow aquifers. Transported through shallow aquifers, chloride associated with the road salts has the potential to reside within groundwater for years based on the pathway, the geologic material, and the recharge rate of the aquifer system. Utilizing MODFLOW and MT3D, simulations employing various road-salt application rates were conducted to assess the net accumulation of chloride and the residence times of chloride in an agriculture-dominated watershed that originates in an urban area. A positive-linear relationship was observed between the application rate of chloride and both the maximum chloride concentration and total mass accumulated within the watershed. Simulated annual recharge rates along impacted surfaces ranged from 1,000 to 10,000 mg/L. After 60 years of application, simulated chloride concentrations in groundwater ranged from 197 to 1,900 mg/L. For all application rates, chloride concentrations within the groundwater rose at an annual rate of >3 mg/L. While concentrations increase throughout the system, the majority of chloride accumulation occurs near the roads and the urban areas. Model simulations reveal a positive relationship between application rate and residence time of chloride (1,123-1,288 days based on application rate). The models indicate that continued accumulation of chloride in shallow aquifers can be expected, and methods that apply less chloride effectively need to be examined.

Fluid shear stress enhances the cell volume decrease of osteoblast cells by increasing the expression of the ClC-3 chloride channel

PubMed Central

LIU, LI; CAI, SIYI; QIU, GUIXING; LIN, JIN

2016-01-01

ClC-3 is a volume-sensitive chloride channel that is responsible for cell volume adjustment and regulatory cell volume decrease (RVD). In order to evaluate the effects of fluid shear stress (FSS) stimulation on the osteoblast ClC-3 chloride channel, MC3T3-E1 cells were stimulated by FSS in the experimental group. Fluorescence quantitative polymerase chain reaction was used to detect changes in ClC-3 mRNA expression, the chloride ion fluorescent probe N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide (MQAE) was used to detect the chloride channel activity, and whole-cell patch clamping was used to monitor the changes in the volume-sensitive chloride current activated by a hypotonic environment following mechanical stimulation. The results show that the expression of the osteoblast chloride channel ClC-3 was significantly higher in the FSS group compared with the control group. MQAE fluorescence intensity was significantly reduced in the FSS group compared to the control group, suggesting that mechanical stimulation increased chloride channel activity and increased the efflux of intracellular chloride ions. Image analysis of osteoblast volume changes showed that osteoblast RVD was enhanced by mechanical stimulation. Whole-cell patch clamping showed that the osteoblast volume-sensitive chloride current was larger in the stimulated group compared to the control group, suggesting that elevated ClC-3 chloride channel expression results in an increased volume-sensitive chloride current. In conclusion, FSS stimulation enhances the RVD of osteoblast cell by increasing the expression of the ClC-3 and enhancing the chloride channel activity. PMID:27073622

Preparation of Carbon-Chitosan-Polyvinyl Chloride (CC-PVC) Material and its Application to Electrochemical Degradation of Methylene Blue in Sodium Chloride Solution

NASA Astrophysics Data System (ADS)

Riyanto; Prawidha, A. D.

2018-01-01

Electrochemical degradation of methylene blue using Carbon-Chitosan-Polyvinyl Chloride (CC-PVC) electrode in sodium chloride have been done. The aim of this work was to degradation of methylene blue using Carbon-Chitosan-Polyvinyl Chloride (CC-PVC). Carbon chitosan composite electrode was preparing by Carbon and Chitosan powder and PVC in 4 mL tetrahydrofuran (THF) solvent and swirled flatly to homogeneous followed by drying in an oven at 100 °C for 3 h. The mixture was placed in stainless steel mould and pressed at 10 ton/cm2. Sodium chloride was used electrolyte solution. The effects of the current and electrolysis time were investigated using spectrophotometer UV-Visible. The experimental results showed that the carbon-chitosan composite electrode have higher effect in the electrochemical degradation of methylene blue in sodium chloride. Based on UV-visible spectra analysis shows current and electrolysis time has high effect to degradation of methylene blue in sodium chloride. Chitosan and polyvinyl chloride can strengthen the bond between the carbons so that the material has the high stability and conductivity. As conclusions is Carbon-Chitosan-Polyvinyl Chloride (CC-PVC) electrode have a high electrochemical activity for degradation of methylene blue in sodium chloride.

Abnormal passive chloride absorption in cystic fibrosis jejunum functionally opposes the classic chloride secretory defect

PubMed Central

Russo, Michael A.; Högenauer, Christoph; Coates, Stephen W.; Santa Ana, Carol A.; Porter, Jack L.; Rosenblatt, Randall L.; Emmett, Michael; Fordtran, John S.

2003-01-01

Due to genetic defects in apical membrane chloride channels, the cystic fibrosis (CF) intestine does not secrete chloride normally. Depressed chloride secretion leaves CF intestinal absorptive processes unopposed, which results in net fluid hyperabsorption, dehydration of intestinal contents, and a propensity to inspissated intestinal obstruction. This theory is based primarily on in vitro studies of jejunal mucosa. To determine if CF patients actually hyperabsorb fluid in vivo, we measured electrolyte and water absorption during steady-state perfusion of the jejunum. As expected, chloride secretion was abnormally low in CF, but surprisingly, there was no net hyperabsorption of sodium or water during perfusion of a balanced electrolyte solution. This suggested that fluid absorption processes are reduced in CF jejunum, and further studies revealed that this was due to a marked depression of passive chloride absorption. Although Na+-glucose cotransport was normal in the CF jejunum, absence of passive chloride absorption completely blocked glucose-stimulated net sodium absorption and reduced glucose-stimulated water absorption 66%. This chloride absorptive abnormality acts in physiological opposition to the classic chloride secretory defect in the CF intestine. By increasing the fluidity of intraluminal contents, absence of passive chloride absorption may reduce the incidence and severity of intestinal disease in patients with CF. PMID:12840066

Electron Detachment Dissociation of Underivatized Chloride-Adducted Oligosaccharides

NASA Astrophysics Data System (ADS)

Kornacki, James R.; Adamson, Julie T.; Håkansson, Kristina

2012-11-01

Chloride anion attachment has previously been shown to aid determination of saccharide anomeric configuration and generation of linkage information in negative ion post-source decay MALDI tandem mass spectrometry. Here, we employ electron detachment dissociation (EDD) and collision activated dissociation (CAD) for the structural characterization of underivatized oligosaccharides bearing a chloride ion adduct. Both neutral and sialylated oligosaccharides are examined, including maltoheptaose, an asialo biantennary glycan (NA2), disialylacto- N-tetraose (DSLNT), and two LS tetrasaccharides (LSTa and LSTb). Gas-phase chloride-adducted species are generated by negative ion mode electrospray ionization. EDD and CAD spectra of chloride-adducted oligosaccharides are compared to the corresponding spectra for doubly deprotonated species not containing a chloride anion to assess the role of chloride adduction in the stimulation of alternative fragmentation pathways and altered charge locations allowing detection of additional product ions. In all cases, EDD of singly chloridated and singly deprotonated species resulted in an increase in observed cross-ring cleavages, which are essential to providing saccharide linkage information. Glycosidic cleavages also increased in EDD of chloride-adducted oligosaccharides to reveal complementary structural information compared to traditional (non-chloride-assisted) EDD and CAD. Results indicate that chloride adduction is of interest in alternative anion activation methods such as EDD for oligosaccharide structural characterization.

40 CFR Table 2 to Subpart Ggg of... - Partially Soluble HAP

Code of Federal Regulations, 2014 CFR

2014-07-01

... Xylene (p) Vinyl chloride N-hexane Xylene (m) Xylene (o) [66 FR 40136, Aug. 2, 2001] ... Acrylonitrile Methylene chloride Allyl chloride N,N-dimethylaniline Benzene Propionaldehyde Benzyl chloride...

40 CFR Table 2 to Subpart Ggg of... - Partially Soluble HAP

Code of Federal Regulations, 2013 CFR

2013-07-01

... Xylene (p) Vinyl chloride N-hexane Xylene (m) Xylene (o) [66 FR 40136, Aug. 2, 2001] ... Acrylonitrile Methylene chloride Allyl chloride N,N-dimethylaniline Benzene Propionaldehyde Benzyl chloride...

[Forensic Analysis for 54 Cases of Suxamethonium Chloride Poisoning].

PubMed

Zhao, Y F; Zhao, B Q; Ma, K J; Zhang, J; Chen, F Y

2017-08-01

To observe and analyze the performance of forensic science in the cases of suxa- methonium chloride poisoning, and to improve the identification of suxamethonium chloride poisoning. Fifty-four cases of suxamethonium chloride poisoning were collected. The rules of determination of suxamethonium chloride poisoning were observed by the retrospective analysis of pathological and toxicological changes as well as case features. The pathological features of suxamethonium chloride poisoning were similar to the general changes of sudden death, which mainly included acute pulmonary congestion and edema, and partly showed myocardial disarray and fracture. Suxamethonium chloride could be detected in the heart blood of all cases and in skin tissue of part cases. Suxa-methonium chloride poisoning has the characteristics with fast death and covert means, which are difficult to rescue and easily miss inspection. For the cases of sudden death or suspicious death, determination of suxamethonium chloride should be taken as a routine detection index to prevent missing inspection. Copyright© by the Editorial Department of Journal of Forensic Medicine

Fiber optic chloride sensing: if corrosion's the problem, chloride sensing is the key

NASA Astrophysics Data System (ADS)

Fuhr, Peter L.; MacCraith, Brian D.; Huston, Dryver R.; Guerrina, Mario; Nelson, Matthew

1997-09-01

The use of chloride-based deicing agents to help clear US highways of roadway hazards leads to associated chemical related problems. Fouling of local rivers and streams due to runoff of the water borne chlorides is significant and has contributed to local ordances are attempting to force state agencies to reduce, if not eliminate, the use of these chlorides. With respect to the corrosion aspects of chloride application, cracks that occur in the roadway/bridge pavement allow water to seep into the pavement carrying the chloride to the rebar with the resultant increase in corrosion. The costs of this corrosion are considerable and have led to the widespread use of chloride/water impermeable membranes on roadways and especially within bridges. Fiber optic sensor have repeatedly been shown to provide measurement capabilities of parameters within such reinforced concrete structures. Development of a fiber optic chloride sensors capable of being embedded within a roadway or bridge deck is reported.

Sequential development of hepatocellular carcinoma and liver angiosarcoma in a vinyl chloride-exposed worker.

PubMed

Guido, Maria; Sarcognato, Samantha; Pelletti, Guido; Fassan, Matteo; Murer, Bruno; Snenghi, Rossella

2016-11-01

Strong experimental and clinical evidences have definitely linked occupational vinyl chloride exposure to development of angiosarcoma of the liver. In contrast, despite the International Agency for Research on Cancer having included vinyl chloride among the causes of hepatocellular carcinoma, the association between vinyl chloride exposure and hepatocellular carcinoma remains debated. This issue is relevant, because occupational exposure to high levels of vinyl chloride may still occur. We report a unique case of sequential occurrences of hepatocellular carcinoma and angiosarcoma of the liver, in a vinyl chloride-exposed worker without cirrhosis and any known risk factor for chronic liver disease. Both the hepatocellular carcinoma and the surrounding normal liver showed micronucleus formation, which reflects genotoxic effect of vinyl chloride. Angiosarcoma showed a KRAS G12D point mutation, which is considered to be characteristic of vinyl chloride-induced angiosarcoma. This case supports the pathogenic role of vinyl chloride in both hepatocellular carcinoma and angiosarcoma development. Copyright © 2016 Elsevier Inc. All rights reserved.

Sweat Chloride as A Biomarker of CFTR Activity: Proof of Concept and Ivacaftor Clinical Trial Data

PubMed Central

Accurso, Frank J.; Van Goor, Fredrick; Zha, Jiuhong; Stone, Anne J.; Dong, Qunming; Ordonez, Claudia L.; Rowe, Steven M.; Clancy, John Paul; Konstan, Michael W.; Hoch, Heather E.; Heltshe, Sonya L.; Ramsey, Bonnie W.; Campbell, Preston W.; Ashlock, Melissa A.

2014-01-01

Background We examined data from a Phase 2 trial {NCT00457821 } of ivacaftor, a CFTR potentiator, in cystic fibrosis (CF) patients with a G551D mutation to evaluate standardized approaches to sweat chloride measurement and to explore the use of sweat chloride and nasal potential difference (NPD) to estimate CFTR activity. Methods Sweat chloride and NPD were secondary endpoints in this placebo-controlled, multicenter trial. Standardization of sweat collection, processing, and analysis was employed for the first time.. Sweat chloride and chloride ion transport (NPD) were integrated into a model of CFTR activity. Results Within-patient sweat chloride determinations showed sufficient precision to detect differences between dose-groups and assess ivacaftor treatment effects. Analysis of changes in sweat chloride and NPD demonstrated that patients treated with ivacaftor achieved CFTR activity equivalent to approximately 35%–40% of normal. Conclusions Sweat chloride is useful in multicenter trials as a biomarker of CFTR activity and to test the effect of CFTR potentiators. PMID:24660233

Sweat chloride as a biomarker of CFTR activity: proof of concept and ivacaftor clinical trial data.

PubMed

Accurso, Frank J; Van Goor, Fredrick; Zha, Jiuhong; Stone, Anne J; Dong, Qunming; Ordonez, Claudia L; Rowe, Steven M; Clancy, John Paul; Konstan, Michael W; Hoch, Heather E; Heltshe, Sonya L; Ramsey, Bonnie W; Campbell, Preston W; Ashlock, Melissa A

2014-03-01

We examined data from a Phase 2 trial {NCT00457821} of ivacaftor, a CFTR potentiator, in cystic fibrosis (CF) patients with aG551D mutation to evaluate standardized approaches to sweat chloride measurement and to explore the use of sweat chloride and nasal potential difference (NPD) to estimate CFTR activity. Sweat chloride and NPD were secondary endpoints in this placebo-controlled, multicenter trial. Standardization of sweat collection, processing,and analysis was employed for the first time. Sweat chloride and chloride ion transport (NPD) were integrated into a model of CFTR activity. Within-patient sweat chloride determinations showed sufficient precision to detect differences between dose-groups and assess ivacaftor treatment effects. Analysis of changes in sweat chloride and NPD demonstrated that patients treated with ivacaftor achieved CFTR activity equivalent to approximately 35%–40% of normal. Sweat chloride is useful in multicenter trials as a biomarker of CFTR activity and to test the effect of CFTR potentiators.