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

PubMed

Soylak, Mustafa; Erdogan, Nilgun D

2006-09-21

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

Selective flotation-spectrophotometric determination of trace copper(II) in natural waters, human blood and drug samples using phenanthraquinone monophenylthiosemicarbazone.

PubMed

Khalifa, M E; Akl, M A; Ghazy, S E

2001-06-01

Copper(II) forms 1:1 and 1:2 intense red complexes with phenanthraquinone monophenylthiosemicarbazone (PPT) at pH 3-3.5 and > or =6.5, respectively. These complexes exhibit maximal absorbance at 545 and 517 nm, the molar absorptivity being 2.3 x 10(4) and 4.8 x 10(4) l mol(-1) cm(-1), respectively. However, the 1:1 complex was quantitatively floated with oleic acid (HOL) surfactant in the pH range 4.5-5.5, providing a highly selective and sensitive procedure for the spectrophotometric determination of CuII. The molar absorptivity of the floated Cu-PPT complex was 1.5 x 10(5) l mol)(-1) cm(-1). Beer's law was obeyed over the range 3-400 ppb at 545 nm. The analytical parameters affecting the flotation process and hence the determination of copper traces were reported. Also, the structure of the isolated solid complex and the mechanism of flotation were suggested. Moreover, the procedure was successfully applied to the analysis of CuII in natural waters, serum blood and some drug samples.

Removal of arsenic from synthetic acid mine drainage by electrochemical pH adjustment and coprecipitation with iron hydroxide.

PubMed

Wang, Jenny Weijun; Bejan, Dorin; Bunce, Nigel J

2003-10-01

Acid mine drainage (AMD), which is caused by the biological oxidation of sulfidic materials, frequently contains arsenic in the form of arsenite, As(III), and/or arsenate, As(V), along with much higher concentrations of dissolved iron. The present work is directed toward the removal of arsenic from synthetic AMD by raising the pH of the solution by electrochemical reduction of H+ to elemental hydrogen and coprecipitation of arsenic with iron(III) hydroxide, following aeration of the catholyte. Electrolysis was carried out at constant current using two-compartment cells separated with a cation exchange membrane. Four different AMD model systems were studied: Fe(III)/As(V), Fe(III)/As(III), Fe(II)/As(V), and Fe(II)/As(III) with the initial concentrations for Fe(III) 260 mg/L, Fe(II) 300 mg/L, As(V), and As(III) 8 mg/L. Essentially quantitative removal of arsenic and iron was achieved in all four systems, and the results were independent of whether the pH was adjusted electrochemically or by the addition of NaOH. Current efficiencies were approximately 85% when the pH of the effluent was 4-7. Residual concentrations of arsenic were close to the drinking water standard proposed by the World Health Organization (10 microg/L), far below the mine waste effluent standard (500 microg/L).

A Bispidol Chelator with a Phosphonate Pendant Arm: Synthesis, Cu(II) Complexation, and 64Cu Labeling.

PubMed

Gillet, Raphaël; Roux, Amandine; Brandel, Jérémy; Huclier-Markai, Sandrine; Camerel, Franck; Jeannin, Olivier; Nonat, Aline M; Charbonnière, Loïc J

2017-10-02

Here we present the synthesis and characterization of a new bispidine (3,7-diazabicyclo[3.3.1]nonane) ligand with N-methanephosphonate substituents (L 2 ). Its physicochemical properties in water, as well as those of the corresponding Cu(II) and Zn(II) complexes, have been evaluated by using UV-visible absorption spectroscopy, potentiometry, 1 H and 31 P NMR, and cyclic voltammetry. Radiolabeling experiments with 64 Cu II have been carried out, showing excellent radiolabeling properties. Quantitative complexation was achieved within 60 min under stoichiometric conditions, at room temperature and in the nanomolar concentration range. It was also demonstrated that the complexation occurred below pH 2. Properties have been compared to those of the analogue bispidol bearing a N-methanecarboxylate substituent (L 1 ). Although both systems meet the required criteria to be used as new chelator for 64/67 Cu in terms of the kinetics of formation, thermodynamic stability, selectivity for Cu(II), and kinetic inertness regarding redox- or acid-assisted decomplexation processes, substitution of the carboxylic acid function by the phosphonic moiety is responsible for a significant increase in the thermodynamic stability of the Cu(II) complex (+2 log units for pCu) and also leads to an increase in the radiochemical yields with 64 Cu II which is quantitative for L 2 .

Quantitative theory of electroosmotic flow in fused-silica capillaries using an extended site-dissociation--site-binding model.

PubMed

Zhou, Marilyn X; Foley, Joe P

2006-03-15

To optimize separations in capillary electrophoresis, it is important to control the electroosmotic mobility of the running buffer and the factors that affect it. Through the application of a site-dissociation-site-binding model, we demonstrated that the electroosmotic mobility could be controlled qualitatively and quantitatively by the parameters related to the physical and chemical properties of the running buffer: pH, cation valence, ionic strength, viscosity, activity, and dissociation constant. Our study illustrated that the logarithm of the number of apparent silanol sites on a fused-silica surface has a linear relationship with the pH of a buffer solution. The extension of the chemical kinetics approach allowed us to obtain the thickness of the electrical double layer when multivalent inorganic cations are present with monovalent cations in a buffer solution, and we found that the thickness of the electrical double layer does not depend on the charge of anions. The general equation to predict the electroosmotic mobility suggested here also indicates the increase of electroosmotic mobility with temperature. The general equation was experimentally verified by three buffer scenarios: (i) buffers containing only monovalent cations; (ii) buffers containing multivalent inorganic cations; and (iii) buffers containing cations and neutral additives. The general equation can explain the experimental observations of (i) a maximum electroosmotic mobility for the first scenario as the pH was varied at constant ionic strength and (ii) the inversion and maximum value of the electroosmotic mobility for the second scenario when the concentration of divalent cations was varied at constant pH. A good agreement between theory and experiment was obtained for each scenario.

Yeast hexokinase: substrate-induced association--dissociation reactions in the binding of glucose to hexokinase P-II.

PubMed

Hoggett, J G; Kellett, G L

1976-06-15

A method is described for the purification of native hexokinases P-I and P-II from yeast using preparative isoelectric focussing to separate the isozymes. The binding of glucose to hexokinase P-II, and the effect of this on the monomer--dimer association--dissociation reaction have been investigated quantitatively by a combination of titrations of intrinsic protein fluorescence and equilibrium ultracentrifugation. Association constants for the monomer-dimer reaction decreased with increasing pH, ionic strength and concentration of glucose. Saturating concentrations of glucose did not bring about complete dissociation of the enzyme showing that both sites were occupired in the dimer. At pH 8.0 and high ionic strength, where the enzyme existed as monomer, the dissociation constant of the enzyme-glucose complex was 3 X 10(-4) mol 1(-1) and was independent of the concentration of enzyme. Binding to the dimeric form at low pH and ionic strength (I=0.02 mol 1(-1), pH less than 7.5) was also independent of enzyme concentration (in the range 10-1000 mug ml-1) but was much weaker. The process could be described by a single dissociation constant, showing that the two available sites on the dimer were equivalent and non-cooperative; values of the intrinsic dissociation constant varied from 2.5 X 10(-3) mol 1(-1) at pH 7.0 to 6 X 10(-3) at pH 6.5. Under intermediate conditions (pH 7.0, ionic strength=0.15 mol 1(-1)), where monomer and dimer coexisted, the binding of glucose showed weak positive cooperatively (Hill coefficient 1.2); in addition, the binding was dependent upon the concentration of enzyme in the direction of stronger binding at lower concentrations. The results show that the phenomenon of half-sites reactivity observed in the binding of glucose to crystalline hexokinase P-II does not occur in solution; the simplest explanation of our finding the two sites to be equivalent is that the dimer results from the homologous association of two identical subunits.

Zincon-modified activated carbon for solid-phase extraction and preconcentration of trace lead and chromium from environmental samples.

PubMed

Li, Zhenhua; Chang, Xijun; Hu, Zheng; Huang, Xinping; Zou, Xiaojun; Wu, Qiong; Nie, Rong

2009-07-15

A new method that utilizes zincon-modified activated carbon (AC-ZCN) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III) and Pb(II) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES). The separation/preconcentration conditions of analytes were investigated, including effects of pH, the shaking time, the sample flow rate and volume, the elution condition and the interfering ions. At pH 4, the maximum adsorption capacity of Cr(III) and Pb(II) onto the AC-ZCN were 17.9 and 26.7 mg g(-1), respectively. The adsorbed metal ions were quantitatively eluted by 1 mL of 0.1 mol L(-1) HCl. Common coexisting ions did not interfere with the separation. According to the definition of IUPAC, the detection limits (3 sigma) of this method for Cr(III) and Pb(II) were 0.91 and 0.65 ng mL(-1), respectively. The relative standard deviation under optimum condition is less than 3.5% (n=8). The method has been applied for the determination of Cr(III) and Pb(II) in biological materials and water samples with satisfactory results.

SP70-alpha-benzoin oxime chelating resin for preconcentration-separation of Pb(II), Cd(II), Co(II) and Cr(III) in environmental samples.

PubMed

Narin, Ibrahim; Surme, Yavuz; Bercin, Erdogan; Soylak, Mustafa

2007-06-25

In the presented work, alpha-benzoin oxime immobilized SP70 chelating resin was synthesized for separation and preconcentration of Pb(II), Cd(II), Co(II) and Cr(III). The optimization procedure for analytical parameters including pH, eluent type, flow rate, etc. was examined in order to gain quantitative recoveries of analyte ions. The effects of foreign ions on the recoveries of studied metal ions were also investigated. The detection limits (3sigma) were found to be 16.0, 4.2, 1.3, 2.4microgL(-1) for Pb, Cd, Co and Cr, respectively. The preconcentration factor was 75 for Pb, 100 for Cd, Co and Cr. The optimized method was validated with certified reference materials and successfully applied to the waters, crops and pharmaceutical samples with good results (recoveries greater than 95%, R.S.D. lower than 10%).

Solid-phase extraction of some heavy metal ions on a double-walled carbon nanotube disk and determination by flame atomic absorption spectrometry.

PubMed

Karatepe, Aslihan; Soylak, Mustafa; Elçi, Latif

2011-01-01

A new preconcentration method was developed for the determination of trace amounts of Cu(II), Fe(III), Pb(II), Ni(II), and Cd(II) on a double-walled carbon nanotube disk. 4-(2-Thiazolylazo) resorcinol was used as a complexing reagent. The effects of parameters, including pH of the solutions, amounts of complexing reagent, eluent type, sample volume, flow rates of solutions, and matrix ions were examined for quantitative recoveries of the studied analyte ions. The retained metal ions were eluted by 2 M HNO3. The LOD values for the analytes were in the range of 0.7-4.4 microg/mL. Natural water samples and standard reference materials were analyzed by the presented method.

Heavy metal contents of play dough, face and finger paint samples sold in turkish markets.

PubMed

Erbas, Zeliha; Karatepe, Aslihan; Soylak, Mustafa

2017-08-01

Lead, cadmium, nickel, manganese, cobalt and copper contents of some play dough, face and finger paint samples were determined by using a new solid phase extraction method which has been developed by using multi-walled carbon nanotube with patent blue (V) sodium salt to selectively separate and preconcentrate these metal ions. Flame atomic absorption spectrometry was used to determine the metal ions. Analytical parameters affecting the complex formation and solid phase extraction performance such as pH, the amount of ligand and volume of sample solution were investigated. The recoveries of the studied metal ions were not affected by the foreign ions. Analytes were recovered quantitatively at pH 5.5 and with a nitric acid of 2molL -1 as eluent. Analysis of a certified reference material was performed to validate the method before applying it to determine the metal ions in the real samples. Detection limits were found to be as Pb(II): 7.71μgL -1 , Cu(II): 1.43μgL -1 , Cd(III): 0.21μgL -1 , Mn(II): 0.47μgL -1 , Ni(II): 3.52μgL -1 and Co(II): 1.96μgL -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

The green hemoproteins of bovine erythrocytes. II. Spectral, ligand-binding, and electrochemical properties.

PubMed

DeFilippi, L J; Hultquist, D E

1978-05-10

The two green hemoproteins isolated from bovine erythrocytes (form I and form II) have been characterized as to spectral, electrochemical, and chemical properties. The absorption spectra of the isolated hemoproteins are typical of high spin ferric states. Reduction of the hemoproteins yields high spin ferrohemoproteins. Complexation of the ferrohemoproteins with CO and the ferrihemoproteins with cyanide yields low spin complexes, demonstrating the presence of an exchangeable weak field ligand in both the ferrous and ferric states of the hemoproteins. The differences in position and intensity of the absorption peaks of the visible spectra allow the two forms to be distinguished from one another. The midpoint potential of forms I and II were found to be +0.075 and +0.019 V, respectively, at pH 6.4 and +0.038 and -0.005 V, respectively, at pH 7.0. This is consistent with the gaining of 1 proton/electron during the reduction. The Nernst plot reveals an unusual 0.5-electron transfer, whereas a quantitative titration demonstrates a 1-electron transfer. Form I binds cyanide more tightly than form II (KD of 84 and 252 micrometer, respectively). The observed spectral, electrochemical, and ligand-binding differences between forms I and II can be explained in terms of a greater electron-withdrawing ability of the side chains of the heme of form I relative to the heme of form II.

DNA-protein crosslinking by trans-platinum(II)diamminedichloride in mammalian cells, a new method of analysis.

PubMed

Kohn, K W; Ewig, R A

1979-03-28

DNA-protien crosslinks produced in mouse leukemia L1210 cells by trans-Pt(II)diamminedichloride were quantitated using the technique of DNA alkaline elution. DNA single-strand segments that were or were not linked to protein were separable into distinct components by alkaline elution after exposure of the cells to 2--15 kR of X-ray. Protein-linked DNA strands were separated on the basis of their retention of filters at pH 12 while free DNA strands of the size generated by 2--15 kR of X-ray passed rapidly through the filters. The retention of protein-linked DNA strands was attributable to adsorption of protein to the filter under the conditions of alkaline elution. The results obeyed a simple quantitative model according to which the frequency of DNA-protein crosslinks could be calculated.

The kinetics of the reaction of nitrogen dioxide with iron(II)- and iron(III) cytochrome c.

PubMed

Domazou, Anastasia S; Gebicka, Lidia; Didik, Joanna; Gebicki, Jerzy L; van der Meijden, Benjamin; Koppenol, Willem H

2014-04-01

The reactions of NO2 with both oxidized and reduced cytochrome c at pH 7.2 and 7.4, respectively, and with N-acetyltyrosine amide and N-acetyltryptophan amide at pH 7.3 were studied by pulse radiolysis at 23 °C. NO2 oxidizes N-acetyltyrosine amide and N-acetyltryptophan amide with rate constants of (3.1±0.3)×10(5) and (1.1±0.1)×10(6) M(-1) s(-1), respectively. With iron(III)cytochrome c, the reaction involves only its amino acids, because no changes in the visible spectrum of cytochrome c are observed. The second-order rate constant is (5.8±0.7)×10(6) M(-1) s(-1) at pH 7.2. NO2 oxidizes iron(II)cytochrome c with a second-order rate constant of (6.6±0.5)×10(7) M(-1) s(-1) at pH 7.4; formation of iron(III)cytochrome c is quantitative. Based on these rate constants, we propose that the reaction with iron(II)cytochrome c proceeds via a mechanism in which 90% of NO2 oxidizes the iron center directly-most probably via reaction at the solvent-accessible heme edge-whereas 10% oxidizes the amino acid residues to the corresponding radicals, which, in turn, oxidize iron(II). Iron(II)cytochrome c is also oxidized by peroxynitrite in the presence of CO2 to iron(III)cytochrome c, with a yield of ~60% relative to peroxynitrite. Our results indicate that, in vivo, NO2 will attack preferentially the reduced form of cytochrome c; protein damage is expected to be marginal, the consequence of formation of amino acid radicals on iron(III)cytochrome c. Copyright © 2014 Elsevier Inc. All rights reserved.

Selective solid-phase extraction using oxidized activated carbon modified with triethylenetetramine for preconcentration of metal ions

NASA Astrophysics Data System (ADS)

Zhang, Li; Chang, Xijun; Li, Zhenhua; He, Qun

2010-02-01

A new selective solid-phase extractant using activated carbon as matrix which was purified, oxidized and modified by triethylenetetramine (AC-TETA) was prepared and characterized by FT-IR spectroscopy. At pH 4, quantitative extraction of trace Cr(III), Fe(III) and Pb(II) was obtained and determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Complete elution of the adsorbed metal ions from the sorbent surface was carried out using 0.5 mol L -1 HCl. The maximum static adsorption capacity of sorbent for Cr(III), Fe(III) and Pb(II) was 34.6, 36.5 and 51.9 mg g -1, respectively. The time of quantitative adsorption was less than 2 min. The detection limits of the method was found to be 0.71, 0.35 and 0.45 ng mL -1 for Cr(III), Fe(III) and Pb(II), and the relative standard deviation (RSD) was 3.7%, 2.2% and 2.5%, respectively. Moreover, the method was free from interference with common coexiting ions. The method was also successfully applied to the preconcentration of trace Cr(III), Fe(III) and Pb(II) in synthetic samples and a real sample with satisfactory results.

Mechanical Properties versus Morphology of Ordered Polymers. Volume III. Part I

DTIC Science & Technology

1982-08-01

measured by wide angle x-ray scattering and differential scanning calorimetry, is unrelated to the diffuse scattered intensity [62]. Cellulose acetate which...increasing void fraction, in air swollen cellulose . Comparison of the volume fraction of voids calculated from the SAXS integrated intensity with...1964). 63. P.H. Hermans, D. Heikens, and A. Weidinger, "A Quantitative Investigation on the X-Ray Small Angle Scattering of Cellulose Fibers. Part II

Interaction of selenite with reduced Fe and/or S species: An XRD and XAS study.

PubMed

Finck, Nicolas; Dardenne, Kathy

2016-05-01

In this study, we investigated the interaction between selenite and either Fe((II))aq or S((-II))aq in solution, and the results were used to investigate the interaction between Se((IV))aq and FeS in suspension. The reaction products were characterized by a combination of methods (SEM, XRD and XAS) and the reaction mechanisms were identified. In a first experiment, Se((IV))aq was reduced to Se((0)) by interaction with Fe((II))aq which was oxidized to Fe((III)), but the reaction was only partial. Subsequently, some Fe((III)) produced akaganeite (β-FeOOH) and the release of proton during that reaction decreased the pH. The pH decrease changed the Se speciation in solution which hindered further Se((IV)) reduction by Fe((II))aq. In a second experiment, Se((IV))aq was quantitatively reduced to Se((0)) by S((-II))aq and the reaction was fast. Two sulfide species were needed to reduce one Se((IV)), and the observed pH increase was due to a proton consumption. For both experiments, experimental results are consistent with expectations based on the oxidation reduction potential of the various species. Upon interaction with FeS, Se((IV))aq was reduced to Se((0)) and minute amounts of pyrite were detected, a consequence of partial mackinawite oxidation at surface sulfur sites. These results are of prime importance with respect to safe deep disposal of nuclear waste which contains the long-lived radionuclide (79)Se. This study shows that after release of (79)Se((IV)) upon nuclear waste matrix corrosion, selenite can be reduced in the near field to low soluble Se((0)) by interaction with Fe((II))aq and/or S((-II))aq species. Because the solubility of Se((0)) species is significantly lower than that of Se((IV)), selenium will become much less (bio)available and its migration out of deep HLW repositories may be drastically hindered. Copyright © 2016. Published by Elsevier B.V.

Sorption and desorption of Pb(II) to biochar as affected by oxidation and pH.

PubMed

Wang, Qian; Wang, Bing; Lee, Xinqing; Lehmann, Johannes; Gao, Bin

2018-09-01

The use of biochar for the removal of heavy metals from water has environmental benefits. In order to elucidate the potential application of highly functionalized biochar for the removal of Pb(II) in aqueous solution, maple wood biochar was oxidized using hydrogen peroxide. The pH values of oxidized biochar ranged from 8.1 to 3.7, with one set being adjusted to a pH of 7 as a comparison. It was found that oxidizing the biochars increased their Pb(II) adsorption capacity if the pH remained below 6 (strong oxidation), but decreased their Pb(II) adsorption ability above pH6 (weak oxidation). After adjusting the pH of oxidized biochar to pH7, the Pb(II) adsorption capacity further increased two to sixfold for oxidized biochars originally at pH3.7-6. The adsorption characteristics of Pb(II) were well described by the Langmuir equation. Adsorption of Pb(II) was not fully reversible in water. Less than 6% of Pb(II) desorbed in water in two consecutive steps than was previously adsorbed, for biochars with a pH below 7, irrespective of oxidation. Recovery using an extraction with 0.1M NaNO 3 increased from 0.7% to 32.7% of Pb(II) undesorbed by both preceding water extractions with increasing oxidation, for biochars with a pH below 7. Unextractable Pb(II) was lower at low oxidation but increased to 99.0% of initially adsorbed amounts at low pH, which indicated that the adsorption of Pb(II) on oxidized biochar is pH independent. Copyright © 2018 Elsevier B.V. All rights reserved.

Understanding the impact of water distribution system conditions on the biodegradation of haloacetic acids and expression of bacterial dehalogenase genes.

PubMed

Behbahani, Mohsen; Lin, Boren; Phares, Tamara L; Seo, Youngwoo

2018-06-05

The objective of this study is to evaluate the influence of water distribution system conditions (pH, total organic carbon, residual chlorine, and phosphate) on haloacetic acids (HAAs) biodegradation. A series of batch microcosm tests were conducted to determine biodegradation kinetics and collected biomass was used for real time quantitative reverse transcription polymerase chain reaction analyses to monitor how these drinking water distribution system conditions affect the relative expression of bacterial dehalogenase genes. It was observed that tested water distribution system conditions affected HAA biodegradation with different removal efficiencies (0-100%). HAA biodegradation was improved in tested samples with TOC (3 mg/L) and pH 8.5 compared to those of TOC (0 mg/L) and pH 7, respectively. However, slight improvement was observed with the increased PO 4 concentration (3.5 mg/L), and the presence of residual chlorine even at low concentration prohibited biodegradation of HAAs. The observed trend in the relative expression of dehII genes was compatible with the HAA biodegradation trend. Overall relative expression ratio of dehII genes was lower at pH 7, phosphate (0.5 mg/L), and TOC (0 mg/L) in comparison with pH 8.5, phosphate (3.5 mg/L), and TOC (3 mg/L) in the same experimental conditions. Copyright © 2018 Elsevier B.V. All rights reserved.

Proton-coupled electron-transfer reduction of dioxygen catalyzed by a saddle-distorted cobalt phthalocyanine.

PubMed

Honda, Tatsuhiko; Kojima, Takahiko; Fukuzumi, Shunichi

2012-03-07

Proton-coupled electron-transfer reduction of dioxygen (O(2)) to afford hydrogen peroxide (H(2)O(2)) was investigated by using ferrocene derivatives as reductants and saddle-distorted (α-octaphenylphthalocyaninato)cobalt(II) (Co(II)(Ph(8)Pc)) as a catalyst under acidic conditions. The selective two-electron reduction of O(2) by dimethylferrocene (Me(2)Fc) and decamethylferrocene (Me(10)Fc) occurs to yield H(2)O(2) and the corresponding ferrocenium ions (Me(2)Fc(+) and Me(10)Fc(+), respectively). Mechanisms of the catalytic reduction of O(2) are discussed on the basis of detailed kinetics studies on the overall catalytic reactions as well as on each redox reaction in the catalytic cycle. The active species to react with O(2) in the catalytic reaction is switched from Co(II)(Ph(8)Pc) to protonated Co(I)(Ph(8)PcH), depending on the reducing ability of ferrocene derivatives employed. The protonation of Co(II)(Ph(8)Pc) inhibits the direct reduction of O(2); however, the proton-coupled electron transfer from Me(10)Fc to Co(II)(Ph(8)Pc) and the protonated [Co(II)(Ph(8)PcH)](+) occurs to produce Co(I)(Ph(8)PcH) and [Co(I)(Ph(8)PcH(2))](+), respectively, which react immediately with O(2). The rate-determining step is a proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) in the Co(II)(Ph(8)Pc)-catalyzed cycle with Me(2)Fc, whereas it is changed to the electron-transfer reduction of [Co(II)(Ph(8)PcH)](+) by Me(10)Fc in the Co(I)(Ph(8)PcH)-catalyzed cycle with Me(10)Fc. A single crystal of monoprotonated [Co(III)(Ph(8)Pc)](+), [Co(III)Cl(2)(Ph(8)PcH)], produced by the proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) with HCl, was obtained, and the crystal structure was determined in comparison with that of Co(II)(Ph(8)Pc). © 2012 American Chemical Society

Synthesis and Characterization of Reduced Graphene Oxide-Supported Nanoscale Zero-Valent Iron (nZVI/rGO) Composites Used for Pb(II) Removal

PubMed Central

Fan, Mingyi; Li, Tongjun; Hu, Jiwei; Cao, Rensheng; Wu, Qing; Wei, Xionghui; Li, Lingyun; Shi, Xuedan; Ruan, Wenqian

2016-01-01

Reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were prepared by chemical deposition method and were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, N2-sorption and X-ray photoelectron spectroscopy (XPS). Operating parameters for the removal process of Pb(II) ions, such as temperature (20–40 °C), pH (3–5), initial concentration (400–600 mg/L) and contact time (20–60 min), were optimized using a quadratic model. The coefficient of determination (R2 > 0.99) obtained for the mathematical model indicates a high correlation between the experimental and predicted values. The optimal temperature, pH, initial concentration and contact time for Pb(II) ions removal in the present experiment were 21.30 °C, 5.00, 400.00 mg/L and 60.00 min, respectively. In addition, the Pb(II) removal by nZVI/rGO composites was quantitatively evaluated by using adsorption isotherms, such as Langmuir and Freundlich isotherm models, of which Langmuir isotherm gave a better correlation, and the calculated maximum adsorption capacity was 910 mg/g. The removal process of Pb(II) ions could be completed within 50 min, which was well described by the pseudo-second order kinetic model. Therefore, the nZVI/rGO composites are suitable as efficient materials for the advanced treatment of Pb(II)-containing wastewater. PMID:28773813

Synthesis and Characterization of Reduced Graphene Oxide-Supported Nanoscale Zero-Valent Iron (nZVI/rGO) Composites Used for Pb(II) Removal.

PubMed

Fan, Mingyi; Li, Tongjun; Hu, Jiwei; Cao, Rensheng; Wu, Qing; Wei, Xionghui; Li, Lingyun; Shi, Xuedan; Ruan, Wenqian

2016-08-12

Reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were prepared by chemical deposition method and were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, N₂-sorption and X-ray photoelectron spectroscopy (XPS). Operating parameters for the removal process of Pb(II) ions, such as temperature (20-40 °C), pH (3-5), initial concentration (400-600 mg/L) and contact time (20-60 min), were optimized using a quadratic model. The coefficient of determination ( R ² > 0.99) obtained for the mathematical model indicates a high correlation between the experimental and predicted values. The optimal temperature, pH, initial concentration and contact time for Pb(II) ions removal in the present experiment were 21.30 °C, 5.00, 400.00 mg/L and 60.00 min, respectively. In addition, the Pb(II) removal by nZVI/rGO composites was quantitatively evaluated by using adsorption isotherms, such as Langmuir and Freundlich isotherm models, of which Langmuir isotherm gave a better correlation, and the calculated maximum adsorption capacity was 910 mg/g. The removal process of Pb(II) ions could be completed within 50 min, which was well described by the pseudo-second order kinetic model. Therefore, the nZVI/rGO composites are suitable as efficient materials for the advanced treatment of Pb(II)-containing wastewater.

Two forms of alpha-amylase in mantle tissue of Mytilus galloprovincialis: purification and molecular properties of form II.

PubMed

Lombraña, M; Suárez, P; San Juan, F

2005-09-01

alpha-Amylase activity has been shown for the first time in a non-digestive tissue from Mytilus galloprovincialis. alpha-amylase from mussel mantle tissue has been purified by affinity chromatography on insoluble starch, followed by gel-filtration chromatography on Superdex-200. The chromatographic and electrophoretic behaviour of M. galloprovincialis alpha-amylase and stability characteristics suggest two forms of this enzyme: one form forming stable aggregates (form I) and a monomeric form (form II) that is more abundant, active and unstable. Both forms show an inverse quantitative variation. Purified form II was highly unstable and the molecular mass was estimated to be 66 kDa by sodium dodecyl sulphate (SDS)-gel electrophoresis. Maximum activity was noted at pH 6.5 and 35 degrees C.

Fast Potentiometric Analysis of Lead in Aqueous Medium under Competitive Conditions Using an Acridono-Crown Ether Neutral Ionophore.

PubMed

Golcs, Ádám; Horváth, Viola; Huszthy, Péter; Tóth, Tünde

2018-05-03

Lead is a particularly toxic heavy metal that is present above acceptable levels in the water of many countries. This article describes a quick detection method of lead(II) ions using a polyvinyl chloride (PVC)-based ion-selective membrane electrode containing an acridono-crown ether ionophore by potentiometry. The electrochemical cell exhibits a Nernstian response for lead(II) ions between the concentration range of 10 −4 to 10 −2 M, and can be used in the pH range of 4⁻7. The applicability of this sensor was verified by measuring a multicomponent aqueous sample. Under the given conditions, this electrode is suitable for the selective quantitative analysis of lead(II) ions in the presence of many additional metal ions.

Synthesis, characterization and analytical applications of Ni(II)-ion imprinted polymer

NASA Astrophysics Data System (ADS)

Singh, D. K.; Mishra, Shraddha

2010-10-01

Ion recognition-based separation techniques have received much attention because of their high selectivity for target ions. In this study, we have prepared a novel ion imprinted polymer (IIP) to remove nickel ions with high selectivity. The imprinted polymer was prepared by copolymerization of 2-hydroxy ethyl methacrylate (HEMA) with nickel vinylbenzoate complex in the presence of ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The polymerization was carried out in bulk with free radical initiation using 2-methoxy ethanol as a solvent and porogen. The adsorbed nickel was completely eluted with 15 mL of 1 M HCl. Control polymer was also prepared by similar experimental conditions without using imprint ion. The above synthesized polymers were characterized by surface area measurements, FT-IR, microanalysis and SEM analysis. The adsorption capacity of IIP and CP was found to be 1.51 and 0.65 mmol g -1, respectively. The optimal pH for quantitative enrichment was 6.5. Nature of eluent, eluent concentration and eluent volume were also studied. The relative selectivity factor ( αr) values of Ni(II)/Zn(II), Ni(II)/Cu(II) and Ni(II)/Co(II) were 78.6, 111.1 and 91.6, respectively. Five replicate determinations of 30 μg L -1 of Ni(II) gave a mean absorbance of 0.067 with a relative standard deviation of 1.06%. The lowest concentration determined by GTA-AAS below which the recovery becomes non-quantitative is 6 μg L -1. IIP was tested for removal of Ni(II) from sea water sample.

Solid Phase Extraction of Trace Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) Ions in Beverages on Functionalized Polymer Microspheres Prior to Flame Atomic Absorption Spectrometric Determinations.

PubMed

Berber, Hale; Alpdogan, Güzin

2017-01-01

In this study, poly(glycidyl methacrylate-methyl methacrylate-divinylbenzene) was synthesized in the form of microspheres, and then functionalized by 2-aminobenzothiazole ligand. The sorption properties of these functionalized microspheres were investigated for separation, preconcentration and determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions using flame atomic absorption spectrometry. The optimum pH values for quantitative sorption were 2 - 4, 5 - 8, 6 - 8, 4 - 6, 2 - 6 and 2 - 3 for Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II), respectively, and also the highest sorption capacity of the functionalized microspheres was found to be for Cu(II) with the value of 1.87 mmol g -1 . The detection limits (3σ; N = 6) obtained for the studied metals in the optimal conditions were observed in the range of 0.26 - 2.20 μg L -1 . The proposed method was successfully applied to different beverage samples for the determination of Al(III), Fe(II), Co(II), Cu(II), Cd(II) and Pb(II) ions, with the relative standard deviation of <3.7%.

[Reduction of nitrobenzene by iron oxides bound Fe(II) system at different pH values].

PubMed

Luan, Fu-Bo; Xie, Li; Li, Jun; Zhou, Qi

2009-07-15

Batch tests were conducted to investigate the reductive transformation of nitrobenzene by goethite, hematite, magnetite and steel converter slag bound Fe(II) system. And the reduction mechanism was explored at different pH values. Experimental results showed that hematite, magnetite and steel converter slag could adsorb Fe(II) on surfaces and form iron oxides bound Fe(II) system at pH from 6.5 to 7.0. The systems had strong reductive capacity and could reduce nitrobenzene to aniline. The reduction efficiency of nitrobenzene in surface bound Fe(II) system followed the sequence of magnetite, hematite and steel converter slag from high to low. The reduction efficiency of hematite and magnetite system increased with pH increasing. While it was almost pH independent in steel converter slag system. Although goethite adsorbed most of Fe(II) in solution, the adsorbed Fe(II) had no reductive activity for nitrobenzene. At pH 6.0, small amount of Fe(II) was adsorbed on magnetite and hematite and the systems did not show reductive activity for nitrobenzene. However, steel converter slag could adsorb Fe(II) at pH 6.0 and reduction efficiency almost equaled to the value at pH 7.0. When pH was above 7.5, dissolved Fe(II) could be converted to Fe(OH)2 and the newly formed Fe(OH)2 became the main redactor in the system. Under alkali condition, the presence of iron oxides inhibited the reduction capacity of system.

Selective solid phase extraction of copper using a new Cu(II)-imprinted polymer and determination by inductively coupled plasma optical emission spectroscopy (ICP-OES).

PubMed

Yilmaz, Vedat; Arslan, Zikri; Hazer, Orhan; Yilmaz, Hayriye

2014-05-01

This work reports the preparation of a novel Cu(II)-ion imprinted polymer using 2-thiozylmethacrylamide (TMA) for on-line preconcentration of Cu(II) prior to its determination by inductively coupled optical emission spectroscopy (ICP-OES). Cu(II)-TMA monomer (complex) was synthesized and copolymerized via bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was washed with 5% (v/v) HNO 3 to remove Cu(II) ions and then with water until a neutral pH. The ion imprinted polymer was characterized by FT-IR and scanning electron microscopy. The experimental conditions were optimized for on-line preconcentration of Cu(II) using a minicolumn of ion imprinted polymer (IIP). Quantitative retention was achieved between pH 5.0 and 6.0, whereas the recoveries for the non-imprinted polymer (NIP) were about 61%. The IIP showed about 30 times higher selectivity to Cu(II) in comparison to NIP. The IIP also exhibited excellent selectivity for Cu(II) against the competing transition and heavy metal ions, including Cd, Co, Cr, Fe, Mn, Ni, Pb and Zn. Computational calculations revealed that the selectivity of IIP was mediated by the stability of Cu(II)-TMA complex which was far more stable than those of Co(II), Ni(II) and Zn(II) that have similar charge and ionic radii to Cu(II). A volume of 10 mL sample solution was loaded onto the column at 4.0 mL min -1 by using a sequential injection system (FIALab 3200) followed by elution with 1.0 mL of 2% (v/v) HNO 3 . The relative standard deviation (RSD) and limit of detection (LOD, 3s) of the method were 3.2% and 0.4 μg L -1 , respectively. The method was successfully applied to determination of Cu(II) in fish otoliths (CRM 22), bone ash (SRM 1400) and coastal seawater and estuarine water samples.

Selective solid phase extraction of copper using a new Cu(II)-imprinted polymer and determination by inductively coupled plasma optical emission spectroscopy (ICP-OES)

PubMed Central

Yilmaz, Vedat; Arslan, Zikri; Hazer, Orhan; Yilmaz, Hayriye

2014-01-01

This work reports the preparation of a novel Cu(II)-ion imprinted polymer using 2-thiozylmethacrylamide (TMA) for on-line preconcentration of Cu(II) prior to its determination by inductively coupled optical emission spectroscopy (ICP-OES). Cu(II)-TMA monomer (complex) was synthesized and copolymerized via bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was washed with 5% (v/v) HNO3 to remove Cu(II) ions and then with water until a neutral pH. The ion imprinted polymer was characterized by FT-IR and scanning electron microscopy. The experimental conditions were optimized for on-line preconcentration of Cu(II) using a minicolumn of ion imprinted polymer (IIP). Quantitative retention was achieved between pH 5.0 and 6.0, whereas the recoveries for the non-imprinted polymer (NIP) were about 61%. The IIP showed about 30 times higher selectivity to Cu(II) in comparison to NIP. The IIP also exhibited excellent selectivity for Cu(II) against the competing transition and heavy metal ions, including Cd, Co, Cr, Fe, Mn, Ni, Pb and Zn. Computational calculations revealed that the selectivity of IIP was mediated by the stability of Cu(II)-TMA complex which was far more stable than those of Co(II), Ni(II) and Zn(II) that have similar charge and ionic radii to Cu(II). A volume of 10 mL sample solution was loaded onto the column at 4.0 mL min−1 by using a sequential injection system (FIALab 3200) followed by elution with 1.0 mL of 2% (v/v) HNO3. The relative standard deviation (RSD) and limit of detection (LOD, 3s) of the method were 3.2% and 0.4 μg L−1, respectively. The method was successfully applied to determination of Cu(II) in fish otoliths (CRM 22), bone ash (SRM 1400) and coastal seawater and estuarine water samples. PMID:24511158

Spectrophotometric determination of vanadium in rutile and in mafic igneous rocks

USGS Publications Warehouse

Marinenko, John; Mei, Leung

1974-01-01

Minor and major levels of vanadium in rutile are separated from titanium and iron by sample fusion with sodium carbonate followed by water leach and filtration. The filtrate is then acidified with hydrochloric acid. Silicates are decomposed with a mixture of hydrofluoric and hydrochloric acids, and iron is separated by extraction of its chloride with diethyl ether. Sample vanadium in hydrochloric acid is then quantitatively reduced to vanadium(IV) with sulfurous acid. The remaining sulfur dioxide is expelled by heating. Vanadium (IV) then is reacted with excess of iron(III) at reduced acidity (pH 5) in the presence of 1,10-phenanthroline to yield the orange-red iron(II) 1,10-phenanthroline complex. Iron(II) generated by vanadium(IV) is a measure of total vanadium in the sample. The proposed method is free from elemental interferences because the color development cannot take place without the two redox reactions described above, and these are, under the outlined experimental conditions, quantitative only for vanadium.

Applications of Known Quantitative Techniques for Developing Airborne ASW Crew Performance Criteria,

DTIC Science & Technology

1967-07-01

environmental foot tunnel enable’s accurate tests to be conducted under specifications, controlled conditions, MA Ch I N E ( ‘OMI ’l ’F t T ION SERVICES C...ph~- 51 olo gical nioni tur ing equ ip— cc i dt’ a r t e ’t~ cci C ~~ii ’ ri iue ’nt s can hi’ ~‘onc1ui-ted u ndc r V a t t e s t s nie ’ni ; I

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag.

PubMed

Xue, Yongjie; Hou, Haobo; Zhu, Shujing

2009-02-15

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.

Speciation analysis of Mn(II)/Mn(VII) using Fe3O4@ionic liquids-β-cyclodextrin polymer magnetic solid phase extraction coupled with ICP-OES.

PubMed

Chen, Songqing; Qin, Xingxiu; Gu, Weixi; Zhu, Xiashi

2016-12-01

Ionic liquids-β-cyclodextrin polymer (ILs-β-CDCP) was attached on Fe 3 O 4 nanoparticles to prepare magnetic solid phase extraction agent (Fe 3 O 4 @ILs-β-CDCP). The properties and morphology of Fe 3 O 4 @ILs-β-CDCP were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction(XRD), size distribution and magnetic analysis. A new method of magnetic solid phase extraction (MSPE) coupled to ICP-OES for the speciation of Mn(II)/Mn(VII) in water samples was established. The results showed that Mn(VII) and total manganese [Mn(II)+Mn(VII)] were quantitatively extracted after adjusting aqueous sample solution to pH 6.0 and 10.0, respectively. Mn(II) was calculated by subtraction of Mn(VII) from total manganese. Fe 3 O 4 @ILs-β-CDCP showed a higher adsorption capacity toward Mn(II) and Mn(VII). Several factors, such as the pH value, extraction temperature and sample volume, were optimized to achieve the best extraction efficiency. Moreover, the adsorption ability of Fe 3 O 4 @ILs-β-CDCP would not be significantly lower after reusing of 10 times. The accuracy of the developed method was confirmed by analyzing certified reference materials (GSB 07-1189-2000), and by spiking spring water, city water and lake water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

The granulocyte-angiotensin system. Angiotensin I-converting activity of cathepsin G.

PubMed

Klickstein, L B; Kaempfer, C E; Wintroub, B U

1982-12-25

Cathepsin G, an Mr = 26,000-29,000 cationic human neutrophil lysosomal serine protease, releases angiotensin II from angiotensinogen and was, therefore, examined for angiotensin I-converting activity. Cathepsin G-dependent angiotensin I conversion was detected by a high performance liquid chromatography assay which permitted independent quantitation of angiotensin I and angiotensin II and detection of angiotensin degradation products. 1.8-5.0 X 10(-9) M cathepsin G converted angiotensin I (3.3 X 10(-4) M) to angiotensin II without further degradation of angiotensin II. The pH optimum for cathepsin G-catalyzed angiotensin I conversion was pH 7.0-7.5, and the Km and Kcat were 2.2 X 10(-4) M and 3.4 s-1, respectively. In contrast to dipeptidyl hydrolase-converting enzyme, cathepsin G did not inactivate bradykinin, did not cleave hippuryl-His-Leu, and was not inhibited by 10(-4) M Captopril or SQ 20881. Purified human neutrophils stimulated with 2.5 X 10(-6) M-10(-10) M fMet-Leu-Phe released angiotensin-converting activity with a Km of 3.3 X 10(-4) M. That the angiotensin-converting activity released from neutrophils was attributable to cathepsin G was indicated by similar susceptibility to inhibitors and adsorption by goat antibody to cathepsin G. The granulocyte-angiotensin system provides a mechanism for the local generation of angiotensin II at sites of neutrophil accumulation and may be of significance in regulation of blood flow in tissue microvasculature.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques.

PubMed

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong; Pan, Min

2017-09-28

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R² > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X₂Cd) at low pH and inner-sphere surface complexation sites (SOCd⁺ and (SO)₂CdOH - species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water-mineral interface.

Trends in Ground-State Entropies for Transition Metal Based Hydrogen Atom Transfer Reactions

PubMed Central

Mader, Elizabeth A.; Manner, Virginia W.; Markle, Todd F.; Wu, Adam; Franz, James A.; Mayer, James M.

2009-01-01

Reported herein are thermochemical studies of hydrogen atom transfer (HAT) reactions involving transition metal H-atom donors MIILH and oxyl radicals. [FeII(H2bip)3]2+, [FeII(H2bim)3]2+, [CoII(H2bim)3]2+ and RuII(acac)2(py-imH) [H2bip = 2,2’-bi-1,4,5,6-tetrahydropyrimidine, H2bim = 2,2’-bi-imidazoline, acac = 2,4-pentandionato, py-imH = 2-(2’-pyridyl)-imidazole)] each react with TEMPO (2,2,6,6-tetramethyl-1-piperidinoxyl) or tBu3PhO• (2,4,6-tri-tert-butylphenoxyl) to give the deprotonated, oxidized metal complex MIIIL, and TEMPOH or tBu3PhOH. Solution equilibrium measurements for the reaction of [CoII(H2bim)3]2+ with TEMPO show a large, negative ground-state entropy for hydrogen atom transfer, −41 ± 2 cal mol−1 K−1. This is even more negative than the ΔSoHAT = −30 ± 2 cal mol−1 K−1 for the two iron complexes and the ΔSoHAT for RuII(acac)2(py-imH) + TEMPO, 4.9 ± 1.1 cal mol−1 K−1, as reported earlier. Calorimetric measurements quantitatively confirm the enthalpy of reaction for [FeII(H2bip)3]2+ + TEMPO, thus also confirming ΔSoHAT. Calorimetry on TEMPOH + tBu3PhO• gives ΔHoHAT = −11.2 ± 0.5 kcal mol−1 which matches the enthalpy predicted from the difference in literature solution BDEs. A brief evaluation of the literature thermochemistry of TEMPOH and tBu3PhOH supports the common assumption that ΔSoHAT ≈ 0 for HAT reactions of organic and small gas-phase molecules. However, this assumption does not hold for transition metal based HAT reactions. The trend in magnitude of |ΔSoHAT| for reactions with TEMPO, RuII(acac)2(py-imH) << [FeII(H2bip)3]2+ = [FeII(H2bim)3]2+ < [CoII(H2bim)3]2+, is surprisingly well predicted by the trends for electron transfer half-reaction entropies, ΔSoET, in aprotic solvents. This is because both ΔSoET and ΔSoHAT have substantial contributions from vibrational entropy, which varies significantly with the metal center involved. The close connection between ΔSoHAT and ΔSoET provides an important link between these two fields and provides a starting point from which to predict which HAT systems will have important ground-state entropy effects. PMID:19275235

Influence of pH, soil humic/fulvic acid, ionic strength, foreign ions and addition sequences on adsorption of Pb(II) onto GMZ bentonite.

PubMed

Wang, Suowei; Hu, Jun; Li, Jiaxing; Dong, Yunhui

2009-08-15

This work contributed to the adsorption of Pb(II) onto GMZ bentonite in the absence and presence of soil humic acid (HA)/fulvic acid (FA) using a batch technique. The influences of pH from 2 to 12, ionic strengths from 0.004M to 0.05M NaNO(3), soil HA/FA concentrations from 1.6 mg/L to 20mg/L, foreign cations (Li+, Na+, K+), anions (Cl(-), NO(3)(-)), and addition sequences on the adsorption of Pb(II) onto GMZ bentonite were tested. The adsorption isotherms of Pb(II) were determined at pH 3.6+/-0.1 and simulated with the Langmuir, Freundlich, and D-R adsorption models, respectively. The results demonstrated that the adsorption of Pb(II) onto GMZ bentonite increased with increasing pH from 2 to 6. HA was shown to enhance Pb(II) adsorption at low pH, but to reduce Pb(II) adsorption at high pH, whereas FA was shown to decrease Pb(II) adsorption at pH from 2 to 11. The results also demonstrated that the adsorption was strongly dependent on ionic strength and slightly dependent on the concentration of HA/FA. The adsorption of Pb(II) onto GMZ bentonite was dependent on foreign ions in solution. The addition sequences of bentonite/Pb(II)/HA had no effect on the adsorption of Pb(II).

Comparative Studies on the Dissolution Profiles of Oral Ibuprofen Suspension and Commercial Tablets using Biopharmaceutical Classification System Criteria

PubMed Central

Rivera-Leyva, J. C.; García-Flores, M.; Valladares-Méndez, A.; Orozco-Castellanos, L. M.; Martínez-Alfaro, M.

2012-01-01

In vitro dissolution studies for solid oral dosage forms have recently widened the scope to a variety of special dosage forms such as suspensions. For class II drugs, like Ibuprofen, it is very important to have discriminative methods for different formulations in physiological conditions of the gastrointestinal tract, which will identify different problems that compromise the drug bioavailability. In the present work, two agitation speeds have been performed in order to study ibuprofen suspension dissolution. The suspensions have been characterised relatively to particle size, density and solubility. The dissolution study was conducted using the following media: buffer pH 7.2, pH 6.8, 4.5 and 0.1 M HCl. For quantitative analysis, the UV/Vis spectrophotometry was used because this methodology had been adequately validated. The results show that 50 rpm was the adequate condition to discriminate the dissolution profile. The suspension kinetic release was found to be dependent on pH and was different compared to tablet release profile at the same experimental conditions. The ibuprofen release at pH 1.0 was the slowest. PMID:23626386

Speciation of Mn(II), Mn(VII) and total manganese in water and food samples by coprecipitation-atomic absorption spectrometry combination.

PubMed

Citak, Demirhan; Tuzen, Mustafa; Soylak, Mustafa

2010-01-15

A speciation procedure based on the coprecipitation of manganese(II) with zirconium(IV) hydroxide has been developed for the investigation of levels of manganese species. The determination of manganese levels was performed by flame atomic absorption spectrometry (FAAS). Total manganese was determined after the reduction of Mn(VII) to Mn(II) by ascorbic acid. The analytical parameters including pH, amount of zirconium(IV), sample volume, etc., were investigated for the quantitative recoveries of manganese(II). The effects of matrix ions were also examined. The recoveries for manganese(II) were in the range of 95-98%. Preconcentration factor was calculated as 50. The detection limit for the analyte ions based on 3 sigma (n=21) was 0.75 microg L(-1) for Mn(II). The relative standard deviation was found to be lower than 7%. The validation of the presented procedure was performed by analysis of certified reference material having different matrices, NIST SRM 1515 (Apple Leaves) and NIST SRM 1568a (Rice Flour). The procedure was successfully applied to natural waters and food samples.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques

PubMed Central

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong

2017-01-01

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd) at low pH and inner-sphere surface complexation sites (SOCd+ and (SO)2CdOH− species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface. PMID:28956849

Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1

USGS Publications Warehouse

Bohu, Tsing; Santelli, Cara M; Akob, Denise M.; Neu, Thomas R; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

2015-01-01

Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH < 6. The lack of low pH Mn-oxidizing bacteria (MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling.

Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1.

PubMed

Bohu, Tsing; Santelli, Cara M; Akob, Denise M; Neu, Thomas R; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

2015-01-01

Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH < 6. The lack of low pH Mn-oxidizing bacteria (MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling.

Solid phase selective separation and preconcentration of Cu(II) by Cu(II)-imprinted polymethacrylic microbeads.

PubMed

Dakova, Ivanka; Karadjova, Irina; Ivanov, Ivo; Georgieva, Ventsislava; Evtimova, Bisera; Georgiev, George

2007-02-12

Ion-imprinted polymer (IIP) particles are prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as crosslinking agent and 2,2'-azo-bis-isobutyronitrile as initiator in the presence of Cu(II), a Cu(II)-4-(2-pyridylazo)resorcinol (Cu(II)-PAR) complex, and PAR only. A batch procedure is used for the determination of the characteristics of the Cu(II) solid phase extraction from the IIP produced. The results obtained show that the Cu(II)-PAR IIP has the greatest adsorption capacity (37.4 micromol g(-1) of dry copolymer) among the IIPs investigated. The optimal pH value for the quantitative preconcentration is 7, and full desorption is achieved by 1 M HNO(3). The selectivity coefficients (S(Cu/Me)) for Me=Ni(II), Co(II) are 45.0 and 38.5, respectively. It is established that Cu(II)-PAR IIPs can be used repeatedly without a considerable adsorption capacity loss. The determination of Cu(II) ions in seawater shows that the interfering matrix does not influence the preconcentration and selectivity values of the Cu(II)-PAR IIPs. The detection and quantification limits are 0.001 micromol L(-1) (3sigma) and 0.003 micromol L(-1) (6sigma), respectively.

Electrohydrodynamic properties of succinoglycan as probed by fluorescence correlation spectroscopy, potentiometric titration and capillary electrophoresis.

PubMed

Duval, Jérôme F L; Slaveykova, Vera I; Hosse, Monika; Buffle, Jacques; Wilkinson, Kevin J

2006-10-01

The electrostatic, hydrodynamic and conformational properties of aqueous solutions of succinoglycan have been analyzed by fluorescence correlation spectroscopy (FCS), proton titration, and capillary electrophoresis (CE) over a large range of pH values and electrolyte (NaCl) concentrations. Using the theoretical formalism developed previously for the electrokinetic properties of soft, permeable particles, a quantitative analysis for the electro-hydrodynamics of succinoglycan is performed by taking into account, in a self-consistent manner, the measured values of the diffusion coefficients, electric charge densities, and electrophoretic mobilities. For that purpose, two limiting conformations for the polysaccharide in solution are tested, i.e. succinoglycan behaves as (i) a spherical, random coil polymer or (ii) a rodlike particle with charged lateral chains. The results show that satisfactory modeling of the titration data for ionic strengths larger than 50 mM can be accomplished using both geometries over the entire range of pH values. Electrophoretic mobilities measured for sufficiently large pH values (pH > 5-6) are in line with predictions based on either model. The best manner to discriminate between these two conceptual models is briefly discussed. For low pH values (pH < 5), both models indicate aggregation, resulting in an increase of the hydrodynamic permeability and a decrease of the diffusion coefficient.

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

PubMed

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

2008-11-15

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

Interactive effects of sulfadiazine and Cu(II) on their sorption and desorption on two soils with different characteristics.

PubMed

Xu, Yonggang; Yu, Wantai; Ma, Qiang; Zhou, Hua

2015-11-01

Antibiotics and heavy metals often coexist in soils due to land application of animal wastes and other sources of inputs. The aim of this study is to evaluate the interaction of Cu(II) and sulfadiazine (SDZ) regarding to their sorption and desorption on Brown soil (BS, luvisols) and Red soil (RS, Udic Ferrosols) using batch experiments. The presence of Cu(II) significantly enhanced sorption of SDZ on BS at pH>5.0, and this trend increased with increasing pH, which was mainly ascribed to the formation of ternary complexes of Cu-SDZ-soil and/or SDZ-Cu-soil. In contrast, Cu(II) only slightly increased SDZ sorption on RS at pH<5.0 due to the decrease of equilibrium solution pH, whereas it hardly affected SDZ sorption at pH>5.0 because RS had high oxides contents and low affinity for Cu(II). In addition, Cu(II) inhibited SDZ desorption from BS but promoted SDZ desorption from RS, which was related to their different sorption mechanisms. The presence of SDZ exerted no significant effect on the sorption of Cu(II) on the two soils at pH<6.5 because of its low sorption coefficients (Kd), while slightly decreased Cu(II) sorption at pH>6.5 by forming water-soluble complexes. Furthermore, SDZ had little effect on Cu(II) desorption from the two soils at natural pH. These results indicate that soil characteristics strongly influence the interactions of Cu(II) and SDZ on their sorption and desorption on soils. Copyright © 2015 Elsevier Ltd. All rights reserved.

Characterization of pH dependent Mn(II) oxidation strategies and formation of a bixbyite-like phase by Mesorhizobium australicum T-G1

PubMed Central

Bohu, Tsing; Santelli, Cara M.; Akob, Denise M.; Neu, Thomas R.; Ciobota, Valerian; Rösch, Petra; Popp, Jürgen; Nietzsche, Sándor; Küsel, Kirsten

2015-01-01

Despite the ubiquity of Mn oxides in natural environments, there are only a few observations of biological Mn(II) oxidation at pH < 6. The lack of low pH Mn-oxidizing bacteria (MOB) isolates limits our understanding of how pH influences biological Mn(II) oxidation in extreme environments. Here, we report that a novel MOB isolate, Mesorhizobium australicum strain T-G1, isolated from an acidic and metalliferous uranium mining area, can oxidize Mn(II) at both acidic and neutral pH using different enzymatic pathways. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy with energy dispersive X-ray spectroscopy revealed that T-G1 initiated bixbyite-like Mn oxide formation at pH 5.5 which coincided with multi-copper oxidase expression from early exponential phase to late stationary phase. In contrast, reactive oxygen species (ROS), particularly superoxide, appeared to be more important for T-G1 mediated Mn(II) oxidation at neutral pH. ROS was produced in parallel with the occurrence of Mn(II) oxidation at pH 7.2 from early stationary phase. Solid phase Mn oxides did not precipitate, which is consistent with the presence of a high amount of H2O2 and lower activity of catalase in the liquid culture at pH 7.2. Our results show that M. australicum T-G1, an acid tolerant MOB, can initiate Mn(II) oxidation by varying its oxidation mechanisms depending on the pH and may play an important role in low pH manganese biogeochemical cycling. PMID:26236307

Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry

PubMed Central

Trnkova, Libuse; Zerzankova, Lenka; Dycka, Filip; Mikelova, Radka; Jelen, Frantisek

2008-01-01

Using a paraffin impregnated graphite electrode (PIGE) and mercury-modified pyrolytic graphite electrode with basal orientation (Hg-PGEb) copper(II) and Cu(II)-DNA purine base solutions have been studied by cyclic (CV) and linear sweep voltammetry (LSV) in connection with elimination voltammetry with linear scan (EVLS). In chloride and bromide solutions (pH 6), the redox process of Cu(II) proceeded on PIGE with two cathodic and two anodic potentially separated signals. According to the elimination function E4, the first cathodic peak corresponds to the reduction Cu(II) + e- → Cu(I) with the possibility of fast disproportionation 2Cu(I) → Cu(II)+ Cu(0). The E4 of the second cathodic peak signalized an electrode process controlled by a surface reaction. The electrode system of Cu(II) on Hg-PGEb in borate buffer (pH 9.2) was characterized by one cathodic and one anodic peak. Anodic stripping voltammetry (ASV) on PIGE and cathodic stripping voltammetry (CSV) on Hg-PGEb were carried out at potentials where the reduction of copper ions took place and Cu(I)-purine complexes were formed. By using ASV and CSV in combination with EVLS, the sensitivity of Cu(I)-purine complex detection was enhanced relative to either ASV or CSV alone, resulting in higher peak currents of more than one order of magnitude. The statistical treatment of CE data was used to determine the reproducibility of measurements. Our results show that EVLS in connection with the stripping procedure is useful for both qualitative and quantitative microanalysis of purine derivatives and can also reveal details of studied electrode processes. PMID:27879715

Evaluation and source attribution of freshwater contributions to Kinvarra Bay, Ireland, using (222)Rn, EC and stable isotopes as natural indicators.

PubMed

Schubert, Michael; Knoeller, Kay; Rocha, Carlos; Einsiedl, Florian

2015-03-01

Freshwater discharge into the coastal sea is of general interest for two reasons: (i) It acts as vehicle for the transport of contaminants or nutrients into the ocean, and (ii) it indicates the loss of significant volumes of freshwater that might be needed for irrigation or drinking water supply. Due to the large-scale and long-term nature of the related hydrological processes, locating and quantitatively assessing freshwater discharge into the sea require naturally occurring tracers that allow fast, inexpensive and straightforward detection. In several studies, the standard water parameters electrical conductivity (EC) and pH have proven their suitability in this regard. However, while distribution patterns of EC and pH in the coastal sea indicate freshwater discharge in general, a separation between discharging surface water and submarine groundwater discharge (SGD) is not possible with these alone. The naturally occurring radionuclide radon-222 has been shown to be useful in the quantification of SGD and its distinction from surface runoff. This study aimed to evaluate and compare the informative value of the three parameters-EC, pH and radon concentration-in detecting and quantifying SGD by carrying out a case study in a bay located in western Ireland. The results reveal that radon activity is the most sensitive parameter for detecting SGD. However, only the combined evaluation of radon, EC and pH allows a quantitative allocation of groundwater and surface water contributions to the overall freshwater discharge into the sea. This conclusion is independently supported by stable isotope data measured on selected samples.

Reactivity of Nanoscale Zero-Valent Iron in Unbuffered Systems: Effect of pH and Fe(II) Dissolution.

PubMed

Bae, Sungjun; Hanna, Khalil

2015-09-01

While most published studies used buffers to maintain the pH, there is limited knowledge regarding the reactivity of nanoscale zerovalent iron (NZVI) in poorly buffered pH systems to date. In this work, the effect of pH and Fe(II) dissolution on the reactivity of NZVI was investigated during the reduction of 4-nitrophenol (4-NP) in unbuffered pH systems. The reduction rate increased exponentially with respect to the NZVI concentration, and the ratio of dissolved Fe(II)/initial NZVI was related proportionally to the initial pH values, suggesting that lower pH (6-7) with low NZVI loading may slow the 4-NP reduction through acceleration of the dissolution of NZVI particles. Additional experiments using buffered pH systems confirmed that high pH values (8-9) can preserve the NZVI particles against dissolution, thereby enhancing the reduction kinetics of 4-NP. Furthermore, reduction tests using ferrous ion in suspensions of magnetite and maghemite showed that surface-bound Fe(II) on oxide coatings can play an important role in enhancing 4-NP reduction by NZVI at pH 8. These unexpected results highlight the importance of pH and Fe(II) dissolution when NZVI technology is applied to poorly buffered systems, particularly at a low amount of NZVI (i.e., <0.075 g/L).

Atmospheric Processing of Volcanic Glass: Effects on Iron Solubility and Redox Speciation.

PubMed

Maters, Elena C; Delmelle, Pierre; Bonneville, Steeve

2016-05-17

Volcanic ash from explosive eruptions can provide iron (Fe) to oceanic regions where this micronutrient limits primary production. Controls on the soluble Fe fraction in ash remain poorly understood but Fe solubility is likely influenced during atmospheric transport by condensation-evaporation cycles which induce large pH fluctuations. Using glass powder as surrogate for ash, we experimentally simulate its atmospheric processing via cycles of pH 2 and 5 exposure. Glass fractional Fe solubility (maximum 0.4%) is governed by the pH 2 exposure duration rather than by the pH fluctuations, however; pH 5 exposure induces precipitation of Fe-bearing nanoparticles which (re)dissolve at pH 2. Glass leaching/dissolution release Fe(II) and Fe(III) which are differentially affected by changes in pH; the average dissolved Fe(II)/Fetot ratio is ∼0.09 at pH 2 versus ∼0.18 at pH 5. Iron release at pH 2 from glass with a relatively high bulk Fe(II)/Fetot ratio (0.5), limited aqueous Fe(II) oxidation at pH 5, and possibly glass-mediated aqueous Fe(III) reduction may render atmospherically processed ash a significant source of Fe(II) for phytoplankton. By providing new insight into the form(s) of Fe associated with ash as wet aerosol versus cloud droplet, we improve knowledge of atmospheric controls on volcanogenic Fe delivery to the ocean.

Development of a reduced-graphene-oxide based superparamagnetic nanocomposite for the removal of nickel (II) from an aqueous medium via a fluorescence sensor platform.

PubMed

Nandi, Debabrata; Saha, Indranil; Ray, Suprakas Sinha; Maity, Arjun

2015-09-15

Reduced-graphene-oxide based superparamagnetic nanocomposite (GC) was fabricated and applied for the remediation of Ni(II) from an aqueous medium. The as-prepared GC was extensively characterized by Raman, TEM, AFM, SEM-EDX, SQUID, and BET analyses. Quantitative immobilization of Ni(II) in an aqueous solution by the fluorescent sensor platform of GC was explored at varying pH, doses, contact times, and temperatures. The pseudo-second-order kinetics equation governed the overall sorption process at optimized pH of 5 (±0.2). The superior monolayer sorption capacity was 228mgg(-1) at 300K. Negative ΔG(0) indicated the spontaneous sorption nature, whereas the positive ΔH(0) resulted from an increase in entropy (positive ΔS(0)) at the solid-liquid interface during the endothermic reaction. The lower enthalpy agreed with the relatively high regeneration (approximately 91%) of the GC by 0.1M HCl, because of the formation of stable tetrahedral complex. The physisorption was well corroborated by calculated sorption energy (EDR ∼7kJmol(-1)) and the nature of the Stern-Volmer plot of the fluorescence-quenching data with reaction time. The GC played a pivotal role as a static fluorescent sensor platform (fluorophore) for Ni(II) adsorption. Magnetic property also indicated that GC could be easily separated from fluids by exploiting its superparamagnetic property. Copyright © 2015 Elsevier Inc. All rights reserved.

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

PubMed

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

2016-09-19

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

Preformulation considerations for controlled release dosage forms. Part II. Selected candidate support.

PubMed

Chrzanowski, Frank

2008-01-01

Practical examples of preformulation support of the form selected for formulation development are provided using several drug substances (DSs). The examples include determination of the solubilities vs. pH particularly for the range pH 1 to 8 because of its relationship to gastrointestinal (GI) conditions and dissolution method development. The advantages of equilibrium solubility and trial solubility methods are described. The equilibrium method is related to detecting polymorphism and the trial solubility method, to simplifying difficult solubility problems. An example of two polymorphs existing in mixtures of DS is presented in which one of the forms is very unstable. Accelerating stability studies are used in conjunction with HPLC and quantitative X-ray powder diffraction (QXRD) to demonstrate the differences in chemical and polymorphic stabilities. The results from two model excipient compatibility methods are compared to determine which has better predictive accuracy for room temperature stability. A DSC (calorimetric) method and an isothermal stress with quantitative analysis (ISQA) method that simulates wet granulation conditions were compared using a 2 year room temperature sample set as reference. An example of a pH stability profile for understanding stability and extrapolating stability to other environments is provided. The pH-stability of omeprazole and lansoprazole, which are extremely unstable in acidic and even mildly acidic conditions, are related to the formulation of delayed release dosage forms and the resolution of the problem associated with free carboxyl groups from the enteric coating polymers reacting with the DSs. Dissolution method requirements for CR dosage forms are discussed. The applicability of a modified disintegration time (DT) apparatus for supporting CR dosage form development of a pH sensitive DS at a specific pH such as duodenal pH 5.6 is related. This method is applicable for DSs such as peptides, proteins, enzymes and natural products where physical observation can be used in place of a difficult to perform analytical method, saving resources and providing rapid preformulation support.

Formation of Hg(II) tetrathiolate complexes with cysteine at neutral pH

DOE PAGES

Warner, Thomas; Jalilehvand, Farideh

2016-01-04

Mercury(II) ions precipitate from aqueous cysteine (H 2Cys) solutions containing H 2Cys/Hg(II) mole ratio ≥ 2.0 as Hg( S-HCys) 2. In absence of additional cysteine, the precipitate dissolves at pH ~12 with the [Hg( S, N-Cys) 2] 2- complex dominating. With excess cysteine (H 2Cys/Hg(II) mole ratio ≥ 4.0), higher complexes form and the precipitate dissolves at lower pH values. Previously, we found that tetrathiolate [Hg( S-Cys) 4] 6- complexes form at pH = 11.0; in this work we extend the investigation to pH values of physiological interest. We examined two series of Hg(II)-cysteine solutions in which C Hg(II) variedmore » between 8 – 9 mM and 80 – 100 mM, respectively, with H 2Cys/Hg(II) mole ratios from 4 to ~20. The solutions were prepared in the pH range 7.1 – 8.8, at the pH at which the initial Hg( S-HCys) 2 precipitate dissolved. The variations in the Hg(II) speciation were followed by 199Hg NMR, X-ray absorption and Raman spectroscopic techniques. Our results show that in the dilute solutions (C Hg(II) = 8 – 9 mM), mixtures of di-, tri- (major) and tetrathiolate complexes exist at moderate cysteine excess (C H2Cys ~ 0.16 M) at pH 7.1. In the more concentrated solutions (C Hg(II) = 80 – 100 mM) with high cysteine excess (C H2Cys > 0.9 M), tetrathiolate [Hg( S-cysteinate) 4] m-6 ( m = 0 – 4) complexes dominate in the pH range 7.3 – 7.8, with lower charge than for the [Hg( S-Cys) 4] 6- complex due to protonation of some ( m) of the amino groups of the coordinated cysteine ligands. In conclusion, the results of this investigation could provide a key to the mechanism of biosorption and accumulation of Hg(II) ions in biological / environmental systems.« less

Evaluating remedial alternatives for an acid mine drainage stream: Application of a reactive transport model

USGS Publications Warehouse

Runkel, R.L.; Kimball, B.A.

2002-01-01

A reactive transport model based on one-dimensional transport and equilibrium chemistry is applied to synoptic data from an acid mine drainage stream. Model inputs include streamflow estimates based on tracer dilution, inflow chemistry based on synoptic sampling, and equilibrium constants describing acid/base, complexation, precipitation/dissolution, and sorption reactions. The dominant features of observed spatial profiles in pH and metal concentration are reproduced along the 3.5-km study reach by simulating the precipitation of Fe(III) and Al solid phases and the sorption of Cu, As, and Pb onto freshly precipitated iron-(III) oxides. Given this quantitative description of existing conditions, additional simulations are conducted to estimate the streamwater quality that could result from two hypothetical remediation plans. Both remediation plans involve the addition of CaCO3 to raise the pH of a small, acidic inflow from ???2.4 to ???7.0. This pH increase results in a reduced metal load that is routed downstream by the reactive transport model, thereby providing an estimate of post-remediation water quality. The first remediation plan assumes a closed system wherein inflow Fe(II) is not oxidized by the treatment system; under the second remediation plan, an open system is assumed, and Fe(II) is oxidized within the treatment system. Both plans increase instream pH and substantially reduce total and dissolved concentrations of Al, As, Cu, and Fe(II+III) at the terminus of the study reach. Dissolved Pb concentrations are reduced by ???18% under the first remediation plan due to sorption onto iron-(III) oxides within the treatment system and stream channel. In contrast, iron(III) oxides are limiting under the second remediation plan, and removal of dissolved Pb occurs primarily within the treatment system. This limitation results in an increase in dissolved Pb concentrations over existing conditions as additional downstream sources of Pb are not attenuated by sorption.

Geochemical interactions between constituents in acidic groundwater and alluvium in an aquifer near Globe, Arizona

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1994-01-01

Acidic water from a copper-mining area has contaminated an alluvial aquifer and stream near Globe, Arizona. The most contaminated groundwater has a pH of 3.3, and contains about 100 mmol/1 SO4, 50 mmol/1 Fe, 11 mmol/1 Al and 3 mmol/1 Cu. Reactions between alluvium and acidic groundwater were first evaluated in laboratory column experiments. A geochemical model was developed and used in the equilibrium speciation program, MINTEQA2, to simulate breakthrough curves for different constituents from the column. The geochemical model was then used to simulate the measured changes in concentration of aqueous constituents along a flow path in the aquifer.The pH was predominantly controlled by reaction with carbonate minerals. Where carbonates had been dissolved, adsorption of H+ by iron oxides was used to simulate pH. Acidic groundwater contained little or no dissolved oxygen, and most aqueous Fe was present as Fe(II). In the anoxic core of the plume, Fe(II) was oxidized by MnO2 to Fe(III), which then precipitated as Fe(OH)3. Attenuation of aqueous Cu, Co, Mn, Ni and Zn was a function of pH and could be quantitatively modeled with the diffuse-layer, surface complexation model in MINTEQA2. Aluminum precipitated as amorphous Al(OH)3 at pH < 4.7 and as AlOHSO4 at pH < 4.7. Aqueous Ca and SO4were close to equilibrium with gypsum.After the alluvium in the column had reached equilibrium with acidic groundwater, uncontaminated groundwater was eluted through the column to evaluate the effect of reactants on groundwater remediation. The concentration of Fe, Mn, Cu, Co, Ni and Zn rapidly decreased to the detection limits within a few pore volumes. All of the gypsum that had precipitated initially redissolved, resulting in elevated Ca and SO4concentrations for about 5 pore volumes. Aluminum and pH exhibited the most potential for continued adverse effects on groundwater quality. As H+ desorbed from Fe(OH)3, pH remained below 4.5 for more than 20 pore volumes, resulting in dissolution of AlOHSO4 and elevated aqueous Al.

Influence of pH and ionic strength (NaCl/Na2SO4) on the reaction HO Cl/ClO- + NO2-

NASA Astrophysics Data System (ADS)

Marcellos da Rosa, M.; Zetzsch, C.

2003-04-01

Equilibria such as HOCl + NO_2^- leftrightarrow ClNO_2 + OH^- and ClNO_2 + H_2O leftrightarrow NO_3^- + 2H^+ + Cl^- play an important role in halogen activation in the troposphere. We studied the oxidation of NO_2^- by HOCl/ClO^- in aqueous phase by stopped-flow measurements at different ionic strengths (bidestilled water, 0.1M NaCl, 1.0M NaCl and 1.0M Na_2SO^4) at various pH values (4.0, 5.5, 6.2 and 10.0) at 293K. The experiments were performed using a SX.18MV Applied Photophysics spectrophotometer, observing the exponential decay of HOCl/ClO^- at λ = 290nm between 10ms and 100s. HOCl (pK_a= 7.50) was obtained by bubbling N_2 with 1% Cl_2 through bidestilled water. The pH of the aqueous solutions of HOCl was determined by a pH meter (CG820, Schott) with a glass electrode N6180 (calibrated with standard buffer solutions at pH = 3.0, 4.0, 7.0 and 10.0), and the pH values were adjusted by dropwise addition of HClO_4 or NaOH. The concentrations of HOCl (ɛHOCl (230nm) = 100M-1cm-1) ([HOCl] = 1.3mM - 10mM) and ClO- (ɛClO- (292nm) = 350 M-1cm-1) ([ClO^-] = 1.3mM - 5mM) were determined by UV spectrometry (Kontron UVIKON 860) at a resolution of 2 nm in 1 cm cells at various pH values. The concentration range of NO_2^- was between 5mM and 50mM. The following second-order rate constant kII were obtained at 293K at various pH values (in units of M-1s-1) in H_2O: pH 4.0, (5.6±0.3)\\cdot 10^3; pH 5.5, (5.0±0.4)\\cdot 10^3; pH 10.0, 3.9±0.4; in 0.1M NaCl: pH 5.5, (4.3±0.4)\\cdot 10^3; pH 10.0, 2.6±0.4; in 1.0M NaCl: pH 5.5, (4.0±0.3); pH 10.0, 0.7±0.2 and in 1.0M Na_2SO_4: pH 5.5, (3.0±0.3)\\cdot 10^3; pH 10.0, 1.9±0.4. There is a strong effect of the pH on the reaction HOCl/ClO^- + NO_2^-, as reflected in the ratio kII_a(pH 5.5, HOCl)/kII_b(pH 10.0, ClO^-): in H_2O (kII_a ˜ 1200 \\cdot kII_b), in 0.1M NaCl (kII_a ˜ 1900 \\cdot kII_b), in 1.0M NaCl (kII_a ˜ 5700 \\cdot kII_b) and in 1.0 M Na_2SO_4 (kII_a ˜ 1500 \\cdot kII_b). A mechanism for the oxidation of NO_2^- by HOCl/ClO^- will be presented and compared with previous work.

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

Warner, Thomas; Jalilehvand, Farideh

Mercury(II) ions precipitate from aqueous cysteine (H 2Cys) solutions containing H 2Cys/Hg(II) mole ratio ≥ 2.0 as Hg( S-HCys) 2. In absence of additional cysteine, the precipitate dissolves at pH ~12 with the [Hg( S, N-Cys) 2] 2- complex dominating. With excess cysteine (H 2Cys/Hg(II) mole ratio ≥ 4.0), higher complexes form and the precipitate dissolves at lower pH values. Previously, we found that tetrathiolate [Hg( S-Cys) 4] 6- complexes form at pH = 11.0; in this work we extend the investigation to pH values of physiological interest. We examined two series of Hg(II)-cysteine solutions in which C Hg(II) variedmore » between 8 – 9 mM and 80 – 100 mM, respectively, with H 2Cys/Hg(II) mole ratios from 4 to ~20. The solutions were prepared in the pH range 7.1 – 8.8, at the pH at which the initial Hg( S-HCys) 2 precipitate dissolved. The variations in the Hg(II) speciation were followed by 199Hg NMR, X-ray absorption and Raman spectroscopic techniques. Our results show that in the dilute solutions (C Hg(II) = 8 – 9 mM), mixtures of di-, tri- (major) and tetrathiolate complexes exist at moderate cysteine excess (C H2Cys ~ 0.16 M) at pH 7.1. In the more concentrated solutions (C Hg(II) = 80 – 100 mM) with high cysteine excess (C H2Cys > 0.9 M), tetrathiolate [Hg( S-cysteinate) 4] m-6 ( m = 0 – 4) complexes dominate in the pH range 7.3 – 7.8, with lower charge than for the [Hg( S-Cys) 4] 6- complex due to protonation of some ( m) of the amino groups of the coordinated cysteine ligands. In conclusion, the results of this investigation could provide a key to the mechanism of biosorption and accumulation of Hg(II) ions in biological / environmental systems.« less

A tunable ratiometric pH sensor based on carbon nanodots for the quantitative measurement of the intracellular pH of whole cells.

PubMed

Shi, Wen; Li, Xiaohua; Ma, Huimin

2012-06-25

The whole picture: Carbon nanodots labeled with two fluorescent dyes have been developed as a tunable ratiometric pH sensor to measure intracellular pH. The nanosensor shows good biocompatibility and cellular dispersibility. Quantitative determinations on intact HeLa cells and pH fluctuations associated with oxidative stress were performed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of humic acid on nickel(II) sorption to Ca-montmorillonite by batch and EXAFS techniques study.

PubMed

Hu, Jun; Tan, Xiaoli; Ren, Xuemei; Wang, Xiangke

2012-09-21

The influence of humic acid (HA) on Ni(II) sorption to Ca-montmorillonite was examined by using a combination of batch sorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy technique. The sorption of Ni(II) on HA-montmorillonite hybrids is strongly dependent on pH and temperature. At low pH, the sorption of Ni(II) is mainly dominated by Ni-HA-montmorillonite and outer-sphere surface complexation. The EXAFS results indicate that the first coordination shell of Ni(II) consists of ∼6 O atoms at the interatomic distances of ∼2.04 Å in an octahedral structure. At high pH, binary Ni-montmorillonite surface complexation is the dominant sorption mechanism. EXAFS analysis indicates the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5, while a Ni-Al layered double hydroxide (LDH) phase at the Ca-montmorillonite surface formed with pH 8.5. At pH 10.0, the dissolved HA-Ni(II) complexation inhibits the precipitation of Ni hydroxide, and Ni-Al LDH phase forms. The rise of temperature increases the sorption capacity of Ni(II), and promotes Ni-Al LDH phase formation and the growth of crystallites. The results are important to evaluate the physicochemical behavior of Ni(II) in the natural environment.

Sorption of Cr(VI), Cu(II) and Pb(II) by growing and non-growing cells of a bacterial consortium.

PubMed

Sannasi, P; Kader, J; Ismail, B S; Salmijah, S

2006-03-01

This paper reports the sorption of three metallic ions, namely Cr(VI), Cu(II) and Pb(II) in aqueous solution by a consortium culture (CC) comprising an acclimatised mixed bacterial culture collected from point and non-point sources. Metal sorption capability of growing and non-growing cells at initial pH of between 3 and 8 in the 1-100mg/L concentration range were studied based on Q(max) and K(f) values of the Langmuir and linearised Freundlich isotherm models, respectively. Maximal metal loading was generally observed to be dependent on the initial pH. Growing cells displayed significant maximal loading (Q(max)) for Pb(II) (238.09 mg/g) and Cu(II) (178.87 mg/g) at pH 6 and at pH 7 for Cr(VI) (90.91 mg/g) compared to non-growing cells (p < 0.05). At the pH range of 6-8, growing cells showed higher loading capacity compared to non-growing cells i.e. 38-52% for Cr, 17-28% for Cu and 3-17% for Pb. At lower metal concentrations and at more acidic pH (3-4) however, non-growing cells had higher metal loading capacity than growing cells. The metal sorption capacity for both populations were as follows: Pb(II) > Cu(II) > Cr(VI).

Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity

DOE PAGES

Semin, B. K.; Davletshina, L. N.; Seibert, M.; ...

2017-11-11

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extractmore » only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster.« less

Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity

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

Semin, B. K.; Davletshina, L. N.; Seibert, M.

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extractmore » only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster.« less

Adsorption of Cu(II) on Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated and Carboxylated Fullerenes

PubMed Central

Wang, Jing; Li, Zhan; Li, Shicheng; Qi, Wei; Liu, Peng; Liu, Fuqiang; Ye, Yuanlv; Wu, Liansheng; Wang, Lei; Wu, Wangsuo

2013-01-01

The adsorption of Cu(II) on oxidized multi-walled carbon nanotubes (oMWCNTs) as a function of contact time, pH, ionic strength, temperature, and hydroxylated fullerene (C60(OH)n) and carboxylated fullerene (C60(C(COOH)2)n) were studied under ambient conditions using batch techniques. The results showed that the adsorption of Cu(II) had rapidly reached equilibrium and the kinetic process was well described by a pseudo-second-order rate model. Cu(II) adsorption on oMWCNTs was dependent on pH but independent of ionic strength. Compared with the Freundlich model, the Langmuir model was more suitable for analyzing the adsorption isotherms. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Cu(II) adsorption on oMWCNTs was spontaneous and endothermic. The effect of C60(OH)n on Cu(II) adsorption of oMWCNTs was not significant at low C60(OH)n concentration, whereas a negative effect was observed at higher concentration. The adsorption of Cu(II) on oMWCNTs was enhanced with increasing pH values at pH < 5, but decreased at pH ≥ 5. The presence of C60(C(COOH)2)n inhibited the adsorption of Cu(II) onto oMWCNTs at pH 4–6. The double sorption site model was applied to simulate the adsorption isotherms of Cu(II) in the presence of C60(OH)n and fitted the experimental data well. PMID:24009683

Biosorption studies on copper (II) and cadmium (II) using pretreated rice straw and rice husk.

PubMed

Li, W C; Law, F Y; Chan, Y H M

2017-04-01

This study investigated the adsorption and removal behaviour of copper (Cu) (II) and cadmium (Cd) (II) ions using rice husk and rice straw in aqueous solutions. Different parameters were used to investigate their adsorption performance in saline conditions and the optimal level of biosorption at different pH levels. The main parameters were pH (3, 6 and 9), initial concentration level of heavy metals (Cu (II) 5, 10, 20, 40 and 60 mg/L and Cd (II) 0.5, 1, 2, 4 and 8 mg/L, respectively), salinity (0, 50 and 100 mM NaCl) and contact time (ranging from 3 to 60 min). Langmuir and Freundlich isotherm models were applied to analyse the removal efficiency and sorption capacity of the pretreated rice husk and rice straw. The removal efficiency and adsorption capacity generally increased with the pH and reached a plateau in alkaline conditions. The percentage removal of Cu (II) by rice husk reached 97 % at pH 9 and 95 % by rice straw at pH 6. Biosorption performance increased in the absence of NaCl. Kinetic studies for both metals revealed that the biosorption of Cu (II) and Cd (II) onto rice straw and husk was pseudo-second order.

An EPR study of the pH dependence of formate effects on Photosystem II.

PubMed

Jajoo, Anjana; Katsuta, Nobuhiro; Kawamori, Asako

2006-04-01

Effects of formate on rates of O(2) evolution and electron paramagnetic resonance (EPR) signals were observed in the oxygen evolving PS II membranes as a function of pH. In formate treated PS II membranes, decrease in pH value resulted in the inhibition of the O(2) evolving activity, a decrease in the intensity of S(2) state multiline signal but an increase in the intensity of the Q(A)(-)Fe(2+) EPR signal. Time-resolved EPR study of the Y(Z)(*) decay kinetics showed that the light-induced intensity of Y(Z)(*) EPR signal was proportional to the formate concentration. The change in the pH affected both the light-induced intensities and the decay rates of Y(Z)(*), which was found to be faster at lower pH. At 253 K, t(1/e) value of Y(Z)(*) decay kinetics was found to be 8-10 s at pH 6.0 and 18-21 s at pH 5.0. The results presented here indicate that the extent of inhibition at the donor and the acceptor side of PS II due to formate is pH dependent, being more effective at lower pH.

Structural alteration of hexagonal birnessite by aqueous Mn(II): Impacts on Ni(II) sorption

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

Lefkowitz, Joshua P.; Elzinga, Evert J.

We studied the impacts of aqueous Mn(II) (1 mM) on the sorption of Ni(II) (200 μM) by hexagonal birnessite (0.1 g L- 1) at pH 6.5 and 7.5 with batch experiments and XRD, ATR-FTIR and Ni K-edge EXAFS analyses. In the absence of Mn(II)aq, sorbed Ni(II) was coordinated predominantly as triple corner-sharing complexes at layer vacancies at both pH values. Introduction of Mn(II)aq into Ni(II)-birnessite suspensions at pH 6.5 caused Ni(II) desorption and led to the formation of edge-sharing Ni(II) complexes. This was attributed to competitive displacement of Ni(II) from layer vacancies by either Mn(II) or by Mn(III) formed throughmore » interfacial Mn(II)-Mn(IV) comproportionation, and/or incorporation of Ni(II) into the birnessite lattice promoted by Mn(II)-catalyzed recrystallization of the sorbent. Similar to Mn(II)aq, the presence of HEPES or MES caused the formation of edge-sharing Ni(II) sorption complexes in Ni(II)-birnessite suspensions, which was attributed to partial reduction of the sorbent by the buffers. At pH 7.5, interaction with aqueous Mn(II) caused reductive transformation of birnessite into secondary feitknechtite that incorporated Ni(II), enhancing removal of Ni(II) from solution. These results demonstrate that reductive alteration of phyllomanganates may significantly affect the speciation and solubility of Ni(II) in anoxic and suboxic environments.« less

Utilization of ICP/OES for the determination of trace metal binding to different humic fractions.

PubMed

de la Rosa, G; Peralta-Videa, J R; Gardea-Torresdey, J L

2003-02-28

In this study, the use of inductively coupled plasma/optical emission spectrometry (ICP/OES) to determine multi-metal binding to three biomasses, Sphagnum peat moss, humin and humic acids is reported. All the investigations were performed under part per billion (ppb) concentrations. Batch pH profile experiments were performed using multi-metal solutions of Cd(II), Cu(II), Pb(II), Ni(II), Cr(III) and Cr(VI). The results showed that at pH 2 and 3, the metal affinity of the three biomasses exposed to the multi-metal solution that included Cr(III) presented the following order: Cu(II), Pb(II)>Ni(II)>Cr(III)>Cd(II). On the other hand, when Cr(VI) was in the heavy metal mixture, Sphagnum peat moss and humin showed the following affinity: Cu(II), Pb(II)>Ni(II)>Cr(VI)>Cd(II); however, the affinity of the humic acids was: Cu(II)>Pb(II), Cr(VI)>Ni(II)>Cd(II). The results demonstrated that pH values of 4 and 5 were the most favorable for the heavy metal binding process. At pH 5, all the metals, except for Cr(VI), were bound between 90 and 100% to the three biomasses. However, the binding capacity of humic acids decreased at pH 6 in the presence of Cr(VI). The results showed that the ICP/OES permits the determination of heavy metal binding to organic matter at ppb concentration. These results will be very useful in understanding the role of humic substances in the fate and transport of heavy metals, and thus could provide information to develop new methodologies for the removal of low concentrations of toxic heavy metals from contaminated waters.

Effect of solvent on the electronic absorption spectral properties of some mixed β-octasubstituted Zn(II)-tetraphenylporphyrins

NASA Astrophysics Data System (ADS)

Bhyrappa, P.; Sankar, M.

2018-01-01

A series of mixed β-octasubstituted Zn(II)-porphyrins, 2,3,12,13-tetra(chloro/cyano/methyl)-5,7,8,10,15,17,18,20-octaphenylporphinato zinc(II), ZnTPP(Ph)4X4 (X = CN, Cl and CH3) have been examined by electronic absorption spectroscopy in various solvents. These Zn(II)-porphyrins exhibited varying degree of red-shift of absorption bands as high as 20-30 nm in 'B' band and 50-60 nm in longest wavelength band, 'Q(0,0)' band in polar solvents relative to that found in nonpolar solvents. The red-shift of B and Q(0,0) bands showed an unusual trend, ZnTPP(Ph)4(CN)4 > ZnTPP(Ph)4(CH3)4 > ZnTPP(Ph)4Cl4 but fails to follow an anticipated anodic shift in first porphyrin ring oxidation (vs Ag/AgCl) potential: ZnTPP(Ph)4(CN)4 (1.02 V) > ZnTPP(Ph)4Cl4 (0.74 V) > ZnTPP(Ph)4(CH3)4 (0.38 V). Such a trend suggests the combined effect of non-planarity of the macrocycle and electronic effect of the peripheral substituents. The equilibrium constants for the binding of nitrogenous bases with the Zn(II)-porphyrins showed as high as twenty fold increase for ZnTPP(Ph)4X4 (X = Br and CN) relative to ZnTPP(Ph)4(CH3)4 and follow the order: ZnTPP(Ph)4(CN)4 > ZnTPP(Ph)4Br4 > ZnTPP(Ph)4(CH3)4 ≤ ZnTPP which is approximately in line with an increase in anodic shift of their first ring redox potentials (ZnTPP(Ph)4(CN)4 (1.02 V) > ZnTPP(Ph)4Br4 (0.72 V) > ZnTPP (0.84 V) > ZnTPP(Ph)4(CH3)4) (0.38 V).

Ferrate(VI)-Prompted Removal of Metals in Aqueous Media: Mechanistic Delineation of Enhanced Efficiency via Metal Entrenchment in Magnetic Oxides

EPA Science Inventory

The removal efficiency of heavy metal ions (cadmium(II) – Cd(II), cobalt(II) – Co(II), nickel(II) – Ni(II), and copper(II) – Cu(II)) by potassium ferrate(VI) (K2FeO4, Fe(VI)), was studied as a function of added amount of Fe(VI) (or Fe) and varying pH. At pH = 6.6, the effective r...

On-line separation and preconcentration of lead(II) by solid-phase extraction using activated carbon loaded with xylenol orange and its determination by flame atomic absorption spectrometry.

PubMed

Ensafi, Ali A; Shiraz, A Zendegi

2008-02-11

Activated carbon loaded with xylenol orange in a mini-column was used for the highly selective separation and preconcentration of Pb(II) ions. An on-line system for enrichment and the determination of Pb(II) was carried out on flame atomic absorption spectrometry. The conditions of preconcentration and quantitative recovery of Pb(II) from diluted solution, such as pH of aqueous phase, amount of the sorbent, volume of the solutions and flow variables were studied as well as effect of potential interfering ions. Under the optimum conditions, Pb(II) in an aqueous sample was concentrated about 200-fold and the detection limit was 0.4 ng mL(-1) Pb(II). The adsorption capacity of the solid phase was 0.20mg of lead per one gram of the modified activated carbon. The modified activated carbon is stable for several treatments of sample solutions without the need for using any chemical reagent. The recovery of lead(II) from river water, waste water, tap water, and in the following reference materials: SRM 2711 Montana soil and GBW-07605 tea were obtained in the range of 97-104% by the proposed method.

Doctoral training in statistics, measurement, and methodology in psychology: replication and extension of Aiken, West, Sechrest, and Reno's (1990) survey of PhD programs in North America.

PubMed

Aiken, Leona S; West, Stephen G; Millsap, Roger E

2008-01-01

In a survey of all PhD programs in psychology in the United States and Canada, the authors documented the quantitative methodology curriculum (statistics, measurement, and research design) to examine the extent to which innovations in quantitative methodology have diffused into the training of PhDs in psychology. In all, 201 psychology PhD programs (86%) participated. This survey replicated and extended a previous survey (L. S. Aiken, S. G. West, L. B. Sechrest, & R. R. Reno, 1990), permitting examination of curriculum development. Most training supported laboratory and not field research. The median of 1.6 years of training in statistics and measurement was mainly devoted to the modally 1-year introductory statistics course, leaving little room for advanced study. Curricular enhancements were noted in statistics and to a minor degree in measurement. Additional coverage of both fundamental and innovative quantitative methodology is needed. The research design curriculum has largely stagnated, a cause for great concern. Elite programs showed no overall advantage in quantitative training. Forces that support curricular innovation are characterized. Human capital challenges to quantitative training, including recruiting and supporting young quantitative faculty, are discussed. Steps must be taken to bring innovations in quantitative methodology into the curriculum of PhD programs in psychology. PsycINFO Database Record (c) 2008 APA, all rights reserved.

Effect of aniline on cadmium adsorption by sulfanilic acid-grafted magnetic graphene oxide sheets.

PubMed

Hu, Xin-jiang; Liu, Yun-guo; Zeng, Guang-ming; Wang, Hui; Hu, Xi; Chen, An-wei; Wang, Ya-qin; Guo, Yi-Mming; Li, Ting-ting; Zhou, Lu; Liu, Shao-heng; Zeng, Xiao-xia

2014-07-15

Cd(II) has posed severe health risks worldwide. To remove this contaminant from aqueous solution, the sulfanilic acid-grafted magnetic graphene oxide sheets (MGOs/SA) were prepared and characterized. The mutual effects of Cd(II) and aniline adsorption on MGOs/SA were studied. The effects of operating parameters such as pH, ionic strength, contact time and temperature on the Cd(II) enrichment, as well as the adsorption kinetics and isotherm were also investigated. The results demonstrated that MGOs/SA could effectively remove Cd(II) and aniline from the aqueous solution and the two adsorption processes were strongly dependent on solution pH. The Cd(II) adsorption was reduced by the presence of aniline at pH<5.4 but was improved at pH>5.4. The presence of Cd(II) diminished the adsorption capacity for aniline at pH<7.8 but enhanced the aniline adsorption at pH>7.8. The decontamination of Cd(II) by MGOs/SA was influenced by ionic strength. Besides, the adsorption process could be well described by pseudo-second-order kinetic model. The intraparticle diffusion study revealed that the intraparticle diffusion was not the only rate-limiting step for the adsorption process. Moreover, the experimental data of isotherm followed the Freundlich isotherm model. Copyright © 2014 Elsevier Inc. All rights reserved.

Doctoral Training in Statistics, Measurement, and Methodology in Psychology: Replication and Extension of Aiken, West, Sechrest, and Reno's (1990) Survey of PhD Programs in North America

ERIC Educational Resources Information Center

Aiken, Leona S.; West, Stephen G.; Millsap, Roger E.

2008-01-01

In a survey of all PhD programs in psychology in the United States and Canada, the authors documented the quantitative methodology curriculum (statistics, measurement, and research design) to examine the extent to which innovations in quantitative methodology have diffused into the training of PhDs in psychology. In all, 201 psychology PhD…

Tartrazine modified activated carbon for the removal of Pb(II), Cd(II) and Cr(III).

PubMed

Monser, Lotfi; Adhoum, Nafaâ

2009-01-15

A two in one attempt for the removal of tartrazine and metal ions on activated carbon has been developed. The method was based on the modification of activated carbon with tartrazine then its application for the removal of Pb(II), Cd(II) and Cr(III) ions at different pH values. Tartrazine adsorption data were modelled using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacities qm were 121.3, 67 and 56.7mgg(-1) at initial pH values of 1.0, 6.0 and 10, respectively. The adsorption of tartrazine onto activated carbon followed second-order kinetic model. The equilibrium time was found to be 240min at pH 1.0 and 120min at pH 10 for 500mgL(-1) tartrazine concentration. A maximum removal of 85% was obtained after 1h of contact time. The presence of tartrazine as modifier enhances attractive electrostatic interactions between metal ions and carbon surface. The adsorption capacity for Pb(II), Cd(II) and Cr(III) ions has been improved with respect to non-modified carbon reaching a maximum of 140%. The adsorption capacity was found to be a pH dependent for both modified and non-modified carbon with a greater adsorption at higher pH values except for Cr(III). The enhancement percent of Pb(II), Cd(II) and Cr(III) at different pH values was varied from 28% to 140% with respect to non-modified carbon. The amount of metal ions adsorbed using static regime was 11-40% higher than that with dynamic mode. The difference between adsorption capacities could be attributed to the applied flow rate.

A novel detection approach based on chromophore-decolorizing with free radical and application to photometric determination of copper with acid chrome dark blue.

PubMed

Gao, Hong-Wen; Chen, Fang-Fang; Chen, Ling; Zeng, Teng; Pan, Lu-Ting; Li, Jian-Hua; Luo, Hua-Fei

2007-03-21

A novel detection approach named chromophore-decolorizing with free radicals is developed for determination of trace heavy metal. The hydroxyl radicals (HO) generated from Fe(III) and hydrogen peroxide will oxidize the free chromophore into almost colorless products. The copper-acid chrome dark blue (ACDB) complexation was investigated at pH 5.07. In the presence of Fe(III) and hydrogen peroxide, the excess ACDB was decolorized in the Cu-ACDB reaction solution, and the final solution contained only one color compound, the Cu-ACDB complex. After oxidation of free hydroxyl radicals, the complexation becomes sensitive and selective and it has been used for the quantitation of trace amounts of Cu(II) dissolved in natural water. Beer's law is obeyed in the range from 0 to 0.500 microg mL(-1) Cu(II) and the limit of detection is only 6 microg L(-1) Cu(II). Besides, the Cu-ACDB complex formed was characterized.

pH Mapping on Tooth Surfaces for Quantitative Caries Diagnosis Using Micro Ir/IrOx pH Sensor.

PubMed

Ratanaporncharoen, Chindanai; Tabata, Miyuki; Kitasako, Yuichi; Ikeda, Masaomi; Goda, Tatsuro; Matsumoto, Akira; Tagami, Junji; Miyahara, Yuji

2018-04-03

A quantitative diagnostic method for dental caries would improve oral health, which directly affects the quality of life. Here we describe the preparation and application of Ir/IrOx pH sensors, which are used to measure the surface pH of dental caries. The pH level is used as an indicator to distinguish between active and arrested caries. After a dentist visually inspected and defined 18 extracted dentinal caries at various positions as active or arrested caries, the surface pH values of sound and caries areas were directly measured with an Ir/IrOx pH sensor with a diameter of 300 μm as a dental explorer. The average pH values of the sound root, the arrested caries, and active caries were 6.85, 6.07, and 5.30, respectively. The pH obtained with an Ir/IrOx sensor was highly correlated with the inspection results by the dentist, indicating that the types of caries were successfully categorized. This caries testing technique using a micro Ir/IrOx pH sensor provides an accurate quantitative caries evaluation and has potential in clinical diagnosis.

Quantum dynamics of small H2 and D2 clusters in the large cage of structure II clathrate hydrate: Energetics, occupancy, and vibrationally averaged cluster structures

NASA Astrophysics Data System (ADS)

Sebastianelli, Francesco; Xu, Minzhong; Bačić, Zlatko

2008-12-01

We report diffusion Monte Carlo (DMC) calculations of the quantum translation-rotation (T-R) dynamics of one to five para-H2 (p-H2) and ortho-D2 (o-D2) molecules inside the large hexakaidecahedral (51264) cage of the structure II clathrate hydrate, which was taken to be rigid. These calculations provide a quantitative description of the size evolution of the ground-state properties, energetics, and the vibrationally averaged geometries, of small (p-H2)n and (o-D2)n clusters, n=1-5, in nanoconfinement. The zero-point energy (ZPE) of the T-R motions rises steeply with the cluster size, reaching 74% of the potential well depth for the caged (p-H2)4. At low temperatures, the rapid increase of the cluster ZPE as a function of n is the main factor that limits the occupancy of the large cage to at most four H2 or D2 molecules, in agreement with experiments. Our DMC results concerning the vibrationally averaged spatial distribution of four D2 molecules, their mean distance from the cage center, the D2-D2 separation, and the specific orientation and localization of the tetrahedral (D2)4 cluster relative to the framework of the large cage, agree very well with the low-temperature neutron diffraction experiments involving the large cage with the quadruple D2 occupancy.

Quantum dynamics of small H2 and D2 clusters in the large cage of structure II clathrate hydrate: energetics, occupancy, and vibrationally averaged cluster structures.

PubMed

Sebastianelli, Francesco; Xu, Minzhong; Bacić, Zlatko

2008-12-28

We report diffusion Monte Carlo (DMC) calculations of the quantum translation-rotation (T-R) dynamics of one to five para-H(2) (p-H(2)) and ortho-D(2) (o-D(2)) molecules inside the large hexakaidecahedral (5(12)6(4)) cage of the structure II clathrate hydrate, which was taken to be rigid. These calculations provide a quantitative description of the size evolution of the ground-state properties, energetics, and the vibrationally averaged geometries, of small (p-H(2))(n) and (o-D(2))(n) clusters, n=1-5, in nanoconfinement. The zero-point energy (ZPE) of the T-R motions rises steeply with the cluster size, reaching 74% of the potential well depth for the caged (p-H(2))(4). At low temperatures, the rapid increase of the cluster ZPE as a function of n is the main factor that limits the occupancy of the large cage to at most four H(2) or D(2) molecules, in agreement with experiments. Our DMC results concerning the vibrationally averaged spatial distribution of four D(2) molecules, their mean distance from the cage center, the D(2)-D(2) separation, and the specific orientation and localization of the tetrahedral (D(2))(4) cluster relative to the framework of the large cage, agree very well with the low-temperature neutron diffraction experiments involving the large cage with the quadruple D(2) occupancy.

EVALUATION OF STACHYBOTRYS CHARTARUM IN THE HOUSE OF AN INFANT WITH PULMONARY HEMORRHAGE: QUANTITATIVE ASSESSMENT BEFORE, DURING, AND AFTER REMEDIATION

EPA Science Inventory

Stachybotrys chartarum is an indoor mold that has been associated with pulmonary hemorrhage (PH) cases in the Cleveland, Ohio area. This study applied two new quantitative measurements to air samples from a home where an infant developed PH. Quantitative polymerase chain reacti...

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion.

PubMed

Shipley, Heather J; Engates, Karen E; Grover, Valerie A

2013-03-01

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.

Synthesis, characterization, and ligand exchange reactivity of a series of first row divalent metal 3-hydroxyflavonolate complexes.

PubMed

Grubel, Katarzyna; Rudzka, Katarzyna; Arif, Atta M; Klotz, Katie L; Halfen, Jason A; Berreau, Lisa M

2010-01-04

A series of divalent metal flavonolate complexes of the general formula [(6-Ph(2)TPA)M(3-Hfl)]X (1-5-X; X = OTf(-) or ClO(4)(-); 6-Ph(2)TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II); 3-Hfl = 3-hydroxyflavonolate) were prepared and characterized by X-ray crystallography, elemental analysis, FTIR, UV-vis, (1)H NMR or EPR, and cyclic voltammetry. All of the complexes have a bidentate coordinated flavonolate ligand. The difference in M-O distances (Delta(M-O)) involving this ligand varies through the series, with the asymmetry of flavonolate coordination increasing in the order Mn(II) approximately Ni(II) < Cu(II) < Zn(II) < Co(II). The hypsochromic shift of the absorption band I (pi-->pi*) of the coordinated flavonolate ligand in 1-5-OTf (relative to that in free anion) increases in the order Ni(II) < Mn(II) < Cu(II) < Zn(II), Co(II). Previously reported 3-Hfl complexes of divalent metals fit well with this ordering. (1)H NMR studies indicate that the 3-Hfl complexes of Co(II), Ni(II), and Zn(II) exhibit a pseudo-octahedral geometry in solution. EPR studies suggest that the Mn(II) complex 1-OTf may form binuclear structures in solution. The mononuclear Cu(II) complex 4-OTf has a distorted square pyramidal geometry. The oxidation potential of the flavonolate ligand depends on the metal ion present and/or the solution structure of the complex, with the Mn(II) complex 1-OTf exhibiting the lowest potential, followed by the pseudo-octahedral Ni(II) and Zn(II) 3-Hfl complexes, and the distorted square pyramidal Cu(II) complex 4-OTf. The Mn(II) complex [(6-Ph(2)TPA)Mn(3-Hfl)]OTf (1-OTf) is unique in the series in undergoing ligand exchange reactions in the presence of M(ClO(4))(2).6H(2)O (M = Co, Ni, Zn) in CD(3)CN to produce [(6-Ph(2)TPA)M(CD(3)CN)(n)](X)(2), [Mn(3-Hfl)(2).0.5H(2)O], and MnX(2) (X = OTf(-) or ClO(4)(-)). Under similar conditions, the 3-Hfl complexes of Co(II), Ni(II), and Cu(II) undergo flavonolate ligand exchange to produce [(6-Ph(2)TPA)M(CD(3)CN)(n)](X)(2) (M = Co, Ni, Cu; n = 1 or 2) and [Zn(3-Hfl)(2).2H(2)O]. An Fe(II) complex of 3-Hfl, [(6-Ph(2)TPA)Fe(3-Hfl)]ClO(4) (8), was isolated and characterized by elemental analysis, FTIR, UV-vis, (1)H NMR, cyclic voltammetry, and a magnetic moment measurement. This complex reacts with O(2) to produce the diiron(III) mu-oxo compound [(6-Ph(2)TPAFe(3Hfl))(2)(mu-O)](ClO(4))(2) (6).

Characterization of sulfate reducing bacteria isolated from urban soil

NASA Astrophysics Data System (ADS)

Zhang, Mingliang; Wang, Haixia

2017-05-01

Sulfate reducing bacteria (SRB) was isolated from urban soil and applied for the remediation of heavy metals pollution from acid mine drainage. The morphology and physiological characteristics (e.g. pH and heavy metals tolerance) of SRB was investigated. The SRB was gram-negative bacteria, long rod with slight curve, cell size 0.5× (1.5-2.0) μm. The pH of medium had significant effect on SRB growth and the efficiency of sulfate reduction, and it showed that the suitable pH range was 5-9 and SRB could not survive at pH less than 4. The maximum tolerance of Fe (II), Zn (II), Cd (II), and Cu (II) under acidic condition (pH 5.0) was about 600 mg/L, 150 mg/L, 25 mg/L and 25 mg/L, respectively. The result indicated that SRB isolated in this study could be used for the bioremediation of acid mine drainage (pH>4) within the heavy metals concentrations tolerance.

A spectroscopic and voltammetric study of the pH-dependent Cu(II) coordination to the peptide GGGTH: relevance to the fifth Cu(II) site in the prion protein.

PubMed

Hureau, Christelle; Charlet, Laurent; Dorlet, Pierre; Gonnet, Florence; Spadini, Lorenzo; Anxolabéhère-Mallart, Elodie; Girerd, Jean-Jacques

2006-09-01

The GGGTH sequence has been proposed to be the minimal sequence involved in the binding of a fifth Cu(II) ion in addition to the octarepeat region of the prion protein (PrP) which binds four Cu(II) ions. Coordination of Cu(II) by the N- and C-protected Ac-GGGTH-NH(2) pentapeptide (P(5)) was investigated by using potentiometric titration, electrospray ionization mass spectrometry, UV-vis spectroscopy, electron paramagnetic resonance (EPR) spectroscopy and cyclic voltammetry experiments. Four different Cu(II) complexes were identified and characterized as a function of pH. The Cu(II) binding mode switches from NO(3) to N(4) for pH values ranging from 6.0 to 10.0. Quasi-reversible reduction of the [Cu(II)(P(5))H(-2)] complex formed at pH 6.7 occurs at E (1/2)=0.04 V versus Ag/AgCl, whereas reversible oxidation of the [Cu(II)(P(5))H(-3)](-) complex formed at pH 10.0 occurs at E (1/2)=0.66 V versus Ag/AgCl. Comparison of our EPR data with those of the rSHaPrP(90-231) (Burns et al. in Biochemistry 42:6794-6803, 2003) strongly suggests an N(3)O binding mode at physiological pH for the fifth Cu(II) site in the protein.

Cyclam Derivatives with a Bis(phosphinate) or a Phosphinato-Phosphonate Pendant Arm: Ligands for Fast and Efficient Copper(II) Complexation for Nuclear Medical Applications.

PubMed

David, Tomáš; Kubíček, Vojtěch; Gutten, Ondrej; Lubal, Přemysl; Kotek, Jan; Pietzsch, Hans-Jürgen; Rulíšek, Lubomír; Hermann, Petr

2015-12-21

Cyclam derivatives bearing one geminal bis(phosphinic acid), -CH2PO2HCH2PO2H2 (H2L(1)), or phosphinic-phosphonic acid, -CH2PO2HCH2PO3H2 (H3L(2)), pendant arm were synthesized and studied as potential copper(II) chelators for nuclear medical applications. The ligands showed good selectivity for copper(II) over zinc(II) and nickel(II) ions (log KCuL = 25.8 and 27.7 for H2L(1) and H3L(2), respectively). Kinetic study revealed an unusual three-step complex formation mechanism. The initial equilibrium step leads to out-of-cage complexes with Cu(2+) bound by the phosphorus-containing pendant arm. These species quickly rearrange to an in-cage complex with cyclam conformation II, which isomerizes to another in-cage complex with cyclam conformation I. The first in-cage complex is quantitatively formed in seconds (pH ≈5, 25 °C, Cu:L = 1:1, cM ≈ 1 mM). At pH >12, I isomers undergo nitrogen atom inversion, leading to III isomers; the structure of the III-[Cu(HL(2))] complex in the solid state was confirmed by X-ray diffraction analysis. In an alkaline solution, interconversion of the I and III isomers is mutual, leading to the same equilibrium isomeric mixture; such behavior has been observed here for the first time for copper(II) complexes of cyclam derivatives. Quantum-chemical calculations showed small energetic differences between the isomeric complexes of H3L(2) compared with analogous data for isomeric complexes of cyclam derivatives with one or two methylphosphonic acid pendant arm(s). Acid-assisted dissociation proved the kinetic inertness of the complexes. Preliminary radiolabeling of H2L(1) and H3L(2) with (64)Cu was fast and efficient, even at room temperature, giving specific activities of around 70 GBq of (64)Cu per 1 μmol of the ligand (pH 6.2, 10 min, ca. 90 equiv of the ligand). These specific activities were much higher than those of H3nota and H4dota complexes prepared under identical conditions. The rare combination of simple ligand synthesis, very fast copper(II) complex formation, high thermodynamic stability, kinetic inertness, efficient radiolabeling, and expected low bone tissue affinity makes such ligands suitably predisposed to serve as chelators of copper radioisotopes in nuclear medicine.

Accurate Quantitative Sensing of Intracellular pH based on Self-ratiometric Upconversion Luminescent Nanoprobe.

PubMed

Li, Cuixia; Zuo, Jing; Zhang, Li; Chang, Yulei; Zhang, Youlin; Tu, Langping; Liu, Xiaomin; Xue, Bin; Li, Qiqing; Zhao, Huiying; Zhang, Hong; Kong, Xianggui

2016-12-09

Accurate quantitation of intracellular pH (pH i ) is of great importance in revealing the cellular activities and early warning of diseases. A series of fluorescence-based nano-bioprobes composed of different nanoparticles or/and dye pairs have already been developed for pH i sensing. Till now, biological auto-fluorescence background upon UV-Vis excitation and severe photo-bleaching of dyes are the two main factors impeding the accurate quantitative detection of pH i . Herein, we have developed a self-ratiometric luminescence nanoprobe based on förster resonant energy transfer (FRET) for probing pH i , in which pH-sensitive fluorescein isothiocyanate (FITC) and upconversion nanoparticles (UCNPs) were served as energy acceptor and donor, respectively. Under 980 nm excitation, upconversion emission bands at 475 nm and 645 nm of NaYF 4 :Yb 3+ , Tm 3+ UCNPs were used as pH i response and self-ratiometric reference signal, respectively. This direct quantitative sensing approach has circumvented the traditional software-based subsequent processing of images which may lead to relatively large uncertainty of the results. Due to efficient FRET and fluorescence background free, a highly-sensitive and accurate sensing has been achieved, featured by 3.56 per unit change in pH i value 3.0-7.0 with deviation less than 0.43. This approach shall facilitate the researches in pH i related areas and development of the intracellular drug delivery systems.

A Fe(II)/citrate/UV/PMS process for carbamazepine degradation at a very low Fe(II)/PMS ratio and neutral pH: The mechanisms.

PubMed

Ling, Li; Zhang, Dapeng; Fan, Chihhao; Shang, Chii

2017-11-01

A novel Fe(II)/citrate/UV/PMS process for degrading a model micropollutant, carbamazepine (CBZ), at a low Fe(II)/PMS ratio and neutral pH has been proposed in this study, and the mechanisms of radical generation in the system was explored. With a UV dose of 302.4 mJ/cm 2 , an initial pH of 7, and CBZ, PMS, Fe(II) and citrate at initial concentrations of 10, 100, 12 and 26 μM, respectively, the CBZ degradation efficiency reached 71% in 20 min in the Fe(II)/citrate/UV/PMS process, which was 4.7 times higher than that in either the citrate/UV/PMS or Fe(II)/citrate/PMS process. The enhanced CBZ degradation in the Fe(II)/citrate/UV/PMS process was mainly attributed to the continuous activation of PMS by the UV-catalyzed regenerated Fe(II) from a Fe(III)-citrate complex, [Fe 3 O(cit) 3 H 3 ] 2- , which not only maintained Fe(III) soluble at neutral pH, but also increased 6.6 and 2.6 times of its molar absorbance and quantum yield as compared to those of ionic Fe(III), respectively. In the Fe(II)/citrate/UV/PMS process, the SO 4 •- produced from the fast reaction between PMS and the initially-added Fe(II) contributed 11% of CBZ degradation. The PMS activation by the UV radiation and regenerated Fe(II) contributed additional 14% and 46% of CBZ removal, respectively. The low iron and citrate doses and the fast radical generation at neutral pH make the Fe(II)/citrate/UV/PMS process suitable for degrading recalcitrant organic compounds in potable water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of pH and Fe/U ratio on the U(VI) removal rate by the synergistic effect of Fe(II) and O2

NASA Astrophysics Data System (ADS)

Fu, Yukui; Luo, Yingfeng; Fang, Qi; Xie, Yanpei; Wang, Zhihong; Zhu, Xiangyu

2018-02-01

As for the decommissioned uranium deposits of acid in-situ leaching, both of the concentrations of U(VI) and Fe(II) are relatively high in groundwater. In the presence of O2, the oxidation of Fe(II) into Fe(III) that forms Fe-hydroxides could effectively remove U(VI) in the forms of sorption or co-precipitation. In this process, pH condition and Fe content will have a significant effect on the U(VI) removal rate by the synergistic effect of Fe(II) and O2. In the present work, a series of batch experiments were carried out to investigate the effect of pH values and Fe/U mass ratio on the U(VI) removal rate by the synergistic effect of Fe(II) and O2. Experiment results show that the removal rate of U(VI) is mainly controlled by pH and secondly by Fe/U mass ratio. In the neutral conditions with pH at 7 and 8, the removal rate of U(VI) reaches up to 90% for all solutions with different initial Fe(II) concentrations. The optimal pH for the removal rate of U(VI) is above 7. In the acidic conditions with pH below 6, the effect of Fe/U mass ratio on the removal rate of U(VI) becomes more obvious and the optimal Fe/U mass ratio for U(VI) removal is 1:2.

Synthesis, characterization and cytotoxic properties of platinum(II) complexes containing the nucleosides adenosine and cytidine.

PubMed

Montagner, Diego; Gandin, Valentina; Marzano, Cristina; Longato, Bruno

2011-06-01

Cytidine (cyt) and adenosine (ado) react with cis-[L(2)Pt(μ-OH)](2)(NO(3))(2) (L=PMe(3), PPh(3)) in various solvents to give the nucleoside complexes cis-[L(2)Pt{cyt(-H),N(3)N(4)}](3)(NO(3))(3) (L=PMe(3), 1),cis-[L(2)Pt{cyt(-H),N(4)}(cyt,N(3))]NO(3) (L=PPh(3), 2), cis-[L(2)Pt{ado(-H),N(1)N(6)}](2)(NO(3))(2) (L=PMe(3), 3) and cis-[L(2)Pt{ado(-H),N(6)N(7)}]NO(3) (L=PPh(3), 4). When the condensation reaction is carried out in solution of nitriles (RCN, R=Me, Ph) the amidine derivatives cis-[(PPh(3))(2)PtNH=C(R){cyt(-2H)}]NO(3) (R=Me, 5a; R=Ph, 5b) and cis-[(PPh(3))(2)PtNH=C(R){ado(-2H)}]NO(3) (R=Me, 6a: R=Ph, 6b) are quantitatively formed. The coordination mode of these nucleosides, characterized in solution by multinuclear NMR spectroscopy and mass spectrometry, is similar to that previously observed for the nucleobases 1-methylcytosine (1-MeCy) and 9-methyladenine (9-MeAd). The cytotoxic properties of the new complexes, and those of the nucleobase analogs, cis-[(PPh(3))(2)PtNH=C(R){1-MeCy(-2H)}]NO(3) (R=Me, 7a: R=Ph, 7b), cis-[(PPh(3))(2)PtNH=C(R){9-MeAd(-2H)}]NO(3) (R=Me, 8a: R=Ph, 8b) have been investigated in a wide panel of human cancer cells. Interestingly, whereas the Pt(II) nucleoside complexes (1-4) did not show appreciable cytotoxicity, the corresponding amidine derivatives (7a, 7b, 8a, 8b, 5b, and 6b) exhibited a significant in vitro antitumor activity. Copyright © 2011 Elsevier Inc. All rights reserved.

pH Dependent Spin State Population and 19F NMR Chemical Shift via Remote Ligand Protonation in an Iron(II) Complex (Postprint)

DTIC Science & Technology

2017-12-11

AFRL-RX-WP-JA-2017-0501 pH- DEPENDENT SPIN STATE POPULATION AND 19F NMR CHEMICAL SHIFT VIA REMOTE LIGAND PROTONATION IN AN IRON(II...From - To) 16 November 2017 Interim 24 January 2014 – 16 October 2017 4. TITLE AND SUBTITLE PH- DEPENDENT SPIN STATE POPULATION AND 19F NMR CHEMICAL...dx.doi.org/10.1039/C7CC08099A 14. ABSTRACT (Maximum 200 words) An FeII complex that features a pH- dependent spin state population, by virtue of a

Stability of urea in solution and pharmaceutical preparations.

PubMed

Panyachariwat, Nattakan; Steckel, Hartwig

2014-01-01

The stability of urea in solution and pharmaceutical preparations was analyzed as a function of temperature (25°-60°C), pH (3.11-9.67), and initial urea concentration (2.5%-20%). This study was undertaken to (i) obtain more extensive, quantitative information relative to the degradation of urea in both aqueous and non-aqueous solutions and in pharmaceutical preparations, and (ii) test the effects of initial urea concentration, pH, buffer, and temperature values on urea degradation. The stability analysis shows that urea is more stable at the pH range of 4-8 and the stability of urea decreases by increase in temperature for all pH values. Within the experimental range of temperature and initial urea concentration values, the lowest urea degradation was found with lactate buffer pH 6.0. The urea decomposition rate in solution and pharmaceutical preparations shows the dependence of the initial urea concentrations. At higher initial urea concentrations, the rate of degradation is a decreasing function with time. This suggests that the reverse reaction is a factor in the degradation of concentrated urea solution. For non-aqueous solvents, isopropanol showed the best effort in retarding the decomposition of urea. Since the losses in urea is directly influenced by its stability at a given temperature and pH, the stability analysis of urea by the proposed model can be used to prevent the loss and optimize the operating condition for urea-containing pharmaceutical preparations.

Finite Element-Galerkin Approximation of the Eigenvalues of Eigenvectors of Selfadjoint Problems

DTIC Science & Technology

1988-07-01

l’ "k, + 1. Combining (3.20), (3.22), and the fact that I-Eh(Ak ) and Ph are orthogonal projections we have I(I-Eh(Xk,)) PhUB 5 Si (I-Eh(xk)) PhT(Ph-I...Its adjoint are equal. (3.23) implies Hf(I-Eh(1kI )Ph)u{1B - P(IPh)UIBI 5 I(I-Eh(Ak )) PhuB -< d i ii ( Ph- I )T II H B_--H,3 1(P h- I ) u liB , and

Mechanistic insights into iron redox transformations in the presence of natural organic matter: Impact of pH and light

NASA Astrophysics Data System (ADS)

Garg, Shikha; Jiang, Chao; David Waite, T.

2015-09-01

The various pathways contributing to the formation and decay of Fe(II) in the presence of Suwanee River Fulvic Acid (SRFA) in acidic solutions are investigated here both in the presence and absence of light and over the pH range of 3-5. Our results show that ligand to metal charge transfer (LMCT) is the dominant pathway for photochemical Fe(III) reduction and resultant Fe(II) formation over the pH range examined. In comparison, under non-irradiated conditions, Fe(III) reduction occurs, for the most part, as a result of the presence of hydroquinone-like moieties in SRFA. Irradiation of SRFA also results in the generation of both long-lived and short-lived Fe(II) oxidants with the long-lived Fe(II) oxidant similar to semiquinone-like radicals with these radicals formed via superoxide-mediated oxidation of the hydroquinone-like moieties present in SRFA. Dioxygen plays an important role in production of the long-lived Fe(II) oxidant since generation of superoxide occurs via reduction of dioxygen. The short-lived Fe(II) oxidant is similar to peroxyl radicals which are generated via hydroxylation of organic moieties. The overall rate of generation of both the short- and long-lived Fe(II) oxidants is dependent on pH with the generation rates of these oxidants increasing with increase in pH. Based on our experimental data, we have developed a kinetic model that satisfactorily describes all Fe transformations observed in SRFA solutions over the pH range 3-5 under non-irradiated, previously irradiated and continuously irradiated conditions. Fe species undergo continual cycling between Fe(II) and Fe(III) oxidation states with Fe(II)-Fe(III) turnover frequencies in the presence of 10 mg.L-1 SRFA of 17.3, 27.4 and 33.2 h-1 at pH 3, 3.5 and 4 on continuous photolysis compared to turnover frequencies of 1.9, 2.5 and 2.9 h-1 at pH 3, 3.5 and 4 in the dark.

Joint neutron crystallographic and NMR solution studies of Tyr residue ionization and hydrogen bonding: Implications for enzyme-mediated proton transfer

PubMed Central

Michalczyk, Ryszard; Unkefer, Clifford J.; Bacik, John-Paul; Schrader, Tobias E.; Ostermann, Andreas; Kovalevsky, Andrey Y.; McKenna, Robert; Fisher, Suzanne Zoë

2015-01-01

Human carbonic anhydrase II (HCA II) uses a Zn-bound OH−/H2O mechanism to catalyze the reversible hydration of CO2. This catalysis also involves a separate proton transfer step, mediated by an ordered solvent network coordinated by hydrophilic residues. One of these residues, Tyr7, was previously shown to be deprotonated in the neutron crystal structure at pH 10. This observation indicated that Tyr7 has a perturbed pKa compared with free tyrosine. To further probe the pKa of this residue, NMR spectroscopic measurements of [13C]Tyr-labeled holo HCA II (with active-site Zn present) were preformed to titrate all Tyr residues between pH 5.4–11.0. In addition, neutron studies of apo HCA II (with Zn removed from the active site) at pH 7.5 and holo HCA II at pH 6 were conducted. This detailed interrogation of tyrosines in HCA II by NMR and neutron crystallography revealed a significantly lowered pKa of Tyr7 and how pH and Tyr proximity to Zn affect hydrogen-bonding interactions. PMID:25902526

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

NASA Astrophysics Data System (ADS)

Wilson, Jessica M.; Farley, Kevin J.; Carbonaro, Richard F.

2018-03-01

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N‧,N‧-tetraacetic acid (TMDTA) was investigated over the pH range 5.50-8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4-5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2- and FeII(H)L- to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2-. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation rates at higher pH. Finally, this work demonstrates that the rate of FeII oxidation is very sensitive to the identity and structure of the polyaminocarboxylate chelating agent, which has implications for any metal or organic chemical that reacts either directly or indirectly with iron.

N2O production in the Fe(II)(EDTA)-NO reduction process: the effects of carbon source and pH.

PubMed

Chen, Jun; Wang, Lei; Zheng, Ji; Chen, Jianmeng

2015-07-01

Chemical absorption-biological reduction (BioDeNOx), which uses Fe(II)(EDTA) as a complexing agent for promoting the mass transfer efficiency of NO from gas to water, is a promising technology for removing nitric oxide (NO) from flue gases. The carbon source and pH are important parameters for Fe(II)(EDTA)-NO (the production of absorption) reduction and N2O emissions from BioDeNOx systems. Batch tests were performed to evaluate the effects of four different carbon sources (i.e., methanol, ethanol, sodium acetate, and glucose) on Fe(II)(EDTA)-NO reduction and N2O emissions at an initial pH of 7.2 ± 0.2. The removal efficiency of Fe(II)(EDTA)-NO was 93.9%, with a theoretical rate of 0.77 mmol L(-1) h(-1) after 24 h of operation. The highest N2O production was 0.025 mmol L(-1) after 3 h when glucose was used as the carbon source. The capacities of the carbon sources to enhance the activity of the Fe(II)(EDTA)-NO reductase enzyme decreased in the following order based on the C/N ratio: glucose > ethanol > sodium acetate > methanol. Over the investigated pH range of 5.5-8.5, the Fe(II)(EDTA)-NO removal efficiency was highest at a pH of 7.5, with a theoretical rate of 0.88 mmol L(-1) h(-1). However, the N2O production was lowest at a pH of 8.5. The primary effect of pH on denitrification resulted from the inhibition of nosZ in acidic conditions.

Identification of prolyl carboxypeptidase as an alternative enzyme for processing of renal angiotensin II using mass spectrometry

PubMed Central

Grobe, Nadja; Weir, Nathan M.; Leiva, Orly; Ong, Frank S.; Bernstein, Kenneth E.; Schmaier, Alvin H.; Morris, Mariana

2013-01-01

Angiotensin-converting enzyme 2 (ACE2) catalyzes conversion of ANG II to ANG-(1–7). The present study uses newly established proteomic approaches and genetic mouse models to examine the contribution of alternative renal peptidases to ACE2-independent formation of ANG-(1–7). In situ and in vitro mass spectrometric characterization showed that substrate concentration and pH control renal ANG II processing. At pH ≥6, ANG-(1–7) formation was significantly reduced in ACE2 knockout (KO) mice. However, at pH <6, formation of ANG-(1–7) in ACE2 KO mice was similar to that in wild-type (WT) mice, suggesting alternative peptidases for renal ANG II processing. Furthermore, the dual prolyl carboxypeptidase (PCP)-prolyl endopeptidase (PEP) inhibitor Z-prolyl-prolinal reduced ANG-(1–7) formation in ACE2 KO mice, while the ACE2 inhibitor MLN-4760 had no effect. Unlike the ACE2 KO mice, ANG-(1–7) formation from ANG II in PEP KO mice was not different from that in WT mice at any tested pH. However, at pH 5, this reaction was significantly reduced in kidneys and urine of PCP-depleted mice. In conclusion, results suggest that ACE2 metabolizes ANG II in the kidney at neutral and basic pH, while PCP catalyzes the same reaction at acidic pH. This is the first report demonstrating that renal ANG-(1–7) formation from ANG II is independent of ACE2. Elucidation of ACE2-independent ANG-(1–7) production pathways may have clinically important implications in patients with metabolic and renal disease. PMID:23392115

Reduction kinetics of hexavalent chromium in soils and its correlation with soil properties.

PubMed

Xiao, Wendan; Zhang, Yibin; Li, Tingqiang; Chen, Bao; Wang, Huan; He, Zhenli; Yang, Xiaoe

2012-01-01

The toxicity of chromium (Cr) to biota is related to its chemical forms and consequently to the redox conditions of soils. Hexavalent Cr[Cr(VI)] may undergo natural attenuation through reduction processes. In this study, the reduction kinetics of Cr(VI) in seven soils and its relationships with soil properties were investigated with laboratory incubation experiments. The results indicate that the reduction of Cr(VI) can be described by a first-order reaction. The reduction rates of Cr(VI) in the seven soils decreased in the order: Udic Ferrisols > Stagnic Anthrosols > Calcaric Regosols > Mollisol > Typic Haplustalf > Periudic Argosols > Ustic Cambosols. Simple correlation analysis revealed that the reduction of Cr(VI) in soils was positively related to organic matter content, dissolved organic matter content, Fe(II) content, clay fraction, and to the diversity index of the bacterial community but negatively correlated with easily reducible Mn content. Using stepwise regression, the reduction of Cr(VI) in soil could be quantitatively predicted by the measurement of dissolved organic matter content, Fe(II) content, pH, and soil particle size distribution, with a fitting level of 95.5%. The results indicated that the reduction of Cr(VI) in natural soils is not controlled by a single soil property but is the result of the combined effects of dissolved organic matter, Fe(II), pH, and soil particle size distribution. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Cadmium(II) and lead(II) adsorption onto hetero-atom functional mesoporous silica and activated carbon

NASA Astrophysics Data System (ADS)

Machida, Motoi; Fotoohi, Babak; Amamo, Yoshimasa; Mercier, Louis

2012-07-01

Adsorption of cadmium(II) and lead(II) on amino-, mercapto-functionalized mesoporous silica (HMS) and carboxylic-functionalized activated carbon (AC) were examined. The resultant isotherms fitted the Langmuir model and amino-functionalized HMS exhibited the highest adsorption capacity for both cadmium(II) and lead(II). Adsorption affinities for cadmium(II) were always greater than those for lead(II) in all three adsorbent types, while the difference between the two values was the largest for mercapto-functionalized HMS indicating a selective adsorption of cadmium(II). Influence of equilibrium solution pH on adsorption of cadmium(II), lead(II) and their binary mixtures was also studied. Carboxylic-functionalized AC adsorbed cadmium(II) and lead(II) in a wide pH range than conditions for the mercapto-functionalized HMS. It was concluded that each functional group had its own characteristics and advantages for adsorption of heavy metal ions; amino-groups showed high adsorption capacity, while mercapto-groups had good selectivity toward cadmium(II) adsorption and a wide solution pH in adsorption by carboxylic-groups were established in this study.

Potential of sawdust as a green and economical sorbent for simultaneous preconcentration of trace amounts of cadmium, cobalt, and lead from water, biological, food, and herbal samples.

PubMed

Baki, Mostafa Hossein; Shemirani, Farzaneh; Khani, Rouhollah

2013-05-01

Application of treated sawdust with NaOH as a green and economical sorbent for simultaneous preconcentration of trace amounts of Cd(II), Co(II), and Pb(II) ions from liver, lettuce, fish, and water as test samples with complicated matrices was investigated. Various parameters, such as effect of pH and contact time, breakthrough volume, type, and concentration of eluent and interference of ions were studied. The sorption was quantitative in the pH of 5.0 to 7.0 and desorption occurred instantaneously with 5.0 mL of mixed solutions of ethanol and 2.0 mol/L HNO3 -HCl and the amount of ions was measured by using flame atomic absorption spectrometry. Linearity was maintained at 3 to 500 μg/L for cobalt, 5.0 to 800 μg/L for lead, and 2.0 to 300 μg/L for cadmium in the original solution. The relative standard deviation was less than 1.80% (n = 6, with concentration of 0.3 mg/L for cadmium and 0.5 mg/L for lead and cobalt). Detection limits and maximum capacity of the sorbent for Co (II), Cd (II), and Pb (II) in the original solution were 0.86, 0.50, and 1.7 μg/L and 28.5, 30.6, and 47.3 mg/g, respectively. The results for spiked real samples, effect of interfering ions, and adsorption capacity indicated that the applicability of this method for lead preconcentration is better than cadmium and cobalt preconcentration from complicated matrices. Practical Application: Sawdust can be applied as a green and economical sorbent for simultaneous preconcentration and solid-phase extraction of metal ions from food and environmental samples with complicated matrices. © 2013 Institute of Food Technologists®

Immobilization of methylene blue onto bentonite and its application in the extraction of mercury (II).

PubMed

Hassanien, Mohamed M; Abou-El-Sherbini, Khaled S; Al-Muaikel, Nayef S

2010-06-15

Methylene blue was immobilized onto bentonite (BNT). The modified clay (MB-BNT) was used to extract Hg(2+) at pH 6.0 yielding Hg-MB-BNT. BNT, MB-BNT and Hg-MB-BNT were characterized by X-ray diffractometry, infrared spectra, and elemental and thermogravimetric analyses. MB is suggested to be intercalated into the major phase of BNT; montmorillonite mineral (MMT), lying parallel to the aluminosilicate layers, with a capacity of 36 mequiv./100g. MB-BNT shows good stability in 0.1-1M hydrochloric or nitric acids, ammonium hydroxide, and concentrated Na(+), K(+) or NH(4)(+) chlorides or iodides. It shows good selectivity towards Hg(2+) with an extraction capacity of 37 mequiv./100g in the presence of I(-) giving rise to a ratio of MB/Hg(2+)/I(-) 1:1:3 in the clay phase. Extracted Hg(2+) could be quantitatively recovered by ammonia buffer at pH 8.5. MB-BNT was successfully applied to recover Hg(2+) from spiked natural water and cinnabar mineral samples using the optimum conditions; pH 6.0, time of stirring 10 min and 10 mL of 0.05 M NH(4)Cl/NH(4)OH at pH 8.5 as eluent. Copyright 2010 Elsevier B.V. All rights reserved.

A study on the bacterial photo-toxicity of phenothiazinium based photosensitisers.

PubMed

Sayed, Zia; Harris, Frederick; Phoenix, David A

2005-03-01

"Comet assay" showed light activated (3.15 Jcm-2 over 30 min) phenothiazinium based photosensitisers (PhBPs) to induce photo-damage of Staphylococcus aureus DNA, as indicated by DNA "tails" between 80 and 120 microm. In general, PhBPs exhibited significant singlet oxygen yields (Phi(DeltaPhBP)>0.7), suggesting the use of type II mechanisms of photo-oxidation. However, the photodynamic action of PhBPs on DNA showed generally insignificant production of 7,8-dihydro-8-oxo-2'-deoxyguanosine, normally a major product of type II DNA photo-oxidation. These combined results show DNA to be a major site of action of PhBPs and suggest that this action may involve type II attack on a nucleoside(s) other than guanosine.

Green Preconcentration of Trace Amounts of Copper from Water and Food Samples onto Novel Organo-Nanoclay Prior to Flame Atomic Absorption Spectrometry.

PubMed

Beyki, Mostafa Hossein; Shemirani, Farzaneh; Khani, Rouhollah

2014-01-01

In this work, the nanoclay was intercalated with acyclovir (9-[(2-hydroxyethoxy) methyl] guanine), the toxicity of which to mammalian cells is very low. We used no organic solvents for preparation of modified clay and desorption of Cu ions from the sorbent. Batch and column methods were used, and sorption of Cu was quantitative (>98%) in the pH range of 7.5 to 10.0. Quantitative desorption occurred with 5.0 mL of 3.0 M HCl, and the amount of Cu(II) was measured by using flame atomic absorption spectrometry. In the initial solution the linear dynamic range and the LOD were 3.0-1000.0 and 0.58 μg/L, respectively. With 500.0 mL of sample, an enrichment factor of 100 was obtained. The RSD was 2.0% (n = 8, concentration = 0.5 mg/L), and the maximum capacity of the sorbent was 45.0 mg/g. The influence of experimental parameters including sample pH, ionic strength, type and volume of the eluent, and interference of some ions on the recoveries of Cu was investigated. The proposed method using a new and easier prepared solid sorbent was applied to the determination of Cu in different real samples with satisfactory results.

Associations among Gastric Juice pH, Atrophic Gastritis, Intestinal Metaplasia and Helicobacter pylori Infection.

PubMed

Sung, Jihee; Kim, Nayoung; Lee, Jongchan; Hwang, Young-Jae; Kim, Hyoung Woo; Chung, Jung Wha; Kim, Jin-Wook; Lee, Dong Ho

2018-03-15

Gastric juice plays a crucial role in the physiology of the stomach. The aim of this study is to evaluate associations among the pH of gastric juice, atrophic gastritis (AG), intestinal metaplasia (IM), pepsinogen, and Helicobacter pylori infection. Gastric biopsies and juice were collected from 46 subjects who underwent endoscopies at Seoul National University Bundang Hospital between November 2011 and March 2013. H. pylori , AG and IM were evaluated, and pepsinogen I or II, I/II ratio, and interleukin (IL)-1β levels were measured. The mean pH of gastric juice was higher in the H. pylori -positive group (n=17) than that in the H. pylori -negative group (n=29) (4.54 vs 2.46, p=0.002). When patients were divided into pH ＜3 (n=28) and pH ≥3 (n=18) groups, H. pylori was lower in the pH ＜3 group (21.4%) than in the pH ≥3 group (61.1%) (p=0.007). The pH ≥3 group demonstrated AG and IM more frequently than the pH ＜3 group in the body (p=0.047 and p=0.051, respectively) but not in the antrum. There were no differences in pepsinogen I or II, I/II ratio, and IL-1β levels between the two groups. There is a relationship between chronic H. pylori infection and gastric juice pH ≥3, which may originate from AG and IM in the body.

Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine.

PubMed

Mohamed, Gehad G; El-Gamel, Nadia E A

2004-11-01

The ternary piroxicam (Pir; 4-hydroxy-2-methyl-N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA chelates were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

Synthesis, investigation and spectroscopic characterization of piroxicam ternary complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with glycine and DL-phenylalanine

NASA Astrophysics Data System (ADS)

Mohamed, Gehad G.; El-Gamel, Nadia E. A.

2004-11-01

The ternary piroxicam (Pir; 4-hydroxy-2-methyl- N-(2-pyridyl)-2H-1,2-benzothiazine-3-carboxamide 1,1-dioxide) complexes of Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with various amino acids (AA) such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized by elemental analyses, molar conductance, IR, UV-Vis, magnetic moment, diffuse reflectance and X-ray powder diffraction. The UV-Vis spectra of Pir and the effect of metal chelation on the different interligand transitions are discussed in detailed manner. IR and UV-Vis spectra confirm that Pir behaves as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its carboxylic group, in addition PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its carboxylic and amino groups. All the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. The molar conductance data reveal that most of these chelates are non electrolytes, while Fe(III)-Pir-Gly, Co(II)-, Ni(II)-, Cu(II)- and Zn(II)-Pir-PhA cheletes were 1:1 electrolytes. X-ray powder diffraction is used as a new tool to estimate the crystallinity of chelates as well as to elucidate their geometrical structures.

Determination of bromhexine in plasma by reversed-phase liquid chromatography. Interference of lipoproteins on extraction.

PubMed

Johansson, M; Lenngren, S

1988-11-18

Extraction of the hydrophobic tertiary amine bromhexine from plasma using cyclohexane-heptafluorobutanol (99.5:0.5, v/v) was studied at different pH values. The extraction yield from buffer solutions was quantitative at pH greater than 4.1, but from plasma the extraction yield decreased with increasing pH. Furthermore, at pH 8.4 the extraction yield varied greatly (56-99%) in different human plasma. The addition of lipoproteins to phosphate buffer, at pH 8.1, decreased the extraction yields considerably. Quantitative extraction from plasma was obtained by using a very long extraction time at pH 8.4 or by decreasing the pH to 5.4. The chromatographic system consisted of a reversed-phase column (Nucleosil C18, 5 microns) with an acidic mobile phase (methanol-phosphate buffer, pH 2) containing an aliphatic tertiary amine. UV detection at 308 or 254 nm was used. The limit of quantitation was 5 ng/ml using 3.00 ml of plasma and detection at 254 nm. The intra-assay precision for bromhexine was better than 3.6% at 5 ng/ml.

Solid-phase extraction of heavy metal ions on bucky tubes disc in natural water and herbal plant samples.

PubMed

Soylak, Mustafa; Unsal, Yunus Emre

2011-10-01

A preconcentration-separation procedure has been established based on solid-phase extraction of Fe(III) and Pb(II) on bucky tubes (BTs) disc. Fe(III) and Pb(II) ions were quantitatively recovered at pH 6. The influences of the analytical parameters like sample volume, flow rates on the recoveries of analytes on BT disc were investigated. The effects of co-existing ions on the recoveries were also studied. The detection limits for iron and lead were found 1.6 and 4.9 μg L⁻¹, respectively. The validation of the presented method was checked by the analysis of TMDA-51.3 fortified water certified reference material. The presented procedure was successfully applied to the separation-preconcentration and determination of iron and lead content of some natural water and herbal plant samples from Kayseri, Turkey.

A Trinuclear Ni(II) Enediolate Complex: Synthesis, Characterization, and O2 Reactivity

PubMed Central

Arif, Atta M.; Berreau, Lisa M.

2009-01-01

Using a new N4-donor chelate ligand having a mixture of hydrophobic phenyl and hydrogen bond donor appendages, a trinuclear Ni(II) complex of the doubly deprotonated form of 2-hydroxy-1,3-diphenylpropane-1,3-dione was isolated, characterized (X-ray crystallography, elemental analysis, UV-vis, 1H NMR, FTIR, magnetic moment measurement), and evaluated for O2 reactivity. This complex, [(6-NA-6-Ph2TPANi)2(μ-PhC(O)C(O)C(O)Ph)2Ni](ClO4)2 (4), has two terminal pseudo octahedral Ni(II) centers supported by the tetradentate chelate ligand, and a central square planar Ni(II) ion ligated by oxygen atoms of two bridging enediolate ligands. In CH3CN, 4 exhibits a deep orange/brown color and λmax = 463 nm (ε = 16,000 M-1cm-1). The room temperature magnetic moment of 4, determined by Evans method, is μeff = 5.3(2) μB. This is consistent with the presence of two non-interacting high-spin Ni(II) centers, a diamagnetic central Ni(II) ion, and an overall quintet ground state. Exposure of a CH3CN solution of 4 to O2 results in the rapid loss of the orange/brown color to give a green solution. The products identified from this reaction are [(κ3-6-NA-6-Ph2TPA)Ni(O2Ph)(H2O)]ClO4 (5), benzil (PhC(O)C(O)Ph), and CO. Identification of 5 was achieved via its independent synthesis and comparison of its 1H NMR and mass spectral features with those of the 6-NA-6-Ph2TPA-containing product generated upon reaction of 4 with O2. The independently prepared sample of 5 was characterized by X-ray crystallography, elemental analysis, UV-vis, mass spectrometry, and FTIR. The O2 reactivity of 4 has relevance to the active site chemistry of Ni(II)-containing acireductone dioxygenase (Ni(II)-ARD). PMID:18959363

Desorption of Mercury(II) on Kaolinite in the Presence of Oxalate or Cysteine

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

Senevirathna, W. U.; Zhang, Hong; Gu, Baohua

2011-01-01

Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio- uptake of Hg in aquatic systems. We studied the desorption of Hg(II) on kaolinite in the presence of oxalate or cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, 7), ligand concentration (0.25, 1.0 mM), and temperature (15, 25, 35 C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH-dependant. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed atmore » pH 3 within 2 h, compared to <10% at pH 7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80 min with the desorption less than 20%, but it appeared to enhance the Hg(II) desorption afterwards. The effect of ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particles and in the solution probably can also affect the Hg(II) desorption.« less

Schwertmannite stability in anoxic Fe(II)-rich aqueous solution

NASA Astrophysics Data System (ADS)

Paikaray, Susanta; Schröder, Christian; Peiffer, Stefan

2017-11-01

Schwertmannite (SHM) is a powerful scavenger for As(III) leading to As(III)-enriched precipitates around acid mine drainage environments that may become exposed to aqueous Fe(II). In this study we have investigated the stability of pure SHM and SHM containing 0.92 wt% As(III) under Fe(II)aq-rich (0.4-1.0 mM) anoxic conditions using XRD, SEM, Mössbauer and FTIR spectroscopic techniques. Schwertmannite transformation proceeded through an alkalinity-driven pathway releasing sulfate and a Fe(II)-catalyzed pathway that generated lepidocrocite and goethite at pH 6 and 6.9 in the presence of 1 mM Fe(II)aq. Lepidocrocite was found to be needle shaped if the SHM contained As(III) and platy for pure SHM. Goethite had a poor degree of crystallinity in As(III) containing SHM. Pre-adsorption of As(III) inhibited the extent of SHM transformation. Fe(II) sorption onto SHM was pH dependent and reflected a sorption edge with complete consumption at pH 6.9, while only ∼20% were adsorbed at pH 5. Surface coverage with Fe(II) appears to be the key parameter controlling extent and products of the transformation process. As(III) concentrations in solution are controlled by two mechanisms: (1) exchange of As(III) for sulfate upon alkalinity-driven transformation of schwertmannite and (2) re-adsorption to new phases formed upon Fe(II)-catalyzed transformation. The adsorbed As(III) has inhibited the extent of transformation and was partly released with the maximum release at pH 5 (0.5%) in the absence of Fe(II)aq.

Effect of amino acid sequence and pH on nanofiber formation of self-assembling peptides EAK16-II and EAK16-IV.

PubMed

Hong, Yooseong; Legge, Raymond L; Zhang, S; Chen, P

2003-01-01

Atomic force microscopy (AFM) and axisymmetric drop shape analysis-profile (ASDA-P) were used to investigate the mechanism of self-assembly of peptides. The peptides chosen consisted of 16 alternating hydrophobic and hydrophilic amino acids, where the hydrophilic residues possess alternating negative and positive charges. Two types of peptides, AEAEAKAKAEAEAKAK (EAK16-II) and AEAEAEAEAKAKAKAK (EAK16-IV), were investigated in terms of nanostructure formation through self-assembly. The experimental results, which focused on the effects of the amino acid sequence and pH, show that the nanostructures formed by the peptides are dependent on the amino acid sequence and the pH of the solution. For pH conditions around neutrality, one of the peptides used in this study, EAK16-IV, forms globular assemblies and has lower surface tension at air-water interfaces than another peptide, EAK16-II, which forms fibrillar assemblies at the same pH. When the pH is lowered below 6.5 or raised above 7.5, there is a transition from globular to fibrillar structures for EAK16-IV, but EAK16-II does not show any structural transition. Surface tension measurements using ADSA-P showed different surface activities of peptides at air-water interfaces. EAK16-II does not show a significant difference in surface tension for the pH range between 4 and 9. However, EAK16-IV shows a noticeable decrease in surface tension at pH around neutrality, indicating that the formation of globular assemblies is related to the molecular hydrophobicity.

Copper(II) directs formation of toxic amorphous aggregates resulting in inhibition of hen egg white lysozyme fibrillation under alkaline salt-mediated conditions.

PubMed

Ghosh, Sudeshna; Pandey, Nitin K; Banerjee, Priyanka; Chaudhury, Koel; Nagy, Nóra Veronika; Dasgupta, Swagata

2015-01-01

Hen egg white lysozyme (HEWL) adopts a molten globule-like state at high pH (~12.75) and is found to form amyloid fibrils at alkaline pH. Here, we report that Cu(II) inhibits self-association of HEWL at pH 12.75 both at 37 and 65 °C. A significant reduction in Thioflavin T fluorescence intensity, attenuation in β-sheet content and reduction in hydrophobic exposure were observed with increasing Cu(II) stoichiometry. Electron paramagnetic resonance spectroscopy suggests a 4N type of coordination pattern around Cu(II) during fibrillation. Cu(II) is also capable of altering the cytotoxicity of the proteinaceous aggregates. Fibrillar species of diverse morphology were found in the absence of Cu(II) with the generation of amorphous aggregates in the presence of Cu(II), which are more toxic compared to the fibrils alone.

A water-soluble and water-coordinated Mn(II) complex: synthesis, characterization and phantom MRI image study.

PubMed

Phukan, Bedika; Patel, Anant B; Mukherjee, Chandan

2015-08-07

Ligand H4bedik was reacted with MnCl2·4H2O at pH ∼ 6.5 to give a highly water-soluble and water-coordinated Mn(ii) complex (). The complex was found to show r1 = 3.11 mM(-1) s(-1) per Mn(ii) at 1.4 T and 6.26 mM(-1) s(-1) per Mn(ii) at 14.1 T at 25 °C, pH = 7.4. In addition to r1, the r2 at 14.1 T was found to be 132.78 mM(-1) s(-1) per Mn(ii) at 25 °C, pH = 7.4.

The facile synthesis of a chitosan Cu(II) complex by solution plasma process and evaluation of their antioxidant activities.

PubMed

Ma, Fengming; Li, Pu; Zhang, Baiqing; Wang, Zhenyu

2017-10-01

Synthesis of chitosan-Cu(II) complex by solution plasma process (SPP) irradiation was investigated. The effects of the distance between the electrodes, initial Cu(II) concentration, and initial pH on the Cu(II) adsorption capacity were evaluated. The results showed that narrower distance between the electrodes, higher initial Cu(II) concentration and higher initial pH (at pH<6) were favourable for the adsorption capacity of Cu(II). Characterization of the chitosan-Cu(II) complex by ultraviolet-visible (UV-vis), fourier transform infrared (FT-IR) and electron spin resonance (ESR) spectroscopy revealed that the main structure of chitosan was not changed after irradiation. Thermogravimetry (TG) analysis indicated that Cu(II) ions were well incorporated into the chitosan. The antioxidant activity of the chitosan-Cu(II) complex was evaluated by DPPH, ABTS, and reducing power assays. The chitosan-Cu(II) complex exhibited greater antioxidant activity than the original chitosan. Thus, SPP could be used for preparation of chitosan-Cu(II) complexes. Copyright © 2017. Published by Elsevier B.V.

Synthesis of a Dual Functional Anti-MDR Tumor Agent PH II-7 with Elucidations of Anti-Tumor Effects and Mechanisms

PubMed Central

Tan, Yaohong; Hu, Yunhui; Zhou, Yuan; Liu, Juanni; Xu, Yuanfu; Xie, Yinliang; Wang, Caiyun; Gao, Yingdai; Wang, Jianxiang; Cheng, Tao; Yang, Chunzheng; Xiong, Dongsheng; Miao, Hua

2012-01-01

Multidrug resistance mediated by P-glycoprotein in cancer cells has been a major issue that cripples the efficacy of chemotherapy agents. Aimed for improved efficacy against resistant cancer cells, we designed and synthesized 25 oxindole derivatives based on indirubin by structure-activity relationship analysis. The most potent one was named PH II-7, which was effective against 18 cancer cell lines and 5 resistant cell lines in MTT assay. It also significantly inhibited the resistant xenograft tumor growth in mouse model. In cell cycle assay and apoptosis assay conducted with flow cytometry, PH II-7 induced S phase cell cycle arrest and apoptosis even in resistant cells. Consistently revealed by real-time PCR, it modulates the expression of genes related to the cell cycle and apoptosis in these cells, which may contributes to its efficacy against them. By side-chain modification and FITC-labeling of PH II-7, we were able to show with confocal microscopy that not only it was not pumped by P-glycoprotein, it also attenuated the efflux of Adriamycin by P-glycoprotein in MDR tumor cells. Real-time PCR and western blot analysis showed that PH II-7 down-regulated MDR1 gene via protein kinase C alpha (PKCA) pathway, with c-FOS and c-JUN as possible mediators. Taken together, PH II-7 is a dual-functional compound that features both the cytotoxicity against cancer cells and the inhibitory effect on P-gp mediated drug efflux. PMID:22403708

The Role of Coordination Environment and pH in Tuning the Oxidation Rate of Europium(II).

PubMed

Ekanger, Levi A; Basal, Lina A; Allen, Matthew J

2017-01-23

The Eu II/III redox couple offers metal-based oxidation-sensing with magnetic resonance imaging making the study of Eu II oxidation chemistry important in the design of new probes. Accordingly, we explored oxidation reactions with a set of Eu II -containing complexes. Superoxide formation from the reaction between Eu II and dioxygen was observed using electron paramagnetic resonance spectroscopy. Additionally, oxidation kinetics of three Eu II -containing complexes with bromate and glutathione disulfide at pH values, including 5 and 7, is reported. In the reaction with bromate, the oxidation rate of two of the complexes increased by 7.3 and 6.7 times upon decreasing pH from 7 to 5, but the rate increased by 17 times for a complex containing amide functional groups over the same pH range. The oxidation rate of a fluorobenzo-functionalized cryptate was relatively slow, indicating that the ligand used to impart thermodynamic oxidative stability might also be useful for controlling oxidation kinetics. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of meat source, pH and production time on zinc protoporphyrin IX formation as natural colouring agent in nitrite-free dry fermented sausages.

PubMed

De Maere, Hannelore; Chollet, Sylvie; De Brabanter, Jos; Michiels, Chris; Paelinck, Hubert; Fraeye, Ilse

2018-01-01

Nitrite is commonly used in meat products due to its plural technological advantages. However, it is controversial because of its detrimental side effects on health. Within the context of nitrite reduction, zinc protoporphyrin IX (Zn(II)PPIX) formation in meat products as natural red colouring agent has been suggested. This investigation presents the evaluation of naturally occurring pigments, namely Zn(II)PPIX, protoporphyrin IX (PPIX) and heme in nitrite-free dry fermented sausages in function of time, meat source (pork, horsemeat and a combination of both meat sources) and pH condition. In function of time, Zn(II)PPIX and PPIX were formed and heme content decreased. Higher pH conditions promoted Zn(II)PPIX and PPIX formation, whereas the influence of pH on heme was less clear. The use of horsemeat also promoted Zn(II)PPIX formation. Moreover, even similar amounts were formed when it was combined with pork. Product redness, however, could not be related to Zn(II)PPIX formation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of pH, buffers and role of quinolinic acid, a novel iron chelating agent, in the determination of hydroxyl radical scavenging activity of plant extracts by Electron Paramagnetic Resonance (EPR).

PubMed

Fadda, Angela; Barberis, Antonio; Sanna, Daniele

2018-02-01

The Fenton reaction is used to produce hydroxyl radicals for the evaluation of the antioxidant activity of plant extracts. In this paper the parameters affecting the production of hydroxyl radicals and their spin trapping with DMPO were studied. The use of quinolinic acid (Quin) as an Fe(II) ligand was proposed for antioxidant activity determination of Green tea, orange juice and asparagus extracts. Quin, buffers and pH affect the DMPO-OH signal intensity of the EPR spectra. Quin/Fe(II) and low pH enhance the OH generation. Phosphate and Tris-HCl buffers decrease the signal intensity measured in Fe(II)-sulfate and Fe(II)-Quin systems. The extracts were analyzed with Fenton systems containing Fe(II)-sulfate and Fe(II)-Quin with and without buffer. The highest activity was shown with Fe(II)-Quin without buffer, this system being less influenced by pH and chelating agents present in the extracts. This paper will help researchers to better design spin trapping experiments for food matrices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Benzyl and Methyl Fatty Hydroxamic Acids Based on Palm Kernel Oil as Chelating Agent for Liquid-Liquid Iron(III) Extraction

PubMed Central

Haron, Md Jelas; Jahangirian, Hossein; Silong, Sidik; Yusof, Nor Azah; Kassim, Anuar; Rafiee-Moghaddam, Roshanak; Mahdavi, Behnam; Peyda, Mazyar; Abdollahi, Yadollah; Amin, Jamileh

2012-01-01

Liquid-liquid iron(III) extraction was investigated using benzyl fatty hydroxamic acids (BFHAs) and methyl fatty hydroxamic acids (MFHAs) as chelating agents through the formation of iron(III) methyl fatty hydroxamate (Fe-MFHs) or iron(III) benzyl fatty hydroxamate (Fe-BFHs) in the organic phase. The results obtained under optimized conditions, showed that the chelating agents in hexane extract iron(III) at pH 1.9 were realized effectively with a high percentage of extraction (97.2% and 98.1% for MFHAs and BFHAs, respectively). The presence of a large amount of Mg(II), Ni(II), Al(III), Mn(II) and Co(II) ions did affect the iron(III) extraction. Finally stripping studies for recovering iron(III) from organic phase (Fe-MFHs or Fe-BFHs dissolved in hexane) were carried out at various concentrations of HCl, HNO3 and H2SO4. The results showed that the desired acid for recovery of iron(III) was 5 M HCl and quantitative recovery of iron(III) was achieved from Fe(III)-MFHs and Fe(III)-BFHs solutions in hexane containing 5 mg/L of Fe(III). PMID:22408444

Synthesis of tin (II) oxide from tin (II) oxohydroxide

NASA Astrophysics Data System (ADS)

Kuznetsova, Svetlana; Lisitsa, Konstantin

2017-11-01

Sufficiently limited use of tin (II) oxide is associated with the difficulties of its preparation without impurities of tin (IV) oxide. Understanding the cause of the oxidation process will make it possible to develop methods for obtaining SnO without impurities. The influence of ammonium chloride concentration in the suspension on the oxide composition was investigated. The temperature of oxidation (400 °C) on the air and temperature decomposition in the argon (350 °C) of Sn6O4(OH)4 in the solid phase were determined by the thermal analysis method. The decomposition temperature of the oxyhydroxide in the suspension of ammonium chloride does not exceed 100 °C. An increase in the content of ammonium chloride in an aqueous solution leads to an increase i n the solubility of oxohydroxide and leads to an increase in pH. The suspensions of Sn6O4(OH)4 were subjected to heat treatment on a sand bath and under microwave irradiation. Samples of tin oxide were obtained. The quantitative composition of the mixture of tin oxides was determined. The research also highlights emphasizes that the oxidation of tin (II) to tin (IV) is associated with the dissolved oxygen content in the suspension.

Investigation of iron(III) reduction and trace metal interferences in the determination of dissolved iron in seawater using flow injection with luminol chemiluminescence detection.

PubMed

Ussher, Simon J; Milne, Angela; Landing, William M; Attiq-ur-Rehman, Kakar; Séguret, Marie J M; Holland, Toby; Achterberg, Eric P; Nabi, Abdul; Worsfold, Paul J

2009-10-12

A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II)+Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100microM concentrations of sulphite a reduction time of 4h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.

Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

USGS Publications Warehouse

Cravotta, Charles A.

2015-01-01

Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the model results for Fe(II) or pH. In contrast, the model results for pH and Fe(II) were sensitive to the CO2 mass transfer rate constant (kL,CO2a). The value of kL,CO2a estimated for the stream (0.010 min−1) was within the range for the batch aeration experiments (0–0.033 min−1). These results indicate that the abiotic homogeneous Fe(II) oxidation rate law, with adjustments for variations in temperature and CO2 outgassing rate, may be applied to predict changes in aqueous iron and pH for net-alkaline, ferruginous waters within a stream (natural conditions) or a CMD treatment system (engineered conditions).

Vibrational investigation on the copper(II) binding mode of carcinine and its pH dependence

NASA Astrophysics Data System (ADS)

Torreggiani, Armida; Reggiani, Matteo; Manco, Immacolata; Tinti, Anna

2007-05-01

A comparative FT-Raman and FT-IR study of Carcinine (Carc), a natural imidazole dipeptide, and its complexes with Cu(II) ions was performed at different pH's. Both Raman and IR spectra present marker bands useful for the identification of the predominant complexes; in particular, Raman spectroscopy appears useful for identifying the metal-coordination site of the imidazole ring (N π or N τ atoms) of Carc. Free Carc shows a strong network of H-bonds and tautomer I (N τ-H) is the preferred form of the imidazolic ring (bands at 1578, 1292 and 988 cm -1). The presence of Cu(II) does not affect the tautomeric equilibrium at pH 7, whereas the deprotonation of both N-imidazolic nitrogens is strongly induced at higher pH. Under neutral and alkaline conditions the primary amino group takes part to the Cu(II) chelation, whereas all the peptidic moieties are involved in coordination only at pH 7. Thus, Carc acts as a tri-dentate ligand at neutral pH, mainly giving a monomeric complex, [CuLH -1], containing tautomer I, whereas an oligonuclear complex, probably [Cu 4L 4H -8], where metal-imidazolate ions connect different ligand molecules, predominates at alkaline pH.

Formation of naturally occurring pigments during the production of nitrite-free dry fermented sausages.

PubMed

De Maere, Hannelore; Fraeye, Ilse; De Mey, Eveline; Dewulf, Lore; Michiels, Chris; Paelinck, Hubert; Chollet, Sylvie

2016-04-01

This study investigates the potential of producing red coloured dry fermented sausages without the addition of nitrite and/or nitrate. Therefore, the formation of zinc protoporphyrin IX (Zn(II)PPIX) as naturally occurring pigment, and the interrelated protoporphyrin IX (PPIX) and heme content were evaluated during nitrite-free dry fermented sausage production at different pH conditions. Zn(II)PPIX was only able to form in dry fermented sausages at pH conditions higher than approximately 4.9. Additionally, the presence of Zn(II)PPIX increased drastically at the later phase of the production process (up to day 177), confirming that in addition to pH, time is also a crucial factor for its formation. Similarly, PPIX also accumulated in the meat products at increased pH conditions and production times. In contrast, a breakdown of heme was observed. This breakdown was more gradual and independent of pH and showed no clear relationship with the formed amounts of Zn(II)PPIX and PPIX. A statistically significant relationship between Zn(II)PPIX formation and product redness was established. Copyright © 2015 Elsevier Ltd. All rights reserved.

Associations among Gastric Juice pH, Atrophic Gastritis, Intestinal Metaplasia and Helicobacter pylori Infection

PubMed Central

Sung, Jihee; Lee, Jongchan; Hwang, Young-Jae; Kim, Hyoung Woo; Chung, Jung Wha; Kim, Jin-Wook; Lee, Dong Ho

2018-01-01

Background/Aims Gastric juice plays a crucial role in the physiology of the stomach. The aim of this study is to evaluate associations among the pH of gastric juice, atrophic gastritis (AG), intestinal metaplasia (IM), pepsinogen, and Helicobacter pylori infection. Methods Gastric biopsies and juice were collected from 46 subjects who underwent endoscopies at Seoul National University Bundang Hospital between November 2011 and March 2013. H. pylori, AG and IM were evaluated, and pepsinogen I or II, I/II ratio, and interleukin (IL)-1β levels were measured. Results The mean pH of gastric juice was higher in the H. pylori-positive group (n=17) than that in the H. pylori-negative group (n=29) (4.54 vs 2.46, p=0.002). When patients were divided into pH <3 (n=28) and pH ≥3 (n=18) groups, H. pylori was lower in the pH <3 group (21.4%) than in the pH ≥3 group (61.1%) (p=0.007). The pH ≥3 group demonstrated AG and IM more frequently than the pH <3 group in the body (p=0.047 and p=0.051, respectively) but not in the antrum. There were no differences in pepsinogen I or II, I/II ratio, and IL-1β levels between the two groups. Conclusions There is a relationship between chronic H. pylori infection and gastric juice pH ≥3, which may originate from AG and IM in the body. PMID:28918609

Development and validation of a discriminative dissolution test for nimesulide suspensions.

PubMed

da Fonseca, Laís Bastos; Labastie, Márcio; de Sousa, Valéria Pereira; Volpato, Nadia Maria

2009-01-01

The dissolution test for oral dosage forms has recently widened to a variety of special dosage forms such as suspensions. For class II drugs, such as nimesulide (NMS), this study is very important because formulation problems may compromise drug bioavailability. In the present work, tests with four brands of commercially available NMS (RA, TS, TB, and TC) have been performed in order to study their dissolution at different conditions. The suspensions have been characterized relatively to particle size, pH, and density besides NMS assay and the amount of drug in solution in the suspension vehicles. The dissolution study was conducted using the following media: simulated intestinal fluid, pH 6.8, containing polysorbate 80 (P80) or sodium lauryl sulfate (SLS); phosphate buffer, pH 7.4, with P80 and aqueous solution of SLS. Concerning the quantitative analysis, the UV-VIS spectrophotometry could have been used in substitution to high-performance liquid chromatography since the methodology had been adequately validated. The influence of the drug particle size distribution was significant on the dissolution profiles of NMS formulations, confirming to be a factor that should be strictly controlled in the development of oral suspensions.

A series of tetraazalene radical-bridged M2 (M = CrIII, MnII, FeII, CoII) complexes with strong magnetic exchange coupling.

PubMed

DeGayner, Jordan A; Jeon, Ie-Rang; Harris, T David

2015-11-13

The ability of tetraazalene radical bridging ligands to mediate exceptionally strong magnetic exchange coupling across a range of transition metal complexes is demonstrated. The redox-active bridging ligand N , N ', N '', N '''-tetra(2-methylphenyl)-2,5-diamino-1,4-diiminobenzoquinone ( NMePh LH 2 ) was metalated to give the series of dinuclear complexes [(TPyA) 2 M 2 ( NMePh L 2- )] 2+ (TPyA = tris(2-pyridylmethyl)amine, M = Mn II , Fe II , Co II ). Variable-temperature dc magnetic susceptibility data for these complexes reveal the presence of weak superexchange interactions between metal centers, and fits to the data provide coupling constants of J = -1.64(1) and -2.16(2) cm -1 for M = Mn II and Fe II , respectively. One-electron reduction of the complexes affords the reduced analogues [(TPyA) 2 M 2 ( NMePh L 3- ˙)] + . Following a slightly different synthetic procedure, the related complex [(TPyA) 2 CrIII2( NMePh L 3- ˙)] 3+ was obtained. X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy indicate the presence of radical NMePh L 3- ˙ bridging ligands in these complexes. Variable-temperature dc magnetic susceptibility data of the radical-bridged species reveal the presence of strong magnetic interactions between metal centers and ligand radicals, with simulations to data providing exchange constants of J = -626(7), -157(7), -307(9), and -396(16) cm -1 for M = Cr III , Mn II , Fe II , and Co II , respectively. Moreover, the strength of magnetic exchange in the radical-bridged complexes increases linearly with decreasing M-L bond distance in the oxidized analogues. Finally, ac magnetic susceptibility measurements reveal that [(TPyA) 2 Fe 2 ( NMePh L 3- ˙)] + behaves as a single-molecule magnet with a relaxation barrier of U eff = 52(1) cm -1 . These results highlight the ability of redox-active tetraazalene bridging ligands to enable dramatic enhancement of magnetic exchange coupling upon redox chemistry and provide a rare opportunity to examine metal-radical coupling trends across a transmetallic series of complexes.

Efficacy and reusability of alginate-immobilized live and heat-inactivated Trichoderma asperellum cells for Cu (II) removal from aqueous solution.

PubMed

Tan, Wei Shang; Ting, Adeline Su Yien

2012-11-01

Cu(II) removal efficacies of alginate-immobilized Trichoderma asperellum using viable and non-viable forms were investigated with respect to time, pH, and initial Cu(II) concentrations. The reusability potential of the biomass was determined based on sorption/desorption tests. Cu(II) biosorption by immobilized heat-inactivated T. asperellum cells was the most efficient, with 134.22mg Cu(II) removed g(-1) adsorbent, compared to immobilized viable cells and plain alginate beads (control) with 105.96 and 94.04mg Cu(II) adsorbed g(-1) adsorbent, respectively. Immobilized non-viable cells achieved equilibrium more rapidly within 4h. For all biosorbents, optimum pH for Cu(II) removal was between pH 4 and 5. Reusability of all biosorbents were similar, with more than 90% Cu(II) desorbed with HCl. These alginate-immobilized cells can be applied to reduce clogging and post-separation process incurred from use of suspended biomass. Copyright © 2012 Elsevier Ltd. All rights reserved.

Desorption of Hg(II) and Sb(V) on extracellular polymeric substances: effects of pH, EDTA, Ca(II) and temperature shocks.

PubMed

Zhang, Daoyong; Lee, Duu-Jong; Pan, Xiangliang

2013-01-01

Extracellular polymeric substances (EPS) existed ubiquitously in biological systems affect the mobility and availability of heavy metals in the environments. The adsorption-desorption behaviors of Hg(II) and Sb(V) on EPS were investigated. The sorption rates follow Sb(V) > Hg(II), and the desorption rates follow reverse order. Applications of ethylene diamine tetraacetic acid (EDTA), Ca(II) and pH shocks affect desorption rates and desorbed quantities of Hg(II) from EPS-Hg complex. Temperature shock minimally affects the desorption rate of Hg(II). Conversely, the EPS-Sb complex is stable subjected to EDTA, Ca(II), temperature or pH shocks. The excitation-emission matrix (EEM) fluorescence spectroscopy and fast-Fourier (FT-IR) analysis showed that Hg(II) and Sb(V) principally interacted with polysaccharides and protein-like compounds in the EPS, respectively. The EPS-Hg complex presents a time bomb that may release high levels of Hg(II) in short time period under environmental shocks. Copyright © 2012 Elsevier Ltd. All rights reserved.

Validity of the Medical College Admission Test for predicting MD-PhD student outcomes.

PubMed

Bills, James L; VanHouten, Jacob; Grundy, Michelle M; Chalkley, Roger; Dermody, Terence S

2016-03-01

The Medical College Admission Test (MCAT) is a quantitative metric used by MD and MD-PhD programs to evaluate applicants for admission. This study assessed the validity of the MCAT in predicting training performance measures and career outcomes for MD-PhD students at a single institution. The study population consisted of 153 graduates of the Vanderbilt Medical Scientist Training Program (combined MD-PhD program) who matriculated between 1963 and 2003 and completed dual-degree training. This population was divided into three cohorts corresponding to the version of the MCAT taken at the time of application. Multivariable regression (logistic for binary outcomes and linear for continuous outcomes) was used to analyze factors associated with outcome measures. The MCAT score and undergraduate GPA (uGPA) were treated as independent variables; medical and graduate school grades, time-to-PhD defense, USMLE scores, publication number, and career outcome were dependent variables. For cohort 1 (1963-1977), MCAT score was not associated with any assessed outcome, although uGPA was associated with medical school preclinical GPA and graduate school GPA (gsGPA). For cohort 2 (1978-1991), MCAT score was associated with USMLE Step II score and inversely correlated with publication number, and uGPA was associated with preclinical GPA (mspGPA) and clinical GPA (mscGPA). For cohort 3 (1992-2003), the MCAT score was associated with mscGPA, and uGPA was associated with gsGPA. Overall, MCAT score and uGPA were inconsistent or weak predictors of training metrics and career outcomes for this population of MD-PhD students.

Structural response of phyllomanganates to wet aging and aqueous Mn(II)

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

Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G.

Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates weremore » studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging with Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. In conclusion, such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems, particularly trace metals and redox-active compounds.« less

Structural response of phyllomanganates to wet aging and aqueous Mn(II)

DOE PAGES

Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G.

2016-08-06

Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates weremore » studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging with Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. In conclusion, such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems, particularly trace metals and redox-active compounds.« less

HEALTH EFFECTS OF CHRONIC EXPOSURE TO ARSENIC VIA DRINKING WATER IN INNER MONGOLIA: II. VIBROTACTILE AND VISUAL MEASURES FINAL DOCUMENT TITLE.

EPA Science Inventory

HEALTH EFFECTS OF CHRONIC EXPOSURE TO ARSENIC IN DRINKING WATER IN INNER MONGOLIA: II. VIBROTACTILE AND VISUAL MEASURES.

David Otto, Ph.D., Judy Mumford, Ph.D., Richard Kwok, M.S.P.H., Ken Hudnell, Ph.D.,
U.S. Environmental Protection Agency; Yanhong Li, M.D., Yajuan ...

Atomic structure of the sweet-tasting protein thaumatin I at pH 8.0 reveals the large disulfide-rich region in domain II to be sensitive to a pH change

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

Masuda, Tetsuya, E-mail: t2masuda@kais.kyoto-u.ac.jp; Department of Natural Resources, Graduate School of Global Environmental Studies, Kyoto University, Gokasho, Uji, Kyoto 611-0011; Ohta, Keisuke

2012-03-02

Highlights: Black-Right-Pointing-Pointer Structure of a recombinant thaumatin at pH 8.0 determined at a resolution of 1.0 A. Black-Right-Pointing-Pointer Substantial fluctuations of a loop in domain II was found in the structure at pH 8.0. Black-Right-Pointing-Pointer B-factors for Lys137, Lys163, and Lys187 were significantly affected by pH change. Black-Right-Pointing-Pointer An increase in mobility might play an important role in the heat-induced aggregation. -- Abstract: Thaumatin, an intensely sweet-tasting plant protein, elicits a sweet taste at 50 nM. Although the sweetness remains when thaumatin is heated at 80 Degree-Sign C for 4 h under acid conditions, it rapidly declines when heating atmore » a pH above 6.5. To clarify the structural difference at high pH, the atomic structure of a recombinant thaumatin I at pH 8.0 was determined at a resolution of 1.0 A. Comparison to the crystal structure of thaumatin at pH 7.3 and 7.0 revealed the root-mean square deviation value of a C{alpha} atom to be substantially greater in the large disulfide-rich region of domain II, especially residues 154-164, suggesting that a loop region in domain II to be affected by solvent conditions. Furthermore, B-factors of Lys137, Lys163, and Lys187 were significantly affected by pH change, suggesting that a striking increase in the mobility of these lysine residues, which could facilitate a reaction with a free sulfhydryl residue produced via the {beta}-elimination of disulfide bonds by heating at a pH above 7.0. The increase in mobility of lysine residues as well as a loop region in domain II might play an important role in the heat-induced aggregation of thaumatin above pH 7.0.« less

In silico prediction of drug dissolution and absorption with variation in intestinal pH for BCS class II weak acid drugs: ibuprofen and ketoprofen.

PubMed

Tsume, Yasuhiro; Langguth, Peter; Garcia-Arieta, Alfredo; Amidon, Gordon L

2012-10-01

The FDA Biopharmaceutical Classification System guidance allows waivers for in vivo bioavailability and bioequivalence studies for immediate-release solid oral dosage forms only for BCS class I. Extensions of the in vivo biowaiver for a number of drugs in BCS class III and BCS class II have been proposed, in particular, BCS class II weak acids. However, a discrepancy between the in vivo BE results and in vitro dissolution results for BCS class II acids was recently observed. The objectives of this study were to determine the oral absorption of BCS class II weak acids via simulation software and to determine if the in vitro dissolution test with various dissolution media could be sufficient for in vitro bioequivalence studies of ibuprofen and ketoprofen as models of carboxylic acid drugs. The oral absorption of these BCS class II acids from the gastrointestinal tract was predicted by GastroPlus™. Ibuprofen did not satisfy the bioequivalence criteria at lower settings of intestinal pH of 6.0. Further the experimental dissolution of ibuprofen tablets in a low concentration phosphate buffer at pH 6.0 (the average buffer capacity 2.2 mmol l (-1) /pH) was dramatically reduced compared with the dissolution in SIF (the average buffer capacity 12.6 mmol l (-1) /pH). Thus these predictions for the oral absorption of BCS class II acids indicate that the absorption patterns depend largely on the intestinal pH and buffer strength and must be considered carefully for a bioequivalence test. Simulation software may be a very useful tool to aid the selection of dissolution media that may be useful in setting an in vitro bioequivalence dissolution standard. Copyright © 2012 John Wiley & Sons, Ltd.

In Silico Prediction of Drug Dissolution and Absorption with variation in Intestinal pH for BCS Class II Weak Acid Drugs: Ibuprofen and Ketoprofen§

PubMed Central

Tsume, Yasuhiro; Langguth, Peter; Garcia-Arieta, Alfredo; Amidon, Gordon L.

2012-01-01

The FDA Biopharmaceutical Classification System guidance allows waivers for in vivo bioavailability and bioequivalence studies for immediate-release solid oral dosage forms only for BCS class I. Extensions of the in vivo biowaiver for a number of drugs in BCS Class III and BCS class II have been proposed, particularly, BCS class II weak acids. However, a discrepancy between the in vivo- BE results and in vitro- dissolution results for a BCS class II acids was recently observed. The objectives of this study were to determine the oral absorption of BCS class II weak acids via simulation software and to determine if the in vitro dissolution test with various dissolution media could be sufficient for in vitro bioequivalence studies of ibuprofen and ketoprofen as models of carboxylic acid drugs. The oral absorption of these BCS class II acids from the gastrointestinal tract was predicted by GastroPlus™. Ibuprofen did not satisfy the bioequivalence criteria at lower settings of intestinal pH=6.0. Further the experimental dissolution of ibuprofen tablets in the low concentration phosphate buffer at pH 6.0 (the average buffer capacity 2.2 mmol L-1/pH) was dramatically reduced compared to the dissolution in SIF (the average buffer capacity 12.6 mmol L -1/pH). Thus these predictions for oral absorption of BCS class II acids indicate that the absorption patterns largely depend on the intestinal pH and buffer strength and must be carefully considered for a bioequivalence test. Simulation software may be very useful tool to aid the selection of dissolution media that may be useful in setting an in vitro bioequivalence dissolution standard. PMID:22815122

Effects of copper on the abundance and diversity of ammonia oxidizers during dairy cattle manure composting.

PubMed

Yin, Yanan; Song, Wen; Gu, Jie; Zhang, Kaiyu; Qian, Xun; Zhang, Xin; Zhang, Yajun; Li, Yang; Wang, Xiaojuan

2016-12-01

This study investigated the effects of adding Cu(II) at two exposure levels (50 and 500mgkg -1 , i.e., Cu50 and Cu500 treatments, respectively) on the activity of ammonia-oxidizing microorganisms during dairy cattle manure composting. The results showed that the pH, NH 4 + -N, NO 3 - -N, and potential ammonia oxidation values were inhibited significantly by the addition of Cu(II). Furthermore, the abundances of the ammonia-oxidizing archaea (AOA) amoA gene and ammonia-oxidizing bacteria (AOB) amoA gene were determined by quantitative PCR, and their compositions were evaluated by denaturing gradient gel electrophoresis (DGGE). AOA was the dominant ammonia oxidizing microorganism, of which the abundance was much higher than AOB during composting. Cu50 and Cu500 had significant inhibitory effects on the abundance of the amoA gene. The DGGE profile and statistical analysis showed that Cu(II) changed the AOA and AOB community structure and diversity, where Nitrosomonas and Crenarchaeota dominated throughout the composting process. Copyright © 2016. Published by Elsevier Ltd.

Iron as a catalyst of human low-density lipoprotein oxidation: Critical factors involved in its oxidant properties.

PubMed

Lapenna, Domenico; Ciofani, Giuliano; Obletter, Gabriele

2017-05-01

Iron-induced human LDL oxidation, which is relevant to atherosclerosis, has not yet been properly investigated. We addressed such issue using iron(II) and (III) basically in the presence of phosphates, which are present in vivo and influence iron oxidative properties, at pH 4.5 and 7.4, representative, respectively, of the lysosomal and plasma environment. In 10mM phosphate buffered saline (PBS), iron(II) induces substantial LDL oxidation at pH 4.5 at low micromolar concentrations, while at pH 7.4 has low oxidative effects; iron(III) promotes small LDL oxidation only at pH 4.5. In 10mM sodium acetate/NaCl buffer, pH 4.5, iron-induced LDL oxidation is far higher than in PBS, highlighting the relevance of phosphates in the inhibitory modulation of iron-induced LDL oxidation. LDL oxidation is related to iron binding to the protein and lipid moiety of LDL, and requires the presence of iron(II) bound to LDL together with iron(III). Chemical modification of LDL carboxyl groups, which could bind iron especially at pH 4.5, decreases significantly iron binding to LDL and iron-induced LDL oxidation. Hydroxyl radical scavengers are ineffective on iron-induced LDL oxidation, which is inhibited by metal chelation, scavengers of alkoxyl/peroxyl radicals, or removal of LDL lipid hydroperoxides (LOOH). Overall, substantial human LDL oxidation is induced LOOH-dependently by iron(II) at pH 4.5 even in the presence of phosphates, suggesting the occurrence of iron(II)-induced LDL oxidation in vivo within lysosomes, where pH is about 4.5, iron(II) and phosphates coexist, plasma with its antioxidants is absent, and glutathione peroxidase is poorly expressed resulting in LOOH accumulation. Copyright © 2017 Elsevier GmbH. All rights reserved.

Kinetic model to explain the effect of ocean warming and acidification on the Fe(II) oxidation rate in oligotrophic and eutrophic natural waters

NASA Astrophysics Data System (ADS)

González-Dávila, M.; Samperio-Ramos, G.; Santana-Casiano, J. M.; Gonzallez, A. G.; Pérez-Almeida, N.

2016-12-01

The speciation of inorganic Fe(II) as a function of the pH and temperature have been modeled in order to elucidate the inorganic Fe(II) redox behavior over a wide range of scenarios of acidification and global warming of the upper ocean, as well as, changes due to natural ambient fluctuations of pH and temperature. In addition, a kinetic modeling approach has been carried out to elucidate the fractional contribution of most kinetically active Fe(II) species to the overall oxidation rate to improve our future and present knowledge with respect to redox iron chemistry in the marine systems. The kinetic model considers the interactions of Fe(II) with the major ions in seawater, including phosphate and silicate and the competition with copper with the ROS. The model has been applied to the experimental results in order to describe the effect of temperature and pH in the speciation of Fe(II) and to compute the fractional contribution of each Fe(II)-specie to the overall oxidation rate. The oxidation rates (kapp) of nanomolar levels of Fe(II) have been studied in seawater enriched with nutrients (SWEN) in air saturated conditions. The nutrient effect (nitrate, phosphate and silicate), on the oxidation of Fe(II), has been evaluated as a function of pH (7.2-8.2), temperature (5-35 ºC) and salinity (10-37.09). The oxidation of Fe(II) was faster in the presence of nutrient with the change in the Fe(II) oxidation rates (Δlogkapp) more intensive at higher temperatures over the entire pH range studied. From the model it can be observed that the inorganic speciation of Fe(II) is controlled largely by pH, either in SW or in SWEN. A greater presence of Fe-nutrient reactive species (FeH3SiO4+ and FePO4-) in SWEN at higher temperatures explained the changes in the oxidation process. The individual oxidation rates by oxygen, for the Fe(II) most kinetically active species (Fe2+, FeOH+, Fe(OH)2, FeCO3(OH)-, FeCO3, Fe(CO3)22-, FeH3SiO3+, FePO4-), were fitted as a function of the temperature.

Removal of some metal ions by activated carbon prepared from Phaseolus aureus hulls.

PubMed

Rao, M Madhava; Ramana, D K; Seshaiah, K; Wang, M C; Chien, S W Chang

2009-07-30

Removal of lead [Pb(II)], zinc [Zn(II)], copper [Cu(II)], and cadmium [Cd(II)] from aqueous solutions using activated carbon prepared from Phaseolus aureus hulls (ACPAH), an agricultural waste was studied. The influence of various parameters such as effect of pH, contact time, adsorbent dose, and initial concentration of metal ions on the removal was evaluated by batch method. The removal of metal ions by ACPAH was pH dependent and the optimum pH values were 7.0, 8.0, 7.0 and 6.0 for Cu(II), Cd(II), Zn(II), and Pb(II), respectively. The sorption isotherms were studied using Langmuir, Freundlich, Dubinin-Radushkevich (D-R), and Temkin isotherm models. The maximum adsorption capacity values of ACPAH for metal ions were 21.8 mg g(-1) for Pb(II), 21.2 mg g(-1) for Zn(II), 19.5 mg g(-1) for Cu(II), and 15.7 mg g(-1) for Cd(II). The experiments demonstrated that the removal of metal ions followed the pseudo-second-order kinetic model. Desorption experiments were carried out using HCl solution with a view to regenerate the spent adsorbent and to recover the adsorbed metal ions.

Determination of nickel in water, food, and biological samples by electrothermal atomic absorption spectrometry after preconcentration on modified carbon nanotubes.

PubMed

Taher, Mohammad Ali; Mazaheri, Lida; Ashkenani, Hamid; Mohadesi, Alireza; Afzali, Daryoush

2014-01-01

A new and sensitive SPE method using modified carbon nanotubes for extraction and preconcentration, and electrothermal atomic absorption spectrometric determination of nickel (Ni) in real samples at ng/L levels was investigated. First, multiwalled carbon nanotubes were oxidized with concentrated HNO3, then modified with 2-(5-bormo-2-pyridylazo)-5-diethylaminophenol reagent. The adsorption was achieved quantitatively on a modified carbon nanotubes column in a pH range of 6.5 to 8.5; the adsorbed Ni(II) ions were then desorbed by passing 5.0 mL of 1 M HNO3. The effects of analytical parameters, including pH of the solution, eluent type and volume, sample volume, flow rate of the eluent, and matrix ions, were investigated for optimization of the presented procedure. The enrichment factor was 180, and the LOD for Ni was 4.9 ng/L. The method was applied to the determination of Ni in water, food, and biological samples, and reproducible results were obtained.

A Quantitative Review and Meta-Models of the Variability and Factors Affecting Oral Drug Absorption-Part I: Gastrointestinal pH.

PubMed

Abuhelwa, Ahmad Y; Foster, David J R; Upton, Richard N

2016-09-01

This study aimed to conduct a quantitative meta-analysis for the values of, and variability in, gastrointestinal (GI) pH in the different GI segments; characterize the effect of food on the values and variability in these parameters; and present quantitative meta-models of distributions of GI pH to help inform models of oral drug absorption. The literature was systemically reviewed for the values of, and the variability in, GI pH under fed and fasted conditions. The GI tract was categorized into the following 10 distinct regions: stomach (proximal, mid-distal), duodenum (proximal, mid-distal), jejunum and ileum (proximal, mid, and distal small intestine), and colon (ascending, transverse, and descending colon). Meta-analysis used the "metafor" package of the R language. The time course of postprandial stomach pH was modeled using NONMEM. Food significantly influenced the estimated meta-mean stomach and duodenal pH but had no significant influence on small intestinal and colonic pH. The time course of postprandial pH was described using an exponential model. Increased meal caloric content increased the extent and duration of postprandial gastric pH buffering. The different parts of the small intestine had significantly different pH. Colonic pH was significantly different for descending but not for ascending and transverse colon. Knowledge of GI pH is important for the formulation design of the pH-dependent dosage forms and in understanding the dissolution and absorption of orally administered drugs. The meta-models of GI pH may also be used as part of semi-physiological pharmacokinetic models to characterize the effect of GI pH on the in vivo drug release and pharmacokinetics.

[Comparative data regarding two HPLC methods for determination of isoniazid].

PubMed

Gârbuleţ, Daniela; Spac, A F; Dorneanu, V

2009-01-01

For the determination of isoniazide (isonicotinic acid hydrazide - HIN) two different HPLC methods were developed and validated. Both experiments were performed using a Waters 2695 liquid chromatograph and a UV - Waters 2489 detector. The first method (I) used a Nucleosil 100-10 C18 column (250 x 4.6 mm), a mobile phase formed by a mixture of acetonitrile/10(-2) M oxalic acid (80/20) and a flow of 1.5 mL/ min; detection was done at 230 nm. The second method (II) used a Luna 100-5 C18 column (250 x 4.6 mm), a mobile phase formed by a mixture of methanol/acetate buffer, pH = 5.0 (20/ 80), a flow of 1 mL/min; detection was done at 270 nm. Both methods were validated, the correlation coefficients were 0.9998 (I) and 0.9999 (II), the detection limits were 0.6 microg/mL (I) and 0.055 microg/mL (II), the quantitation limits were 1.9 microg/mL (I) and 0.2 microg/ mL (II). There were also studied: the system precision (RSD = 0.1692% (I) and 0.2000% (II)), the method precision (RSD = 1.1844% (I) and 0.6170% (II)) and the intermediate precision (RSD = 1.8058% (I) and 0.5970% (II)). The accuracy was good, the calculated recoveries were 102.66% (I) and 101.36 (II). Both validated methods were applied for HIN determination from tablets with good and comparable results.

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

PubMed

Pekel, Nursel; Salih, Bekir; Güven, Olgun

2005-05-10

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

Quantum, characterization and spectroscopic studies on Cu(II), Pd(II) and Pt(II) complexes of 1-(benzo[d]thiazol-2-yl)-3-phenylthiourea and its biological application as antimicrobial and antioxidant

NASA Astrophysics Data System (ADS)

Jambi, M. S.

2017-09-01

Divalent platinum, palladium and copper chelates of H2PhT have been isolated and identified. Their structures have been elucidated by partial elemental analyses, magnetic susceptibilities and spectroscopic estimations and additionally mass spectra. The FTIR and 1H NMR studies illustrated that H2PhT performs as mono-negative bi-dentate in Cu(II) and Pd(II) complexes while it behaves as neutral bi-dentate in both Pt(II) complexes. Both magnetic moments and spectral studies suggests a tetrahedral coordination geometry for [Cu(HPhT)(H2O)Cl] complex, a square planar geometry for both [Pd(HPhT)2] and [Pt(H2PhT)2Cl2] complexes and octahedral geometry for [Pt(H2PhT)2Cl2] complex. The molecular modeling are drawn and demonstrated both bond lengths and angles, chemical reactivity, MEP, NLO, Mulliken atomic charges, and binding energy (kcal/mol) for the investigated compounds. Theoretical infrared intensities and 1H NMR of H2PhT was computed utilizing DFT technique. An examination of the experimental and hypothetical spectra can be extremely valuable in making right assignments and analyzing the main chemical shift. DNA bioassay, antibacterial and antifungal activities of the investigated compounds have been determined.

Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation.

PubMed

Sheng, Guodong; Shen, Runpu; Dong, Huaping; Li, Yimin

2013-06-01

This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)2Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.

On-line solid phase selective separation and preconcentration of Cd(II) by solid-phase extraction using carbon active modified with methyl thymol blue.

PubMed

Ensafi, Ali A; Ghaderi, Ali R

2007-09-05

An on-line flow system was used to develop a selective and efficient on-line sorbent extraction preconcentration system for cadmium. The method is based on adsorption of cadmium ions onto the activated carbon modified with methyl thymol blue. Then the adsorbed ions were washed using 0.5M HNO(3) and the eluent was used to determine the Cd(II) ions using flame atomic absorption spectrometry. The results obtained show that the modified activated carbon has the greatest adsorption capacity of 80 microg of Cd(II) per 1.0 g of the solid phase. The optimal pH value for the quantitative preconcentration was 9.0 and full desorption is achieved by using 0.5M HNO(3) solution. It is established that the solid phase can be used repeatedly without a considerable adsorption capacity loss. The detection limit was less than 1 ngmL(-1) Cd(II), with an enrichment factor of 1000. The calibration graph was linear in the range of 1-2000 ngmL(-1) Cd(II). The developed method has been applied to the determination of trace cadmium (II) in water samples and in the following reference materials: sewage sludge (CRM144R), and sea water (CASS.4) with satisfactory results. The accuracy was assessed through recovery experiments.

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

NASA Astrophysics Data System (ADS)

Boyanov, Maxim I.; O'Loughlin, Edward J.; Roden, Eric E.; Fein, Jeremy B.; Kemner, Kenneth M.

2007-04-01

The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, "dead-end" U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).

Stabilization of photosystem II reaction centers: influence of bile salt detergents and low pH.

PubMed

Gall, B; Scheer, H

1998-07-17

Rapid deterioration of samples is a major obstacle in research on the isolated reaction center of photosystem II. Its stability was tested systematically using a wide range of detergents, varying pH and temperature. Stability and activity did not depend on ionic properties of detergents or on critical micellar concentration. However, both were significantly increased by bile salt detergents in the dark as well as in the light. Low pH (5.5) and low temperature further improved stability. The results suggest that in particular the zwitterionic bile salt detergent, CHAPS, in pH 5.5 buffers is a very useful detergent and even superior to dodecylmaltoside for work with photosystem II reaction centers.

Prediction of equilibrium parameters of adsorption of lead (II) ions onto diatomite

NASA Astrophysics Data System (ADS)

Salman, Taylan; Ardalı, Yüksel; Gamze Turan, N.

2013-04-01

Heavy metals from industrial wastewaters are one of the most important environmental issues to be solved today. Due to their toxicity and nonbiodegradable nature, heavy metals cause environmental and public health problems. Various techniques have been developed to remove heavy metals from aqueous solutions. These include chemical precipitation, reverse osmosis, ion Exchange and adsorption. Among them, adsorption is considered to be a particularly competitive and effective process for the removal of heavy metals from aqueous solutions. There is growing interest in using low cost, commercially available materials for the adsorption of heavy metals. Diatomite is a siliceous sedimentary rock having an amorphous form of silica (SiO2. nH2O) containing a small amount of microcrystalline material. It has unique combination of physical and chemical properties such as high porosity, high permeability, small particle size, large surface area, and low thermal conductivity. In addition, it is available in Turkey and in various locations around the world. Therefore, diatomite has been successfully used as adsorbent for the removal of heavy metals. The aim of the study is to investigate the adsorption properties of diatomite. The equilibrium adsorption data were applied to the Langmuir, Freundlich and Dubinin-Radushkevic (D-R) isotherm models. Adsorption experiments were performed under batch process, using Pb (II) initial concentration, pH of solution and contact time as variables. The results demonstrated that the adsorption of Pb (II) was strongly dependent on pH of solution. The effect of pH on adsorption of Pb(II) on diatomite was conducted by varying pH from 2 to 12 at 20 oC. In the pH range of 2.0-4.0, the adsorption percentage increases slightly as the pH increasing. At pH>4, the adsorption percentage decreases with increasing pH because hydrolysis product and the precipitation begin to play an important role in the sorption of Pb (II). At pH4, the maximum adsorption capacity of diatomite was found as 26.158 mg/g. The adsorption isotherms of Pb (II) on diatomite can be described well by the Freundlich model. The high adsorption capacity of diatomite makes it suitable low-cost material in the removal of Pb (II) from aqueous solutions.

Solid Phase Extraction of Trace Elements in Waterand Tissue Samples on a Mini Column with Diphenylcarbazone Impregnated Nano-TiO2 and Their Determination by Inductively Coupled Plasma Optical Emission Spectrometry

PubMed Central

Baytak, Sıtkı; Arslan, Zikri

2015-01-01

This study presents a simple, robust and environmentally friendly solid phase preconcentration procedure for multielement determination by inductively coupled plasma optical emission spectrometry (ICP-OES) using diphenylcarbazone (DPC) impregnated TiO2 nanopowder (n-TiO2). DPC was successfully impregnated onto n-TiO2 in colloidal solution. A number of elements, including Co(II), Cr(III), Cu(II), Fe(III), Mn(II) and Zn(II) were quantitatively preconcentrated from aqueous solutions between pH 8 and 8.5 at a flow rate of 2 mL min−1, and then eluted with 2 mL of 5% (v/v) HNO3. A mini-column packed with 0.12 g DPC impregnated n-TiO2 retained all elements quantitatively from up to 250 mL multielement solution (2.5 μg per analyte) affording an enrichment factor of 125. The limits of detection (LOD) for preconcentration of 50 mL blank solutions (n = 12) were 0.28, 0.15, 0.25, 0.22, 0.12, and 0.10 μg L−1 for Co, Cr, Cu, Fe, Mn, and Zn, respectively. The relative standard deviation (RSD) for five replicate determinations was 0.8, 3.4, 2.6, 2.2, 1.2 and 3.3% for Co, Cr, Cu, Fe, Mn and Zn, respectively, at 5 μg L−1 level. The method was validated with analysis of Freshwater (SRM 1643e) and Lobster hepatopancreas (TORT-2) certified reference materials, and then applied to the determination of the elements from tap water and lake water samples by ICP-OES. PMID:26236403

An efficient, cost effective, sensing behaviour liquid-liquid extraction and spectrophotometric determination of copper(II) incorporated with 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole: Analysis of food samples, leafy vegetables, fertilizers and environmental samples

NASA Astrophysics Data System (ADS)

Barache, Umesh B.; Shaikh, Abdul B.; Lokhande, Tukaram N.; Kamble, Ganesh S.; Anuse, Mansing A.; Gaikwad, Shashikant H.

2018-01-01

The aim of the present work is to develop an efficient, simple and selective moreover cost-effective method for the extractive spectrophotometric determination of copper(II) by using the Schiff base 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole [CBIMMT]. This chromogenic reagent forms a yellow coloured complex with copper(II) in acetate buffer at pH 4.2. The copper(II) complex with ligand is instantly extracted into chloroform and shows a maximum absorbance at 414 nm which remains stable for > 48 h. The composition of extracted complex is found to be 1:2 [copper(II): reagent] which was ascertained using Job's method of continuous variation, mole ratio method and slope ratio method. Under optimal conditions, the copper(II) complex in chloroform adheres to Beer's law up to 17.5 μg mL- 1 of copper(II). The optimum concentration range obtained from Ringbom's plot is from 5 μg mL- 1 to 17.5 μg mL- 1. The molar absorptivity, Sandell's sensitivity and enrichment factor of the extracted copper(II) chelate are 0.33813 × 104 L mol- 1 cm- 1, 0.01996 μg cm- 2 and 2.49 respectively. In the extraction of copper(II), several affecting factors including the solution pH, ligand concentration, equilibrium time, effect of foreign ions are optimized. The interfering effects of various cations and anions were also studied and use of masking agents enhances the selectivity of the method. The chromogenic sulphur containing reagent, 4-(4‧-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole has been synthesized in a single step with high purity and yield. The synthesized reagent has been successfully applied first time for determination of copper(II). The reagent forms stable chelate with copper(II) in buffer medium instantly and quantitatively extracted in chloroform within a minute. The method is successfully applied for the determination of copper(II) in various synthetic mixtures, complexes, fertilizers, environmental samples such as food samples, leafy vegetables, and water samples. The results are compared with those obtained with a reference procedure. Good agreement was attained. All the obtained results are indicative of a convenient, fast method for the extraction and quantification of micro levels of copper(II) from various environmental matrices without use of sophisticated instrumentation and procedure. The method showed a relative standard deviation of 0.42%.

An efficient, cost effective, sensing behaviour liquid-liquid extraction and spectrophotometric determination of copper(II) incorporated with 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole: Analysis of food samples, leafy vegetables, fertilizers and environmental samples.

PubMed

Barache, Umesh B; Shaikh, Abdul B; Lokhande, Tukaram N; Kamble, Ganesh S; Anuse, Mansing A; Gaikwad, Shashikant H

2018-01-15

The aim of the present work is to develop an efficient, simple and selective moreover cost-effective method for the extractive spectrophotometric determination of copper(II) by using the Schiff base 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole [CBIMMT]. This chromogenic reagent forms a yellow coloured complex with copper(II) in acetate buffer at pH4.2. The copper(II) complex with ligand is instantly extracted into chloroform and shows a maximum absorbance at 414nm which remains stable for >48h. The composition of extracted complex is found to be 1:2 [copper(II): reagent] which was ascertained using Job's method of continuous variation, mole ratio method and slope ratio method. Under optimal conditions, the copper(II) complex in chloroform adheres to Beer's law up to 17.5μgmL -1 of copper(II). The optimum concentration range obtained from Ringbom's plot is from 5μgmL -1 to 17.5μgmL -1 . The molar absorptivity, Sandell's sensitivity and enrichment factor of the extracted copper(II) chelate are 0.33813×10 4 Lmol -1 cm -1 , 0.01996μgcm -2 and 2.49 respectively. In the extraction of copper(II), several affecting factors including the solution pH, ligand concentration, equilibrium time, effect of foreign ions are optimized. The interfering effects of various cations and anions were also studied and use of masking agents enhances the selectivity of the method. The chromogenic sulphur containing reagent, 4-(4'-chlorobenzylideneimino)-3-methyl-5-mercapto-1, 2, 4-triazole has been synthesized in a single step with high purity and yield. The synthesized reagent has been successfully applied first time for determination of copper(II). The reagent forms stable chelate with copper(II) in buffer medium instantly and quantitatively extracted in chloroform within a minute. The method is successfully applied for the determination of copper(II) in various synthetic mixtures, complexes, fertilizers, environmental samples such as food samples, leafy vegetables, and water samples. The results are compared with those obtained with a reference procedure. Good agreement was attained. All the obtained results are indicative of a convenient, fast method for the extraction and quantification of micro levels of copper(II) from various environmental matrices without use of sophisticated instrumentation and procedure. The method showed a relative standard deviation of 0.42%. Copyright © 2017 Elsevier B.V. All rights reserved.

Design and validation of a new ratiometric intracellular pH imaging probe using lanthanide-doped upconverting nanoparticles.

PubMed

Du, Shuoren; Hernández-Gil, Javier; Dong, Hao; Zheng, Xiaoyu; Lyu, Guangming; Bañobre-López, Manuel; Gallo, Juan; Sun, Ling-Dong; Yan, Chun-Hua; Long, Nicholas J

2017-10-17

pH homeostasis is strictly controlled at a subcellular level. A deregulation of the intra/extra/subcellular pH environment is associated with a number of diseases and as such, the monitoring of the pH state of cells and tissues is a valuable diagnostic tool. To date, only a few tools have been developed to measure the pH in living cells with the spatial resolution needed for intracellular imaging. Among the techniques available, only optical imaging offers enough resolution and biocompatibility to be proposed for subcellular pH monitoring. We present herein a ratiometric probe based on upconversion nanoparticles modified with a pH sensitive moiety for the quantitative imaging of pH at the subcellular level in living cells. This system provides the properties required for live cell quantitative imaging i.e. positive cellular uptake, biocompatibility, long wavelength excitation, sensitive response to pH within a biologically relevant range, and self-referenced signal.

Formation of aerobic granular sludge and the influence of the pH on sludge characteristics in a SBR fed with brewery/bottling plant wastewater.

PubMed

Stes, Hannah; Aerts, Sven; Caluwé, Michel; Dobbeleers, Thomas; Wuyts, Sander; Kiekens, Filip; D'aes, Jolien; De Langhe, Piet; Dries, Jan

2018-05-01

A laboratory-scale sequencing batch reactor (SBR) was operated for 450 days to assess aerobic granule formation when treating brewery/bottling plant wastewater by consistent application of a feast/famine regime. The experiment was divided into three major periods according to the different operational conditions: (I) no pH control and strong fluctuations in organic loading rate (OLR) (1.18 ± 0.25 kgCOD·(m 3 ·day) -1 ), (II) pH control and aeration control strategy to reduce OLR fluctuations (1.45 ± 0.65 kgCOD·(m 3 ·day) -1 ) and (III) no pH control and stable OLR (1.42 ± 0.18 kgCOD·(m 3 ·day) -1 ). Aerobic granule formation was successful after 80 days and maintained during the subsequent 380 days. The aerobic granular sludge was characterized by SVI 5 and SVI 30 values below 60 mL.g -1 and dominated by granular, dense structures. An oxygen uptake rate based aeration control strategy insured endogenous respiration at the end of the aerobic phase, resulting in stable SBR operation when the influent composition fluctuated. The quantitative polymerase chain reaction results show no significant enrichment of Accumulibacter or Competibacter during the granulation process. The 16S rRNA sequencing results indicate enrichment of other, possibly important species during aerobic granule formation while treating brewery wastewaters.

Modeling the effects of pH and ionic strength on swelling of anionic polyelectrolyte gels

NASA Astrophysics Data System (ADS)

Drozdov, A. D.; deClaville Christiansen, J.

2015-07-01

A constitutive model is developed for the elastic response of an anionic polyelectrolyte gel under swelling in water with an arbitrary pH and an arbitrary molar fraction of dissolved monovalent salt. A gel is treated as a three-phase medium consisting of a solid phase (polymer network), solvent (water), and solute (mobile ions). Transport of solvent and solute is thought of as their diffusion through the polymer network accelerated by an electric field formed by mobile and fixed ions and accompanied by chemical reactions (dissociation of functional groups attached to polymer chains and formation of ion pairs between bound charges and mobile counter-ions). Constitutive equations are derived by means of the free energy imbalance inequality for an arbitrary three-dimensional deformation with finite strains. These relations are applied to analyze equilibrium swelling diagrams on poly(acrylic acid) gel, poly(methacrylic acid) gel, and three composite hydrogels under water uptake in a bath (i) with a fixed molar fraction of salt and varied pH, and (ii) with a fixed pH and varied molar fraction of salt. To validate the ability of the model to predict observations quantitatively, material constants are found by matching swelling curves under one type of experimental conditions and results of simulation are compared with experimental data in the other type of tests.

Fabrication of the tea saponin functionalized reduced graphene oxide for fast adsorptive removal of Cd(II) from water

NASA Astrophysics Data System (ADS)

Li, Zhigang; Liu, Zhifeng; Wu, Zhibin; Zeng, Guangming; Shao, Binbin; Liu, Yujie; Jiang, Yilin; Zhong, Hua; Liu, Yang

2018-05-01

A novel graphene-based material of tea saponin functionalized reduced graphene oxide (TS-RGO) was synthesized via a facil thermal method, and it was characterized as the absorbent for Cd(II) removal from aqueous solutions. The factors on adsorption process including solution pH, contact time, initial concentration of Cd(II) and background electrolyte cations were studied to optimize the conditions for maximum adsorption at room temperature. The results indicated that Cd(II) adsorption was strongly dependent on pH and could be strongly affected by background electrolytes and ionic strength. The optimal pH and required equilibrium time was 6.0 and 10 min, respectively. The Cd(II) removal decreased with the presence of background electrolyte cations (Na+ < Ca2+ < Al3+). The adsorption kinetics of Cd(II) followed well with the pseudo-second-order model. The adsorption isotherm fitted well to the Langmuir model, indicating that the adsorption was a monolayer adsorption process occurred on the homogeneous surfaces of TS-RGO. The maximum monolayer adsorption capacity was 127 mg/g at 313 K and pH 6.0. Therefore, the TS-RGO was considered to be a cost-effective and promising material for the removal of Cd(II) from wastewater.

Autocatalytic formation of an iron(IV)-oxo complex via scandium ion-promoted radical chain autoxidation of an iron(II) complex with dioxygen and tetraphenylborate.

PubMed

Nishida, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi

2014-06-04

A non-heme iron(IV)-oxo complex, [(TMC)Fe(IV)(O)](2+) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was formed by oxidation of an iron(II) complex ([(TMC)Fe(II)](2+)) with dioxygen (O2) and tetraphenylborate (BPh4(-)) in the presence of scandium triflate (Sc(OTf)3) in acetonitrile at 298 K via autocatalytic radical chain reactions rather than by a direct O2 activation pathway. The autocatalytic radical chain reaction is initiated by scandium ion-promoted electron transfer from BPh4(-) to [(TMC)Fe(IV)(O)](2+) to produce phenyl radical (Ph(•)). The chain propagation step is composed of the addition of O2 to Ph(•) and the reduction of the resulting phenylperoxyl radical (PhOO(•)) by scandium ion-promoted electron transfer from BPh4(-) to PhOO(•) to produce phenyl hydroperoxide (PhOOH), accompanied by regeneration of phenyl radical. PhOOH reacts with [(TMC)Fe(II)](2+) to yield phenol (PhOH) and [(TMC)Fe(IV)(O)](2+). Biphenyl (Ph-Ph) was formed via the radical chain autoxidation of BPh3 by O2. The induction period of the autocatalytic radical chain reactions was shortened by addition of a catalytic amount of [(TMC)Fe(IV)(O)](2+), whereas addition of a catalytic amount of ferrocene that can reduce [(TMC)Fe(IV)(O)](2+) resulted in elongation of the induction period. Radical chain autoxidation of BPh4(-) by O2 also occurred in the presence of Sc(OTf)3 without [(TMC)Fe(IV)(O)](2+), initiating the autocatalytic oxidation of [(TMC)Fe(II)](2+) with O2 and BPh4(-) to yield [(TMC)Fe(IV)(O)](2+). Thus, the general view for formation of non-heme iron(IV)-oxo complexes via O2-binding iron species (e.g., Fe(III)(O2(•-))) without contribution of autocatalytic radical chain reactions should be viewed with caution.

Molecular characterization of the group II chaperonin from the hyperthermophilic archaeum Pyrococcus horikoshii OT3.

PubMed

Okochi, Mina; Matsuzaki, Hiroki; Nomura, Tomoko; Ishii, Noriyuki; Yohda, Masafumi

2005-04-01

The group II chaperonin from the hyperthermophilic archaeum Pyrococcus horikoshii OT3 (PhCPN) and its functional cooperation with the cognate prefoldin were investigated. PhCPN existed as a homo-oligomer in a double-ring structure, which protected the citrate synthase of a porcine heart from thermal aggregation at 45 degrees C, and did the same on the isopropylmalate dehydrogenase (IPMDH) of a thermophilic bacterium, Thermus thermophilus HB8, at 90 degrees C. PhCPN also enhanced the refolding of green fluorescent protein (GFP), which had been unfolded by low pH, in an ATP-dependent manner. Unexpectedly, functional cooperation between PhCPN and Pyrococcus prefoldin (PhPFD) in the refolding of GFP was not observed. Instead, cooperation between PhCPN and PhPFD was observed in the refolding of IPMDH unfolded with guanidine hydrochloride. Although PhCPN alone was not effective in the refolding of IPMDH, the refolding efficiency was enhanced by the cooperation of PhCPN with PhPFD.

Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous Fe¹¹ solutions

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

Boparai, Hardiljeet K.; Comfort, Steve; Satapanajaru, Tunlawit

Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated FeII phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron FeII/FeIII minerals. This was accomplished by quantifying the effects of initial FeII concentration, pH, and the presence of aquifermore » solids (FeIII phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing FeII concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous FeII during HE treatment under anaerobic conditions. Geochemical modeling also predicted FeII activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated FeII/FeIII minerals in aqueous FeII solutions play in the transformation of high explosives.« less

p53-mediated inhibition of angiogenesis through up-regulation of a collagen prolyl hydroxylase.

PubMed

Teodoro, Jose G; Parker, Albert E; Zhu, Xiaochun; Green, Michael R

2006-08-18

Recent evidence suggests that antiangiogenic therapy is sensitive to p53 status in tumors, implicating a role for p53 in the regulation of angiogenesis. Here we show that p53 transcriptionally activates the alpha(II) collagen prolyl-4-hydroxylase [alpha(II)PH] gene, resulting in the extracellular release of antiangiogenic fragments of collagen type 4 and 18. Conditioned media from cells ectopically expressing either p53 or alpha(II)PH selectively inhibited growth of primary human endothelial cells. When expressed intracellularly or exogenously delivered, alpha(II)PH significantly inhibited tumor growth in mice. Our results reveal a genetic and biochemical linkage between the p53 tumor suppressor pathway and the synthesis of antiangiogenic collagen fragments.

pH-Dependent Assembly and Conversions of Six Cadmium(II)-Based Coordination Complexes

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

Fang, Hua-Cai; Zhu, Ji-Qin; Zhou, Li-Jiang

2010-07-07

Six cadmium(II) complexes containing N2O2 donor tetradentate asymmetrical Schiff base ligand 2-{[2-(dimethylamino)ethylimino]methyl}-6-methoxyphenol (HL5), namely, [(Cd3L52Cl4)2]•CH3OH•H2O (1), [Cd(L5)Cl]2•CH3OH (2), [Cd2(HL5)Cl4]n (3), {[Cd3(H2L5)2Cl8]•2H2O}n (4), [(H2L5)2]2+•[CdCl4]2-•H2O (5), and [(H2L5)2]2+•[CdCl4]2- (6), have been synthesized using cadmium(II) chloride and asymmetrical Schiff base ligand HL5 under different pH conditions at room temperature. The diverse structures show the marked sensitivity of the structural chemistry of the tetradentate asymmetrical Schiff base ligand HL5. Complex 1 formed at pH = 10 exhibits a rare zero- dimensional structure of trinuclear cadmium (II). At pH = 8-9, a dinuclear cadmium (II) complex 2 is formed. The reaction at pH = 5-7more » leads to two one-dimensional structures of 3 and 4. A further decrease of the pH to 3-5 results in a zero-dimensional structure 5. Owing to the departure of lattice water molecules in the crystal, complex 5 at room temperature can gradually undergo single-crystal-to-single-crystal transformation to result complex 6. The results further show that conversions of complex 1 to 5 can also be achieved by adjusting the pH value of the reaction solution, 1→2pH=8→5pH=3 and 3→4pH=5. Comparing these experimental results, it is clear that the pH plays a crucial role in the formation of the resulting structures, which simultaneously provide very effective strategies for constructing the CdII compounds with N2O2 donor tetradentate asymmetrical Schiff base ligand. The strong fluorescent emissions of the six compounds (1-6) make them potentially useful photoactive materials. Furthermore, six Schiff base cadmium complexes (1–6), with DPPH (2,2-dipheny1-1-picrylhydrazy1) as a co-oxidant exhibited the stronger scavenging activity.« less

Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate.

PubMed

Song, Jia; Jia, Shao-Yi; Yu, Bo; Wu, Song-Hai; Han, Xu

2015-08-30

Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of the Iron(II) Release Mechanism of Human H-Ferritin as a Function of pH.

PubMed

Sala, Davide; Ciambellotti, Silvia; Giachetti, Andrea; Turano, Paola; Rosato, Antonio

2017-09-25

We investigated the kinetics of the release of iron(II) ions from the internal cavity of human H-ferritin as a function of pH. Extensive molecular dynamics simulations of the entire 24-mer ferritin provided atomic-level information on the release mechanism. Double protonation of His residues at pH 4 facilitates the removal of the iron ligands within the C3 channel through the formation of salt bridges, resulting in a significantly lower release energy barrier than pH 9.

Binding of mercury(II) to aquatic humic substances: Influence of pH and source of humic substances

USGS Publications Warehouse

Haitzer, M.; Aiken, G.R.; Ryan, J.N.

2003-01-01

Conditional distribution coefficients (KDOM???) for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that KDOM??? values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (1022.5??1.0-1023.5??1.0 L kg-1), suggesting similar Hg(II) binding environments, presumably involving thiol groups, for the different isolates. KDOM??? values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)-DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (pKa = 10.3) and one other group (pKa = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)-DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).

Characterization of diatomite and its application for the retention of radiocobalt: role of environmental parameters.

PubMed

Sheng, Guodong; Dong, Huaping; Li, Yimin

2012-11-01

Clay minerals have been extensively studied because of their strong sorption and complexation ability. In this work, diatomite was characterized by using acid-base titration. Retention of radionuclide (60)Co(II) from aqueous solution by sorption onto diatomite was investigated by using batch technique under various environmental conditions such as pH, ionic strength, humic acid (HA), fulvic acid (FA), and temperature. The results indicated that the sorption of Co(II) onto diatomite was strongly dependent on pH. At low pH value, the sorption of Co(II) was dominated by outer-sphere surface complexation and ion exchange with Na(+)/H(+) on diatomite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH value. The D-R model fitted the sorption isotherms better than the Langmuir and Freundlich models. The thermodynamic parameters (ΔH(0), ΔS(0) and ΔG(0)) calculated from the temperature-dependent sorption isotherms suggested that the sorption of Co(II) was an endothermic and spontaneous process. In addition, diatomite showed higher sorption capacity than that of lots of the sorbents reported in the literatures we surveyed. From the results of Co(II) removal by diatomite, the optimum reaction conditions can be obtained for the maximum removal of Co(II) from water. It is clear that the best pH values of the system to remove Co(II) from solution by using diatomite are 7-8. Considering the low cost and effective disposal of Co(II)-contaminated wastewaters, the best condition for Co(II) removal is at room temperature and solid content of 0.5 g/L. The results might be important for assessing the potential of practical application of diatomite in Co(II) and related radionuclide pollution management. Copyright © 2012 Elsevier Ltd. All rights reserved.

Purification and characterization of two distinct acidic phytases with broad pH stability from Aspergillus niger NCIM 563.

PubMed

Soni, S K; Magdum, A; Khire, J M

2010-11-01

Aspergillus niger NCIM 563 produced two different extracellular phytases (Phy I and Phy II) under submerged fermentation conditions at 30°C in medium containing dextrin-glucose-sodium nitrate-salts. Both the enzymes were purified to homogeneity using Rotavapor concentration, Phenyl-Sepharose column chromatography and Sephacryl S-200 gel filtration. The molecular mass of Phy I and II as determined by SDS-PAGE and gel filtration were 66, 264, 150 and 148 kDa respectively, indicating that Phy I consists of four identical subunits and Phy II is a monomer. The pI values of Phy I and II were 3.55 and 3.91, respectively. Phy I was highly acidic with optimum pH of 2.5 and was stable over a broad pH range (1.5-9.0) while Phy II showed a pH optimum of 5.0 with stability in the range of pH 3.5-9.0. Phy I exhibited very broad substrate specificity while Phy II was more specific for sodium phytate. Similarly Phy II was strongly inhibited by Ag(+), Hg(2+) (1 mM) metal ions and Phy I was partially inhibited. Peptide analysis by Mass Spectrometry (MS) MALDI-TOF also indicated that both the proteins were totally different. The K(m) for Phy I and II for sodium phytate was 2.01 and 0.145 mM while V(max) was 5,018 and 1,671 μmol min(-1) mg(-1), respectively. The N-terminal amino acid sequences of Phy I and Phy II were FSYGAAIPQQ and GVDERFPYTG, respectively. Phy II showed no homology with Phy I and any other known phytases from the literature suggesting its unique nature. This, according to us, is the first report of two distinct novel phytases from Aspergillus niger.

Sorption and reduction of selenite on chlorite surfaces in the presence of Fe(II) ions.

PubMed

Baik, Min Hoon; Lee, Seung Yeop; Jeong, Jongtae

2013-12-01

The sorption and reduction of selenite on chlorite surfaces in the presence of Fe(II) ions were investigated as a function of pH, Se(IV) concentration, and Fe(II) concentration under an anoxic condition. The sorption of Se(IV) onto chlorite surfaces followed the Langmuir isotherm regardless of the presence of Fe(II) ions in the solution. The Se(IV) sorption was observed to be very low at all pH values when the solution was Fe(II)-free or the concentration of Fe(II) ions was as low as 0.5 mg/L. However, the Se(IV) sorption was enhanced at a pH > 6.5 when the Fe(II) concentration was higher than 5 mg/L because of the increased sorption of Fe(II) onto the chlorite surfaces. XANES (X-ray absorption near edge structure) spectra of the Se K-edge showed that most of the sorbed Se(IV) was reduced to Se(0) by Fe(II) sorbed onto the chlorite surfaces, especially at pH > 9. The combined results of field-emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) also showed that elemental selenium and goethite were formed and precipitated on the chlorite surfaces during the sorption of selenite. Consequently it can be concluded that Se(IV) can be reduced to Se(0) in the presence of Fe(II) ions by the surface catalytic oxidation of Fe(II) into Fe(III) and the formation of goethite at neutral and particularly alkaline conditions. Thus the mobility of selenite in groundwater is expected to be reduced by the presence of a relatively higher concentration of Fe(II) in subsurface environments. Copyright © 2013 Elsevier Ltd. All rights reserved.

Relative abundance of chemical forms of Cu(II) and Cd(II) on soybean roots as influenced by pH, cations and organic acids

PubMed Central

Zhou, Qin; Liu, Zhao-dong; Liu, Yuan; Jiang, Jun; Xu, Ren-kou

2016-01-01

Little information is available on chemical forms of heavy metals on integrate plant roots. KNO3 (1 M), 0.05M EDTA at pH6 and 0.01 M HCl were used sequentially to extract the exchangeable, complexed and precipitated forms of Cu(II) and Cd(II) from soybean roots and then to investigate chemical form distribution of Cu(II) and Cd(II) on soybean roots. Cu(II) and Cd(II) adsorbed on soybean roots were mainly exchangeable form, followed by complexed form, while their precipitated forms were very low under acidic conditions. Soybean roots had a higher adsorption affinity to Cu(II) than Cd(II), leading to higher toxic of Cu(II) than Cd(II). An increase in solution pH increased negative charge on soybean and thus increased exchangeable Cu(II) and Cd(II) on the roots. Ca2+, Mg2+ and NH4+ reduced exchangeable Cu(II) and Cd(II) levels on soybean roots and these cations showed greater effects on Cd(II) than Cu(II) due to greater adsorption affinity of the roots to Cu(II) than Cd(II). L-malic and citric acids decreased exchangeable and complexed Cu(II) on soybean roots. In conclusion, Cu(II) and Cd(II) mainly existed as exchangeable and complexed forms on soybean roots. Ca2+ and Mg2+ cations and citric and L-malic acids can potentially alleviate Cu(II) and Cd(II) toxicity to plants. PMID:27805020

Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite

NASA Astrophysics Data System (ADS)

Jones, Adele M.; Collins, Richard N.; Waite, T. David

2017-12-01

The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, -13.5 and -122.3 mV vs. SHE at pH 6.5, and -22.9, -84.1 and -189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to -126.4 mV over a week, and from -20.1 mV to -188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe(II) species with which it is in equilibrium. As an Fe(III) (oxyhydr)oxide suspension in equilibrium with aqueous and adsorbed Fe(II) species possesses a single, unique reduction potential, this suggests that adsorbed Fe(II) is a more facile reductant than aqueous Fe(II).

Newly developed vaginal atrophy symptoms II and vaginal pH: a better correlation in vaginal atrophy?

PubMed

Tuntiviriyapun, P; Panyakhamlerd, K; Triratanachat, S; Chatsuwan, T; Chaikittisilpa, S; Jaisamrarn, U; Taechakraichana, N

2015-04-01

The primary objective of this study was to evaluate the correlation among symptoms, signs, and the number of lactobacilli in postmenopausal vaginal atrophy. The secondary objective was to develop a new parameter to improve the correlation. A cross-sectional descriptive study. Naturally postmenopausal women aged 45-70 years with at least one clinical symptom of vaginal atrophy of moderate to severe intensity were included in this study. All of the objective parameters (vaginal atrophy score, vaginal pH, the number of lactobacilli, vaginal maturation index, and vaginal maturation value) were evaluated and correlated with vaginal atrophy symptoms. A new parameter of vaginal atrophy, vaginal atrophy symptoms II, was developed and consists of the two most bothersome symptoms (vaginal dryness and dyspareunia). Vaginal atrophy symptoms II was analyzed for correlation with the objective parameters. A total of 132 naturally postmenopausal women were recruited for analysis. Vaginal pH was the only objective parameter found to have a weak correlation with vaginal atrophy symptoms (r = 0.273, p = 0.002). The newly developed vaginal atrophy symptoms II parameter showed moderate correlation with vaginal pH (r = 0.356, p < 0.001) and a weak correlation with the vaginal atrophy score (r = 0.230, p < 0.001). History of sexual intercourse within 3 months was associated with a better correlation between vaginal atrophy symptoms and the objective parameters. Vaginal pH was significantly correlated with vaginal atrophy symptoms. The newly developed vaginal atrophy symptoms II was associated with a better correlation. The vaginal atrophy symptoms II and vaginal pH may be better tools for clinical evaluation and future study of the vaginal ecosystem.

TOXNET: Toxicology Data Network

MedlinePlus

... 4. Supporting Data for Carcinogenicity Expand II.B. Quantitative Estimate of Carcinogenic Risk from Oral Exposure II. ... of Confidence (Carcinogenicity, Oral Exposure) Expand II.C. Quantitative Estimate of Carcinogenic Risk from Inhalation Exposure II. ...

Kinetics, equilibrium, and thermodynamics investigation on the adsorption of lead(II) by coal-based activated carbon.

PubMed

Yi, Zhengji; Yao, Jun; Zhu, Mijia; Chen, Huilun; Wang, Fei; Liu, Xing

2016-01-01

The goal of this research is to investigate the feasibility of using activated coal-based activated carbon (CBAC) to adsorb Pb(II) from aqueous solutions through batch tests. Effects of contact time, pH, temperature and initial Pb(II) concentration on the Pb(II) adsorption were examined. The Pb(II) adsorption is strongly dependent on pH, but insensitive to temperature. The best pH for Pb(II) removal is in the range of 5.0-5.5 with more than 90 % of Pb(II) removed. The equilibrium time was found to be 60 min and the adsorption data followed the pseudo-second-order kinetics. Isotherm data followed Langmuir isotherm model with a maximum adsorption capacity of 162.33 mg/g. The adsorption was exothermic and spontaneous in nature. The Fourier transform infrared spectroscopy and scanning electron microscopy analysis suggested that CBAC possessed a porous structure and was rich in carboxyl and hydroxyl groups on its surface, which might play a major role in Pb(II) adsorption. These findings indicated that CBAC has great potential as an alternative adsorbent for Pb(II) removal.

Exploring the Effect of Surface Functionality on the Self-Assembly of Polyoxopalladate Macroions

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

Haso, Fadi; Yang, Peng; Gao, Yunyi

2015-05-12

The solution behavior of the two polyoxo-13-palladates(II) ([Pd(II) 13 As(V) 8 O34 (OH)6 ](8-) and [Pd(II) 13 (As(V) Ph)8 O32 ](6-) ) was studied in detail. We discovered that the countercation-mediated attraction is the driving force for their self-assembly into larger architectures. However, the presence of phenyl groups in the periphery of [Pd(II) 13 (As(V) Ph)8 O32 ](6-) results in an enhanced attraction among these polyanions through hydrophobic interactions, which leads to completely different trends of assembly size for these two very similar clusters when decreasing solvent polarity. An increase of assembly size with increasing solvent polarity was observed formore » [Pd(II) 13 (As(V) Ph)8 O32 ](6-) , whereas for [Pd(II) 13 As (V) 8 O34 (OH)6 ](8-) it was the opposite, due to the absence of hydrophobic interactions.« less

Thermodynamic controls on the kinetics of microbial low-pH Fe(II) oxidation.

PubMed

Larson, Lance N; Sánchez-España, Javier; Kaley, Bradley; Sheng, Yizhi; Bibby, Kyle; Burgos, William D

2014-08-19

Acid mine drainage (AMD) is a major worldwide environmental threat to surface and groundwater quality. Microbial low-pH Fe(II) oxidation could be exploited for cost-effective AMD treatment; however, its use is limited because of uncertainties associated with its rate and ability to remove Fe from solution. We developed a thermodynamic-based framework to evaluate the kinetics of low-pH Fe(II) oxidation. We measured the kinetics of low-pH Fe(II) oxidation at five sites in the Appalachian Coal Basin in the US and three sites in the Iberian Pyrite Belt in Spain and found that the fastest rates of Fe(II) oxidation occurred at the sites with the lowest pH values. Thermodynamic calculations showed that the Gibbs free energy of Fe(II) oxidation (ΔG(oxidation)) was also most negative at the sites with the lowest pH values. We then conducted two series of microbial Fe(II) oxidation experiments in laboratory-scale chemostatic bioreactors operated through a series of pH values (2.1-4.2) and found the same relationships between Fe(II) oxidation kinetics, ΔG(oxidation), and pH. Conditions that favored the fastest rates of Fe(II) oxidation coincided with higher Fe(III) solubility. The solubility of Fe(III) minerals, thus plays an important role on Fe(II) oxidation kinetics. Methods to incorporate microbial low-pH Fe(II) oxidation into active and passive AMD treatment systems are discussed in the context of these findings. This study presents a simplified model that describes the relationship between free energy and microbial kinetics and should be broadly applicable to many biogeochemical systems.

Unexpected dependence on pH of NO release from Paracoccus pantotrophus cytochrome cd1.

PubMed

Sam, Katharine A; Tolland, John D; Fairhurst, Shirley A; Higham, Christopher W; Lowe, David J; Thorneley, Roger N F; Allen, James W A; Ferguson, Stuart J

2008-07-11

A previous study of nitrite reduction by Paracoccus pantotrophus cytochrome cd(1) at pH 7.0 identified early reaction intermediates. The c-heme rapidly oxidised and nitrite was reduced to NO at the d(1)-heme. A slower equilibration of electrons followed, forming a stable complex assigned as 55% cFe(III)d(1)Fe(II)-NO and 45% cFe(II)d(1)Fe(II)-NO(+). No catalytically competent NO release was observed. Here we show that at pH 6.0, a significant proportion of the enzyme undergoes turnover and releases NO. An early intermediate, which was previously overlooked, is also identified; enzyme immediately following product release is a candidate. However, even at pH 6.0 a considerable fraction of the enzyme remains bound to NO so another component is required for full product release. The kinetically stable product formed at the end of the reaction differs significantly at pH 6.0 and 7.0, as does its rate of formation; thus the reaction is critically dependent on pH.

Application of mucilage from Dicerocaryum eriocarpum plant as biosorption medium in the removal of selected heavy metal ions.

PubMed

Jones, Bassey O; John, Odiyo O; Luke, Chimuka; Ochieng, Aoyi; Bassey, Bridget J

2016-07-15

The ability of mucilage from Dicerocaryum eriocarpum (DE) plant to act as biosorption medium in the removal of metals ions from aqueous solution was investigated. Functional groups present in the mucilage were identified using Fourier transform infrared spectroscopy (FTIR). Mucilage was modified with sodium and potassium chlorides. This was aimed at assessing the biosorption efficiency of modified mucilage: potassium mucilage (PCE) and sodium mucilage (SCE) and comparing it with non-modified deionised water mucilage (DCE) in the uptake of metal ions. FTIR results showed that the functional groups providing the active sites in PCE and SCE and DCE include: carboxyl, hydroxyl and carbonyl groups. The chloride used in the modification of the mucilage did not introduce new functional groups but increased the intensity of the already existing functional groups in the mucilage. Results from biosorption experiment showed that DE mucilage displays good binding affinity with metals ions [Zn(II), Cd(II) Ni(II), Cr(III) and Fe(II)] in the aqueous solution. Increase in the aqueous solution pH, metal ions initial concentration and mucilage concentration increased the biosorption efficiency of DE mucilage. The maximum contact time varied with each species of metal ions. Optimum pH for [Zn(II), Cd(II) Ni(II) and Fe(II)] occurred at pH 4 and pH 6 for Cr(III). Kinetic models result fitted well to pseudo-second-order with a coefficient values of R(2) = 1 for Cd(II), Ni(II), Cr(III), Fe(II) and R(2) = 0.9974 for Zn(II). Biosorption isotherms conforms best with Freundlich model for all the metal ions with correlation factors of 0.9994, 0.9987, 0.9554, 0.9621 and 0.937 for Zn(II), Ni(II), Fe(II), Cr(III) and Cd(II), respectively. Biosorption capacity of DE mucilage was 0.010, 2.387, 4.902, 0688 and 0.125 for Zn(II), Cr(III), Fe(II), Cd(II) and Ni(II) respectively. The modified mucilage was found to be highly efficient in the removal of metal ions than the unmodified mucilage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems.

PubMed

Nie, Zhe; Finck, Nicolas; Heberling, Frank; Pruessmann, Tim; Liu, Chunli; Lützenkirchen, Johannes

2017-04-04

Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints.

Sensitive and selective detection of Cu(II) ion: A new effective 1,8-naphthalimide-based fluorescence 'turn off' sensor.

PubMed

Huang, Guozhen; Li, Chuang; Han, Xintong; Aderinto, Stephen Opeyemi; Shen, Kesheng; Mao, Shanshan; Wu, Huilu

2018-06-01

The present study reports the development of a new 1,8-naphthalimide-based fluorescent sensor V for monitoring Cu(II) ions. The sensor exhibited pH independence over a wide pH range 2.52-9.58, and indicated its possible use for monitoring Cu(II) ions in a competitive pH medium. The sensor also showed high selectivity and sensitivity towards the Cu(II) ions over other competitive metal ions in DMSO-HEPES buffer (v/v, 1:1; pH 7.4) with a fluorescence 'turn off' mode of 79.79% observed. A Job plot indicated the formation of a 1:1 binding mode of the sensor with Cu(II) ions. The association constant and detection limit were 1.14 × 10 6  M -1 and 4.67 × 10 -8 M, respectively. The fluorescence spectrum of the sensor was quenched due to the powerful paramagnetic nature of the Cu(II) ions. Potential application of this sensor was also demonstrated when determining Cu(II) ion levels in two different water samples. Copyright © 2018 John Wiley & Sons, Ltd.

Copper-Hydroperoxo Mediated N-Debenzylation Chemistry Mimicking Aspects of Copper Monoxygenases

PubMed Central

Maiti, Debabrata; Narducci Sarjeant, Amy A.; Karlin, Kenneth D.

2008-01-01

Substantial oxidative N-debenzylation reaction along with PhCH=O formation occurs from a hydroperoxo copper(II) complex which has a dibenzylamino substrate (-N(CH2Ph)2 appended as a substituent on one pyridyl group of its tripodal tetradentate TMPA {≡ TPA ≡ tris(2-pyridylmethyl)amine)} ligand framework. During the course of the (LN(CH2Ph)2)CuII(−OOH) reactivity, formation of a substrate and −OOH (an oxygen atom) derived alkoxo CuII(−OR) complex occurs. The observation that the same CuII(−OR) species occurs from CuI/PhIO chemistry suggests the possibility that a copper-oxo (cupryl) reactive intermediate forms during alkoxo species formation, and new ESI-MS data obtained provides some further support for this high-valent intermediate. Net H-atom abstraction chemistry is proposed, based on kinetic isotope effect studies provided here and that previously published for a closely related CuII(−OOH) species incorporating dimethylamine (-N(CH3)2) as the internal substrate (J. Am. Chem. Soc. 2007, 129, 6720-6721); the CuI/PhIO reactivity, with similar isotope effect results, provides further support. The reactivity of these chemical systems closely resembles proposed oxidative N-dealkylation mechanisms effected by the copper-monooxygenases dopamine β-monooxygenase (DβM) or peptidylglycine-α-hydroxylating monooxygenase (PHM). PMID:18783212

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

Liu, Juan; Wang, Zheming; Belchik, Sara M.

The Gram-negative bacterium Sideroxydans lithotrophicus ES-1 (ES-1) grows on FeCO{sub 3} or FeS at oxic-anoxic interfaces at circumneutral pH, and the ES-1-mediated Fe(II) oxidation occurs extracellularly. However, the molecular mechanisms underlying ES-1's ability to oxidize Fe(II) remain unknown. Survey of the ES-1 genome for the genes known for microbial extracellular Fe(II) oxidation revealed that it contained a three-gene cluster encoding an MtrA homologue, an MtrB homologue and a CymA homologue. The homologues of MtrA, MtrB and/or CymA were previously shown to be involved in extracellular Fe(II) oxidation by Rhodopseudomonas palustris TIE-1 and in extracellular Fe(III) reduction by Shewanella oneidensis MR-1more » (MR-1). To distinguish them from those found in MR-1, the identified homologues were named MtoAB and CymA{sub ES-1}, respectively. The gene for MtoA was cloned, and cloned mtoA partially complemented an MR-1 mutant without MtrA in ferrihydrite reduction. Following overexpression in MR-1 cells, recombinant MtoA was purified. Characterization of purified MtoA showed that it was a decaheme c-type cytochrome and oxidized soluble Fe(II). Oxidation of Fe(II) by MtoA was pH- and Fe(II)-complexing ligand-dependent. Under conditions tested, MtoA oxidized Fe(II) at pH ranging from 7-9, and optimal oxidation occurred at pH 9, possibly because of the attendant net increase of [Fe(OH){sup +}] at higher pH. MtoA oxidized Fe(II) complexed with different ligands at different rates. The reaction rates followed the order Fe(II)Cl2 > Fe(II)-citrate > Fe(III)-NTA > Fe(II)-EDTA with the second-order rate constants ranging from 5.5 x 10{sup -3} {micro}M{sup -1}s{sup -1} for oxidation of Fe(II)Cl{sub 2} to 1.0 x 10{sup -3} {micro}M{sup -1}s{sup -1} for oxidation of Fe(II)-EDTA. Thermodynamic modeling shows that redox reaction rate differences for the different Fe(II)-complexes correlated with estimated reaction-free energies. Collectively, these results suggest that MtoA is a functional Fe(II)-oxidizing protein that, by working in concert with MtoB and CymAES 1, may oxidize the Fe(II) on the bacterial surface and transfer released electrons across the bacterial cell envelope to the quinone pool in the inner membrane during extracellular Fe(II) oxidation by ES-1.« less

Use of red mud (bauxite residue) for the retention of aqueous inorganic mercury(II).

PubMed

Rubinos, David A; Barral, María Teresa

2015-11-01

The effectiveness of the oxide-rich residue from bauxite refining (red mud) to remove inorganic Hg(II) from aqueous solutions was assessed. The aspects studied comprised the kinetics of the process (t = 1 min-24 h), the effect of pH (3.5-11.5), the interacting effect between salt concentration (0.01-1 M NaNO3) and pH and the Hg(II) sorption isotherm. Hg leaching from spent red mud was evaluated using the toxicity characteristics leaching procedure (TCLP) method. The sorption of Hg(II) onto red mud was very fast, with most of Hg(II) (97.0-99.7%) being removed from 0.5-50 μM Hg solutions in few minutes. The kinetic process was best described by Ho's pseudo-second order equation, pointing to chemisorption as the rate controlling step. Hg(II) sorption efficiency was very high (% removal between 93.9 and 99.8%) within all the studied pH range (3.5-11.5) and added Hg concentrations (5 and 50 μM), being optimal at pH 5-8 and decreasing slightly at both lowest and highest pH. The effect of background electrolyte concentration suggests specific sorption as the main interaction mechanism between Hg(II) and red mud, but the increasing non-sorbed Hg concentrations at low and high pH for higher electrolyte concentrations also revealed the contribution of an electrostatic component to the process. The sorption isotherm showed the characteristic shape of high affinity sorbents, and it was better described by the Redlich-Peterson and Freundlich equations, which are models that assume sorbent heterogeneity and involvement of more than one mechanism. The estimated Hg(II) sorption capacity from the Langmuir equation (q m ~9 mmol/kg) was comparable to those of some inorganic commercial sorbents but lower than most bio- or specifically designed sorbents. The leachability of retained Hg(II) from spent red mud (0.02, 0.25 and 2.42 mmol Hg/kg sorbed concentration) was low (0.28, 1.15 and 2.23 μmol/kg, respectively) and accounted for 1.2, 0.5 and 0.1% of previously sorbed Hg, indicating that Hg(II) is tightly bound by red mud once sorbed.

Ion-imprinted polymethacrylic microbeads as new sorbent for preconcentration and speciation of mercury.

PubMed

Dakova, Ivanka; Karadjova, Irina; Georgieva, Ventsislava; Georgiev, George

2009-04-30

Metal ion-imprinted polymer particles have been prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as cross-linking agent and 2,2'-azobisisobutyronitrile as initiator, in the presence of Hg(II)-1-(2-thiazolylazo)-2-naphthol complex. The separation and preconcentration characteristics of the Hg-ion-imprinted microbeads for inorganic mercury have been investigated by batch procedure. The optimal pH value for the quantitative sorption is 7. The adsorbed inorganic mercury is easily eluted by 2 mL 4M HNO(3). The adsorption capacity of the newly synthesized Hg ion-imprinted microbeads is 32.0 micromol g(-1) for dry copolymer. The selectivity of the copolymer toward inorganic mercury (Hg(II)) ion is confirmed through the comparison of the competitive adsorptions of Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II)) and high values of the selectivity and distribution coefficients have been calculated. Experiments performed for selective determination of inorganic mercury in mineral and sea waters showed that the interfering matrix does not influence the extraction efficiency of Hg ion-imprinted microbeads. The detection limit for inorganic mercury is 0.006 microg L(-1) (3 sigma), determined by cold vapor atomic adsorption spectrometry. The relative standard deviation varied in the range 5-9 % at 0.02-1 microg L(-1) Hg levels. The new Hg-ion-imprinted microbeads have been tested and applied for the speciation of Hg in river and mineral waters: inorganic mercury has been determined selectively in nondigested sample, while total mercury e.g. sum of inorganic and methylmercury, has been determined in digested sample.

Removal Efficiency of the Heavy Metals Zn(II), Pb(II) and Cd(II) by Saprolegnia delica and Trichoderma viride at Different pH Values and Temperature Degrees

PubMed Central

Hashem, Mohamed

2007-01-01

The removal efficiency of the heavy metals Zn, Pb and Cd by the zoosporic fungal species Saprolegnia delica and the terrestrial fungus Trichoderma viride, isolated from polluted water drainages in the Delta of Nile in Egypt, as affected by various ranges of pH values and different temperature degrees,was extensively investigated. The maximum removal efficiency of S. delica for Zn(II) and Cd(II) was obtained at pH 8 and for Pb(II) was at pH 6 whilst the removal efficiency of T. viride was found to be optimum at pH 6 for the three applied heavy metals. Regardless the median lethal doses of the three heavy metals, Zn recorded the highest bioaccumulation potency by S. delica at all pH values except at pH 4, followed by Pb whereas Cd showed the lowest removal potency by the fungal species and vice versa in case of T. viride. The optimum biomass dry weight production by S. delica was found when the fungus was grown in the medium treated with the heavy metal Pb at pH 6, followed by Zn at pH 8 and Cd at pH 8. The optimum biomass dry weight yield by T. viride amended with Zn,Pb and Cd was obtained at pH 6 for the three heavy metals with the maximum value at Zn. The highest yield of biomass dry weight was found when T. viride treated with Cd at all different pH values followed by Pb whilst Zn output was the lowest and this result was reversed in case of S. delica. The maximum removal efficiency and the biomass dry weight production for the three tested heavy metals was obtained at the incubation temperature 20℃ in case of S. delica while it was 25℃ for T. viride. Incubation of T. viride at higher temperatures (30℃ and 35℃) enhanced the removal efficiency of Pb and Cd than low temperatures (15℃ and 20℃) and vice versa in case of Zn removal. At all tested incubation temperatures, the maximum yield of biomass dry weight was attained at Zn treatment by the two tested fungal species. The bioaccumulation potency of S. delica for Zn was higher than that for Pb at all temperature degrees of incubation and Cd bioaccumulation was the lowest whereas T. viride showed the highest removal efficiency for Pb followed by Cd and Zn was the minor of the heavy metals. PMID:24015084

Carbon dioxide, oxygen, and pH detection in animal adipose tissue by means of extracorporeal microdialysis

NASA Astrophysics Data System (ADS)

Baldini, F.; Bizzarri, A.; Cajlakovic, M.; Feichtner, F.; Gianesello, L.; Giannetti, A.; Gori, G.; Konrad, C.; Mencaglia, A. A.; Mori, E.; Pavoni, V.; Perna, A. M.; Trono, C.

2007-05-01

Atypical physiological symptoms can be developed in healthy people under critically ill conditions. pH, pO II and pCO II are informative indicators of the conditions of a living system and can be valuable in determining the physiologic status of the critically ill patients. The continuous monitoring of these small molecules into the interstitial fluid (ISF) is a promising approach to reduce diagnostic blood loss and painful stress associated with blood sampling. Microdialysis is the approach followed for the extraction of the sample from the subcutaneous adipose tissue; the drawn interstitial fluid flows through a microfluidic circuit formed by the microdialysis catheter in series with a glass capillary on the internal wall of which the appropriate chemistry for sensing is immobilised. Absorption changes for pH sensor and modulation of the fluorescence lifetime for pO II and pCO II are the working principle. Phenol red covalently bound into the internal wall of a glass capillary by means of the Mannich reaction and platinum(II) tetrakis-pentafluorophenyl-porphyrine entrapped within a polymerised polystyrene layer are the chemical transducers used for pH and oxygen detection; the ion pair 8- hydroxypyrene-1,3,6-trisulfonic acid trisodium salt/ tetraoctylammonium hydroxide, dissolved in a silicon-based polymeric matrix, is used for the carbon dioxide detection. A suitable hemorrhagic shock model was developed in order to validate clinically the developed sensors in the condition of extreme stress and the obtained results show that the adipose tissue can become an alternative site for the continuous oitoring of pH, pO II and pCO II.

Te(II)/Te(IV) Mediated C-N Bond Formation on 2,5-Diphenyltellurophene and a Reassignment of the Product from the Reaction of PhI(OAc)2 with 2 TMS-OTf.

PubMed

Aprile, Antonino; Iversen, Kalon J; Wilson, David J D; Dutton, Jason L

2015-05-18

We report a novel C-H to C-N bond metathesis at the 3-position of 1,2-diphenyltellurophene via oxidation of the Te(II) center to Te(IV) using the I(III) oxidant [PhI(4-DMAP)2](2+). Spontaneous reduction of a transient Te(IV) coordination compound to Te(II) generates an electrophilic equivalent of 4-DMAP that substitutes at a C-H bond at the 3-position of the tellurophene. Theoretical and synthetic reaction pathway studies confirm that a Te(IV) coordination complex with 4-DMAP is an intermediate. In the course of these pathway studies, it was also found that the identity of the I(III) oxidant generated from PhI(OAc)2 and 2 TMS-OTf is PhI(OAc)(OTf) and not PhI(OTf)2, as had been previously thought.

Redox Non-Innocence of Nitrosobenzene at Nickel

DOE PAGES

Kundu, Subrata; Stieber, S. Chantal; Ferrier, Maryline Ghislaine; ...

2016-08-22

Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox-active nitric oxide derivative. Capture of nitrosobenzene at the electrondeficient β-diketiminato nickel(I) complex [ iPr 2NN F6]Ni results in reduction of the PhNO ligand to a (PhNO) ./ ⁻ species coordinated to a square planar Ni II center in [ iPr 2NN F6]Ni(η 2- ONPh). Ligand centered reduction leads to the (PhNO) -2 moiety bound to Ni II supported by XAS studies. Ultimately, systematic investigation of structure–reactivity patterns of (PhNO) ./ ⁻ and (PhNO) 2- ligands reveals parallels with superoxo (O 2) ./ ⁻ and peroxo (Omore » 2) 2- ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand.« less

Evaluation of Sorption Mechanism of Pb (II) and Ni (II) onto Pea (Pisum sativum) Peels.

PubMed

Haq, Atta Ul; Saeed, Muhammad; Anjum, Salma; Bokhari, Tanveer Hussain; Usman, Muhammad; Tubbsum, Saiqa

2017-07-01

The present study was carried out to know the sorption mechanism of Pb (II) and Ni (II) in aqueous solution using pea peels under the influence of sorbent dose, pH, temperature, initial metal ion concentration and contact time. SEM and FTIR were used for characterization of pea peels. The study showed that solution pH affects sorption process and the optimum pH for Pb (II) was 6.0 while for that of Ni (II) was 7.0. Pseudo-second order kinetic model was found to be the most suitable one to explain the kinetic data not only due to high value of R 2 (>0.99) but also due to the closeness of the experimental sorption capacity values to that of calculated sorption capacity values of pseudo second order kinetic model. It can be seen from the results that Freundlich isotherm explains well the equilibrium data (R 2 >0.99). Sorption capacity of pea peels was 140.84 and 32.36 for Pb (II) and Ni (II) mg g -1 respectively. The positive value of ΔH° and negative values of ΔG° suggest that sorption of Pb (II) and Ni (II) onto pea peels is an endothermic and spontaneous process respectively.

Estimation of the IC to CG Ratio Using JEM-GLIMS and Ground-based Lightning Network Data

NASA Astrophysics Data System (ADS)

Bandholnopparat, K.; Sato, M.; Takahashi, Y.; Adachi, T.; Ushio, T.

2017-12-01

The ratio between intracloud (IC) discharge and cloud-to-ground (CG) discharge, which is denoted by Z, is the important parameter for the studies on the climatological differences of thunderstorm structures and for the quantitative evaluation of lightning contributions to the global electric circuit. However, the latitudinal, regional, and seasonal dependences of Z-value are not fully clarified. The purposes of this study are (i) to develop new methods to identify IC and CG discharges using optical data obtained by the Global Lightning and Sprite Measurements on Japanese Experiment Module (JEM-GLIMS) from space and ground-based lightning data, (ii) to estimate Z-value and its latitudinal, regional, and seasonal dependences. As a first step, we compared the JEM-GLIMS data to the ground-based lightning data obtained by JLDN, NLDN, WWLLN, and GEON in order to distinguish the lightning discharge type detected by JEM-GLIMS. As a next step, we have calculated intensity ratios between the blue and red PH channels, that is, PH2(337 nm)/PH3(762 nm), PH5(316 nm)/PH3, PH6(392 nm)/PH3, PH2/PH4(599-900 nm), PH5/PH4, and PH6/PH4 for each lightning event. From these analyses, it is found that 447 and 454 of 8355 lightning events were identified to be CG and IC discharges, respectively. It is also found that the PH intensity ratio of IC discharges is clearly higher than that of CG discharges. In addition, the difference of the PH2/PH3, PH2/PH4, and PH6/PH4 ratio between IC and CG cases is relatively large, which means these three ratios are the useful proxy to classify the discharge types for other 7454 lightning events. Finally, the estimated Z-value varies from 0.18 - 0.84 from the equator to the higher latitude. The decrease of the Z-value from the equator to the higher latitude is confirmed both in the northern and the southern hemispheres. Although this latitudinal dependence of the Z-value is similar to previous studies, i.e., Boccippio et al. (2001), the estimated absolute Z-value is smaller than that in previous studies. The reason of the smaller absolute Z-value may be because JEM-GLIMS used the high threshold for the event triggering and missed many lightning events having lower optical energies. At the presentation, we will show the regional and seasonal dependences of the Z-value in detail.

Removal of bisphenol A and some heavy metal ions by polydivinylbenzene magnetic latex particles.

PubMed

Marzougui, Zied; Chaabouni, Amel; Elleuch, Boubaker; Elaissari, Abdelhamid

2016-08-01

In this study, magnetic polydivinylbenzene latex particles MPDVB with a core-shell structure were tested for the removal of bisphenol A (BPA), copper Cu(II), lead Pb(II), and zinc Zn(II) from aqueous solutions by a batch-adsorption technique. The effect of different parameters, such as initial concentration of pollutant, contact time, adsorbent dose, and initial pH solution on the adsorption of the different adsorbates considered was investigated. The adsorption of BPA, Cu(II), Pb(II), and Zn(II) was found to be fast, and the equilibrium was achieved within 30 min. The pH 5-5.5 was found to be the most suitable pH for metal removal. The presence of electrolytes and their increasing concentration reduced the metal adsorption capacity of the adsorbent. Whereas, the optimal pH for BPA adsorption was found 7, both hydrogen bonds and π-π interaction were thought responsible for the adsorption of BPA on MPDVB. The adsorption kinetics of BPA, Cu(II), Pb(II), and Zn(II) were found to follow a pseudo-second-order kinetic model. Equilibrium data for BPA, Cu(II), Pb(II), and Zn(II) adsorption were fitted well by the Langmuir isotherm model. Furthermore, the desorption and regeneration studies have proven that MPDVB can be employed repeatedly without impacting its adsorption capacity.

Adsorption behavior and mechanism of Cd(II) on loess soil from China.

PubMed

Wang, Yan; Tang, Xiaowu; Chen, Yunmin; Zhan, Liangtong; Li, Zhenze; Tang, Qiang

2009-12-15

Cadmium is a toxic heavy metal that has caused serious public health problems. It is necessary to find a cost effective method to deal with wastewater containing Cd(II). Loess soils in China have proven to be a potential adsorbent for Cd(II) removal from wastewater. The adsorption capacity of loess towards Cd(II) has been determined to be about 9.37 mg g(-1). Slurry concentration, initial solution pH, reaction time and temperature have also been found to significantly influence the efficiency of Cd(II) removal. The adsorption isotherms and kinetics of loess soil from China can be best-fit with the Langmuir model and pseudo-second order kinetics model, respectively. The thermodynamic analysis revealed that the adsorption process was spontaneous, endothermic and the system disorder increased with duration. The natural organic matter in loess soil is mainly responsible for Cd(II) removal at pH < 4.2, while clay minerals contribute to a further gradual adsorption process. Chemical precipitation dominates the adsorption stage at pH > 8.97. Further studies using X-ray diffraction, Fourier transform infrared spectra of Cd(II) laden loess soil and Cd(II) species distribution have confirmed the adsorption mechanism.

Efficacy of pyropheophorbide-a-hexyl ether for photodynamic therapy of rat 9L gliosarcoma

NASA Astrophysics Data System (ADS)

Autry-Conwell, Susan A.; Edwards, Benjamin F.; Boggan, James E.; Gandour-Edwards, Regina; Pandey, Ravindra K.; Dougherty, Thomas J.

1993-06-01

In preliminary studies, the efficacy of a new photosensitizer, pyropheophorbide-(alpha) - hexyl ether (HPPH #23), for use in photodynamic therapy (PDT) was assessed using the rat 9L gliosarcoma tumor model in subcutaneous flank tumors, intracranial tumors, and in vivo. Flank and intracranial tumors were irradiated with 75 - 203 J/cm2 24 hours after 0.3 - 0.6 mg/kg IV injection of HPPH #23. At 24 hours post-PDT, and flank tumors showed a range of necrosis at the highest laser dose from 50 - 100%. The overlying skin and underlying muscle were spared. Intracranial tumors exhibited moderate to severe hemorrhagic necrosis. Areas of brain adjacent to tumor within the irradiated field also showed some damage. In vitro phototoxicity of HPPH #23 was compared to that of Photofrin II (PhII). Cells growing in culture dishes were exposed to HPPH #23 or PhII for 20 hours, washed free of unbound drug, then irradiated at 2.5 J/cm2, 17 mW/cm2 at 665 nm (HPPH #23) or 630 nm (PhII). Irradiated cultures were maintained in dark incubators for an additional 4 - 5 days, and phototoxic inhibition of cell proliferation was quantified by the sulphorhodamine B spectrophotometric assay. Under identical irradiation conditions, the IC50 for HPPH #23 (0.25 (mu) g/ml) was 10-fold lower than that of PhII (2.5 (mu) g/ml). Complete cell kill was achieved at sensitizer doses of 0.5 (mu) g/ml (HPPH #23) and 5.0 (mu) g/ml (PhII).

Removal of mercury (II) from aqueous solution by activated carbon obtained from furfural.

PubMed

Yardim, M F; Budinova, T; Ekinci, E; Petrov, N; Razvigorova, M; Minkova, V

2003-08-01

The adsorption of Hg(II) from aqueous solution at 293 K by activated carbon obtained from furfural is studied. The carbon is prepared by polymerization of furfural following carbonization and activation of the obtained polymer material with water vapor at 800 degrees C. Adsorption studies of Hg(II) are carried out varying some conditions: treatment time, metal ion concentration, adsorbent amount and pH. It is determined that Hg(II) adsorption follows both Langmuir and Freundlich isotherms. The adsorption capacity of the carbon is 174 mg/g. It is determined that Hg(II) uptake increases with increasing pH. Desorption studies are performed with hot water. The percent recovery of Hg(II) is 6%.

Biosorption of heavy metals by lactic acid bacteria and identification of mercury binding protein.

PubMed

Kinoshita, Hideki; Sohma, Yui; Ohtake, Fumika; Ishida, Mitsuharu; Kawai, Yasushi; Kitazawa, Haruki; Saito, Tadao; Kimura, Kazuhiko

2013-09-01

Heavy metals cause various health hazards. Using lactic acid bacteria (LAB), we tested the biosorption of heavy metals e.g. cadmium (Cd) (II), lead (Pb) (II), arsenic (As) (III), and mercury (Hg) (II). Cd (II) sorption was tested in 103 strains using atomic absorption spectrophotometery (AAS). Weissella viridescens MYU 205 (1 × 10(8) cells/ml) decreased Cd (II) levels in citrate buffer (pH 6.0) from one ppm to 0.459 ± 0.016 ppm, corresponding to 10.46 μg of Cd (II). After screening, 11 LAB strains were tested using various pH (pH 4.0, 5.0, 6.0, 7.0) showing the sorption was acid sensitive; and was cell concentration dependent, where the Cd (II) concentration decreased from one ppm to 0.042 (max)/0.255 (min) ppm at 1 × 10(10) cells/ml. Additionally, the biosorption of Pb (II), As (III), and Hg (II) were tested using an inductively coupled plasma mass spectrometer (ICP-MS). The Hg (II) concentration was reduced the most followed by Pb (II) and As (III). Many of the bacterial cell surface proteins of W. viridescens MYU 205 showed binding to Hg (II) using the Hg (II) column assay. Having a CXXC motif, a ∼14 kDa protein may be one of the Hg (II) binding proteins. LAB biosorption may aid the detoxification of people exposed to heavy metals. Copyright © 2013 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Self-Assembled Fluorescent Bovine Serum Albumin Nanoprobes for Ratiometric pH Measurement inside Living Cells.

PubMed

Yang, Qiaoyu; Ye, Zhongju; Zhong, Meile; Chen, Bo; Chen, Jian; Zeng, Rongjin; Wei, Lin; Li, Hung-wing; Xiao, Lehui

2016-04-20

In this work, we demonstrated a new ratiometric method for the quantitative analysis of pH inside living cells. The structure of the nanosensor comprises a biofriendly fluorescent bovine serum albumin (BSA) matrix, acting as a pH probe, and pH-insensitive reference dye Alexa 594 enabling ratiometric quantitative pH measurement. The fluorescent BSA matrix was synthesized by cross-linking of the denatured BSA proteins in ethanol with glutaraldehyde. The size of the as-synthesized BSA nanoparticles can be readily manipulated from 30 to 90 nm, which exhibit decent fluorescence at the peak wavelength of 535 nm with a pH response range of 6-8. The potential of this pH sensor for intracellular pH monitoring was demonstrated inside living HeLa cells, whereby a significant change in fluorescence ratio was observed when the pH of the cell was switched from normal to acidic with anticancer drug treatment. The fast response of the nanosensor makes it a very powerful tool in monitoring the processes occurring within the cytosol.

Synthesis, characterization, and application of novel Zn(II)-ionic imprinted polymer for preconcentration of Zn(II) ions from aqueous solution

NASA Astrophysics Data System (ADS)

Wirawan, T.; Supriyanto, G.; Soegianto, A.

2018-04-01

Preparation of a new Zn2+ ion-imprinted polymer (Zn-IIP) is presented in this report. The Zn-IIP are prepared by precipitation polymerization using 8-hydroxyquinoline (8HQ) as a ligand, methacrylic acid (MAA) as functional monomer, and ethylene glycol dimethacrylate (EGDMA) as a cross-linker has been prepared. The benzoyl peroxide and ethanol/acetonitrile (2:1) mixture were used as initiator and porogen, respectively. Precipitation polymerization was carried out by heating in a water bath at 60°C for 8 hours. After polymerization, cavities in the polymer particles corresponding to the Zn2+ ions were created by leaching the polymer with 2 mol L-1 HNO3. The polymer was washed with aquabidest and dried in an oven at the temperature of 60°C for 24 hours. The Zn-IIP was characterized by Fourier Transform Infrared Spectrophotometry (FT-IR) and Scanning Electron Microscopy (SEM). The synthesized Zn-IIP was used as a new adsorbent for solid phase extraction (SPE) of Zn(II) prior to Flame Atomic Absorption Spectrometry (FAAS) determination. The experimental parameters for SPE, such as pH of the sample, loading rate, and elution volume, have been optimized. The effect of pH of the sample on the extraction of analyte was studied in batch mode. The effects of loading rate and elution volume on the extraction of analyte were studied in dynamic mode by loading of the sample through IIP-SPE cartridge containing 100 mg of the synthesized Zn-IIP. The imprinted polymer (Zn-IIP) have bands at 3433.06 cm-1 (O-H), 1508.23 cm-1 (C=N aromatics), 1284.5 cm-1 (C-N aromatics), 1056.9 cm-1 (C-O phenol), 1724.24 cm-1 (C=O), and 1639.38 cm-1 (conjugated C=O with C=C). The Scanning Electron Microscopy (SEM) images of IIP and IIP show that the IIP is seen to have more cavities than NIP. The optimum pH for quantitative Zn(II) retention was 5.5, and the elution was completed with 2 mL of 1.0 mol L-1 nitric acid. The optimum loading rate was 0.5 mL min-1. The recovery of Zn(II) from solution samples after its SPE extraction on IIP with 50-fold theoretical preconcentration was 94.60-104.50%. The LOD and LOQ with 50-fold theoretical preconcentration obtained were 0.0073 mg L-1 and 0.0244 mg L-1, respectively.

Uranium Reduction by Fe(II) in the Presence of Montmorillonite and Nontronite.

PubMed

Tsarev, Sergey; Waite, T David; Collins, Richard N

2016-08-02

Uranium(VI) interactions with three smectites (one montmorillonite and two nontronites - NAu1 and NAu2) were examined with 0, 1, and 2 mM aqueous concentrations of Fe(II) over the pH range of 3-9.5 in a background electrolyte of 100 mM NaCl and 1 mM CaCl2 in equilibration with 400 ppmv CO2(g) ([U(VI)] = 4 μM and 0.5 g smectite/L). In the absence of Fe(II), no differences were observed in the U(VI) sorption curves for the three clay minerals. In the presence of 1 or 2 mM Fe(II), under anoxic conditions, U(VI) uptake by the smectites changed slightly between ∼pH 3 and 6; however, uranium uptake increased significantly above ∼pH 6 and was proportional to the concentration of Fe(II) added to the system, particularly at pH values >8. The uptake of Fe(II) showed a sharp edge starting from ∼pH 6.5 with 95%-100% uptake occurring at pH values >7.5, with no difference observed between the iron-rich nontronites and montmorillonite. After 3 days of reaction at pH 7.6 (i.e., above the Fe(II) "sorption" edge), U(VI) was transformed to a mixture of U(IV) and U(VI) sorption complexes, and after 14 days of reaction, 100% of the U was found to be reduced to U(IV) in the form of nanocrystalline uraninite. In contrast, U remained as sorbed species until 14 days of reaction at pH 6.5. Ferrihydrite (NAu1), lepidocrocite, and magnetite (NAu2) were detected as secondary mineralization products upon reaction of the nontronites with Fe(II) but appeared to have no effect on the partitioning or speciation of uranium.

Synthesis and thermal characterization of new ternary chelates of piroxicam and tenoxicam with glycine and DL-phenylalanine and some transition metals.

PubMed

Zayed, M A; El-Dien, F A Nour; Mohamed, Gehad G; El-Gamel, Nadia E A

2006-05-01

The ternary chelates of piroxicam (Pir) and tenoxicam (Ten) with Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) in the presence of various amino acids such as glycine (Gly) or dl-phenylalanine (PhA) were prepared and characterized with different physicochemical methods. IR spectra confirm that Pir and Ten behave as a neutral bidentate ligand coordinated to the metal ions via the pyridine-N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its deprotonated carboxylic group. In addition, PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its deprotonated carboxylic and amino groups. The solid reflectance spectra and magnetic moment measurements confirm that all the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. Thermal behaviour of the complexes is extensively studied using TG and DTA techniques. TG results show that water molecules (hydrated and coordinated) and anions are removed in the first and second steps while Gly, PhA, Pir and Ten are decomposed in the next and subsequent steps. The pyrolyses of the chelates into different gases are observed in the DTA curves as exo- or endothermic peaks. Also, phase transition states are observed in some chelates. Different thermodynamic parameters are calculated using Coats-Redfern method and the results are interpreted.

Synthesis and thermal characterization of new ternary chelates of piroxicam and tenoxicam with glycine and DL-phenylalanine and some transition metals

NASA Astrophysics Data System (ADS)

Zayed, M. A.; El-Dien, F. A. Nour; Mohamed, Gehad G.; El-Gamel, Nadia E. A.

2006-05-01

The ternary chelates of piroxicam (Pir) and tenoxicam (Ten) with Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) in the presence of various amino acids such as glycine (Gly) or DL-phenylalanine (PhA) were prepared and characterized with different physicochemical methods. IR spectra confirm that Pir and Ten behave as a neutral bidentate ligand coordinated to the metal ions via the pyridine- N and carbonyl group of the amide moiety. Gly molecule acted as a uninegatively monodentate ligand and coordinate to the metal ions through its deprotonated carboxylic group. In addition, PhA acted as a uninegatively bidentate ligand and coordinate to the metal ions through its deprotonated carboxylic and amino groups. The solid reflectance spectra and magnetic moment measurements confirm that all the chelates have octahedral geometrical structures while Cu(II)- and Zn(II)-ternary chelates with PhA have square planar geometrical structures. Thermal behaviour of the complexes is extensively studied using TG and DTA techniques. TG results show that water molecules (hydrated and coordinated) and anions are removed in the first and second steps while Gly, PhA, Pir and Ten are decomposed in the next and subsequent steps. The pyrolyses of the chelates into different gases are observed in the DTA curves as exo- or endothermic peaks. Also, phase transition states are observed in some chelates. Different thermodynamic parameters are calculated using Coats-Redfern method and the results are interpreted.

Biological low pH Mn(II) oxidation in a manganese deposit influenced by metal-rich groundwater

USGS Publications Warehouse

Bohu, Tsing; Akob, Denise M.; Abratis, Michael; Lazar, Cassandre S.; Küsel, Kirsten

2016-01-01

The mechanisms, key organisms, and geochemical significance of biological low-pH Mn(II) oxidation are largely unexplored. Here, we investigated the structure of indigenous Mn(II)-oxidizing microbial communities in a secondary subsurface Mn oxide deposit influenced by acidic (pH 4.8) metal-rich groundwater in a former uranium mining area. Microbial diversity was highest in the Mn deposit compared to the adjacent soil layers and included the majority of known Mn(II)-oxidizing bacteria (MOB) and two genera of known Mn(II)-oxidizing fungi (MOF). Electron X-ray microanalysis showed that romanechite [(Ba,H2O)2(Mn4+,Mn3+)5O10] was conspicuously enriched in the deposit. Canonical correspondence analysis revealed that certain fungal, bacterial, and archaeal groups were firmly associated with the autochthonous Mn oxides. Eight MOB within the Proteobacteria, Actinobacteria, and Bacteroidetes and one MOF strain belonging to Ascomycota were isolated at pH 5.5 or 7.2 from the acidic Mn deposit. Soil-groundwater microcosms demonstrated 2.5-fold-faster Mn(II) depletion in the Mn deposit than adjacent soil layers. No depletion was observed in the abiotic controls, suggesting that biological contribution is the main driver for Mn(II) oxidation at low pH. The composition and species specificity of the native low-pH Mn(II) oxidizers were highly adapted to in situ conditions, and these organisms may play a central role in the fundamental biogeochemical processes (e.g., metal natural attenuation) occurring in the acidic, oligotrophic, and metalliferous subsoil ecosystems.

Adsorption of Hg(II) and Pb(II) ions by nanoscale zero valent iron supported on ostrich bone ash in a fixed-bed column system.

PubMed

Amiri, Mohammad Javad; Abedi-Koupai, Jahangir; Eslamian, Saeid

2017-07-01

In this research, ostrich bone ash (OBA) was modified with nanoscale zerovalent iron (nZVI) particles and applied as a novel composite adsorbent (OBA/nZVI) for dynamic adsorption/reduction of Hg(II) and Pb(II) ions in a fixed-bed column system. Entrapment of nZVI in OBA beads barricades the particles from oxidation and aggregation. The dynamic behavior of metal ions removal by OBA/nZVI was assessed as a function of inlet flow rates, bed height, initial pollutants concentration and pH. The synthesized OBA/nZVI composite was characterized by several physicochemical techniques. Increase in pH and bed height and decrease in flow rates and initial metal concentration resulted in delay of breakthrough time. OBA breakthrough profile is sharper than the OBA/nZVI breakthrough curve for both metal ions and the breakthrough times increase in the order OBA/nZVI-Hg(II) > OBA/nZVI-Pb(II) > OBA-Pb(II) > OBA-Hg(II). Based on the experiment results, redox reaction is expected to occur to a certain extent, as the standard reduction potentials of Hg(II) and Pb(II) are more than that of Fe(II). From a practical point of view, the OBA/nZVI could be applied as a material to remove Hg(II) and Pb(II) ions from natural surface and ground water with a pH value of 5-9.

Variation of iron redox kinetics and its relation with molecular composition of standard humic substances at circumneutral pH.

PubMed

Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Terao, Koumei; Yoshimura, Chihiro

2017-01-01

Oxidation and reduction kinetics of iron (Fe) and proportion of steady-state Fe(II) concentration relative to total dissolved Fe (steady-state Fe(II) fraction) were investigated in the presence of various types of standard humic substances (HS) with particular emphasis on the photochemical and thermal reduction of Fe(III) and oxidation of Fe(II) by dissolved oxygen (O2) and hydrogen peroxide (H2O2) at circumneutral pH (pH 7-8). Rates of Fe(III) reduction were spectrophotometrically determined by a ferrozine method under the simulated sunlight and dark conditions, whereas rates of Fe(II) oxidation were examined in air-saturated solution using luminol chemiluminescence technique. The reduction and oxidation rate constants were determined to substantially vary depending on the type of HS. For example, the first-order rate constants varied by up to 10-fold for photochemical reduction and 7-fold for thermal reduction. The degree of variation in Fe(II) oxidation was larger for the H2O2-mediated reaction compared to the O2-mediated reaction (e.g., 15- and 3-fold changes for the former and latter reactions, respectively, at pH 8). The steady-state Fe(II) fraction under the simulated sunlight indicated that the Fe(II) fraction varies by up to 12-fold. The correlation analysis indicated that variation of Fe(II) oxidation is significantly associated with aliphatic content of HS, suggesting that Fe(II) complexation by aliphatic components accelerates Fe(II) oxidation. The reduction rate constant and steady-state Fe(II) fractions in the presence of sunlight had relatively strong positive relations with free radical content of HS, possibly due to the reductive property of radical semiquinone in HS. Overall, the findings in this study indicated that the Fe reduction and oxidation kinetics and resultant Fe(II) formation are substantially influenced by chemical properties of HS.

Alginate-immobilized bentonite clay: adsorption efficacy and reusability for Cu(II) removal from aqueous solution.

PubMed

Tan, Wei Shang; Ting, Adeline Su Yien

2014-05-01

This study evaluated the use of alginate-immobilized bentonite to remove Cu(II) as an alternative to mitigate clogging problems. The adsorption efficacy (under the influence of time, pH and initial Cu(II) concentration) and reusability of immobilized-bentonite (1% w/v bentonite) was tested against plain alginate beads. Results revealed that immobilized bentonite demonstrated significantly higher sorption efficacy compared to plain alginate beads with 114.70 and 94.04 mg Cu(II) adsorbed g(-1) adsorbent, respectively. Both sorbents were comparable in other aspects where sorption equilibrium was achieved within 6 h, with optimum pH between pH 4 and 5 for adsorption, displayed maximum adsorption capacity at initial Cu(II) concentrations of 400 mg l(-1), and demonstrated excellent reusability potential with desorption greater than 90% throughout three consecutive adsorption-desorption cycles. Both sorbents also conformed to Langmuir isotherm and pseudo-second order kinetic model. Immobilized bentonite is therefore recommended for use in water treatments to remove Cu(II) without clogging the system. Copyright © 2013 Elsevier Ltd. All rights reserved.

Spectroscopic Investigations of Catalase Compound II: Characterization of an Iron(IV) Hydroxide Intermediate in a Non-thiolate-Ligated Heme Enzyme

PubMed Central

Yosca, Timothy H.; Langston, Matthew C.; Krest, Courtney M.; Onderko, Elizabeth L.; Grove, Tyler L.; Livada, Jovan; Green, Michael T.

2018-01-01

We report on the protonation state of Helicobacter pylori catalase compound II. UV/visible, Mössbauer, and X-ray absorption spectroscopies have been used to examine the intermediate from pH 5 to 14. We have determined that HPC-II exists in an iron(IV) hydroxide state up to pH 11. Above this pH, the iron(IV) hydroxide complex transitions to a new species (pKa = 13.1) with Mössbauer parameters that are indicative of an iron(IV)-oxo intermediate. Recently, we discussed a role for an elevated compound II pKa in diminishing the compound I reduction potential. This has the effect of shifting the thermodynamic landscape toward the two-electron chemistry that is critical for catalase function. In catalase, a diminished potential would increase the selectivity for peroxide disproportionation over off-pathway one-electron chemistry, reducing the buildup of the inactive compound II state and reducing the need for energetically expensive electron donor molecules. PMID:27960340

Adsorption of Ni(II) onto Chemically Modified Spent Grated Coconut (Cocos Nucifera)

NASA Astrophysics Data System (ADS)

Hamzah, F. I.; Khalid, K.; Hanafiah, M. A. K. M.

2017-06-01

A new adsorbent of plant waste origin from coconut processing food factory was explored for removing Ni(II) from aqueous solutions. Several parameters such as pH, dosage, concentration and contact time were studied to obtain optimum conditions for treatment of Ni(II) contaminated wastewater. Spent grated coconut (Cocos nucifera) treated with sulfuric acid (SSGC) showed good adsorption capacity for Ni(II) ion. The amount adsorbed was affected by solution pH with the highest value achieved at pH 5. Other optimum conditions found were; dosage of 0.02 g, and 60 min of equilibrium time. Ni(II) adsorption obeyed the pseudo-second order kinetic model which suggested that chemisorption mechanism occurred in the adsorption process. The equilibrium data presented a better fitting to the Langmuir isotherm model, an indication that monolayer adsorption occurred onto a homogeneous surface. The maximum adsorption capacity, qmax was 97.09 mg g-1, thus SSGC can be classified as good and comparable with other plant waste adsorbents.

Delicate crystal structure changes govern the magnetic properties of 1D coordination polymers based on 3d metal carboxylates.

PubMed

Gavrilenko, Konstantin S; Cador, Olivier; Bernot, Kevin; Rosa, Patrick; Sessoli, Roberta; Golhen, Stéphane; Pavlishchuk, Vitaly V; Ouahab, Lahcène

2008-01-01

Homo- and heterometallic 1D coordination polymers of transition metals (Co II, Mn II, Zn II) have been synthesized by an in-situ ligand generation route. Carboxylato-based complexes [Co(PhCOO)2]n (1 a, 1 b), [Co(p-MePhCOO)2]n (2), [ZnMn(PhCOO)4]n (3), and [CoZn(PhCOO)4]n (4) (PhCOOH=benzoic acid, p-MePhCOOH=p-methylbenzoic acid) have been characterized by chemical analysis, single-crystal X-ray diffraction, and magnetization measurements. The new complexes 2 and 3 crystallize in orthorhombic space groups Pnab and Pcab respectively. Their crystal structures consist of zigzag chains, with alternating M(II) centers in octahedral and tetrahedral positions, which are similar to those of 1 a and 1 b. Compound 4 crystallizes in monoclinic space group P2 1/c and comprises zigzag chains of M II ions in a tetrahedral coordination environment. Magnetic investigations reveal the existence of antiferromagnetic interactions between magnetic centers in the heterometallic complexes 3 and 4, while ferromagnetic interactions operate in homometallic compounds (1 a, 1 b, and 2). Compound 1 b orders ferromagnetically at TC=3.7 K whereas 1 a does not show any magnetic ordering down to 330 mK and displays typical single-chain magnet (SCM) behavior with slowing down of magnetization relaxation below 0.6 K. Single-crystal measurements reveal that the system is easily magnetized in the chain direction for 1 a whereas the chain direction coincides with the hard magnetic axis in 1 b. Despite important similarities, small differences in the molecular and crystal structures of these two compounds lead to this dramatic change in properties.

Pilot study of Iopamidol-based quantitative pH imaging on a clinical 3T MR scanner.

PubMed

Müller-Lutz, Anja; Khalil, Nadia; Schmitt, Benjamin; Jellus, Vladimir; Pentang, Gael; Oeltzschner, Georg; Antoch, Gerald; Lanzman, Rotem S; Wittsack, Hans-Jörg

2014-12-01

The objective of this study was to show the feasibility to perform Iopamidol-based pH imaging via clinical 3T magnetic resonance imaging (MRI) using chemical exchange saturation transfer (CEST) imaging with pulse train presaturation. The pulse train presaturation scheme of a CEST sequence was investigated for Iopamidol-based pH measurements using a 3T magnetic resonance (MR) scanner. The CEST sequence was applied to eight tubes filled with 100-mM Iopamidol solutions with pH values ranging from 5.6 to 7.0. Calibration curves for pH quantification were determined. The dependence of pH values on the concentration of Iopamidol was investigated. An in vivo measurement was performed in one patient who had undergone a previous contrast-enhanced computed tomography (CT) scan with Iopamidol. The pH values of urine measured with CEST MRI and with a pH meter were compared. In the measured pH range, pH imaging using CEST imaging with pulse train presaturation was possible. Dependence between the pH value and the concentration of Iopamidol was not observed. In the in vivo investigation, the pH values in the human bladder measured by the Iopamidol CEST sequence and in urine were consistent. Our study shows the feasibility of using CEST imaging with Iopamidol for quantitative pH mapping in vitro and in vivo on a 3T MR scanner.

Impact of constitutional isomers of (BMes(2))phenylpyridine on structure, stability, phosphorescence, and Lewis acidity of mononuclear and dinuclear Pt(II) complexes.

PubMed

Rao, Ying-Li; Wang, Suning

2009-08-17

The impact of two constitutional isomers, 2-(4-BMes(2)-Ph)-pyridine (p-B-ppy, 1) and 5-BMes(2)-2-ph-pyridine (p-ppy-B, 2), as N,C-chelate ligands on the structures, stabilities, electronic and photophysical properties, and Lewis acidities of Pt(II) complexes has been investigated. Six Pt(II) complexes, Pt(p-B-ppy)Ph(DMSO) (1a), Pt(p-B-ppy)Ph(py) (1b), [Pt(p-B-ppy)Ph](2)(4,4'-bipy) (1c), Pt(p-ppy-B)Ph(DMSO) (2a), Pt(p-ppy-B)Ph(py) (2b), and [Pt(p-ppy-B)Ph](2)(4,4'-bipy) (2c), have been synthesized and fully characterized. The structures of 1a, 1c, 2a, and 2c were established by single-crystal X-ray diffraction analysis. All complexes adopt a cis geometry with the phenyl ligand being cis to the phenyl ring of the ppy chelate. The dinuclear complexes 2a and 2c were found to exist in two isomeric forms in solution, syn and anti, with respect to the relative orientation of the two BMes(2) groups in the molecule. While all complexes are stable in solution under ambient air, compound 2a was found to react with H(2)O slowly in solution and form complex 2a-OH, where one of the mesityl groups on the boron center was replaced by an OH group. This instability of 2a is attributed to an internal dimethylsulfoxide-directed hydrolysis process via hydrogen bonds. The electron-accepting ability of the free ligands and the complexes were examined by cyclic voltammetry, establishing that, for p-ppy-B, Pt(II) chelation enhances the electron-accepting ability while, for p-B-ppy, Pt(II) chelation has little impact. All Pt(II) complexes display oxygen-sensitive phosphorescence in solution at ambient temperature, dominated by B-ppy or ppy-B centered pi --> pi* transitions. The Lewis acidity of the complexes was examined by fluoride titration experiments using UV-vis, phosphorescence, and NMR spectroscopic methods, establishing that the p-ppy-B complexes have similar and strong binding constants while the p-B-ppy complexes have a much lower affinity toward F(-), compared to the free ligands. In the dinuclear complexes, weak electronic communication between the two Pt(II) units is evident in 1c but absent in 2c, attributable to the different steric interactions in the two molecules.

Surface complexation modeling of zinc sorption onto ferrihydrite.

PubMed

Dyer, James A; Trivedi, Paras; Scrivner, Noel C; Sparks, Donald L

2004-02-01

A previous study involving lead(II) [Pb(II)] sorption onto ferrihydrite over a wide range of conditions highlighted the advantages of combining molecular- and macroscopic-scale investigations with surface complexation modeling to predict Pb(II) speciation and partitioning in aqueous systems. In this work, an extensive collection of new macroscopic and spectroscopic data was used to assess the ability of the modified triple-layer model (TLM) to predict single-solute zinc(II) [Zn(II)] sorption onto 2-line ferrihydrite in NaNO(3) solutions as a function of pH, ionic strength, and concentration. Regression of constant-pH isotherm data, together with potentiometric titration and pH edge data, was a much more rigorous test of the modified TLM than fitting pH edge data alone. When coupled with valuable input from spectroscopic analyses, good fits of the isotherm data were obtained with a one-species, one-Zn-sorption-site model using the bidentate-mononuclear surface complex, (triple bond FeO)(2)Zn; however, surprisingly, both the density of Zn(II) sorption sites and the value of the best-fit equilibrium "constant" for the bidentate-mononuclear complex had to be adjusted with pH to adequately fit the isotherm data. Although spectroscopy provided some evidence for multinuclear surface complex formation at surface loadings approaching site saturation at pH >/=6.5, the assumption of a bidentate-mononuclear surface complex provided acceptable fits of the sorption data over the entire range of conditions studied. Regressing edge data in the absence of isotherm and spectroscopic data resulted in a fair number of surface-species/site-type combinations that provided acceptable fits of the edge data, but unacceptable fits of the isotherm data. A linear relationship between logK((triple bond FeO)2Zn) and pH was found, given by logK((triple bond FeO)2Znat1g/l)=2.058 (pH)-6.131. In addition, a surface activity coefficient term was introduced to the model to reduce the ionic strength dependence of sorption. The results of this research and previous work with Pb(II) indicate that the existing thermodynamic framework for the modified TLM is able to reproduce the metal sorption data only over a limited range of conditions. For this reason, much work still needs to be done in fine-tuning the thermodynamic framework and databases for the TLM.

Irreversible insertion of benzonitrile into platinum(II)-nitrogen bonds of nucleobase complexes. Synthesis and structural characterization of stable azametallacycle compounds.

PubMed

Montagner, Diego; Venzo, Alfonso; Zangrando, Ennio; Longato, Bruno

2010-03-01

Deprotonation of 1-methylcytosine (1-MeCy) and 9-methyladenine (9-MeAd) promoted by cis-[L(2)Pt(mu-OH)](2)(NO(3))(2) (L = PPh(3), PMePh(2), (1)/(2)dppe) in PhCN causes the irreversible insertion of a nitrile molecule into the Pt-N4 and Pt-N6 bonds of the cytosinate and adeninate ligands, respectively, to form the stable azametallacycle complexes cis-[L(2)PtNH=C(Ph){1-MeCy(-2H)}]NO(3) (L = PPh(3), 1; PMePh(2), 2; (1)/(2)dppe, 3) and cis-[L(2)PtNH=C(Ph){9-MeAd(-2H)}]NO(3) (L = PPh(3), 4; PMePh(2), 5) containing the deprotonated form of the molecules (Z)-9-N-(1-methyl-2-oxo-2,3-dihydropyrimidin-4(1H)-ylidene)benzimidamide and (Z)-N-(9-methyl-1H-purin-6(9H)-ylidene)benzimidamide. Single-crystal X-ray analyses of 2 and 4 show the metal coordinated to the N3 cytosine site [Pt-N3 = 2.112(7) A] and to the N1 site of adenine [Pt-N1 = 2.116(6) A] and to the nitrogen atom of the inserted benzonitrile [Pt-N2 = 2.043(6) and 2.010(6) A in 2 and 4, respectively], with the exocyclic nucleobase amino nitrogen bound to the carbon atom of the CN group. Complex 2, in solution, undergoes a dynamic process related to a partially restricted rotation around Pt-P bonds, arising from a steric interaction of the oxygen atom of the cytosine with one ring of the phosphine ligands. The reaction of 4 with acetylacetone (Hacac) causes the quantitative protonation of the anionic ligand, affording the acetylacetonate complex cis-[(PPh(3))(2)Pt(acac)]NO(3) and the free benzimidamide NH=C(Ph){9-MeAd(-H)}. In the same experimental conditions, complex 3 reacts with Hacac only partially.

Structural, Spectroscopic, and Electrochemical Properties of Nonheme Fe(II)-Hydroquinonate Complexes: Synthetic Models of Hydroquinone Dioxygenases

PubMed Central

Baum, Amanda E.; Park, Heaweon; Wang, Denan; Lindeman, Sergey V.; Fiedler, Adam T.

2012-01-01

Using the tris(3,5-diphenylpyrazol-1-yl)borate (Ph2Tp) supporting ligand, a series of mono- and dinuclear ferrous complexes containing hydroquinonate (HQate) ligands have been prepared and structurally characterized with X-ray crystallography. The monoiron(II) complexes serve as faithful mimics of the substrate-bound form of hydroquinone dioxygenases (HQDOs) – a family of nonheme Fe enzymes that catalyze the oxidative cleavage of 1,4-dihydroxybenzene units. Reflecting the variety of HQDO substrates, the synthetic complexes feature both mono- and bidentate HQate ligands. The bidentate HQates cleanly provide five-coordinate, high-spin Fe(II) complexes with the general formula [Fe(Ph2Tp)(HLX)] (1X), where HLX is a HQate(1-) ligand substituted at the 2-position with a benzimidazolyl (1A), acetyl (1B and 1C), or methoxy (1D) group. In contrast, the monodentate ligand 2,6-dimethylhydroquinone (H2LF) exhibited a greater tendency to bridge between two Fe(II) centers, resulting in formation of [Fe2(Ph2Tp)2(μ-LF)(MeCN)] [2F(MeCN)]. However, addition of one equivalent of “free” pyrazole (Ph2pz) ligand provided the mononuclear complex, [Fe(Ph2Tp)(HLF)(Ph2pz)] [1F(Ph2pz)], which is stabilized by an intramolecular hydrogen bond between the HLF and Ph2pz donors. Complex 1F(Ph2pz) represents the first crystallographically-characterized example of a monoiron complex bound to an untethered HQate ligand. The geometric and electronic structures of the Fe/HQate complexes were further probed with spectroscopic (UV-vis absorption, 1H NMR) and electrochemical methods. Cyclic voltammograms of complexes in the 1X series revealed an Fe-based oxidation between 0 and −300 mV (vs. Fc+/0), in addition to irreversible oxidation(s) of the HQate ligand at higher potentials. The one-electron oxidized species (1Xox) were examined with UV-vis absorption and electron paramagnetic resonance (EPR) spectroscopies. PMID:22930005

Metal Ions Removal Using Nano Oxide Pyrolox™ Material

NASA Astrophysics Data System (ADS)

Gładysz-Płaska, A.; Skwarek, E.; Budnyak, T. M.; Kołodyńska, D.

2017-02-01

The paper presents the use of Pyrolox™ containing manganese nano oxides used for the removal of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions. Their concentrations were analyzed using the atomic absorption spectrometer SpectrAA 240 FS (Varian) as well as UV-vis method. For this purpose the static kinetic and equilibrium studies were carried out using the batch technique. The effect of solution pH, shaking time, initial metal ion concentrations, sorbent dosage, and temperature was investigated. The equilibrium data were analyzed using the sorption isotherm models proposed by Freundlich, Langmuir-Freundlich, Temkin, and Dubinin-Radushkevich. The kinetic results showed that the pseudo second order kinetic model was found to correlate the experimental data well. The results indicate that adsorption of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions is strongly dependent on pH. The value of pH 4-7 was optimal adsorption. The time to reach the equilibrium was found to be 24 h, and after this time, the sorption percentage reached about 70%. Kinetics of Cu(II), Zn(II), Cd(II), Pb(II), and U(VI) adsorption on the adsorbent can be described by the pseudo second order rate equation. Nitrogen adsorption/desorption, infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) measurements for adsorbent characterization were performed. Characteristic points of the double layer determined for the studied Pyrolox™ sample in 0.001 mol/dm3 NaCl solution are pHPZC = 4 and pHIEP < 2.

[Effects of soil acidity on Pinus resinosa seedlings photosynthesis and chlorophyll fluorescence].

PubMed

Liu, Shuang; Wang, Qing-cheng; Liu, Ya-li; Tian, Yu-ming; Sun, Jing; Xu, Jing

2009-12-01

Red pine (Pinus resinosa) is one of the most important tree species for timber plantation in North America, and preliminary success has been achieved in its introduction to the mountainous area of Northeast China since 2004. In order to expand its growth area in other parts of Northeast China, a pot experiment was conducted to study the adaptability of this tree species to varying soil acidity. P. resinosa seedlings were grown in soils with different acidity (pH = 4.5, 5.5, 6.5, 7.5, and 8.0) to test the responses of their photosynthesis and chlorophyll fluorescence parameters to soil pH levels, and the appropriate soil acidity was evaluated. Dramatic responses in chlorophyll a and b contents, Pn and chlorophyll fluorescence parameters (Fo, Fm, Fv, Fv/Fm, and phi(PS II)) were detected under different soil acidity (P < 0.05), with the highest chlorophyll content and Pn under soil pH 5.5, and significantly lower chlorophyll content and Pn under soil pH 7.5 and 8.0. The chlorophyll content and Pn were 41% and 50%, and 61% and 88% higher under soil pH 5.5 than under soil pH 7.5 and 8.0. The seedlings had a significant photosynthetic inhibition under soil pH 7.5 and 8.0, but the highest Fv/Fm and phi (PS II) under soil pH 5.5. Comparing with those under soil pH 7.5 and 8.0, the Fv/Fm and phi (PS II) under soil pH 5.5 were 8% and 12%, and 22% and 35% higher, respectively. It was suggested that soil pH 5.5 was most appropriate for P. resinosa growth.

Complexation Key to a pH Locked Redox Reaction

ERIC Educational Resources Information Center

Rizvi, Masood Ahmad; Dangat, Yuvraj; Shams, Tahir; Khan, Khaliquz Zaman

2016-01-01

An unfavorable pH can block a feasible electron transfer for a pH dependent redox reaction. In this experiment, a series of potentiometric titrations demonstrate the sequential loss in feasibility of iron(II) dichromate redox reaction over a pH range of 0-4. The pH at which this reaction failed to occur was termed as a pH locked reaction. The…

Extending the working pH of nitrobenzene degradation using ultrasonic/heterogeneous Fenton to the alkaline range via amino acid modification.

PubMed

ElShafei, Gamal M S; Yehia, F Z; Dimitry, O I H; Badawi, A M; Eshaq, Gh

2015-11-01

Oxides of iron, α-Fe2O3 (I), and copper, CuO (II) prepared by usual precipitation method without surfactant were used at room temperature in the process of nitrobenzene (10mgL(-1)) degradation at different pH values with ultrasonic at 20kHz. The degradation was complete in 20 and 30min for (I) and (II), respectively in the pH range 2-7 using1.0gL(-1) of solids and 10mM of H2O2. A remarkable decrease in degradation efficiency was recorded on increasing the pH to values higher than the neutral range. This loss in efficiency was cancelled to a great extent through modifying the used oxides with amino acids. Arginine showed higher improving effect to (II) (1:1 weight ration) than glycine or glutamic acid. Modification of both oxides with increasing amounts of arginine increased the degradation efficiency of (I) in a more regular way than in case of (II). However, the extent of improvement due to amino acid modification was higher in case of (II) because of its originally low degradation efficiency in strongly alkaline media. Copyright © 2014 Elsevier Ltd. All rights reserved.

Dynamics of Chromium(VI) Removal from Drinking Water by Iron Electrocoagulation.

PubMed

Pan, Chao; Troyer, Lyndsay D; Catalano, Jeffrey G; Giammar, Daniel E

2016-12-20

The potential for new U.S. regulations for Cr(VI) in drinking water have spurred strong interests in improving technologies for Cr(VI) removal. This study examined iron electrocoagulation for Cr(VI) removal at conditions directly relevant to drinking water treatment. Cr(VI) is chemically reduced to less soluble Cr(III) species by the Fe(II) produced from an iron anode, and XANES spectra indicate that the Cr is entirely Cr(III) in solid-phases produced in electrocoagulation. The dynamics of Cr(VI) removal in electrocoagulation at pH 6 and pH 8 at both oxic and anoxic conditions can be described by a new model that incorporates Fe(II) release from the anode and heterogeneous and homogeneous reduction of Cr(VI) by Fe(II). Heterogeneous Cr(VI) reduction by adsorbed Fe(II) was critical to interpreting Cr(VI) removal at pH 6, and the Fe- and Cr-containing EC product was found to catalyze the redox reaction. Dissolved oxygen (DO) did not observably inhibit Cr(VI) removal because Fe(II) reacts with DO more slowly than it does with Cr(VI), and Cr(VI) removal was faster at higher pH. Even in the presence of common groundwater solutes, iron electrocoagulation lowered Cr(VI) concentrations to levels well below California's 10 μg/L.

Characterization of Cu(II) and Cd(II) resistance mechanisms in Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH and their potential application in the bioremediation of heavy metal-phenanthrene co-contaminated sites.

PubMed

Chen, Chen; Lei, Wenrui; Lu, Min; Zhang, Jianan; Zhang, Zhou; Luo, Chunling; Chen, Yahua; Hong, Qing; Shen, Zhenguo

2016-04-01

Soil that is co-contaminated with heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) is difficult to bioremediate due to the ability of toxic metals to inhibit PAH degradation by bacteria. We demonstrated the resistance mechanisms to Cu(II) and Cd(II) of two newly isolated strains of Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH and further tested their potential application in the bioremediation of HM-phenanthrene (PhA) co-contaminated sites. The PHE-SPH and PHE-OCH strains tolerated 4.63 and 4.34 mM Cu(II) and also showed tolerance to 0.48 and 1.52 mM Cd(II), respectively. Diverse resistance patterns were detected between the two strains. In PHE-OCH cells, the maximum accumulation of Cu(II) occurred in the cell wall, while the maximum accumulation was in the cytoplasm of PHE-SPH cells. This resulted in a sudden suppression of growth in PHE-OCH and a gradual inhibition in PHE-SPH as the concentration of Cu(II) increased. Organic acid production was markedly higher in PHE-OCH than in PHE-SPH, which may also have a role in the resistance mechanisms, and contributes to the higher Cd(II) tolerance of PHE-OCH. The factors involved in the absorption of Cu(II) or Cd(II) in PHE-SPH and PHE-OCH were identified as proteins and carbohydrates by Fourier transform infrared (FT-IR) spectroscopy. Furthermore, both strains showed the ability to efficiently degrade PhA and maintained this high degradation efficiency under HM stress. The high tolerance to HMs and the PhA degradation capacity make Sphingobium sp. PHE-SPH and Ochrobactrum sp. PHE-OCH excellent candidate organisms for the bioremediation of HM-PhA co-contaminated sites.

Binding Selectivity of Methanobactin from Methylosinus trichosporium OB3b for Copper(I), Silver(I), Zinc(II), Nickel(II), Cobalt(II), Manganese(II), Lead(II), and Iron(II)

NASA Astrophysics Data System (ADS)

McCabe, Jacob W.; Vangala, Rajpal; Angel, Laurence A.

2017-12-01

Methanobactin (Mb) from Methylosinus trichosporium OB3b is a member of a class of metal binding peptides identified in methanotrophic bacteria. Mb will selectively bind and reduce Cu(II) to Cu(I), and is thought to mediate the acquisition of the copper cofactor for the enzyme methane monooxygenase. These copper chelating properties of Mb make it potentially useful as a chelating agent for treatment of diseases where copper plays a role including Wilson's disease, cancers, and neurodegenerative diseases. Utilizing traveling wave ion mobility-mass spectrometry (TWIMS), the competition for the Mb copper binding site from Ag(I), Pb(II), Co(II), Fe(II), Mn(II), Ni(II), and Zn(II) has been determined by a series of metal ion titrations, pH titrations, and metal ion displacement titrations. The TWIMS analyses allowed for the explicit identification and quantification of all the individual Mb species present during the titrations and measured their collision cross-sections and collision-induced dissociation patterns. The results showed Ag(I) and Ni(II) could irreversibly bind to Mb and not be effectively displaced by Cu(I), whereas Ag(I) could also partially displace Cu(I) from the Mb complex. At pH ≈ 6.5, the Mb binding selectivity follows the order Ag(I)≈Cu(I)>Ni(II)≈Zn(II)>Co(II)>>Mn(II)≈Pb(II)>Fe(II), and at pH 7.5 to 10.4 the order is Ag(I)>Cu(I)>Ni(II)>Co(II)>Zn(II)>Mn(II)≈Pb(II)>Fe(II). Breakdown curves of the disulfide reduced Cu(I) and Ag(I) complexes showed a correlation existed between their relative stability and their compact folded structure indicated by their CCS. Fluorescence spectroscopy, which allowed the determination of the binding constant, compared well with the TWIMS analyses, with the exception of the Ni(II) complex. [Figure not available: see fulltext.

Binding Selectivity of Methanobactin from Methylosinus trichosporium OB3b for Copper(I), Silver(I), Zinc(II), Nickel(II), Cobalt(II), Manganese(II), Lead(II), and Iron(II).

PubMed

McCabe, Jacob W; Vangala, Rajpal; Angel, Laurence A

2017-12-01

Methanobactin (Mb) from Methylosinus trichosporium OB3b is a member of a class of metal binding peptides identified in methanotrophic bacteria. Mb will selectively bind and reduce Cu(II) to Cu(I), and is thought to mediate the acquisition of the copper cofactor for the enzyme methane monooxygenase. These copper chelating properties of Mb make it potentially useful as a chelating agent for treatment of diseases where copper plays a role including Wilson's disease, cancers, and neurodegenerative diseases. Utilizing traveling wave ion mobility-mass spectrometry (TWIMS), the competition for the Mb copper binding site from Ag(I), Pb(II), Co(II), Fe(II), Mn(II), Ni(II), and Zn(II) has been determined by a series of metal ion titrations, pH titrations, and metal ion displacement titrations. The TWIMS analyses allowed for the explicit identification and quantification of all the individual Mb species present during the titrations and measured their collision cross-sections and collision-induced dissociation patterns. The results showed Ag(I) and Ni(II) could irreversibly bind to Mb and not be effectively displaced by Cu(I), whereas Ag(I) could also partially displace Cu(I) from the Mb complex. At pH ≈ 6.5, the Mb binding selectivity follows the order Ag(I)≈Cu(I)>Ni(II)≈Zn(II)>Co(II)>Mn(II)≈Pb(II)>Fe(II), and at pH 7.5 to 10.4 the order is Ag(I)>Cu(I)>Ni(II)>Co(II)>Zn(II)>Mn(II)≈Pb(II)>Fe(II). Breakdown curves of the disulfide reduced Cu(I) and Ag(I) complexes showed a correlation existed between their relative stability and their compact folded structure indicated by their CCS. Fluorescence spectroscopy, which allowed the determination of the binding constant, compared well with the TWIMS analyses, with the exception of the Ni(II) complex. Graphical abstract ᅟ.

The reduction of chromium (VI) by iron (II) in aqueous solutions

NASA Astrophysics Data System (ADS)

Pettine, Maurizio; D'Ottone, Luca; Campanella, Luigi; Millero, Frank J.; Passino, Roberto

1998-05-01

The rates of the reduction of Cr(VI) with Fe(II) were measured in NaCl, NaClO 4, and natural seawater as a function of pH (1.5-8.7), temperature (5-40°C) and ionic strength (I = 0.01-2 M). The pseudo first-order rate constant (log k 1) showed a parabolic dependence on pH decreasing from 1.5 to 4.5 and increasing from 5.5 to 8.7. The kinetics of the reaction in these two regions of pH also showed different influences of temperature, ionic strength, and reductant concentration. The rate of Cr(VI) reduction is described by the general expression -d[Cr(VI)]/dt = k [Cr(VI)] [Fe(II)] where k (M -1 min -1) can be determined from the log k=6.74-1.01 pH-188.5/T for the pH range 1.5-4.5 (σ = 0.2) and log k=11.93+0.95 pH-4260.1/T-1.06 I 0.5 for the pH range 5-8.7 (σ = 0.2) from 5 to 40°C and 0.01 to 2 M ionic strength. The effect of pH, temperature, and ionic strength on the reaction indicates that the reactions at low pH are due to H2CrO4+ Fe2+limit→k H2 A-Feproducts While the reactions at high pH are due to HCrO4-+ FeOH+limit→k HA-FeOHproductsHCrO4-+ Fe(OH)2limit→k HA-Fe(OH)2 products The overall rate expression over the entire pH range can be determined from (H 2A = H 2CrO 4) k=k H2 A-Feα( H2A)α( Fe2+)+k HA-FeOHα( HA-)α( FeOH+)+k HA-Fe(OH)2 α( HA-)α( Fe(OH)2) where k H2A-Fe = 5 x 10 6, k HA-FeOH = 1 x 10 6, k HA-Fe (OH)2= 5 x 10 11. In oxic aqueous systems Cr(VI) competes with O 2 in the oxidation of Fe(II) and an extension of the rate law for Cr(VI) reduction with Fe(II) in oxygenated solutions is proposed. The application of this extended rate law to environmental conditions suggests that this reaction influences the distribution of oxidized and reduced species of chromium in oxic and anoxic waters.

Quantitative Chemical Exchange Saturation Transfer MRI of Intervertebral Disc in a Porcine Model

PubMed Central

Zhou, Zhengwei; Bez, Maxim; Tawackoli, Wafa; Giaconi, Joseph; Sheyn, Dmitriy; de Mel, Sandra; Maya, Marcel M.; Pressman, Barry D.; Gazit, Zulma; Pelled, Gadi; Gazit, Dan; Li, Debiao

2017-01-01

Purpose Previous studies have associated low pH in interver-tebral discs (IVDs) with discogenic back pain. The purpose of this study was to determine whether quantitative CEST (qCEST) MRI can be used to detect pH changes in IVDs in vivo. Methods The exchange rate ksw between glycosaminoglycan (GAG) protons and water protons was determined from qCEST analysis. Its dependence on pH value was investigated in GAG phantoms with varying pH and concentrations. The relationship between ksw and pH was studied further in vivo in a porcine model on a 3T MR scanner and validated using a pH meter. Sodium lactate was injected into the IVDs to induce various pH values within the discs ranging from 5 to 7. Results Phantom and animal results revealed that ksw measured using qCEST MRI is highly correlated with pH level. In the animal studies, the relationship can be described as ksw =9.2 × 106 × 10−pH + 196.9, R2 = 0.7883. Conclusion The exchange rate between GAG and water protons determined from qCEST MRI is closely correlated with pH value. This technique has the potential to noninvasively measure pH in the IVDs of patients with discogenic pain. PMID:27670140

Reaction of cytochrome c with nitrite and nitric oxide. A model of dissimilatory nitrite reductase.

PubMed

Orii, Y; Shimada, H

1978-12-01

The reaction of bovine heart ferrocytochrome c with nitrite was studied under various conditions. The reaction product was ferricytochrome c at around pH 5, whereas at around pH 3 it was Compound I, characterized by twin peaks at 529 and 563 nm of equal intensity. However, ferrocytochrome c decreased obeying first-order kinetics over the pH range examined, irrespective of the presence or absence of molecular oxygen. The apparent first-order rate constant was proportional to the square of the nitrite concentration at pH 4.4 and it increased as the pH was lowered. At pH 3 the reaction was so rapid that it had to be followed by stopped-flow and rapid-scanning techniques. The apparent rate constant at this pH was found to increase linearly with the nitrite concentration. Based on these results the active species of nitrite was concluded to be dinitrogen trioxide at pH 4.4 and nitrosonium ion, no+, at pH 3. Compound II was formed by reaction of ferrocytochrome c and NO gas at acidic and alkaline pH values. The absorption peaks were at 533 and 563 nm at pH 3, and at 538 and 567 nm at pH 12.9. This compound was also formed by reducing Compound I with reductants. Compound I prepared from ferricytochrome c and NO was stable below pH 6. However, appreciable absorption peaks for ferrocytochrome c appeared between pH 8 and 10, because Compound I was dissociated into ferrocytochrome c and NO+, and because ferrocytochrome c thus formed reacted with NO very slowly in this pH region. Saccharomyces ferricytochrome c under NO gas behaved differently from mammalian cytochrome, indicating the significance of the nature of the heme environment in determing the reactivity. Only at extreme pH values was Compound II formed exclusively and persisted. A model system for dissimilatory nitrite reductase was constructed by using bovine heart cytochrome c, nitrite and NADH plus PMS at pH 3.3, and a scheme involving cyclic turnover of ferrocytochrome c, Compound I and Compound II is presented, with kinetic parameters.

Surface catalysis of uranium(VI) reduction by iron(II)

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

Liger, E.; Charlet, L.; Van Cappellen, P.

1999-10-01

Colloidal hematite ({alpha}-Fe{sub 2}O{sub 3}) is used as model solid to investigate the kinetic effect of specific adsorption interactions on the chemical reduction of uranyl (U{sup VI}O{sub 2}{sup 2+}) by ferrous iron. Acid-base titrations and Fe(II) and uranyl adsorption experiments are performed on hematite suspensions, under O{sub 2}- and CO{sub 2}-free conditions. The results are explained in terms of a constant capacitance surface complexation model of the hematite-aqueous solution interface. Two distinct Fe(II) surface complexes are required to reproduce the data: ({equivalent{underscore}to}Fe{sup III}OFe{sup II}){sup +} (or {equivalent{underscore}to}Fe{sup III}OFe{sup II}(OH{sub 2}){sub n}{sup +}) and {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0} (or {equivalent{underscore}to}Fe{sup III}OFe{supmore » II}(OH{sub 2}){sub n{minus}1}OH{sup 0}). The latter complex represents a significant fraction of total adsorbed Fe(II) at pH {gt} 6.5. Uranyl binding to the hematite particles is characterized by a sharp adsorption edge between pH 4 and pH 5.5. Because of the absence of competing aqueous carbonate complexes, uranyl remains completely adsorbed at pH {gt} 7. A single mononuclear surface complex accounts for the adsorption of uranyl over the entire range of experimental conditions. Although thermodynamically feasible, no reaction between uranyl and Fe(II) is observed in homogeneous solution at pH 7.5, for periods of up to three days. In hematite suspensions, however, surface-bound uranyl reacts on a time scale of hours. Based on Fourier Transformed Infrared spectra, chemical reduction of U(VI) is inferred to be the mechanism responsible for the disappearance of uranyl. The kinetics of uranyl reduction are quantified by measuring the decrease with time of the concentration of U(VI) extractable from the hematite particles by NaHCO{sub 3}. In the presence of excess Fe(II), the initial rate of U(VI) reduction exhibits a first-order dependence on the concentration of adsorbed uranyl. The pseudo-first-order rate constant varies with pH (range, 6--7.5) and the total (dissolved + adsorbed) concentration of Fe(II) (range, 2--160 {micro}M). When analyzing the rate data in terms of the calculated surface speciation, the variability of the rate constant can be accounted for entirely by changes in the concentration of the Fe(II) monohydroxo surface complex {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0}. Therefore, the rate law is derived for the hematite-catalyzed reduction of uranyl by Fe(II), where the bimolecular rate constant {kappa} has a value of 399 {+-} 25 M{sup {minus}1} min{sup {minus}1} at 25 C. The hydroxo surface complex is the rate-controlling reductant species, because it provides the most favorable coordination environment in which electrons are removed from Fe(II). Natural particulate matter collected in the hypolimnion of a seasonally stratified lake also causes the rapid reduction of uranyl by Fe(II), Ferrihydrite, identified in the particulate matter by X-ray diffraction, is one possible mineral phase accelerating the reaction between U(VI) and Fe(II). At near-neutral pH and total Fe(II) levels less than 1 mM, the pseudo-first-order rate constants of chemical U(VI) reduction, measured in the presence of the hematite and lake particles, are of the same order of magnitude as the highest corresponding rate coefficients for enzymatic U(VI) reduction in bacterial cultures. Hence, based on the results of this study, surface-catalyzed U(VI) reduction by Fe(II) is expected to be a major pathway of uranium immobilization in a wide range of redox-stratified environments.« less

Skin thickness effects on in vivo LXRF

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

Preiss, I.L.; Washington, W. II

The analysis of lead concentration in bone utilizing LXRF can be adversely effected by overlying issue. A quantitative measure of the attenuation of the 10.5 keV Pb L a x-ray signal by skin and skin equivalent plastic has been conducted. Concentration ranges in plaster of Paris and goat bone from 7 to 90 ppm with attenuators of Lucite{reg_sign} and pig skin were examined. It is concluded that no quantitative or semi quantitative analysis can be achieved if overlying sue thickness exceeds 3 mm for Ph concentrations of less than 30 porn Ph in bone.

Kinetics of Electrocatalysis of Dibromoalkyl Reductions Using Electrodes with Covalently Immobilized Metallotetraphenylporphyrins.

DTIC Science & Technology

1981-01-29

Technical Report Using Electrodes with Covalently Immobilized Metal l otetraphenyl porphyri ns G. PERFORMING ORG. REPORT NUMBER 7. AU𔄁IOR(’.) 0...and CH2BrCHBrCH 3 at the surfaces of electrodes to which cobalt(II) or copper (II) tetra(p-aminophenyl)porphyrin has been covalently attached is strongly...27514 ABSTRACT The reduction of PhCHBrCH 2 Br, PhCHBrCHBrPh, and CH2BrCHBrCH3 at the surfaces of electrodes to which cobalt(lI) or copper (If) tetra(p

Role of the Ca-pectates on the accumulation of heavy metals in the root apoplasm.

PubMed

Castaldi, Paola; Lauro, Giampaolo; Senette, Caterina; Deiana, Salvatore

2010-12-01

In order to better understand the processes that regulate the accumulation in the apoplasm of heavy metals and their mobilization by the plant metabolites it is essential to study the mechanisms that regulate the interactions between metal ions and pectins. In such a context, the sorption of Cd(II), Zn(II), Cu(II) and Pb(II) from single and multi-metal solutions, by a Ca-polygalacturonate gel with a degree of esterification of 18.0 (PGAM(1)) and 65.5% (PGAM(2)) was studied in the 3.0-6.0 pH range in the presence of CaCl(2) 2.5mM. The sorption of Cr(III) from single metal solution was also considered. The results show that the amount of each metal ion sorbed increases with increasing the initial metal ion concentration and pH. The data from the single metal solution tests show that at pH 6.0 the affinity of the metal ions towards the PGAM(1) matrix follows the order: Cr(III)>Cu(II)≅Pb(II)≫Zn(II)≅Cd(II). The simultaneous sorption of the bivalent metal ions by the PGAM(1) gels indicates that Pb(II) is selectively sorbed. The FT-IR spectra show that the carboxylate groups are mainly responsible for the metal ion coordination. The ability of PGAM(2) to accumulate Cr(III), Cu(II), and Pb(II) was lower than that found in the PGAM(1) systems whereas the sorption of Zn(II) and Cd(II) was negligible. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

Long period grating-based fiber-optic PH sensor for ocean monitoring

NASA Astrophysics Data System (ADS)

Wang, Ke; Klimov, Denis; Kolber, Zbigniew

2007-09-01

A fiber-optic PH sensor is developed based-on the long period grating (LPG). The LPG is fabricated by using CO II laser with a point-by-point technique. Then the grating portion is coated with PH sensitive hydrogel. The hydrogel, made of PVA/PAA, swells its volume in response to the PH change in the surrounding environment and results in a change in the refractive index. As a result, the LPG can response to the refractive index change in the coating by shifting its wavelength. Therefore, change in refractive index can be measured by tracking the wavelength shift using an optical spectrum analyzer (OSA). In this research, the LPG is dip-coated by the hydrogel. A chemostat is designed to simulate the marine environment. The PH in the chemostat is varied by controlling the CO II concentration in the sea water. A PH resolution 0.046/nm using the OSA has been obtained. This sensor is designed to monitor the sea water PH change in a long term basis.

Preparation of a novel pH optical sensor using orange (II) based on agarose membrane as support.

PubMed

Heydari, Rouhollah; Hosseini, Mohammad; Amraei, Ahmadreza; Mohammadzadeh, Ali

2016-04-01

A novel and cost effective optical pH sensor was prepared using covalent immobilization of orange (II) indicator on the agarose membrane as solid support. The fabricated optical sensor was fixed into a sample holder of a spectrophotometer instrument for pH monitoring. Variables affecting sensor performance including pH of dye bonding to agarose membrane and dye concentration were optimized. The sensor responds to the pH changes in the range of 3.0-10.0 with a response time of 2.0 min and appropriate reproducibility (RSD ≤ 0.9%). No significant variation was observed on sensor response after increasing the ionic strength in the range of 0.0-0.5M of sodium chloride. Determination of pH using the proposed optical sensor is quick, simple, inexpensive, selective and sensitive in the pH range of 3.0-10.0. Copyright © 2015 Elsevier B.V. All rights reserved.

Nickel adsorption onto polyurethane ethylene and vinyl acetate sorbents.

PubMed

Iqbal, Munawar; Ali, Zahid; Qamar, M Afzal; Ali, Abid; Hussain, Fida; Abbas, Mazhar; Nisar, Jan

2017-07-01

The present study was conducted to appraise the efficiencies of polyurethane ethylene sorbent (PES) and vinyl acetate sorbent (VAS) for nickel (Ni) adsorption. Process variables, i.e. Ni(II) ions initial concentration, pH, contact time and adsorbent dosage were optimized by response surface methodology (RSM) approach. The Ni(II) adsorption was fitted to the kinetic models (pseudo-first-order and pseudo-second-order) and adsorption isotherms (Freundlich and Langmuir). At optimum conditions of process variables, 171.99 mg/g (64.7%) and 388.08 mg/g (92.7%) Ni(II) was adsorbed onto PES and VAS, respectively. The RSM analysis revealed that maximum Ni(II) adsorption can be achieved at 299 mg/L Ni(II) ions initial concentration, 4.5 pH, 934 min contact time and 1.3 g adsorbent dosage levels for PES, whereas the optimum values for VAS were found to be 402 mg/L Ni(II) ions initial concentration, 4.6 pH, 881 min contact time and 1.2 g adsorbent dosage, respectively. The -OH and -C = O- were involved in the Ni(II) adsorption onto PES and VAS adsorbents. At optimum levels, up to 53.67% and 80.0% Ni(II) was removed from chemical industry wastewater using PES and VAS, respectively, which suggest that PES and VAS could possibly be used for Ni(II) adsorption from industrial wastewater.

Bench-scale evaluation of ferrous iron oxidation kinetics in drinking water: effect of corrosion control and dissolved organic matter.

PubMed

Rahman, Safiur; Gagnon, Graham A

2014-01-01

Corrosion control strategies are important for many utilities in maintaining water quality from the water treatment plant to the customers' tap. In drinking water with low alkalinity, water quality can become significantly degraded in iron-based pipes if water utilities are not diligent in maintaining proper corrosion control. This article reports on experiments conducted in bicarbonate buffered (5 mg-C/L) synthetic water to determine the effects of corrosion control (pH and phosphate) and dissolved organic matter (DOM) on the rate constants of the Fe(II) oxidation process. A factorial design approach elucidated that pH (P = 0.007, contribution: 42.5%) and phosphate (P = 0.025, contribution: 22.7%) were the statistically significant factors in the Fe(II) oxidation process at a 95% confidence level. The comprehensive study revealed a significant dependency relationship between the Fe(II) oxidation rate constants (k) and phosphate-to- Fe(II) mole ratio. At pH 6.5, the optimum mole ratio was found to be 0.3 to reduce the k values. Conversely, the k values were observed to increase for the phosphate-to- Fe(II) mole ratio > 1. The factorial design approach revealed that chlorine and DOM for the designated dosages did not cause a statistically significant (α = 0.05, P > 0.05)change in rate constants. However, an increment of the chlorine to ferrous iron mole ratio by a factor of ∼ 2.5 resulted in an increase k values by a factor of ∼ 10. This study conclusively demonstrated that the lowest Fe(II) oxidation rate constant was obtained under low pH conditions (pH ≤ 6.5), with chlorine doses less than 2.2 mg/L and with a phosphate-to-Fe(II) mole ratio ≈ 0.3 in the iron water systems.

Equilibrium Partitioning Sediment Guidelines (ESGs) for the ...

EPA Pesticide Factsheets

... PLC = partial life-cycle ... 5 ii mini iiiiiiiii iiiiiii mi 1 1 iii mini ii i B : - Benthic vs WQC i— w ~_ ~ _ o° _ -0 ° - - - ii mini iiiiiiiii iiiiiii iiiiiiiii mini ii 0.1 ... PhD thesis. ...

A series of tetraazalene radical-bridged M2 (M = CrIII, MnII, FeII, CoII) complexes with strong magnetic exchange coupling† †Electronic supplementary information (ESI) available: Experimental details, UV/Vis/NIR spectra for 2–8, additional magnetic data for 4–8, crystallographic data, selected bond distances, and crystallographic information files (CIFs) for 1, 2·0.4THF, 3·2.5THF, 4·2.5THF, and 5·2.9MeCN (CCDC 1414648–1414652). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02725j

PubMed Central

DeGayner, Jordan A.; Jeon, Ie-Rang

2015-01-01

The ability of tetraazalene radical bridging ligands to mediate exceptionally strong magnetic exchange coupling across a range of transition metal complexes is demonstrated. The redox-active bridging ligand N,N′,N′′,N′′′-tetra(2-methylphenyl)-2,5-diamino-1,4-diiminobenzoquinone (NMePhLH2) was metalated to give the series of dinuclear complexes [(TPyA)2M2(NMePhL2–)]2+ (TPyA = tris(2-pyridylmethyl)amine, M = MnII, FeII, CoII). Variable-temperature dc magnetic susceptibility data for these complexes reveal the presence of weak superexchange interactions between metal centers, and fits to the data provide coupling constants of J = –1.64(1) and –2.16(2) cm–1 for M = MnII and FeII, respectively. One-electron reduction of the complexes affords the reduced analogues [(TPyA)2M2(NMePhL3–˙)]+. Following a slightly different synthetic procedure, the related complex [(TPyA)2CrIII2(NMePhL3–˙)]3+ was obtained. X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy indicate the presence of radical NMePhL3–˙ bridging ligands in these complexes. Variable-temperature dc magnetic susceptibility data of the radical-bridged species reveal the presence of strong magnetic interactions between metal centers and ligand radicals, with simulations to data providing exchange constants of J = –626(7), –157(7), –307(9), and –396(16) cm–1 for M = CrIII, MnII, FeII, and CoII, respectively. Moreover, the strength of magnetic exchange in the radical-bridged complexes increases linearly with decreasing M–L bond distance in the oxidized analogues. Finally, ac magnetic susceptibility measurements reveal that [(TPyA)2Fe2(NMePhL3–˙)]+ behaves as a single-molecule magnet with a relaxation barrier of Ueff = 52(1) cm–1. These results highlight the ability of redox-active tetraazalene bridging ligands to enable dramatic enhancement of magnetic exchange coupling upon redox chemistry and provide a rare opportunity to examine metal–radical coupling trends across a transmetallic series of complexes. PMID:29435213

Development of a novel MWCNTs-triazene-modified carbon paste electrode for potentiometric assessment of Hg(II) in the aquatic environments.

PubMed

Mashhadizadeh, Mohammad Hossein; Ramezani, Soleyman; Rofouei, Mohammad Kazem

2015-02-01

In this approach, a new chemically modified carbon paste electrode was assembled for potentiometric assay of mercury(II) ion in the aqueous environments. Hereby, MWCNTs were used in the carbon paste composition to meliorate the electrical conductivity and sensitivity of the carbon paste owing to its exceptional physicochemical characteristics. Likewise, participation of the BEPT as a super-selective ionophore in the carbon paste composition boosted significantly the selectivity of the modified electrode towards Hg(II) ions over a wide concentration range of 4.0 × 10(-9)-2.2 × 10(-3) mol L(-1) with a lower detection limit of 3.1 × 10(-9) mol L(-1). Besides, Nernstian slope of the proposed sensor was 28.9(± 0.4)mV/decade over a pH range of 3.0-5.2 with potentiometric short response time of 10s. In the interim, by storing in the dark and cool dry place during non-usage period, the electrode can be used for at least 30 days without any momentous divergence of the potentiometric response. Eventually, to judge about its practical efficiency, the arranged sensor was utilized successfully as an indicator electrode for potentiometric titration of mercury(II) with standard solution of EDTA. As well, the quantitative analysis of mercury(II) ions in some aqueous samples with sensible accuracy and precision was satisfactorily performed. Copyright © 2014 Elsevier B.V. All rights reserved.

Biosorption of Pb (II) from aqueous solution by extracellular polymeric substances extracted from Klebsiella sp. J1: Adsorption behavior and mechanism assessment

NASA Astrophysics Data System (ADS)

Wei, Wei; Wang, Qilin; Li, Ang; Yang, Jixian; Ma, Fang; Pi, Shanshan; Wu, Dan

2016-08-01

The adsorption performance and mechanism of extracellular polymeric substances (EPS) extracted from Klebsiella sp. J1 for soluble Pb (II) were investigated. The maximum biosorption capacity of EPS for Pb (II) was found to be 99.5 mg g-1 at pH 6.0 and EPS concentration of 0.2 g/L. The data for adsorption process satisfactorily fitted to both Langmuir isotherm and pseudo-second order kinetic model. The mean free energy E and activation energy Ea were determined at 8.22- 8.98 kJ mol-1 and 42.46 kJ mol-1, respectively. The liquid-film diffusion step might be the rate-limiting step. The thermodynamic parameters (ΔGo, ΔHo and ΔSo) revealed that the adsorption process was spontaneous and exothermic under natural conditions. The interactions between EPS system and Pb (II) ions were investigated by qualitative analysis methods (i.e Zeta potential, FT-IR and EDAX). Based on the strong experimental evidence from the mass balance of the related elements participating in the sorption process, an ion exchange process was identified quantitatively as the major mechanism responsible for Pb (II) adsorption by EPS. Molar equivalents of both K+ and Mg2+ could be exchanged with Pb2+ molar equivalents in the process and the contribution rate of ion exchange to adsorption accounted for 85.72% (Δmequiv = -0.000541).

Biosorption of Pb (II) from aqueous solution by extracellular polymeric substances extracted from Klebsiella sp. J1: Adsorption behavior and mechanism assessment

PubMed Central

Wei, Wei; Wang, Qilin; Li, Ang; Yang, Jixian; Ma, Fang; Pi, Shanshan; Wu, Dan

2016-01-01

The adsorption performance and mechanism of extracellular polymeric substances (EPS) extracted from Klebsiella sp. J1 for soluble Pb (II) were investigated. The maximum biosorption capacity of EPS for Pb (II) was found to be 99.5 mg g−1 at pH 6.0 and EPS concentration of 0.2 g/L. The data for adsorption process satisfactorily fitted to both Langmuir isotherm and pseudo-second order kinetic model. The mean free energy E and activation energy Ea were determined at 8.22– 8.98 kJ mol−1 and 42.46 kJ mol−1, respectively. The liquid-film diffusion step might be the rate-limiting step. The thermodynamic parameters (ΔGo, ΔHo and ΔSo) revealed that the adsorption process was spontaneous and exothermic under natural conditions. The interactions between EPS system and Pb (II) ions were investigated by qualitative analysis methods (i.e Zeta potential, FT-IR and EDAX). Based on the strong experimental evidence from the mass balance of the related elements participating in the sorption process, an ion exchange process was identified quantitatively as the major mechanism responsible for Pb (II) adsorption by EPS. Molar equivalents of both K+ and Mg2+ could be exchanged with Pb2+ molar equivalents in the process and the contribution rate of ion exchange to adsorption accounted for 85.72% (Δmequiv = −0.000541). PMID:27514493

Enrichment and purification of six Aconitum alkaloids from Aconiti kusnezoffii radix by macroporous resins and quantification by HPLC-MS.

PubMed

Liu, Jingjing; Li, Qing; Liu, Ran; Yin, Yidi; Chen, Xiaohui; Bi, Kaishun

2014-06-01

Aconitine, mesaconitine, hypaconitine, benzoylaconine, benzoylmesaconine and benzoylhypaconine are six main Aconitum alkaloids from traditional Chinese medicine, Aconiti kusnezoffii radix, which possess highly bioactive as well as highly toxic character for medicinal use. In the present study, for the purpose of better utilizing the toxic herbal material, the performance characteristics of NKA-II, D101, X-5, AB-8, S-8, HPD722 and HPD750 macroporous resins for the enrichment and purification of these six Aconitum alkaloids were critically evaluated. Results showed that NKA-II offered the best adsorption and desorption capacities for six Aconitum alkaloids among the seven macroporous resins tested, which were affected significantly by the pH value. Subsequently, dynamic adsorption and desorption experiments had been carried out with the column packed by NKA-II resin to optimize the separation process of six Aconitum alkaloids. After one run treatment with NKA-II resin, the content of total six Aconitum alkaloids were increased from 5.87% to 60.3%, the recovery was 75.8%. Meanwhile, a validated HPLC-MS method had been developed to qualitative and quantitative these six Aconitum alkaloids. This method would provide scientific references to the large-scale production of six Aconitum alkaloids from Aconiti kusnezoffii radix or other plants and might also expand the secure application of these highly toxic components for pharmacy. Copyright © 2014 Elsevier B.V. All rights reserved.

Drastic Effect of the Peptide Sequence on the Copper-Binding Properties of Tripeptides and the Electrochemical Behaviour of Their Copper(II) Complexes.

PubMed

Mena, Silvia; Mirats, Andrea; Caballero, Ana B; Guirado, Gonzalo; Barrios, Leoní A; Teat, Simon J; Rodriguez-Santiago, Luis; Sodupe, Mariona; Gamez, Patrick

2018-04-06

The binding and electrochemical properties of the complexes Cu II -HAH, Cu II -HWH, Cu II -Ac-HWH, Cu II -HHW, and Cu II -WHH have been studied by using NMR and UV/Vis spectroscopies, CV, and density functional calculations. The results obtained highlight the importance of the peptidic sequence on the coordination properties and, consequently, on the redox properties of their Cu II complexes. For Cu II -HAH and Cu II -HWH, no cathodic processes are observed up to -1.2 V; that is, the complexes exhibit very high stability towards copper reduction. This behaviour is associated with the formation of very stable square-planar (5,5,6)-membered chelate rings (ATCUN motif), which enclose two deprotonated amides. In contrast, for non-ATCUN Cu II -Ac-HWH, Cu II -HHW complexes, simulations seem to indicate that only one deprotonated amide is enclosed in the coordination sphere. In these cases, the main electrochemical feature is a reductive irreversible one electron-transfer process from Cu II to Cu I , accompanied with structural changes of the metal coordination sphere and reprotonation of the amide. Finally, for Cu II -WHH, two major species have been detected: one at low pH (<5), with no deprotonated amides, and another one at high pH (>10) with an ATCUN motif, both species coexisting at intermediate pH. The present study shows that the use of CV, using glassy carbon as a working electrode, is an ideal and rapid tool for the determination of the redox properties of Cu II metallopeptides. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO4 oxidation of a Mn(ii) precursor.

PubMed

Lorenz, Volker; Ehle, Sophie; Liebing, Phil; Engelhardt, Felix; Hashemi-Haeri, Haleh; Oehler, Florian; Hinderberger, Dariush; Busse, Sabine; Urbaschok, Jens; Edelmann, Frank T

2017-12-19

A unique trivalent manganese siloxide complex, blue-violet Mn III Li 2 Cl[(Ph 2 SiO) 2 O] 2 (THF) 4 ·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (Ph 2 SiOH) 2 O (1) followed by reaction with MnCl 2 (THF) 2 gave the structurally remarkable Mn(ii) precursor Mn II Li 4 Cl 2 [(Ph 2 SiO) 2 O] 2 (THF) 5 ·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO 4 in THF to provide the Mn(iii) species 3 in high yield (91%). Both title compounds were structurally characterized by single-crystal X-ray diffraction.

Colorimetric Determination of pH.

ERIC Educational Resources Information Center

Tucker, Sheryl; And Others

1989-01-01

Presented is an activity in which the pH of a solution can be quantitatively measured using a spectrophotometer. The theory, experimental details, sample preparation and selection, instrumentation, and results are discussed. (CW)

Left Ventricular End-Systolic Eccentricity Index for Assessment of Pulmonary Hypertension in Infants.

PubMed

Abraham, Sharon; Weismann, Constance G

2016-06-01

Pulmonary hypertension (PH) is a common problem in the neonatal intensive care unit and is associated with significant morbidity and mortality. The aim of this study was to identify a quantitative echocardiographic marker of septal curvature that can be used to accurately identify PH in NICU infants with concern for PH. Echocardiograms of infants who were prematurely born and infants with persistent pulmonary hypertension of the newborn were performed using a defined protocol for evaluation of PH. Qualitative assessment by a single pediatric cardiologist was used as a reference standard. Qualitative and quantitative parameters of right ventricular (RV) size, pressure, and function were documented. Left ventricular end-systolic eccentricity index (EI) was defined as the ratio of the anterior-inferior and septal-posterolateral cavity dimensions at the mid-ventricular level. A total of 216 infants at risk for PH were included in this study. One hundred forty-three (66%) had an interpretable tricuspid regurgitation jet velocity. While systolic septal flattening was recognized at EIs ≥ 1.15, more than half-systemic RV pressure became apparent at EIs ≥ 1.3. Unlike qualitative assessment of septal flattening, there was high inter-observer agreement for EIs. Quantitative parameters of RV systolic function were impaired only at EIs ≥ 1.3. We suggest that EIs should be incorporated into routine protocols when there is a concern for PH in neonates. This may lead to a more reliable assessment of PH and may reduce inter-observer variability. Correlation of EIs with invasive hemodynamic data is needed to validate our results. © 2016, Wiley Periodicals, Inc.

Electroless Cu Plating on Anodized Al Substrate for High Power LED.

PubMed

Rha, Sa-Kyun; Lee, Youn-Seoung

2015-03-01

Area-selective copper deposition on screen printed Ag pattern/anodized Al/Al substrate was attempted using a neutral electroless plating processes for printed circuit boards (PCBs), according to a range of variation of pH 6.5-pH 8 at 70 °C. The utilized basic electroless solution consisted of copper(II) sulfate pentahydrate, sodium phosphinate monohydrate, sodium citrate tribasic dihydrate, ammonium chloride, and nickel(II) sulfate hexahydrate. The pH of the copper plating solutions was adjusted from pH 6.5 to pH 8 using NH4OH. Using electroless plating in pH 6.5 and pH 7 baths, surface damage to the anodized Al layer hardly occurred; the structure of the plated Cu-rich films was a typical fcc-Cu, but a small Ni component was co-deposited. In electroless plating at pH 8, the surface of the anodized Al layer was damaged and the Cu film was composed of a lot of Ni and P which were co-deposited with Cu. Finally, in a pH 7 bath, we can make a selectively electroless plated Cu film on a PCB without any lithography and without surface damage to the anodized Al layer.

Fe(II)-induced transformation from ferrihydrite to lepidocrocite and goethite

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

Liu Hui; Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 China; Li Ping

2007-07-15

The transformation of Fe(II)-adsorbed ferrihydrite was studied. Data tracking the formation of products as a function of pH, temperature and time is presented. The results indicate that trace of Fe(II) adsorbed on ferrihydrite can accelerate its transformation obviously. The products are lepidocrocite and/or goethite and/or hematite, which is different from those without Fe(II). That is, Fe(II) not only accelerates the transformation of ferrihydrite but also leads to the formation of lepidocrocite by a new path. The behavior of Fe(II) is shown in two aspects-catalytic dissolution-reprecipitation and catalytic solid-state transformation. The results indicate that a high temperature and a high pH(inmore » the range from 5 to 9) are favorable to solid-state transformation and the formation of hematite, while a low temperature and a low pH are favorable to dissolution-reprecipitation mechanism and the formation of lepidocrocite. Special attentions were given to the formation mechanism of lepidocrocite and goethite. - Graphical abstract: Fe(II)-adsorbed ferrihydrite can rapidly transform into lepidocrocite or/and goethite or/and hematite. Which product dominates depends on the transformation conditions of ferrihydrite such as temperature, pH, reaction time, etc. In the current system, there exist two transformation mechanisms. One is dissolution/reprecipitation and the other is solid-state transformation. The transformation mechanisms from Fe(II)-adsorbed ferrihydrite to lepidocrocite and goethite were investigated.« less

Quantitative trait locus analysis of heterosis for plant height and ear height in an elite maize hybrid zhengdan 958 by design III.

PubMed

Li, Hongjian; Yang, Qingsong; Fan, Nannan; Zhang, Ming; Zhai, Huijie; Ni, Zhongfu; Zhang, Yirong

2017-04-17

Plant height (PH) and ear height (EH) are two important agronomic traits in maize selection breeding. F 1 hybrid exhibit significant heterosis for PH and EH as compared to their parental inbred lines. To understand the genetic basis of heterosis controlling PH and EH, we conducted quantitative trait locus (QTL) analysis using a recombinant inbreed line (RIL) based design III population derived from the elite maize hybrid Zhengdan 958 in five environments. A total of 14 environmentally stable QTLs were identified, and the number of QTLs for Z 1 and Z 2 populations was six and eight, respectively. Notably, all the eight environmentally stable QTLs for Z 2 were characterized by overdominance effect (OD), suggesting that overdominant QTLs were the most important contributors to heterosis for PH and EH. Furthermore, 14 environmentally stable QTLs were anchored on six genomic regions, among which four are trait-specific QTLs, suggesting that the genetic basis for PH and EH is partially different. Additionally, qPH.A-1.3, modifying about 10 centimeters of PH, was further validated in backcross populations. The genetic basis for PH and EH is partially different, and overdominant QTLs are important factors for heterosis of PH and EH. A major QTL qPH.A-1.3 may be a desired target for genetic improvement of maize plant height.

Catalytic copolymerization of CO and ethylene with a charge neutral palladium(II) zwitterion.

PubMed

Lu, Connie C; Peters, Jonas C

2002-05-15

The synthesis of a zwitterionic Pd(II) complex supported by an anionic bis(phosphino)borate ligand, Ph(2)B(CH(2)PPh(2))(2) (abbreviated as [Ph(2)BP(2)]), is reported. The new complex, [Ph(2)BP(2)]PdMe(THF), is active for CO and ethylene copolymerization. The copolymerization activity and polyketone molecular weight for the neutral, zwitterionic system are compared with those for the cationic systems [R(2)E(CH(2)PPh(2))(2)PdMe(THF)][B(C(6)F(5))(4)] where ER(2) = SiPh(2) and CH(2). Surprisingly, the more electron rich zwitterionic system is a catalyst of activity comparable to that of the more conventional cationic systems.

Cu(II) Binding to the Peptide Ala-His-His, a Chimera of the Canonical Cu(II)-Binding Motifs Xxx-His and Xxx-Zzz-His.

PubMed

Gonzalez, Paulina; Vileno, Bertrand; Bossak, Karolina; El Khoury, Youssef; Hellwig, Petra; Bal, Wojciech; Hureau, Christelle; Faller, Peter

2017-12-18

Peptides and proteins with the N-terminal motifs NH 2 -Xxx-His and NH 2 -Xxx-Zzz-His form well-established Cu(II) complexes. The canonical peptides are Gly-His-Lys and Asp-Ala-His-Lys (from the wound healing factor and human serum albumin, respectively). Cu(II) is bound to NH 2 -Xxx-His via three nitrogens from the peptide and an external ligand in the equatorial plane (called 3N form here). In contrast, Cu(II) is bound to NH 2 -Xxx-Zzz-His via four nitrogens from the peptide in the equatorial plane (called 4N form here). These two motifs are not mutually exclusive, as the peptides with the sequence NH 2 -Xxx-His-His contain both of them. However, this chimera has never been fully explored. In this work, we use a multispectroscopic approach to analyze the Cu(II) binding to the chimeric peptide Ala-His-His (AHH). AHH is capable of forming the 3N- and 4N-type complexes in a pH dependent manner. The 3N form predominates at pH ∼ 4-6.5 and the 4N form at ∼ pH 6.5-10. NMR experiments showed that at pH 8.5, where Cu(II) is almost exclusively bound in the 4N form, the Cu(II)-exchange between AHH or the amidated AHH-NH 2 is fast, in comparison to the nonchimeric 4N form (AAH). Together, the results show that the chimeric AHH can access both Cu(II) coordination types, that minor changes in the second (or further) coordination sphere can impact considerably the equilibrium between the forms, and that Cu kinetic exchange is fast even when Cu-AHH is mainly in the 4N form.

Heavy metal removal from waste waters by ion flotation.

PubMed

Polat, H; Erdogan, D

2007-09-05

Flotation studies were carried out to investigate the removal of heavy metals such as copper (II), zinc (II), chromium (III) and silver (I) from waste waters. Various parameters such as pH, collector and frother concentrations and airflow rate were tested to determine the optimum flotation conditions. Sodium dodecyl sulfate and hexadecyltrimethyl ammonium bromide were used as collectors. Ethanol and methyl isobutyl carbinol (MIBC) were used as frothers. Metal removal reached about 74% under optimum conditions at low pH. At basic pH it became as high as 90%, probably due to the contribution from the flotation of metal precipitates.

Neutron structure of human carbonic anhydrase II: a hydrogen-bonded water network "switch" is observed between pH 7.8 and 10.0.

PubMed

Fisher, Zoë; Kovalevsky, Andrey Y; Mustyakimov, Marat; Silverman, David N; McKenna, Robert; Langan, Paul

2011-11-08

The neutron structure of wild-type human carbonic anhydrase II at pH 7.8 has been determined to 2.0 Å resolution. Detailed analysis and comparison to the previously determined structure at pH 10.0 show important differences in the protonation of key catalytic residues in the active site as well as a rearrangement of the H-bonded water network. For the first time, a completed H-bonded network stretching from the Zn-bound solvent to the proton shuttling residue, His64, has been directly observed.

Effect of coexisting Al(III) ions on Pb(II) sorption on biochars: Role of pH buffer and competition.

PubMed

Yang, Yuxi; Zhang, Weihua; Qiu, Hao; Tsang, Daniel C W; Morel, Jean-Louis; Qiu, Rongliang

2016-10-01

Biochar is being widely considered as a promising amendment agent for immobilizing heavy metals in contaminated acidic soils, where plenty of soluble Al(III) ions exist. In view of uncertain significance of the effects of coexisting Al(III) on Pb(II) sorption by biochars, this study used kenaf core biochar (KB550; high carbon, low ash) and sewage sludge biochar (SB550; low carbon, high ash) pyrolyzed at 550 °C to elucidate the influence of coexisting Al(III) species and biochars' mineral components on Pb(II) immobilization conducted in aqueous solution with initial pHs of 3.0-4.5. Results showed that Al(III) reduced Pb(II) sorption on KB550 primarily via pH buffering against biochar alkalinity, thus inhibiting lead carbonate formation. In contrast, the reduction on SB550 mainly resulted from direct competition for sorption sites, especially on Fe-rich phengite 2M1 and metakaolinite. Because of Pb-P precipitation and Pb-K interlayer exchange, the residual Pb(II) adsorption capacity resistant to coexisting Al(III) was 3-5 times higher on SB550 than on KB550. The Pb-K interlayer exchange was enhanced by lower pH and coexisting Al(III), while Pb-P precipitation was the dominant Pb(II) sorption mechanism on SB550 resistant to Al(III) buffering and competition at higher pH. Application of these two biochars as amendments confirmed that the mineral-rich SB550 was more suitable for Pb(II) immobilization in acidic soils with high levels of extractable Al(III). Copyright © 2016 Elsevier Ltd. All rights reserved.

Removal of Heavy Metals by Adsorption onto Activated Carbon Derived from Pine Cones of Pinus roxburghii.

PubMed

Saif, Muhammad Jawwad; Zia, Khalid Mahmood; Fazal-ur-Rehman; Usman, Muhammad; Hussain, Abdullah Ijaz; Chatha, Shahzad Ali Shahid

2015-04-01

Activated carbon derived from cones of Pinus roxburghii (Himalayan Pine) was used as an adsorbent for the removal of copper, nickel and chromium ions from waste water. Surface analysis was carried out to determine the specific surface area and pore size distribution of the pine cone derived activated carbon. Optimal parameters, effect of adsorbent quantity, pH, equilibrium time, agitation speed and temperature were studied. Equilibrium data were evaluated by Langmuir and Freundlich isotherm models. Langmuir isotherm afforded the best fit to the equilibrium data with a maximum adsorption capacity of 14.2, 31.4 and 29.6 mg/g for Cu(II), Ni(II) and Cr(VI) respectively. Maximum adsorption of Cu(II), Ni(II) was observed in the pH range 4.0 to 4.5, whereas the best adsorption of Cr(VI) was observed at pH 2.5. It was found that 180 minutes was sufficient to gain adsorption equilibrium. The adsorption process follows a pseudo-second-order kinetic model.

Differential plating medium for quantitative detection of histamine-producing bacteria.

PubMed Central

Niven, C F; Jeffrey, M B; Corlett, D A

1981-01-01

A histidine-containing agar medium has been devised for quantitative detection of histamine-producing bacteria that are alleged to be associated with scombroid fish poisoning outbreaks. The responsible bacteria produce a marked pH change in the agar, with attendant color change of pH indicator adjacent to the colonies, thus facilitating their recognition. Proteus morganii and Klebsiella pneumoniae were the two most common histidine-decarboxylating species isolated from scombroid fish and mahi mahi. PMID:7013698

Structure and action of the binary C2 toxin from Clostridium botulinum.

PubMed

Schleberger, Christian; Hochmann, Henrike; Barth, Holger; Aktories, Klaus; Schulz, Georg E

2006-12-08

C2 toxin from Clostridium botulinum is composed of the enzyme component C2-I, which ADP-ribosylates actin, and the binding and translocation component C2-II, responsible for the interaction with eukaryotic cell receptors and the following endocytosis. Three C2-I crystal structures at resolutions of up to 1.75 A are presented together with a crystal structure of C2-II at an appreciably lower resolution and a model of the prepore formed by fragment C2-IIa. The C2-I structure was determined at pH 3.0 and at pH 6.1. The structural differences are small, indicating that C2-I does not unfold, even at a pH value as low as 3.0. The ADP-ribosyl transferase activity of C2-I was determined for alpha and beta/gamma-actin and related to that of Iota toxin and of mutant S361R of C2-I that introduced the arginine observed in Iota toxin. The substantial activity differences between alpha and beta/gamma-actin cannot be explained by the protein structures currently available. The structure of the transport component C2-II at pH 4.3 was established by molecular replacement using a model of the protective antigen of anthrax toxin at pH 6.0. The C-terminal receptor-binding domain of C2-II could not be located but was present in the crystals. It may be mobile. The relative orientation and positions of the four other domains of C2-II do not differ much from those of the protective antigen, indicating that no large conformational changes occur between pH 4.3 and pH 6.0. A model of the C2-IIa prepore structure was constructed based on the corresponding assembly of the protective antigen. It revealed a surprisingly large number of asparagine residues lining the pore. The interaction between C2-I and C2-IIa and the translocation of C2-I into the target cell are discussed.

Biosorption of Lead(II) by Arthrobacter sp. 25: Process Optimization and Mechanism.

PubMed

Jin, Yu; Wang, Xin; Zang, Tingting; Hu, Yang; Hu, Xiaojing; Ren, Guangming; Xu, Xiuhong; Qu, Juanjuan

2016-08-28

In the present work, Arthrobacter sp. 25, a lead-tolerant bacterium, was assayed to remove lead(II) from aqueous solution. The biosorption process was optimized by response surface methodology (RSM) based on the Box-Behnken design. The relationships between dependent and independent variables were quantitatively determined by second-order polynomial equation and 3D response surface plots. The biosorption mechanism was explored by characterization of the biosorbent before and after biosorption using atomic force microscopy (AFM), scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The results showed that the maximum adsorption capacity of 9.6 mg/g was obtained at the initial lead ion concentration of 108.79 mg/l, pH value of 5.75, and biosorbent dosage of 9.9 g/l (fresh weight), which was close to the theoretically expected value of 9.88 mg/g. Arthrobacter sp. 25 is an ellipsoidalshaped bacterium covered with extracellular polymeric substances. The biosorption mechanism involved physical adsorption and microprecipitation as well as ion exchange, and functional groups such as phosphoryl, hydroxyl, amino, amide, carbonyl, and phosphate groups played vital roles in adsorption. The results indicate that Arthrobacter sp. 25 may be potentially used as a biosorbent for low-concentration lead(II) removal from wastewater.

Investigation of complexes tannic acid and myricetin with Fe(III)

NASA Astrophysics Data System (ADS)

Sungur, Şana; Uzar, Atike

2008-01-01

The pH dependence of the complexes was determined by both potentiometric and spectrophotometric studies. Stability constants and stoichiometries of the formed complexes were determined using slope ratio method. Fe(III) was formed complexes with tannic acid of various stoichiometries, which in the 1:1 molar ratio at pH < 3, in the 2:1 molar ratio at pH 3-7 and in the 4:1 molar ratio at pH > 7. Fe(III) was formed complexes with myricetin in the 1:2 molar ratio at pH 4 and 5 and in the 1:1 molar ratio at pH 6. Stability constant values were found to be 10 5 to 10 17 and 10 5 to 10 9 for Fe(III)-tannic acid complexes and Fe(III)-myricetin complexes. Both tannic acid and myricetin were possessed minimum affinities to Cu(II) and Zn(II). They had less affinity for Al(III) than for Fe(III).

Removal of Cu(II) in water by polymer enhanced ultrafiltration: Influence of polymer nature and pH.

PubMed

Kochkodan, Olga D; Kochkodan, Viktor M; Sharma, Virender K

2018-01-02

This study presents an efficient removal of Cu(II) in water using the polymer enhanced ultrafiltration (PEUF) method. Polymer of different molecular weight (MW) (polyethyleneimine (PEI), sodium lignosulfonates (SLS) and dextrans) were investigated to evaluate efficiency in removal of Cu(II) in water by the PEUF method. The decomposition of Cu(II)-polymer complex was also evaluated in order to reuse polymers. Cu(II) complexation depends on the MW of chelating polymer and the pH of feed solution. It was found that the Cu(II) rejection increased with the polymer dosage with high removal of Cu(II) when using PEI and SLS at a 10:20 (mg/mg) ratio ([Cu(II)]:[polymer]). It was found that the maximum chelating capacity was 15 mg of Cu(II) per 20 mg of PEI. The Cu(II)-PEI complex could be decomposed by acid addition and the polymer could be efficiently reused with multiple complexation-decomplexation cycles. A conceptual flow chart of the integrated process of efficient removal of Cu(II) by PEUF method is suggested.

[Relationship between blood glucose levels and salivary pH and buffering capacity in type II diabetes patients].

PubMed

Elkafri, I H; Mashlah, A; Shaqifa, A

2014-03-13

This study was evaluated the relationship between blood glucose levels and salivary pH and buffering capacity in type II diabetic patients. The sample comprised 210 participants (age ranged 40-60 years). Based on fasting blood glucose levels the participants were divided into 3 groups: controls with normal blood glucose levels; diabetic patients with levels ≤ 200 mg/dL; and diabetic patients with levels > 200 mg/dL. Salivary pH and buffering capacity were determined in a sample of resting (non-stimulated) saliva taken from each participant. Salivary pH levels in diabetic patients with blood glucose levels > 200 mg/dL were lower than in the controls and diabetic patients with levels ≤ 200 mg/dL. Salivary pH levels were comparable in controls and diabetic patients with blood glucose levels ≤ 200 mg/dL. Salivary buffering capacity in the 3 groups was comparable.

The use of a polymer inclusion membrane in a paper-based sensor for the selective determination of Cu(II).

PubMed

Jayawardane, B Manori; Coo, Lilibeth dlC; Cattrall, Robert W; Kolev, Spas D

2013-11-25

A disposable paper-based sensor (PBS) is described for the determination of Cu(II) in natural and waste waters at approximately 2 cents per measurement. The device makes use of a polymer inclusion membrane (PIM) to provide the selectivity for Cu(II). The PIM consists of 40 wt% di(2-ethlyhexyl) phosphoric acid (D2EHPA) as the carrier, 10 wt% dioctyl phthalate (DOP) as a plasticizer, 49.5 wt% poly(vinyl chloride) (PVC) as the base polymer and 0.5 wt% (mm(-1)) 1-(2'-pyridylazo)-2-naphthol (PAN) as the colourimetric reagent. High selectivity under mildly acidic conditions (HCl, pH 2.0) is achieved for Cu(II) in the presence of frequently encountered metal ions in natural and waste waters such as Fe(III), Al(III), Zn(II), Cd(II), Pb(II), Ca(II), Mg(II), and Ni(II). The laminated PBS consists of a PIM sensing disc (2mm in diameter) attached to the centre of a circular hydrophilic zone (7 mm in diameter) pretreated with 0.01 M HCl. This hydrophilic zone separates the sample port (a circular hole in the plastic cover) from the PIM sensing disc. After introducing 19.2 μL of a sample/standard solution to the sample port, Cu(II) diffuses across the hydrophilic zone and is extracted into the PIM disc as the Cu(II)-D2EHPA complex which subsequently reacts with PAN to produce the red-purple coloured Cu(II)-PAN complex. The colour intensity of the PIM disc is measured 15 min after sample/standard introduction by scanning using a flatbed scanner. Under optimal conditions the device is characterized by a limit of detection (LOD) and limit of quantitation (LOQ) of 0.06 and 0.21 mg L(-1) Cu(II), respectively, with two linear ranges together covering the Cu(II) concentration range from 0.1 to 30.0 mg L(-1). The PBS was successfully applied to the determination of Cu(II) in hot tap water and mine tailings water. Copyright © 2013 Elsevier B.V. All rights reserved.

Separation of thorium from lanthanides by solvent extraction with ionizable crown ethers.

PubMed

Du, H S; Wood, D J; Elshani, S; Wai, C M

1993-02-01

Thorium and the lanthanides are extracted by alpha-(sym-dibenzo-16-crown-5-oxy)acetic acid and its analogues in different pH ranges. At pH 4.5, Th is quantitatively extracted by the crown ether carboxylic acids into chloroform whereas the extraction of the lanthanides is negligible. Separation of Th from the lanthanides can be achieved by solvent extraction under this condition. The extraction does not require specific counteranions and is reversible with respect to pH. Trace amounts of Th in water can be quantitatively recovered using this extraction system for neutron activation analysis. The nature of the extracted Th complex and the mechanism of extraction are discussed.

Precision Sensing by Two Opposing Gradient Sensors: How Does Escherichia coli Find its Preferred pH Level?

PubMed Central

Hu, Bo; Tu, Yuhai

2013-01-01

It is essential for bacteria to find optimal conditions for their growth and survival. The optimal levels of certain environmental factors (such as pH and temperature) often correspond to some intermediate points of the respective gradients. This requires the ability of bacteria to navigate from both directions toward the optimum location and is distinct from the conventional unidirectional chemotactic strategy. Remarkably, Escherichia coli cells can perform such a precision sensing task in pH taxis by using the same chemotaxis machinery, but with opposite pH responses from two different chemoreceptors (Tar and Tsr). To understand bacterial pH sensing, we developed an Ising-type model for a mixed cluster of opposing receptors based on the push-pull mechanism. Our model can quantitatively explain experimental observations in pH taxis for various mutants and wild-type cells. We show how the preferred pH level depends on the relative abundance of the competing sensors and how the sensory activity regulates the behavioral response. Our model allows us to make quantitative predictions on signal integration of pH and chemoattractant stimuli. Our study reveals two general conditions and a robust push-pull scheme for precision sensing, which should be applicable in other adaptive sensory systems with opposing gradient sensors. PMID:23823247

Geochemical Niches of Iron-Oxidizing Acidophiles in Acidic Coal Mine Drainage

PubMed Central

Kohl, Courtney; Grettenberger, Christen; Larson, Lance N.; Burgos, William D.

2014-01-01

A legacy of coal mining in the Appalachians has provided a unique opportunity to study the ecological niches of iron-oxidizing microorganisms. Mine-impacted, anoxic groundwater with high dissolved-metal concentrations emerges at springs and seeps associated with iron oxide mounds and deposits. These deposits are colonized by iron-oxidizing microorganisms that in some cases efficiently remove most of the dissolved iron at low pH, making subsequent treatment of the polluted stream water less expensive. We used full-cycle rRNA methods to describe the composition of sediment communities at two geochemically similar acidic discharges, Upper and Lower Red Eyes in Somerset County, PA, USA. The dominant microorganisms at both discharges were acidophilic Gallionella-like organisms, “Ferrovum” spp., and Acidithiobacillus spp. Archaea and Leptospirillum spp. accounted for less than 2% of cells. The distribution of microorganisms at the two sites could be best explained by a combination of iron(II) concentration and pH. Populations of the Gallionella-like organisms were restricted to locations with pH >3 and iron(II) concentration of >4 mM, while Acidithiobacillus spp. were restricted to pH <3 and iron(II) concentration of <4 mM. Ferrovum spp. were present at low levels in most samples but dominated sediment communities at pH <3 and iron(II) concentration of >4 mM. Our findings offer a predictive framework that could prove useful for describing the distribution of microorganisms in acid mine drainage, based on readily accessible geochemical parameters. PMID:25501473

Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

PubMed

Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

2011-09-15

Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

Investigation of simultaneous biosorption of copper(II) and chromium(VI) on dried Chlorella vulgaris from binary metal mixtures: Application of multicomponent adsorption isotherms

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

Aksu, Z.; Acikel, U.; Kutsal, T.

1999-02-01

Although the biosorption of single metal ions to various kinds of microorganisms has been extensively studied and the adsorption isotherms have been developed for only the single metal ion situation, very little attention has been given to the bioremoval and expression of adsorption isotherms of multimetal ions systems. In this study the simultaneous biosorption of copper(II) and chromium(VI) to Chlorella vulgaris from a binary metal mixture was studied and compared with the single metal ion situation in a batch stirred system. The effects of pH and single- and dual-metal ion concentrations on the equilibrium uptakes were investigated. In previous studiesmore » the optimum biosorption pH had been determined as 4.0 for copper(II) and as 2.0 for chromium(VI). Multimetal ion biosorption studies were performed at these two pH values. It was observed that the equilibrium uptakes of copper(II) or chromium(VI) ions were changed due to the biosorption pH and the presence of other metal ions. Adsorption isotherms were developed for both single- and dual-metal ions systems at these two pH values, and expressed by the mono- and multicomponent Langmuir and Freundlich adsorption models. Model parameters were estimated by nonlinear regression. It was seen that the adsorption equilibrium data fitted very well to the competitive Freundlich model in the concentration ranges studied.« less

Activation of heteroallenes by coordinatively unsaturated nickel(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methyl)pyrazolyl borate (Tp(Ph,Me)) ligand.

PubMed

Abubekerov, Mark; Eymann, Léonard Y M; Gianetti, Thomas L; Arnold, John

2016-10-07

Activation of sulfur containing heteroallenes by nickel(ii) alkyl complexes supported by the bulky hydrotris(3-phenyl-5-methylpyrazolyl)borate (Tp(Ph,Me)) ligand is described. Exposure of Tp(Ph,Me)NiCH2Ph (1a) and Tp(Ph,Me)NiCH2Si(CH3)3 (1b) to CS2 resulted in formation of the insertion products Tp(Ph,Me)Ni(η(2)-CS2)CH2Ph (2a) and Tp(Ph,Me)Ni(η(2)-CS2)CH2Si(CH3)3 (2b) in moderate yields. Reaction of 1a and MeNCS produced two species in a 1 : 1 ratio, identified as Tp(Ph,Me)Ni(η(2)-MeNC)CH2Ph (3) and Tp(Ph,Me)Ni(η(2)-MeNCS)SCH2Ph (4). Isolation of the unexpected insertion product (3) prompted an investigation into the activity of 1a-b in the presence of isocyanides (i.e.(t)BuNC), which resulted in isolation of Tp(Ph,Me)Ni(η(2-t)BuNC)CH2Ph (5a) and Tp(Ph,Me)Ni(η(2-t)BuNC)CH2Si(CH3)3 (5b). Similarly, reaction of 1a with OCS led to the isolation of a rare example of a Ni(i) carbonyl species Tp(Ph,Me)NiCO (6). Alternatively, complex 6 was also formed by exposure of 1a-b to an atmosphere of CO. Isolation of the intermediate species (Tp(Ph,Me)Ni(η(2)-CO)CH2TMS (7b) and Tp(Ph,Me)Ni(CO)(C(O)R, (8a-b) with R = Ph, TMS)) shed light on the formation of such species.

Recrystallization of Manganite (γ-MnOOH) and Implications for Trace Element Cycling.

PubMed

Hens, Tobias; Brugger, Joël; Cumberland, Susan A; Etschmann, Barbara; Frierdich, Andrew J

2018-02-06

The recrystallization of Mn(III,IV) oxides is catalyzed by aqueous Mn(II) (Mn(II) aq ) during (bio)geochemical Mn redox cycling. It is poorly understood how trace metals associated with Mn oxides (e.g., Ni) are cycled during such recrystallization. Here, we use X-ray absorption spectroscopy (XAS) to examine the speciation of Ni associated with Manganite (γ-Mn(III)OOH) suspensions in the presence or absence of Mn(II) aq under variable pH conditions (pH 5.5 and 7.5). In a second set of experiments, we used a 62 Ni isotope tracer to quantify the amount of dissolved Ni that exchanges with Ni incorporated in the Manganite crystal structure during reactions in 1 mM Mn(II) aq and in Mn(II)-free solutions. XAS spectra show that Ni is initially sorbed on the Manganite mineral surface and is progressively incorporated into the mineral structure over time (13% after 51 days) even in the absence of dissolved Mn(II). The amount of Ni incorporation significantly increases to about 40% over a period of 51 days when Mn(II) aq is present in solution. Similarly, Mn(II) aq promotes Ni exchange between Ni-substituted Manganite and dissolved Ni(II), with around 30% of Ni exchanged at pH 7.5 over the duration of the experiment. No new mineral phases are detected following recrystallization as determined by X-ray diffraction and XAS. Our results reveal that Mn(II)-catalyzed mineral recrystallization partitions Ni between Mn oxides and aqueous fluids and can therefore affect Ni speciation and mobility in the environment.

Effect of Cu(II), Cd(II) and Zn(II) on Pb(II) biosorption by algae Gelidium-derived materials.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2008-06-15

Biosorption of Pb(II), Cu(II), Cd(II) and Zn(II) from binary metal solutions onto the algae Gelidium sesquipedale, an algal industrial waste and a waste-based composite material was investigated at pH 5.3, in a batch system. Binary Pb(II)/Cu(II), Pb(II)/Cd(II) and Pb(II)/Zn(II) solutions have been tested. For the same equilibrium concentrations of both metal ions (1 mmol l(-1)), approximately 66, 85 and 86% of the total uptake capacity of the biosorbents is taken by lead ions in the systems Pb(II)/Cu(II), Pb(II)/Cd(II) and Pb(II)/Zn(II), respectively. Two-metal results were fitted to a discrete and a continuous model, showing the inhibition of the primary metal biosorption by the co-cation. The model parameters suggest that Cd(II) and Zn(II) have the same decreasing effect on the Pb(II) uptake capacity. The uptake of Pb(II) was highly sensitive to the presence of Cu(II). From the discrete model it was possible to obtain the Langmuir affinity constant for Pb(II) biosorption. The presence of the co-cations decreases the apparent affinity of Pb(II). The experimental results were successfully fitted by the continuous model, at different pH values, for each biosorbent. The following sequence for the equilibrium affinity constants was found: Pb>Cu>Cd approximately Zn.

Porous silicon powder as an adsorbent of heavy metal (nickel)

NASA Astrophysics Data System (ADS)

Nabil, Marwa; Motaweh, Hussien A.

2018-04-01

New and inexpensive nanoporous silicon (NPS) powder was prepared by alkali chemical etching using sonication technique and was subsequently investigated as an adsorbent in batch systems for the adsorption Ni(II) ions in an aqueous solution. The optimum conditions for the Ni(II) ion adsorption capacity of the NPS powder were studied in detail by varying parameters such as the initial Ni(II) concentration, the solution pH value, the adsorption temperature and contact time. The results indicated that the maximum adsorption capacity and the maximum removal percent of Ni(II) reached 2665.33 mg/g and 82.6%, respectively, at an initial Ni(II) concentration of 100 mg/L, adsorption time of 30 min and no effect of the solution pH and adsorption temperature.

Adsorption of Pb(ll) and Eu(III) by oxide minerals in the presence of natural and synthetic hydroxamate siderophores.

PubMed

Kraemer, Stephan M; Xu, Jide; Raymond, Kenneth N; Sposito, Garrison

2002-03-15

Trihydroxamate siderophores have been proposed for use as mediators of actinide and heavy metal mobility in contaminated subsurface zones. These microbially produced ligands, common in terrestrial and marine environments, recently have been derivatized synthetically to enhance their affinity for transuranic metal cations. However, the interactions between these synthetic derivative and adsorbed trace metals have not been characterized. In this paper we compare a natural siderophore, desferrioxamine-B (DFO-B), with its actinide-specific catecholate derivative, N-(2,3-dihydroxy-4-(methylamido)benzoyl)desferrioxamine-B (DFOMTA), as to their effect on the adsorption of Pb(II) and Eu(III) by goethite and boehmite. In the presence of 240 microM DFO-B, a strongly depleting effect on Eu(III) adsorption by goethite and boehmite occurred above pH 6. By contrast, almost total removal of Eu(III) from solution in the neutral to slightly acidic pH range was observed in the presence of either 10 or 100 microM DFOMTA, due primarilyto the formation of metal-DFOMTA precipitates. Addition of DFOMTA caused an increase in Pb(II) adsorption by goethite below pH 5, but a decrease above pH 5, such that the Pb(II) adsorption edge in the presence of DFOMTA strongly resembled the DFOMTA adsorption envelope, which showed a maximum near pH 5 and decreasing adsorption toward lower and higher pH.

Hexavalent chromium adsorption from aqueous solution using carbon nano-onions (CNOs).

PubMed

Sakulthaew, Chainarong; Chokejaroenrat, Chanat; Poapolathep, Amnart; Satapanajaru, Tunlawit; Poapolathep, Saranya

2017-10-01

The capacity of carbon nano-onions (CNOs) to remove hexavalent chromium (Cr(VI)) from aqueous solution was investigated. Batch experiments were performed to quantify the effects of the dosage rate, pH, counter ions, and temperature. The adsorption of Cr(VI) onto CNOs was best described by a pseudo-second order rate expression. The adsorption efficiency increased with increasing adsorbent dosage and contact time and reached equilibrium in 24 h. The equilibrium data showed better compliance with a Langmuir isotherm than a Freundlich isotherm. Effective removal of Cr(VI) was demonstrated at pH values ranging from 2 to 10. The adsorption capacity of Cr(VI) was found to be highest (82%) at pH 3.4 and greatly depended on the solution pH. We found that Cr(VI) adsorption decreased with increasing pH over the pH range of 3.4-10. The adsorption capacity increased dramatically when the temperature increased from 10 °C to 50 °C regardless of the amount of CNOs used. Cr(VI) removal decreased by ∼13% when Zn(II), Cu(II), and Pb(II) were present, while there were no significant changes observed when NO 3 - or SO 4 2- was present. The overall results support that CNOs can be used as an alternative adsorbent material to remove Cr(VI) in the water treatment industry. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis, spectral, and structural studies of porphyrins having sterically hindered [η(5)-CpCo(η(4)-C4Ph4)] cobalt sandwich units at the meso positions.

PubMed

Keshav, Karunesh; Kumar, Dheeraj; Elias, Anil J

2013-11-04

Synthesis, spectral, and structural studies of the first examples of porphyrins substituted at the meso positions with sterically hindered η(5)-CpCo(η(4)-C4Ph4) cobalt sandwich units are described. The novel dipyrromethane derived cobalt sandwich compound {η(5)-[(C4H4N)2CH]C5H4}Co(η(4)-C4Ph4) 1, as well as its parent aldehyde, η(5)-[C5H4(CHO)]Co(η(4)-C4Ph4), were used in the synthesis of porphyrins having one or two η(5)-CpCo(η(4)-C4Ph4) groups at their meso positions. 1,9-Diformyldipyrromethane derived η(5)-CpCo(η(4)-C4Ph4) 2 was synthesized using dipyrromethane 1 under Vilsmeier conditions. A reaction of 2 with unsubstituted dipyrromethane under basic conditions in the presence of Pd(C6H5CN)2Cl2 yielded an A-type palladium coordinated porphyrin 3 [where A = η(5)-CpCo(η(4)-C4Ph4)]. A similar reaction of 2 with meso aryl and ferrocenyl-substituted dipyrromethanes yielded trans-AB type palladium coordinated porphyrins 4-6 [where A = η(5)-CpCo(η(4)-C4Ph4) and B = 4-tert-butylphenyl 4, ferrocenyl 5, and pentafluorophenyl 6]. Reactions of 2 with 5-ferrocenyl dipyrromethane under the same reaction conditions in the presence of Ni(acac)2 and Zn(OAc)2 gave the trimetallic nickel(II) and zinc(II) complexed trans-AB type porphyrins 7 and 8 having both cobalt and iron sandwich units at the meso positions. Crystal structure of the Pd(II) porphyrin 5 and nickel(II) porphyrin 7 showed nonplanar structures having distinct ruffle type distortion of the porphyrin ring. Demetalation of the zinc(II) trans-AB type porphyrin 8 in the presence of trifluoroacetic acid gave the metal free base porphyrin 9. Reactions of the cobalt sandwich aldehyde [(η(5)-C5H4(CHO)]Co(η(4)-C4Ph4) with sterically hindered dipyrromethane derivatives under acid-catalyzed condensation reactions gave trans-A2B2 type porphyrins [where A = η(5)-CpCo(η(4)-C4Ph4) and B = pentafluorophenyl, 10 mesityl 11]. In contrast, reactions of [η(5)-C5H4(CHO)]Co(η(4)-C4Ph4) with sterically unhindered meso-4-tert-butylphenyl dipyrromethane resulted in both AB3 12 and cis-A2B2 13 type porphyrins [where A = η(5)-CpCo(η(4)-C4Ph4) and B = (4-tert-butylphenyl] as a result of scrambling. The new porphyrin derivatives have been structurally characterized, and their spectral and electrochemical features were determined.

Flotation-separation and ICP-AES determination of ultra trace amounts of copper, cadmium, nickel and cobalt using 2-aminocyclopentene-1-dithiocarboxylic acid.

PubMed

Shamsipur, Mojtaba; Hashemi, Omid Reza; Safavi, Afsaneh

2005-09-01

A rapid flotation method for separation and enrichment of ultra trace amounts of copper(II), cadmium(II), nickel(II) and cobalt(II) ions from water samples is established. At pH 6.5 and with sodium dodecylsulfate used as a foaming reagent, Cu2+, Cd2+, Ni2+ and Co2+ were separated simultaneously with 2-aminocyclopentene-1-dithiocarboxylic acid (ACDA) added to 1 l of aqueous solution. The proposed procedure of preconcentration is applied prior to the determination of these four analytes using inductivity coupled plasma-atomic emission spectrometry (ICP-AES). The effects of pH, concentration of ACDA, applicability of different surfactants and foreign ions on the separation efficiency were investigated. The preconcentration factor of the method is 1000 and the detection limits of copper(II), cadmium(II), nickel(II) and cobalt(II) ions are 0.078, 0.075, 0.072 and 0.080 ng ml(-1), respectively.

Quantitative structure-permeability relationships at various pH values for acidic and basic drugs and drug-like compounds.

PubMed

Oja, M; Maran, U

2015-01-01

Absorption in gastrointestinal tract compartments varies and is largely influenced by pH. Therefore, considering pH in studies and analyses of membrane permeability provides an opportunity to gain a better understanding of the behaviour of compounds and to obtain good permeability estimates for prediction purposes. This study concentrates on relationships between the chemical structure and membrane permeability of acidic and basic drugs and drug-like compounds. The membrane permeability of 36 acidic and 61 basic compounds was measured using the parallel artificial membrane permeability assay (PAMPA) at pH 3, 5, 7.4 and 9. Descriptive and/or predictive single-parameter quantitative structure-permeability relationships were derived for all pH values. For acidic compounds, membrane permeability is mainly influenced by hydrogen bond donor properties, as revealed by models with r(2) > 0.8 for pH 3 and pH 5. For basic compounds, the best (r(2) > 0.7) structure-permeability relationships are obtained with the octanol-water distribution coefficient for pH 7.4 and pH 9, indicating the importance of partition properties. In addition to the validation set, the prediction quality of the developed models was tested with folic acid and astemizole, showing good matches between experimental and calculated membrane permeabilities at key pHs. Selected QSAR models are available at the QsarDB repository ( http://dx.doi.org/10.15152/QDB.166 ).

Characteristics and adsorption study of the activated carbon derived from municipal sewage sludge.

PubMed

Guo, Tiecheng; Yao, Sicong; Chen, Hengli; Yu, Xin; Wang, Meicheng; Chen, Yao

2017-10-01

Sewage sludge-based activated carbon is proved to be an efficient and low-cost adsorbent in treatment of various industrial wastewaters. The produced carbon had a well-developed pore structure and relatively low Brunauer-Emmett-Teller (BET) surface area. Adsorptive capacity of typical pollutants, i.e. copper Cu(II) and methylene blue (MB) on the carbon was studied. Adsorptions were affected by the initial solution pH, contact time and adsorbent dose. Results showed that adsorption of Cu(II) and MB on the produced carbon could reach equilibrium after 240 min. The average removal rate for Cu(II) on the carbon was high, up to 97% in weak acidic conditions (pH = 4-6) and around 98% for MB in a very wide pH range (pH = 2-12). The adsorption kinetics were well fitted by the pseudo-second order model, and both Langmuir and Freundlich isotherm models could well describe the adsorption process at room temperature. The theoretical maximum adsorption capacities of Cu(II) and MB on sewage sludge-based activated carbon were 114.94 mg/g and 125 mg/g, respectively. Compared with commercial carbon, the sewage sludge-based carbon was more suitable for heavy metal ions' removal than dyes'.

The use of macroalgae (Gracilaria changii) as bio-adsorbent for Copper (II) removal

NASA Astrophysics Data System (ADS)

Lavania-Baloo; Idayu, Nordin; Umar Salihi, Ibrahim; Zainoddin, Jamari

2017-05-01

Biosorption of heavy metals using marine macroalgae biomass can be an effective process and alternative to conventional methods. Activated carbon was developed from macroalgae (Gracilaria changii) and used as adsorbents for the removal of copper (II) from wastewater. Gracilaria changii based activated carbon (GCBAC) was prepared using muffle furnace at a constant temperature of 300 °C for 1 hour. Batch adsorption experiments were conducted to investigate the effets of important parameters such as pH, contact time, initial metal concentration and adsorbent dosage on the removal of Cu (II) from synthetic aqueous solution. Batch adsorption study shows that removal of Cu (II) using GCBAC relied upon pH, contact time, initial metal concentration and GCBAC dosage. The optimum conditions parameters were found to be pH 6.0, time of 60 minutes and GCBAC dosage of 0.3 g, respectively. Adsorption data was described better by Freundlich isotherm model with R2 value of 0.7936. The maximum Cu (II) adsorption capacity of GCBAC was found to be 0.07 mg/g. The experimental adsorption data obtained fitted well into Pseudo-second-order kinetic model, with R2 value near unity. Thus, GCBAC can be used as an effective adsorbent for the removal of Cu (II) from aqueous solution.

Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite.

PubMed

Flynn, Elaine D; Catalano, Jeffrey G

2018-06-05

During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.

Suitability Screening Test for Marine Corps Air Traffic Controllers Phase 2

DTIC Science & Technology

2013-06-10

Karen M. Walker, Ph.D. William L. Farmer, Ph.D. Rebecca C. Roberts, MS Navy Personnel Research, Studies, and Technology NPRST-TR-13-2...June 2013 Suitability Screening Test for Marine Corps Air Traffic Controllers Phase II Karen M. Walker, Ph.D. William L. Farmer, Ph.D. Rebecca...C. Roberts, MS Navy Personnel Research, Studies, and Technology Reviewed by Tanja Blackstone , Ph.D. Approved and released by D. M. Cashbaugh

Suitability Screening Test for Marine Corps Air Traffic Controllers. Phase 2

DTIC Science & Technology

2013-06-01

Karen M. Walker, Ph.D. William L. Farmer, Ph.D. Rebecca C. Roberts, MS Navy Personnel Research, Studies, and Technology NPRST-TR-13-2...June 2013 Suitability Screening Test for Marine Corps Air Traffic Controllers Phase II Karen M. Walker, Ph.D. William L. Farmer, Ph.D. Rebecca...C. Roberts, MS Navy Personnel Research, Studies, and Technology Reviewed by Tanja Blackstone , Ph.D. Approved and released by D. M. Cashbaugh

Equilibrium and thermodynamic studies on biosorption of Pb(II) onto Candida albicans biomass.

PubMed

Baysal, Zübeyde; Cinar, Ercan; Bulut, Yasemin; Alkan, Hüseyin; Dogru, Mehmet

2009-01-15

Biosorption of Pb(II) ions from aqueous solutions was studied in a batch system by using Candida albicans. The optimum conditions of biosorption were determined by investigating the initial metal ion concentration, contact time, temperature, biosorbent dose and pH. The extent of metal ion removed increased with increasing contact time, initial metal ion concentration and temperature. Biosorption equilibrium time was observed in 30min. The Freundlich and Langmuir adsorption models were used for the mathematical description of biosorption equilibrium and isotherm constants were also evaluated. The maximum biosorption capacity of Pb(II) on C. albicans was determined as 828.50+/-1.05, 831.26+/-1.30 and 833.33+/-1.12mgg(-1), respectively, at different temperatures (25, 35 and 45 degrees C). Biosorption showed pseudo second-order rate kinetics at different initial concentration of Pb(II) and different temperatures. The activation energy of the biosorption (Ea) was estimated as 59.04kJmol(-1) from Arrhenius equation. Using the equilibrium constant value obtained at different temperatures, the thermodynamic properties of the biosorption (DeltaG degrees , DeltaH degrees and DeltaS degrees ) were also determined. The results showed that biosorption of Pb(II) ions on C. albicans were endothermic and spontaneous. The optimum initial pH for Pb(II) was determined as pH 5.0. FTIR spectral analysis of Pb(II) adsorbed and unadsorbed C. albicans biomass was also discussed.

Cu(II) binding by a pH-fractionated fulvic acid

USGS Publications Warehouse

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

1999-01-01

The relationship between acidity, Cu(II) binding and sorption to XAD resin was examined using Suwannee River fulvic acid (SRFA). The work was based on the hypothesis that fractions of SRFA eluted from an XAD column at various pH's from 1.0 to 12.0 would show systematic variations in acidity and possibly aromaticity which in turn would lead to different Cu(II) binding properties. We measured equilibrium Cu(II) binding to these fractions using Cu2+ ion-selective electrode (ISE) potentiometry at pH 6.0. Several model ligands were also examined, including cyclopentane-1,2,3,4-tetracarboxylic acid (CP-TCA) and tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THF-TCA), the latter binding Cu(II) much more strongly as a consequence of the ether linkage. The SRFA Cu(II) binding properties agreed with previous work at high ionic strength, and binding was enhanced substantially at lower ionic strength, in agreement with Poisson-Boltzmann predictions for small spheres. Determining Cu binding constants (K(i)) by non-linear regression with total ligand concentrations (L(Ti)) taken from previous work, the fractions eluted at varying pH had K(i) similar to the unfractionated SRFA, with a maximum enhancement of 0.50 log units. We conclude that variable-pH elution from XAD does not isolate significantly strong (or weak) Cu(II)-binding components from the SRFA mixture. Copyright (C) 1999 Elsevier Science B.V.

Oxidation of manganese(II) with ferrate: Stoichiometry, kinetics, products and impact of organic carbon.

PubMed

Goodwill, Joseph E; Mai, Xuyen; Jiang, Yanjun; Reckhow, David A; Tobiason, John E

2016-09-01

Manganese is a contaminant of concern for many drinking water utilities, and future regulation may be pending. An analysis of soluble manganese (Mn(II)) oxidation by ferrate (Fe(VI)) was executed at the bench-scale, in a laboratory matrix, both with and without the presence of natural organic matter (NOM) and at two different pH values, 6.2 and 7.5. In the matrix without NOM, the oxidation of Mn(II) by Fe(VI) followed a stoichiometry of 2 mol Fe(VI) to 3 mol Mn(II). The presence of NOM did not significantly affect the stoichiometry of the oxidation reaction, indicating relative selectivity of Fe(VI) for Mn(II). The size distribution of resulting particles included significant amounts of nanoparticles. Resulting manganese oxide particles were confirmed to be MnO2 via X-ray photoelectron spectroscopy. The rate of the Mn(II) oxidation reaction was fast relative to typical time scales in drinking water treatment, with an estimated second order rate constant of approximately 1 × 10(4) M(-1) s(-1) at pH 9.2 and > 9 × 10(4) M(-1) s(-1) at pH 6.2. In general, ferrate is a potential option for Mn(II) oxidation in water treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Solid-phase extraction of copper(II) in water and food samples using silica gel modified with bis(3-aminopropyl)amine and determination by flame atomic absorption spectrometry.

PubMed

Cagirdi, Duygu; Altundag, Hüseyin; Imamoglu, Mustafa; Tuzen, Mustafa

2014-01-01

A simple and selective separation and preconcentration method was developed for the determination of Cu(ll) ions. This method is based on adsorption of Cu(ll) ions from aqueous solution on a bis(3-aminopropyl)amine modified silica gel column and flame atomic absorption spectrometric determination after desorption. Various analytical parameters such as pH, type of eluent solution and its volume, flow rate of sample and eluent, and sample volume were optimized. Effects of some cation, anion, and transition metal ions on the recoveries of Cu(ll) ions were also investigated. Cu(ll) ions were quantitatively recovered at pH 6; 5.0 mL of 2 M HCI was used as the eluent. The preconcentration factor was found to be 150. The LOD was 0.12 microg/L for Cu(ll). The accuracy of the method was confirmed by analysis of Tea Leaves (INCT-TL-1) and Fish Protein (DORM-3) certified reference materials. The optimized method was applied to various water and food samples for the determination of Cu(ll).

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides: I. Effects of pH

USGS Publications Warehouse

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

2004-01-01

The study of mercury sorption products in model systems using appropriate in situ molecular-scale probes can provide detailed information on the modes of sorption at mineral/water interfaces. Such studies are essential for assessing the influence of sorption processes on the transport of Hg in contaminated natural systems. Macroscopic uptake of Hg(II) on goethite (??-FeOOH), ??-alumina (??-Al2O3), and bayerite (??-Al(OH)3) as a function of pH has been combined with Hg L III-edge EXAFS spectroscopy, FTIR spectroscopy, and bond valence analysis of possible sorption products to provide this type of information. Macroscopic uptake measurements show that Hg(II) sorbs strongly to fine-grained powders of synthetic goethite (Hg sorption density ??=0.39-0.42 ??mol/m2) and bayerite (??=0.39-0.44 ??mol/m2), while sorbing more weakly to ??-alumina (??=0.04-0.13 ??mol/m 2). EXAFS spectroscopy on the sorption samples shows that the dominant mode of Hg sorption on these phases is as monodentate and bidentate inner-sphere complexes. The mode of Hg(II) sorption to goethite was similar over the pH range 4.3-7.4, as were those of Hg(II) sorption to bayerite over the pH range 5.1-7.9. Conversion of the ??-Al2O3 sorbent to a bayerite-like phase in addition to the apparent reduction of Hg(II) to Hg(I), possibly by photoreduction during EXAFS data collection, resulted in enhanced Hg uptake from pH 5.2-7.8 and changes in the modes of sorption that correlate with the formation of the bayerite-like phase. Bond valence calculations are consistent with the sorption modes proposed from EXAFS analysis. EXAFS analysis of Hg(II) sorption products on a natural Fe oxyhydroxide precipitate and Al/Si-bearing flocculent material showed sorption products and modes of surface attachment similar to those for the model substrates, indicating that the model substrates are useful surrogates for the natural sediments. ?? 2003 Elsevier Inc. All rights reserved.

Evolution of the chemistry of Fe bearing waters during CO2 degassing

USGS Publications Warehouse

Geroni, J.N.; Cravotta, C.A.; Sapsford, D.J.

2012-01-01

The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO2 can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO2 during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO2 initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO2 by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO2 led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO2 removal at the flow rates measured.

Fe-As sludge stability and effluent quality for a two-stage As-contaminated water treatment with Fe(II) and aeration.

PubMed

Zhuang, J Ming; Hobenshield, Evan; Walsh, Tony

2009-02-01

A two-stage (I and II) lab-scale treatment system has been studied for arsenic removal from water using Fe(II) and lignosulphonates with aeration. In stage I, using an Fe/As mole ratio of 1.5-2.5 at a pH of around 6.5-7.5, the dissolved arsenic can be reduced with Fe(II) oxidation-precipitation from an initial 72 mg L(-1) to < 2 mg L(-1). The generated sludge is entirely recycled to the second tank of stage II. In the first tank of stage II, the water is further treated with the same amount of Fe(II) as that used in stage I, in the presence of lignosulphonates and aeration. The air-oxidization of Fe(II) to Fe(III) is continued for about 30 minutes at a pH of around 7.0-8.0. The water output from the first tank is transferred to the second tank in which mixing under aeration occurs with the sludge recycled from stage I. Accordingly, the dissolved arsenic in the effluent is reduced to < 0.1 mg L(-1). The results show that this two-stage process can save more than 50% of total chemical costs, and reduce the amount of sludge by more than 50%, in comparison with the conventional Fe(III)/lime-treatment process. According to US EPA regulations, the final Fe-As sludge is classified as non-hazardous materials by the Toxicity Characteristic Leaching Procedure. But, the study shows that the instability of Fe-As sludge could be influenced by some factors, such as higher pH levels, a longer water-leaching time and larger water-leaching volume, leading to the liberation of more dissolvable As species. After being treated with Ligmet stabilizer, the Fe-As sludge showed an improved stability under varying pH conditions and large amounts of water leaching. The treated Fe-As sludge is suitable for landfill disposal.

Removal of Cu(II) from acidic electroplating effluent by biochars generated from crop straws.

PubMed

Tong, Xuejiao; Xu, Renkou

2013-04-01

The removal efficiency of copper (Cu(II)) from an actual acidic electroplating effluent by biochars generated from canola, rice, soybean and peanut straws was investigated. The biochars simultaneously removed Cu(II) from the effluent, mainly through the mechanisms of adsorption and precipitation, and neutralized its acidity. The removal efficiency of Cu(II) by the biochars followed the order: peanut straw char > soybean straw char > canola straw char > rice straw char > a commercial activated carbonaceous material, which is consistent with the alkalinity of the biochars. The pH of the effluent was a key factor determining the removal efficiency of Cu(II) by biochars. Raising the initial pH of the effluent enhanced the removal of Cu(II) from it. The optimum pyrolysis temperature was 400 degrees C for producing biochar from crop straws for acidic wastewater treatment, and the optimum reaction time was 8 hr.

Iron and manganese removal: Recent advances in modelling treatment efficiency by rapid sand filtration.

PubMed

Vries, D; Bertelkamp, C; Schoonenberg Kegel, F; Hofs, B; Dusseldorp, J; Bruins, J H; de Vet, W; van den Akker, B

2017-02-01

A model has been developed that takes into account the main characteristics of (submerged) rapid filtration: the water quality parameters of the influent water, notably pH, iron(II) and manganese(II) concentrations, homogeneous oxidation in the supernatant layer, surface sorption and heterogeneous oxidation kinetics in the filter, and filter media adsorption characteristics. Simplifying assumptions are made to enable validation in practice, while maintaining the main mechanisms involved in iron(II) and manganese(II) removal. Adsorption isotherm data collected from different Dutch treatment sites show that Fe(II)/Mn(II) adsorption may vary substantially between them, but generally increases with higher pH. The model is sensitive to (experimentally) determined adsorption parameters and the heterogeneous oxidation rate. Model results coincide with experimental values when the heterogeneous rate constants are calibrated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Regression model, artificial neural network, and cost estimation for biosorption of Ni(II)-ions from aqueous solutions by Potamogeton pectinatus.

PubMed

Fawzy, Manal; Nasr, Mahmoud; Adel, Samar; Helmi, Shacker

2018-03-21

This study investigated the application of Potamogeton pectinatus for Ni(II)-ions biosorption from aqueous solutions. FTIR spectra showed that the functional groups of -OH, C-H, -C = O, and -COO- could form an organometallic complex with Ni(II)-ions on the biomaterial surface. SEM/EDX analysis indicated that the voids on the biosorbent surface were blocked due to Ni(II)-ions uptake via an ion exchange mechanism. For Ni(II)-ions of 50 mg/L, the adsorption efficiency recorded 63.4% at pH: 5, biosorbent dosage: 10 g/L, and particle-diameter: 0.125-0.25 mm within 180 minutes. A quadratic model depicted that the plot of removal efficiency against pH or contact time caused quadratic-linear concave up curves, whereas the curve of initial Ni(II)-ions was quadratic-linear convex down. Artificial neural network with a structure of 5 - 6 - 1 was able to predict the adsorption efficiency (R 2 : 0.967). The relative importance of inputs was: initial Ni(II)-ions > pH > contact time > biosorbent dosage > particle-size. Freundlich isotherm described well the adsorption mechanism (R 2 : 0.974), which indicated a multilayer adsorption onto energetically heterogeneous surfaces. The net cost of using P. pectinatus for the removal of Ni(II)-ions (4.25 ± 1.26 mg/L) from real industrial effluents within 30 minutes was 3.4 $USD/m 3 .

Candida tropicalis biofilm and human epithelium invasion is highly influenced by environmental pH.

PubMed

Ferreira, Carina; Gonçalves, Bruna; Vilas Boas, Diana; Oliveira, Hugo; Henriques, Mariana; Azeredo, Joana; Silva, Sónia

2016-11-01

The main goal of this study was to investigate the role of pH on Candida tropicalis virulence determinants, namely the ability to form biofilms and to colonize/invade reconstituted human vaginal epithelia. Biofilm formation was evaluated by enumeration of cultivable cells, total biomass quantification and structural analysis by scanning electron microscopy and confocal laser scanning microscopy. Candida tropicalis human vaginal epithelium colonization and invasiveness were examined qualitatively by epifluorescence microscopy and quantitatively by a novel quantitative real-time PCR protocol for Candida quantification in tissues. The results revealed that environmental pH influences C. tropicalis biofilm formation as well as the colonization and potential to invade human epithelium with intensification at neutral and alkaline conditions compared to acidic conditions. For the first time, we have demonstrated that C. tropicalis biofilm formation and invasion is highly influenced by environmental pH. © Crown copyright 2016.

Reactivity and operational stability of N-tailed TAMLs through kinetic studies of the catalyzed oxidation of orange II by H2 O2 : synthesis and X-ray structure of an N-phenyl TAML.

PubMed

Warner, Genoa R; Mills, Matthew R; Enslin, Clarissa; Pattanayak, Shantanu; Panda, Chakadola; Panda, Tamas Kumar; Gupta, Sayam Sen; Ryabov, Alexander D; Collins, Terrence J

2015-04-13

The catalytic activity of the N-tailed ("biuret") TAML (tetraamido macrocyclic ligand) activators [Fe{4-XC6 H3 -1,2-(NCOCMe2 NCO)2 NR}Cl](2-) (3; N atoms in boldface are coordinated to the central iron atom; the same nomenclature is used in for compounds 1 and 2 below), [X, R=H, Me (a); NO2 , Me (b); H, Ph (c)] in the oxidative bleaching of Orange II dye by H2 O2 in aqueous solution is mechanistically compared with the previously investigated activator [Fe{4-XC6 H3 -1,2-(NCOCMe2 NCO)2 CMe2 }OH2 ](-) (1) and the more aggressive analogue [Fe(Me2 C{CON(1,2-C6 H3 -4-X)NCO}2 )OH2 ](-) (2). Catalysis by 3 of the reaction between H2 O2 and Orange II (S) occurs according to the rate law found generally for TAML activators (v=kI kII [Fe(III) ][S][H2 O2 ]/(kI [H2 O2 ]+kII [S]) and the rate constants kI and kII at pH 7 both decrease within the series 3 b>3 a>3 c. The pH dependency of kI and kII was investigated for 3 a. As with all TAML activators studied to-date, bell-shaped profiles were found for both rate constants. For kI , the maximal activity was found at pH 10.7 marking it as having similar reactivity to 1 a. For kII , the broad bell pH profile exhibits a maximum at pH about 10.5. The condition kI ≪kII holds across the entire pH range studied. Activator 3 b exhibits pronounced activity in neutral to slightly basic aqueous solutions making it worthy of consideration on a technical performance basis for water treatment. The rate constants ki for suicidal inactivation of the active forms of complexes 3 a-c were calculated using the general formula ln([S0 ]/[S∞ ])=(kII /ki )[Fe(III) ]; here [Fe(III) ], [S0 ], and [S∞ ] are the total catalyst concentration and substrate concentration at time zero and infinity, respectively. The synthesis and X-ray characterization of 3 c are also described. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Effects of simulated acid rain on Quercus glauca seedlings photosynthesis and chlorophyll fluorescence].

PubMed

Li, Jia; Jiang, Hong; Yu, Shu-quan; Jiang, Fu-wei; Yin, Xiu-min; Lu, Mei-juan

2009-09-01

Taking the seedlings of Quercus glauca, a dominant evergreen broadleaf tree species in subtropical area, as test materials, this paper studied their photosynthesis, chlorophyll fluorescence, and chlorophyll content under effects of simulated acid rain with pH 2.5, 4.0, and 5.6 (CK). After 2-year acid rain stress, the net photosynthetic rate of Q. glauca increased significantly with decreasing pH of acid rain. The acid rain with pH 2.5 and 4.0 increased the stomatal conductance and transpiration rate, and the effect was more significant under pH 2.5. The intercellular CO2 concentration decreased in the order of pH 2.5 > pH 5.6 > pH 4.0. The maximum photosynthetic rate, light compensation point, light saturation point, and dark respiration rate were significantly higher under pH 2.5 and 4.0 than under pH 5.6, while the apparent quantum yield was not sensitive to acid rain stress. The maximal photochemical efficiency of PS II and the potential activity of PS II under pH 2.5 and 4.0 were significantly higher than those under pH 5.6. The relative chlorophyll content was in the order of pH 2.5 > pH 5.6 > pH 4.0, and there was a significant difference between pH 2.5 and 4.0. All the results suggested that the photosynthesis and chlorophyll fluorescence of Q. glauca increased under the effects of acid rain with pH 2.5 and 4.0, and the acid rain with pH 2.5 had more obvious effects.

Copper(II)-based metal affinity chromatography for the isolation of the anticancer agent bleomycin from Streptomyces verticillus culture.

PubMed

Gu, Jiesi; Codd, Rachel

2012-10-01

The glycopeptide-based bleomycins are structurally complex natural products produced by Streptomyces verticillus used in combination therapy against testicular and other cancers. Bleomycin has a high affinity towards a range of transition metal ions with the 1:1 Fe(II) complex relevant to its mechanism of action in vivo and the 1:1 Cu(II) complex relevant to its production from culture. The affinity between Cu(II) and bleomycin was the underlying principle for using Cu(II)-based metal affinity chromatography in this work to selectively capture bleomycin from crude S. verticillus culture. A solution of standard bleomycin was retained at a binding capacity of 300 nmol mL(-1) on a 1-mL bed volume of Cu(II)-loaded iminodiacetate (IDA) resin at pH 9 via the formation of the heteroleptic immobilized complex [Cu(IDA)(bleomycin)]. Bleomycin was eluted from the resin at pH 5 as the metal-free ligand under conditions where pK(a) (IDA)

A green separation strategy for neodymium (III) from cobalt (II) and nickel (II) using an ionic liquid-based aqueous two-phase system.

PubMed

Chen, Yuehua; Wang, Huiyong; Pei, Yuanchao; Wang, Jianji

2018-05-15

It is significant to develop sustainable strategies for the selective separation of rare earth from transition metals from fundamental and practical viewpoint. In this work, an environmentally friendly solvent extraction approach has been developed to selectively separate neodymium (III) from cobalt (II) and nickel (II) by using an ionic liquid-based aqueous two phase system (IL-ATPS). For this purpose, a hydrophilic ionic liquid (IL) tetrabutylphosphonate nitrate ([P 4444 ][NO 3 ]) was prepared and used for the formation of an ATPS with NaNO 3 . Binodal curves of the ATPSs have been determined for the design of extraction process. The extraction parameters such as contact time, aqueous phase pH, content of phase-formation components of NaNO 3 and the ionic liquid have been investigated systematically. It is shown that under optimal conditions, the extraction efficiency of neodymium (III) is as high as 99.7%, and neodymium (III) can be selectively separated from cobalt (II) and nickel (II) with a separation factor of 10 3 . After extraction, neodymium (III) can be stripped from the IL-rich phase by using dilute aqueous sodium oxalate, and the ILs can be quantitatively recovered and reused in the next extraction process. Since [P 4444 ][NO 3 ] works as one of the components of the ATPS and the extractant for the neodymium, no organic diluent, extra etractant and fluorinated ILs are used in the separation process. Thus, the strategy described here shows potential in green separation of neodymium from cobalt and nickel by using simple IL-based aqueous two-phase system. Copyright © 2018 Elsevier B.V. All rights reserved.

[Effects of acid rain stress on Eleocarpus glabripetalus seedlings leaf chlorophyll fluorescence characteristics and growth].

PubMed

Yin, Xiu-Min; Yu, Shu-Quan; Jiang, Hong; Liu, Mei-Hu

2010-06-01

A pot experiment was conducted to study the Eleocarpus glabripetalus seedlings leaf chlorophyll fluorescence characteristics and growth in different seasons under simulated acid rain stress (heavy, pH = 2. 5; moderate, pH = 4.0; and control, pH = 5.6). In the same treatments, the leaf relative chlorophyll content (SPAD), maximum PS II photochemical efficiency (F(v)/F(m)), actual PSII photochemical quantum yield (phi(PS II)), plant height, and stem diameter in different seasons were all in the order of October > July > April > January. In the same seasons, all the parameters were in the order of heavy acid rain > moderate acid rain > control. The interactions between different acid rain stress and seasons showed significant effects on the SPAD, F(v)/F(m), plant height, and stem diameter, but lesser effects on phi(PS II), qp and qN.

Reaction of tris(bipyridine)ruthenium(III) with hydroxide and its application in a solar energy storage system

PubMed Central

Creutz, Carol; Sutin, Norman

1975-01-01

Irradiation of Ru(bipy)32+ (bipy = 2,2′-bipyridine) with light below 560 nm results in the formation of a charge-transfer excited state potentially capable of reducing water to dihydrogen with concomitant production of Ru(bipy)33+. The latter may be reduced by hydroxide [Formula: see text] to form dioxygen and regenerate the starting complex. The use of these reactions in a cell designed to bring about the photochemical decomposition of water is proposed. The stoichiometry, kinetics, and mechanism of the Ru(bipy)33+-hydroxide reaction have been investigated by conventional and stopped-flow spectrophotometry. The dioxygen yield is a sharp function of pH, attaining its maximum value (about 80%) at pH 9. At low pH (3 and 4.8) the production of ruthenium(II) is first order with kobsd = (1.41 ± 0.04) × 10-4 sec-1 (25°, ionic strength μ = 1.00 M with sodium sulfate). In the intermediate pH range (7.9-10.0) complex kinetics are observed. In the hydroxide range 0.01-0.50 M, ruthenium(II) production is predominantly first order with kobsd = ka[OH-] + kb[OH-]2 sec-1; ka = 148 M-1 sec-1 and kb = 138 M-2 sec-1 (25°, μ = 1.00 M, sodium sulfate). For the ka term, the activation parameters are ΔH‡ = 15.3 ± 1.0 kcal mol-1 and ΔS‡ = 7 ± 3 cal deg-1 mol-1 (1 cal = 4.184 J). An intermediate species (λmax 800 nm) forms at the same rate as ruthenium(II) in this hydroxide range. It disappears with kobsd = 1.2 + 1.1 × 102 [OH-] sec-1 at 25°. Similarly absorbing (λmax 750 to 800 nm) species are generated by the addition of hydroxyl radical to M(bipy)32+/3+ [M = Fe(II), Os(II), Ru(II), Cr(III), Ru(III)] in pulse radiolysis experiments. The kinetics above pH 7 are described in terms of rate-determining nucleophilic attack by hydroxide on the bound bipyridine ring. The hydroxide adduct so generated is tentatively identified with that observed in the pulse radiolysis experiments with Ru(bipy)32+. For reduction of Ru(bipy)33+ by hydrogen peroxide ruthenium(II) production is first order with kobsd = kc[HO2-] + kd[H2O2] where kc = 5.4 × 107 M-1 sec-1 and kd = 8.3 M-1 sec-1 (25°, μ = 1.00 M, pH 3.5 to 9.7). This reaction produces dioxygen in 83 ± 15% yield at pH 6.8 and in 1.0 N sulfuric acid. PMID:16592265

Adsorption of Cd(II) Metal Ion on Adsorbent beads from Biomass Saccharomycess cereviceae - Chitosan

NASA Astrophysics Data System (ADS)

Hasri; Mudasir

2018-01-01

The adsorbent beads that was preparation from Saccharomycess cereviceae culture strain FN CC 3012 and shrimp shells waste and its application for adsorption of Cd (II) metal ion has been studied. The study start with combination of Saccharomycess cereviceae biomass to chitosan (Sc-Chi), contact time, pH of solution and initial concentration of cations. Total Cd(II) metal ion adsorbed was calculated from the difference of metal ion concentration before and after adsorption by AAS. The results showed that optimum condition for adsorption of Cd(II) ions by Sc-Chi beads was achieved with solution pH of 4, contact time of 60 minutes and initial concentration adsorption 100mg/L. The hydroxyl (-OH) and amino (-NH2) functional groups were believed to be responsible for the adsorption of Cd(II) ions.

High stability and biological activity of the copper(II) complexes of alloferon 1 analogues containing tryptophan.

PubMed

Kadej, Agnieszka; Kuczer, Mariola; Czarniewska, Elżbieta; Urbański, Arkadiusz; Rosiński, Grzegorz; Kowalik-Jankowska, Teresa

2016-10-01

Copper(II) complex formation processes between the alloferon 1 (Allo1) (HGVSGHGQHGVHG) analogues where the tryptophan residue is introducing in the place His residue H1W, H6W, H9W and H12W have been studied by potentiometric, UV-visible, CD and EPR spectroscopic, and MS methods. For all analogues of alloferon 1 complex speciation have been obtained for a 1:1 metal-to-ligand molar ratio and 2:1 of H1W because of precipitation at higher (2:1, 3:1 and 4:1) ratios. At physiological pH7.4 and a 1:1 metal-to-ligand molar ratio the tryptophan analogues of alloferon 1 form the CuH -1 L and/or CuH -2 L complexes with the 4N binding mode. The introduction of tryptophan in place of histidine residues changes the distribution diagram of the complexes formed with the change of pH and their stability constants compared to the respective substituted alanine analogues of alloferon 1. The CuH -1 L, CuH -2 L and CuH -3 L complexes of the tryptophan analogues are more stable from 1 to 5 log units in comparison to those of the alanine analogues. This stabilization of the complexes may result from cation(Cu(II))-π and indole/imidazole ring interactions. The induction of apoptosis in vivo, in Tenebrio molitor cells by the ligands and their copper(II) complexes at pH7.4 was studied. The biological results show that copper(II) ions in vivo did not cause any apparent apoptotic features. The most active were the H12W peptide and Cu(II)-H12W complex formed at pH7.4. Copyright © 2016 Elsevier Inc. All rights reserved.

U.S. EPA, Pesticide Product Label, FLIGHT BRAND TOXAPHENE-METHYL PARATHION EC 6-3, 06/04/1973

EPA Pesticide Factsheets

2011-04-14

I \\ " I'll )( 1 II \\ " " ! II.:. \\ I \\ I i J '1< I \\ I \\ 1 i :\\ : ( \\I I IIlH)' .. I'll' Sf(i \\ '\\ 1'(" "4)'\\1:\\(, \\ I Il' r I " S'\\1I'141'\\\\ \\ II \\ II l \\ \\' \\ \\ I( "t' \\ PH" H) I' \\!( \\ 1"" SIt 1.\\", \\ II BII \\ )\\\\ ...

Activation of Oxygen and Hydrogen Peroxide by Copper(II) Coupled with Hydroxylamine for Oxidation of Organic Contaminants.

PubMed

Lee, Hongshin; Lee, Hye-Jin; Seo, Jiwon; Kim, Hyung-Eun; Shin, Yun Kyung; Kim, Jae-Hong; Lee, Changha

2016-08-02

This study reports that the combination of Cu(II) with hydroxylamine (HA) (referred to herein as Cu(II)/HA system) in situ generates H2O2 by reducing dissolved oxygen, subsequently producing reactive oxidants through the reaction of Cu(I) with H2O2. The external supply of H2O2 to the Cu(II)/HA system (i.e., the Cu(II)/H2O2/HA system) was found to further enhance the production of reactive oxidants. Both the Cu(II)/HA and Cu(II)/H2O2/HA systems effectively oxidized benzoate (BA) at pH between 4 and 8, yielding a hydroxylated product, p-hydroxybenzoate (pHBA). The addition of a radical scavenger, tert-butyl alcohol, inhibited the BA oxidation in both systems. However, electron paramagnetic resonance (EPR) spectroscopy analysis indicated that (•)OH was not produced under either acidic or neutral pH conditions, suggesting that the alternative oxidant, cupryl ion (Cu(III)), is likely a dominant oxidant.

Validity of the Medical College Admission Test for Predicting MD-PhD Student Outcomes

ERIC Educational Resources Information Center

Bills, James L.; VanHouten, Jacob; Grundy, Michelle M.; Chalkley, Roger; Dermody, Terence S.

2016-01-01

The Medical College Admission Test (MCAT) is a quantitative metric used by MD and MD-PhD programs to evaluate applicants for admission. This study assessed the validity of the MCAT in predicting training performance measures and career outcomes for MD-PhD students at a single institution. The study population consisted of 153 graduates of the…

The Benefits of Publishing Systematic Quantitative Literature Reviews for PhD Candidates and Other Early-Career Researchers

ERIC Educational Resources Information Center

Pickering, Catherine; Byrne, Jason

2014-01-01

Universities increasingly expect students to publish during a PhD candidature because it benefits the candidate, supervisor, institution, and wider community. Here, we describe a method successfully used by early-career researchers including PhD candidates to undertake and publish literature reviews--a challenge for researchers new to a field. Our…

Adsorption of tetracycline on soil and sediment: effects of pH and the presence of Cu(II).

PubMed

Zhang, Zheyun; Sun, Ke; Gao, Bo; Zhang, Guixiang; Liu, Xitao; Zhao, Ye

2011-06-15

Tetracycline (TC) is frequently detected in the environment, however, knowledge on the environmental fate and transport of TC is still limited. Batch adsorption experiments of TC by soil and sediment samples were conducted. The distribution of charge and electrostatic potential of individual atoms of various TC species in the aqueous solution were determined using MOPAC version 0.034 W program in ChemBio3D Ultra software. Most of the adsorption isotherms on the soil, river and marine sediments were well fitted with the Freundlich and Polanyi-Manes (PMM) models. The single point organic carbon (OC)-normalized adsorption distribution coefficients (K(OC)) and PMM saturated adsorption capacity (Q(OC)(0)) values of TC were associated with the mesopore volume and clay content to a greater extent, indicating the mesopore volume of the soil and sediments and their clay content possibly influenced the fate and transport of TC in the natural environment. The adsorption of TC on soil and sediments strongly depended on the pH and presence of Cu(II). The presence of Cu(II) facilitated TC adsorption on soil and sediments at low pH (pH<5), possibly due to the metallic complexation and surface-bridging mechanism by Cu(II) adsorption on soil and sediments. The cation exchange interaction, metallic complexation and Coulombic interaction of mechanisms for adsorption of TC to soils and sediments were further supported by quantum chemical calculation of various TC species in different pH. Copyright © 2011 Elsevier B.V. All rights reserved.

Catalysis of copper corrosion products on chlorine decay and HAA formation in simulated distribution systems.

PubMed

Zhang, Hong; Andrews, Susan A

2012-05-15

This study investigated the effect of copper corrosion products, including Cu(II), Cu(2)O, CuO and Cu(2)(OH)(2)CO(3), on chlorine degradation, HAA formation, and HAA speciation under controlled experimental conditions. Chlorine decay and HAA formation were significantly enhanced in the presence of copper with the extent of copper catalysis being affected by the solution pH and the concentration of copper corrosion products. Accelerated chlorine decay and increased HAA formation were observed at pH 8.6 in the presence of 1.0 mg/L Cu(II) compared with that observed at pH 6.6 and pH 7.6. Further investigation of chlorine decay in the presence of both Suwannee River NOM and Cu(II) indicated that an increased reactivity of NOM with dissolved and/or solid surface-associated Cu(II), rather than chlorine auto-decomposition, was a primary reason for the observed rapid chlorine decay. Copper corrosion solids [Cu(2)O, CuO, Cu(2)(OH)(2)CO(3)] exhibited catalytic effects on both chlorine decay and HAA formation. Contrary to the results observed when in the absence of copper corrosion products, DCAA formation was consistently predominant over other HAA species in the presence of copper corrosion products, especially at neutral and high pH. This study improves the understanding for water utilities and households regarding chlorine residuals and HAA concentrations in distribution systems, in particular once the water reaches domestic plumbing where copper is widely used. Copyright © 2012 Elsevier Ltd. All rights reserved.

Nickel(II) biosorption from aqueous solutions by shrimp head biomass.

PubMed

Hernández-Estévez, Alejandro; Cristiani-Urbina, Eliseo

2014-11-01

The present study evaluates the capacity of shrimp (Farfantepenaeus aztecus) head to remove toxic Ni(II) ions from aqueous solutions. Relevant parameters that could affect the biosorption process, such as shrimp head pretreatment, solution pH level, contact time and initial Ni(II) concentration, were studied in batch systems. An increase in Ni(II) biosorption capacity and a reduction in the time required to reach Ni(II) biosorption equilibrium was manifested by shrimp head biomass pretreated by boiling in 0.5 N NaOH for 15 min; this biomass was thereafter denominated APSH. The optimum biosorption level of Ni(II) ions onto APSH was observed at pH 7.0. Biosorption increased significantly with rising initial Ni(II) concentration. In terms of biosorption dynamics, the pseudo-second-order kinetic model described Ni(II) biosorption onto APSH best. The equilibrium data adequately fitted the Langmuir isotherm model within the studied Ni(II) ion concentration range. According to this isotherm model, the maximum Ni(II) biosorption capacity of APSH was 104.22 mg/g. Results indicate that APSH could be used as a low-cost, environmentally friendly, and promising biosorbent with high biosorption capacity to remove Ni(II) from aqueous solutions.

Removal of Copper(II) Ions in Aqueous Solutions Using Tannin-Rich Plants as Natural Bio-Adsorbents

NASA Astrophysics Data System (ADS)

Paksamut, J.; Boonsong, P.

2018-03-01

In this study, the purpose of our interest is to investigatethe adsorption behavior of copper (II) ions in aqueous solution using some tannin-rich plants as natural bio-adsorbents such as mangosteen peels (Garciniamangostana L.), cassava leaves (Manihotesculenta Crantz) and Thai copper pod leaves (Sennasiamea (Lam.)) as powder form in different dosage of adsorbent plant materials.The adsorption capacities at different pH of solution and contact time were performed.All the experiments in this studywere chosen at room temperature by batch technique. From the experimental results showed that cassava leaves gave better adsorbent properties than mangosteen peels and Thai copper pod leaves. The increasing dosage of all adsorbents and contact time have been found to increase adsorption capacities. In this respect, the adsorption capacities depend crucially on the adsorbents and contact time. The optimum pH of copper (II) ions adsorption was pH4. According to this work, it was observed that bioadsorbent materials from tannin-rich plants could be used to remove copper (II) ions from aqueous solutions.

Precision sensing by two opposing gradient sensors: how does Escherichia coli find its preferred pH level?

PubMed

Hu, Bo; Tu, Yuhai

2013-07-02

It is essential for bacteria to find optimal conditions for their growth and survival. The optimal levels of certain environmental factors (such as pH and temperature) often correspond to some intermediate points of the respective gradients. This requires the ability of bacteria to navigate from both directions toward the optimum location and is distinct from the conventional unidirectional chemotactic strategy. Remarkably, Escherichia coli cells can perform such a precision sensing task in pH taxis by using the same chemotaxis machinery, but with opposite pH responses from two different chemoreceptors (Tar and Tsr). To understand bacterial pH sensing, we developed an Ising-type model for a mixed cluster of opposing receptors based on the push-pull mechanism. Our model can quantitatively explain experimental observations in pH taxis for various mutants and wild-type cells. We show how the preferred pH level depends on the relative abundance of the competing sensors and how the sensory activity regulates the behavioral response. Our model allows us to make quantitative predictions on signal integration of pH and chemoattractant stimuli. Our study reveals two general conditions and a robust push-pull scheme for precision sensing, which should be applicable in other adaptive sensory systems with opposing gradient sensors. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Combined effect of polarity and pH on the chromatographic behavior of some angiotensin II receptor antagonists and optimization of their determination in pharmaceutical dosage forms.

PubMed

Demiralay, Ebru Cubuk; Cubuk, Burcu; Ozkan, Sibel A; Alsancak, Guleren

2010-11-02

In the present study, the combined effect of mobile phase polarity and pH on retention behavior of some ARA-IIs (irbesartan, losartan, valsartan and telmisartan) is investigated. The linear relationships established between retention factors of the species and the polarity parameter of the mobile phase has proved to predict accurately retention in LC as a function of the acetonitrile content (50%, 55%, 60%, v/v). The suggested model uses the pH value in the acetonitrile-water mixture as mobile phase instead of pH value in water and takes into account the effect of activity coefficients. Moreover, correlation between retention and the mobile phase pH can be established allowing prediction of the retention behavior as a function of the mobile phase pH. The model can be used to estimate the pKa in an acetonitrile percentage between 50% and 60%, at 30 degrees C. The developed method was successfully applied to both the simultaneous separation of these drug-active compounds and individual determination in their commercial pharmaceutical dosage forms.

Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH

NASA Astrophysics Data System (ADS)

Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.

2017-12-01

In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in low-pH abiologic systems, and such results bear on the search for biosignatures in Mars and Mars-analog settings. [1] Crosby et al., 2007 Geobiol. 5, 169-189 [2] Beard et al., 2010 Earth Planet. Sci. Lett. 295, 241-250 [3] Wu et al., 2011 Environ. Sci. Technol. 45, 1847-1852 [4] Reddy et al., 2015 Chem. Geol. 397, 118-127 [5] Amenabar et al., 2017 Nat. Geosci. In press

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

PubMed

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

Biological Low-pH Mn(II) Oxidation in a Manganese Deposit Influenced by Metal-Rich Groundwater

PubMed Central

Bohu, Tsing; Akob, Denise M.; Abratis, Michael; Lazar, Cassandre S.

2016-01-01

ABSTRACT The mechanisms, key organisms, and geochemical significance of biological low-pH Mn(II) oxidation are largely unexplored. Here, we investigated the structure of indigenous Mn(II)-oxidizing microbial communities in a secondary subsurface Mn oxide deposit influenced by acidic (pH 4.8) metal-rich groundwater in a former uranium mining area. Microbial diversity was highest in the Mn deposit compared to the adjacent soil layers and included the majority of known Mn(II)-oxidizing bacteria (MOB) and two genera of known Mn(II)-oxidizing fungi (MOF). Electron X-ray microanalysis showed that romanechite [(Ba,H2O)2(Mn4+,Mn3+)5O10] was conspicuously enriched in the deposit. Canonical correspondence analysis revealed that certain fungal, bacterial, and archaeal groups were firmly associated with the autochthonous Mn oxides. Eight MOB within the Proteobacteria, Actinobacteria, and Bacteroidetes and one MOF strain belonging to Ascomycota were isolated at pH 5.5 or 7.2 from the acidic Mn deposit. Soil-groundwater microcosms demonstrated 2.5-fold-faster Mn(II) depletion in the Mn deposit than adjacent soil layers. No depletion was observed in the abiotic controls, suggesting that biological contribution is the main driver for Mn(II) oxidation at low pH. The composition and species specificity of the native low-pH Mn(II) oxidizers were highly adapted to in situ conditions, and these organisms may play a central role in the fundamental biogeochemical processes (e.g., metal natural attenuation) occurring in the acidic, oligotrophic, and metalliferous subsoil ecosystems. IMPORTANCE This study provides multiple lines of evidence to show that microbes are the main drivers of Mn(II) oxidation even at acidic pH, offering new insights into Mn biogeochemical cycling. A distinct, highly adapted microbial community inhabits acidic, oligotrophic Mn deposits and mediates biological Mn oxidation. These data highlight the importance of biological processes for Mn biogeochemical cycling and show the potential for new bioremediation strategies aimed at enhancing biological Mn oxidation in low-pH environments for contaminant mitigation. PMID:26969702

Redox Cycling, pH Dependence, and Ligand Effects of Mn(III) in Oxalate Decarboxylase from Bacillus subtilis.

PubMed

Twahir, Umar T; Ozarowski, Andrew; Angerhofer, Alexander

2016-11-29

This contribution describes electron paramagnetic resonance (EPR) experiments on Mn(III) in oxalate decarboxylase of Bacillus subtilis, an interesting enzyme that catalyzes the redox-neutral dissociation of oxalate into formate and carbon dioxide. Chemical redox cycling provides strong evidence that both Mn centers can be oxidized, although the N-terminal Mn(II) appears to have the lower reduction potential and is most likely the carrier of the +3 oxidation state under moderate oxidative conditions, in agreement with the general view that it represents the active site. Significantly, Mn(III) was observed in untreated OxDC in succinate and acetate buffers, while it could not be directly observed in citrate buffer. Quantitative analysis showed that up to 16% of the EPR-visible Mn is in the +3 oxidation state at low pH in the presence of succinate buffer. The fine structure and hyperfine structure parameters of Mn(III) are affected by small carboxylate ligands that can enter the active site and have been recorded for formate, acetate, and succinate. The results from a previous report [Zhu, W., et al. (2016) Biochemistry 55, 429-434] could therefore be reinterpreted as evidence of formate-bound Mn(III) after the enzyme is allowed to turn over oxalate. The pH dependence of the Mn(III) EPR signal compares very well with that of enzymatic activity, providing strong evidence that the catalytic reaction of oxalate decarboxylase is driven by Mn(III), which is generated in the presence of dioxygen.

Functionalized iron oxide/SBA-15 sorbent: investigation of adsorption performance towards glyphosate herbicide.

PubMed

Rivoira, Luca; Appendini, Marta; Fiorilli, Sonia; Onida, Barbara; Del Bubba, Massimo; Bruzzoniti, Maria Concetta

2016-11-01

Glyphosate is a worldwide-used herbicide occurring in many monitoring campaigns. Efficient technologies are currently unavailable for glyphosate removal from waters. In this work, a SBA-15 mesoporous silica-based material (Fe-NH 2 -SBA-15) was synthesized and studied for the adsorption of glyphosate from waters. In order to promote specific interactions between the sorbent and glyphosate via phosphoric group, iron oxide nanoparticles were encapsulated and a surface functionalization with (3-aminopropyl)triethoxysilane was accomplished. The adsorption of glyphosate on Fe-NH 2 -SBA-15 was investigated as a function of (i) pH, (ii) ionic strength (I), and (iii) adsorbate to adsorbent ratio (C), using a two-level, three-factor experimental design. The experimental design allowed for understanding the effect of the abovementioned variables and for proposing experimental conditions for quantitative removal (pH = 2.1, I = 1⋅10 -2  M and C = 0.35) under both batch and dynamic conditions. Interaction mechanism between glyphosate and Fe-NH 2 -SBA-15 sorbent was elucidated by studying the adsorption behavior of sorbents derived from the intermediate stages of synthesis and by desorption tests. Fe-NH 2 -SBA-15 sorbent can be quantitatively regenerated by 12.5 mM NaOH, and can be reused at least for five adsorption/desorption cycles. Quantitative removal of glyphosate from inlet and effluent wastewaters from a wastewater treatment plant is shown.

Sorption mechanisms of metals to graphene oxide

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

Showalter, Allison R.; Duster, Thomas A.; Szymanowski, Jennifer E. S.

2016-05-01

Environmental toxic metal contamination remediation and prevention is an ongoing issue. Graphene oxide is highly sorptive for many heavy metals over a wide pH range under different ionic strength conditions. We present x-ray absorption fine structure (XAFS) spectroscopy results investigating the binding environment of Pb(II), Cd(II) and U(VI) ions onto multi-layered graphene oxide (MLGO). Analysis indicates that the dominant sorption mechanism of Pb to MLGO changes as a function of pH, with increasing inner sphere contribution as pH increases. In contrast, the sorption mechanism of Cd to MLGO remains constant under the studied pH range. This adsorption mechanism is anmore » electrostatic attraction between the hydrated Cd+2 ion and the MLGO surface. The U(VI), present as the uranyl ion, changes only subtly as a function of pH and is bound to the surface via an inner sphere bond. Knowledge of the binding mechanism for each metal is necessary to help in optimizing environmental remediation or prevention in filtration systems.« less

Structural differences between native Hen egg white lysozyme and its fibrils under different environmental conditions

NASA Astrophysics Data System (ADS)

Bhattacharya, Susmita; Ghosh, Sudeshna; Dasgupta, Swagata; Roy, Anushree

2013-10-01

The difference in molecular structure of native HEWL and its fibrils, grown at a pH value near physiological pH 7.4 and at a pH value just above the pI, 10.7 in presence and absence of Cu(II) ions, is discussed. We focus on differences between the molecular structure of the native protein and fibrils using principal component analysis of their Raman spectra. The overlap areas of the scores of each species are used to quantify the difference in the structure of the native HEWL and fibrils in different environments. The overall molecular structures are significantly different for fibrils grown at two pH values. However, in presence of Cu(II) ions, the fibrils have similarities in their molecular structures at these pH environments. Spectral variation within each species, as obtained from the standard deviations of the scores in PCA plots, reveals the variability in the structure within a particular species.

Analysis and physiological implications of renal 2-oxoglutaramate metabolism.

PubMed Central

Nissim, I; Wehrli, S; States, B; Nissim, I; Yudkoff, M

1991-01-01

The relative significance of the flux through the glutamine aminotransferase (glutaminase II) pathway to renal ammoniagenesis is poorly understood. A basic and unresolved question is whether 2-oxoglutaramate (2-OGM), a product of the glutaminase II reaction, is deamidated to yield 2-oxoglutarate and NH3, or whether 2-OGM accumulates as an unreactive lactam, depending on the environmental pH. In the current studies we utilized 13C n.m.r. as well as 15N n.m.r. as well as 15N n.m.r. to demonstrate that 2-OGM occurs as a lactam, i.e. 5-hydroxypyroglutamate, regardless of the environmental pH. Our additional aims were to determine whether human kidney cells (HK cells) in culture can produce 2-OGM and to ascertain a pH-dependent relationship between NH3 and 2-OGM production from glutamine. We therefore developed an isotope dilution assay for 2-OGM utilizing 5-hydroxy[4-13C,1-15N]pyroglutamate as the labelled species. Incubations of HK cells in minimal essential medium supplemented with 1 mM-[2-15N]glutamine demonstrated significantly higher production of 2-OGM at pH 6.8 and lower production at pH 7.6 compared with pH 7.4. Similarly both 15NH3 and [15N]alanine formation were significantly higher in acute acidosis (pH 6.8) and lower in acute alkalosis (pH 7.6) compared with that at physiological pH. Addition of 1 mM-amino-oxyacetate to the incubation medium at pH 7.4 significantly diminished [15N]alanine and 2-OGM production, but the production of 15NH3 via the glutamate dehydrogenase pathway was significantly stimulated. The current observations indicate that the glutaminase II pathway plays a minor role and that flux through glutamate dehydrogenase is the predominant site for regulation of ammoniagenesis in human kidney. PMID:1854345

Analysis and physiological implications of renal 2-oxoglutaramate metabolism.

PubMed

Nissim, I; Wehrli, S; States, B; Nissim, I; Yudkoff, M

1991-07-01

The relative significance of the flux through the glutamine aminotransferase (glutaminase II) pathway to renal ammoniagenesis is poorly understood. A basic and unresolved question is whether 2-oxoglutaramate (2-OGM), a product of the glutaminase II reaction, is deamidated to yield 2-oxoglutarate and NH3, or whether 2-OGM accumulates as an unreactive lactam, depending on the environmental pH. In the current studies we utilized 13C n.m.r. as well as 15N n.m.r. as well as 15N n.m.r. to demonstrate that 2-OGM occurs as a lactam, i.e. 5-hydroxypyroglutamate, regardless of the environmental pH. Our additional aims were to determine whether human kidney cells (HK cells) in culture can produce 2-OGM and to ascertain a pH-dependent relationship between NH3 and 2-OGM production from glutamine. We therefore developed an isotope dilution assay for 2-OGM utilizing 5-hydroxy[4-13C,1-15N]pyroglutamate as the labelled species. Incubations of HK cells in minimal essential medium supplemented with 1 mM-[2-15N]glutamine demonstrated significantly higher production of 2-OGM at pH 6.8 and lower production at pH 7.6 compared with pH 7.4. Similarly both 15NH3 and [15N]alanine formation were significantly higher in acute acidosis (pH 6.8) and lower in acute alkalosis (pH 7.6) compared with that at physiological pH. Addition of 1 mM-amino-oxyacetate to the incubation medium at pH 7.4 significantly diminished [15N]alanine and 2-OGM production, but the production of 15NH3 via the glutamate dehydrogenase pathway was significantly stimulated. The current observations indicate that the glutaminase II pathway plays a minor role and that flux through glutamate dehydrogenase is the predominant site for regulation of ammoniagenesis in human kidney.

Thermostable purified endoglucanase II from Acidothermus cellulolyticus ATCC

DOEpatents

Adney, William S.; Thomas, Steven R.; Nieves, Rafael A.; Himmel, Michael E.

1994-01-01

A purified low molecular weight endoglucanase II from Acidothermus cellulolyticus (ATCC 43068) is disclosed. The endoglucanase is water soluble, possesses both C.sub.1, and C.sub.x types of enzyme activity, a high degree of stability toward heat, and exhibits optimum temperature activity at about 81.degree. C. at pH's from about 2 to about 9, and at a inactivation temperature of about 100.degree. C. at pH's from about 2 to about 9.

Thermostable purified endoglucanase II from Acidothermus cellulolyticus ATCC

DOEpatents

Adney, W.S.; Thomas, S.R.; Nieves, R.A.; Himmel, M.E.

1994-11-22

A purified low molecular weight endoglucanase II from Acidothermus cellulolyticus (ATCC 43068) is disclosed. The endoglucanase is water soluble, possesses both C[sub 1], and C[sub x] types of enzyme activity, a high degree of stability toward heat, and exhibits optimum temperature activity at about 81 C at pH's from about 2 to about 9, and at a inactivation temperature of about 100 C at pH's from about 2 to about 9. 9 figs.

Synthesis and adsorption of silica gel modified 3-aminopropyltriethoxysilane (APTS) from corn cobs against Cu(II) in water

NASA Astrophysics Data System (ADS)

Purwanto, Agung; Yusmaniar, Ferdiani, Fatmawati; Damayanti, Rachma

2017-03-01

Silica gel modified APTS was synthesized from silica gel which was obtained from corn cobs via sol-gel process. Silica gel was synthesized from corn cobs and then chemically modified with silane coupling agent which has an amine group (NH2). This process resulting modified silica gel 3-aminopropyltriethoxysilane (APTS). Characterization of silica gel modified APTS by SEM-EDX showed that the size of the particles of silica gel modified APTS was 20µm with mass percentage of individual elements were nitrogen (N) 15.56%, silicon (Si) 50.69% and oxygen (O) 33.75%. In addition, silica gel modified APTS also showed absorption bands of functional groups silanol (Si-OH), siloxane (Si-O-Si), and an aliphatic chain (-CH2-), as well as amine (NH2) from FTIR spectra. Based on the characterization of XRD, silica gel 2θ of 21.094° and 21.32° respectively. It indicated that both material were amorphous. Determination of optimum pH and contact time on adsorption of silica gel 3-aminopropyltriethoxysilane (APTS) against Cu(II). The optimum pH and contact time was measured by using AAS. Optimum pH of adsorption silica gel modified APTS against metal Cu(II) could be obtained at pH 6 while optimum contact time was at 30 minutes, with the process of adsorption metal Cu(II) occured based on the model Freundlich isotherm.

A macrocyclic ligand as receptor and Zn(II)-complex receptor for anions in water: binding properties and crystal structures.

PubMed

Ambrosi, Gianluca; Formica, Mauro; Fusi, Vieri; Giorgi, Luca; Macedi, Eleonora; Micheloni, Mauro; Paoli, Paola; Pontellini, Roberto; Rossi, Patrizia

2011-02-01

Binding properties of 24,29-dimethyl-6,7,15,16-tetraoxotetracyclo[19.5.5.0(5,8).0(14,17)]-1,4,9,13,18,21,24,29-octaazaenatriaconta-Δ(5,8),Δ(14,17)-diene ligand L towards Zn(II) and anions, such as the halide series and inorganic oxoanions (phosphate (Pi), sulfate, pyrophosphate (PPi), and others), were investigated in aqueous solution; in addition, the Zn(II)/L system was tested as a metal-ion-based receptor for the halide series. Ligand L is a cryptand receptor incorporating two squaramide functions in an over-structured chain that connects two opposite nitrogen atoms of the Me(2)[12]aneN(4) polyaza macrocyclic base. It binds Zn(II) to form mononuclear species in which the metal ion, coordinated by the Me(2)[12]aneN(4) moiety, lodges inside the three-dimensional cavity. Zn(II)-containing species are able to bind chloride and fluoride at the physiologically important pH value of 7.4; the anion is coordinated to the metal center but the squaramide units play the key role in stabilizing the anion through a hydrogen-bonding network; two crystal structures reported here clearly show this aspect. Free L is able to bind fluoride, chloride, bromide, sulfate, Pi, and PPi in aqueous solution. The halides are bound at acidic pH, whereas the oxoanions are bound in a wide range of pH values ranging from acidic to basic. The cryptand cavity, abundant in hydrogen-bonding sites at all pH values, allows excellent selectivity towards Pi to be achieved mainly at physiological pH 7.4. By joining amine and squaramide moieties and using this preorganized topology, it was possible, with preservation of the solubility of the receptor, to achieve a very wide pH range in which oxoanions can be bound. The good selectivity towards Pi allows its discrimination in a manner not easily obtainable with nonmetallic systems in aqueous environment. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Precipitation of molybdenum(V) as the hydroxide and its separation from rhenium.

PubMed

Yatirajam, V; Ahuja, U; Kakkar, L R

1975-03-01

A study of the conditions for precipitation of molybdenum(V) hydroxide shows that for Mo concentration 1 mg ml about 97.5% of the Mo can be precipitated between pH 5 and 5.8. Lower concentrations of molybdenum(V) or molybdenum(VI) can be precipitated quantitatively by using 20 times the amount of zirconium as collector, at the same pH. On this basis, a simple method is given for quantitative separation of rhenium from large amounts of molybdenum and is attested by analysis of synthetic and molybdenite samples.

TRANSFORMATION OF NITROSOBENZENES AND HYDROXYLANILINES BY FE II SPECIES: ELUCIDATION OF MECHANISM, EFFECT OF FERRIC OXIDES AND PH

EPA Science Inventory

Nitrosobenzenes, the first intermediates in the reduction of nitrobenzenes, were reduced by Fe(II) solutions as well as by Fe(II)-treated goethite suspensions (Fe(II)/G). Results indicate a reactivity trend in which electron-withdrawing groups in the para position increased the ...

Comparative evaluation of two quantitative test methods for determining the efficacy of liquid sporicides and sterilants on a hard surface: a precollaborative study.

PubMed

Tomasino, Stephen F; Hamilton, Martin A

2007-01-01

Two quantitative carrier-based test methods for determining the efficacy of liquid sporicides and sterilants on a hard surface, the Standard Quantitative Carrier Test Method-ASTM E 2111-00 and an adaptation of a quantitative micro-method as reported by Sagripanti and Bonifacino, were compared in this study. The methods were selected based on their desirable characteristics (e.g., well-developed protocol, previous use with spores, fully quantitative, and use of readily available equipment) for testing liquid sporicides and sterilants on a hard surface. In this paper, the Sagripanti-Bonifacino procedure is referred to as the Three Step Method (TSM). AOAC Official Method 966.04 was included in this study as a reference method. Three laboratories participated in the evaluation. Three chemical treatments were tested: (1) 3000 ppm sodium hypochlorite with pH adjusted to 7.0, (2) a hydrogen peroxide/peroxyacetic acid product, and (3) 3000 ppm sodium hypochlorite with pH unadjusted (pH of approximately 10.0). A fourth treatment, 6000 ppm sodium hypochlorite solution with pH adjusted to 7.0, was included only for Method 966.04 as a positive control (high level of efficacy). The contact time was 10 min for all chemical treatments except the 6000 ppm sodium hypochlorite treatment which was tested at 30 min. Each chemical treatment was tested 3 times using each of the methods. Only 2 of the laboratories performed the AOAC method. Method performance was assessed by the within-laboratory variance, between-laboratory variance, and total variance associated with the log reduction (LR) estimates generated by each quantitative method. The quantitative methods performed similarly, and the LR values generated by each method were not statistically different for the 3 treatments evaluated. Based on feedback from the participating laboratories, compared to the TSM, ASTM E 2111-00 was more resource demanding and required more set-up time. The logistical and resource concerns identified for ASTM E 2111-00 were largely associated with the filtration process and counting bacterial colonies on filters. Thus, the TSM was determined to be the most suitable method.

Improving training in methodology enriches the science of psychology.

PubMed

Aiken, Leona S; West, Stephen G; Millsap, Roger E

2009-01-01

Replies to the comment Ramifications of increased training in quantitative methodology by Herbet Zimiles on the current authors original article "Doctoral training in statistics, measurement, and methodology in psychology: Replication and extension of Aiken, West, Sechrest, and Reno's (1990) survey of PhD programs in North America". The current authors state that in their recent article, they reported the results of an extensive survey of quantitative training in all PhD programs in North America. They compared these results with those of a similar survey conducted 12 years earlier (Aiken, West, Sechrest, & Reno, 1990), and raised issues for the future methodological training of substantive and quantitative researchers in psychology. The authors then respond to Zimiles three questions. PsycINFO Database Record 2009 APA.

Quantitative evaluation of malignant gliomas damage induced by photoactivation of IR700 dye

NASA Astrophysics Data System (ADS)

Sakuma, Morito; Kita, Sayaka; Higuchi, Hideo

2016-01-01

The processes involved in malignant gliomas damage were quantitatively evaluated by microscopy. The near-infrared fluorescent dye IR700 that is conjugated to an anti-CD133 antibody (IR700-CD133) specifically targets malignant gliomas (U87MG) and stem cells (BT142) and is endocytosed into the cells. The gliomas are then photodamaged by the release of reactive oxygen species (ROS) and the heat induced by illumination of IR700 by a red laser, and the motility of the vesicles within these cells is altered as a result of cellular damage. To investigate these changes in motility, we developed a new method that measures fluctuations in the intensity of phase-contrast images obtained from small areas within cells. The intensity fluctuation in U87MG cells gradually decreased as cell damage progressed, whereas the fluctuation in BT142 cells increased. The endocytosed IR700 dye was co-localized in acidic organelles such as endosomes and lysosomes. The pH in U87MG cells, as monitored by a pH indicator, was decreased and then gradually increased by the illumination of IR700, while the pH in BT142 cells increased monotonically. In these experiments, the processes of cell damage were quantitatively evaluated according to the motility of vesicles and changes in pH.

Biochemical profile of stone-forming patients with diabetes mellitus.

PubMed

Pak, Charles Y C; Sakhaee, Khashayar; Moe, Orson; Preminger, Glenn M; Poindexter, John R; Peterson, Roy D; Pietrow, Paul; Ekeruo, Wesley

2003-03-01

To test the hypothesis that stone-forming patients with type II diabetes (DM-II) have a high prevalence of uric acid (UA) stones and present with some of the biochemical features of gouty diathesis (GD). The demographic and initial biochemical data from 59 stone-forming patients with DM-II (serum glucose greater than 126 mg/dL, no insulin therapy, older than 35 years of age) from Dallas, Texas and Durham, North Carolina were retrieved and compared with data from 58 patients with GD and 116 with hyperuricosuric calcium oxalate urolithiasis (HUCU) without DM. UA stones were detected in 33.9% of patients with DM-II compared with 6.2% of stone-forming patients without DM (P <0.001). Despite similar ingestion of alkali, the urinary pH in patients with DM-II and UA stones (n = 20) was low (pH = 5.5), as it is in patients with GD, and was significantly lower than in patients with HUCU. The urinary pH in patients with DM-II and calcium stones (n = 39) was intermediate between that in those with DM-II and UA stones and those with HUCU. However, both DM groups had fractional excretion of urate that was not depressed, as it is in those with GD, and was comparable to the value obtained in those with HUCU. The urinary content of undissociated UA was significantly higher, and the saturation of calcium phosphate (brushite) and sodium urate was significantly lower in those with DM-II and UA stones than in those with HUCU. Stone-forming patients with DM-II have a high prevalence of UA stones. Diabetic patients with UA stones share a key feature of those with GD, namely the passage of unusually acid urine, but not the low fractional excretion of urate.

Experiment, modeling and optimization of liquid phase adsorption of Cu(II) using dried and carbonized biomass of Lyngbya majuscula

NASA Astrophysics Data System (ADS)

Kushwaha, Deepika; Dutta, Susmita

2017-05-01

The present work aims at evaluation of the potential of cyanobacterial biomass to remove Cu(II) from simulated wastewater. Both dried and carbonized forms of Lyngbya majuscula, a cyanobacterial strain, have been used for such purpose. The influences of different experimental parameters viz., initial Cu(II) concentration, solution pH and adsorbent dose have been examined on sorption of Cu(II). Kinetic and equilibrium studies on Cu(II) removal from simulated wastewater have been done using both dried and carbonized biomass individually. Pseudo-second-order model and Langmuir isotherm have been found to fit most satisfactorily to the kinetic and equilibrium data, respectively. Maximum 87.99 and 99.15 % of Cu(II) removal have been achieved with initial Cu(II) concentration of 10 and 25 mg/L for dried and carbonized algae, respectively, at an adsorbent dose of 10 g/L for 20 min of contact time and optimum pH 6. To optimize the removal process, Response Surface Methodology has been employed using both the dried and carbonized biomass. Removal with initial Cu(II) concentration of 20 mg/L, with 0.25 g adsorbent dose in 50 mL solution at pH 6 has been found to be optimum with both the adsorbents. This is the first ever attempt to make a comparative study on Cu(II) removal using both dried algal biomass and its activated carbon. Furthermore, regeneration of matrix was attempted and more than 70% and 80% of the adsorbent has been regenerated successfully in the case of dried and carbonized biomass respectively upto the 3rd cycle of regeneration study.

Removal of copper(II) from some environmental samples by sorptive-flotation using powdered marble wastes as sorbents and oleic acid as surfactant.

PubMed

Ghazy, S E; Samra, S E; Mahdy, A F M; El-Morsy, S M

2004-11-01

A simple and economic experimental sorptive -flotation procedure is presented for the removal of copper(II) species from aqueous solutions. It is based on using powdered marble wastes (PMW), which are widespread and inexpensive and may represent an environmental problem, as the effective inorganic sorbent and oleic (HOL) as the surfactant. The main parameters (i.e. initial solution pH, sorbent, surfactant and copper concentrations, stirring times, ionic strength, temperature and the presence of foreign ions) influencing the flotation of PMW and /or Cu(II) were examined. Nearly, 100% of PMW and Cu(II) were removed from aqueous solutions at pH7 after stirring for 10 min and at room temperature, (approximately 25 degrees C). The procedure was successfully applied to recover Cu(II) spiked to some natural water samples. A mechanism for sorption and flotation is suggested.

Performance of Spent Mushroom Farming Waste (SMFW) Activated Carbon for Ni (II) Removal

NASA Astrophysics Data System (ADS)

Desa, N. S. Md; Ghani, Z. Ab; Talib, S. Abdul; Tay, C. C.

2016-07-01

The feasibility of a low cost agricultural waste of spent mushroom farming waste (SMFW) activated carbon for Ni(II) removal was investigated. The batch adsorption experiments of adsorbent dosage, pH, contact time, metal concentration, and temperature were determined. The samples were shaken at 125 rpm, filtered and analyzed using ICP-OES. The fifty percent of Ni(II) removal was obtained at 0.63 g of adsorbent dosage, pH 5-6 (unadjusted), 60 min contact time, 50 mg/L Ni(II) concentration and 25 °C temperature. The evaluated SMFW activated carbon showed the highest performance on Ni(II) removal compared to commercial Amberlite IRC86 resin and zeolite NK3. The result indicated that SMFW activated carbon is a high potential cation exchange adsorbent and suitable for adsorption process for metal removal. The obtained results contribute toward application of developed SMFW activated carbon in industrial pilot study.

Trends in Ph.D. Productivity and Diversity in Top-50 U.S. Chemistry Departments: An Institutional Analysis

ERIC Educational Resources Information Center

Laursen, Sandra L.; Weston, Timothy J.

2014-01-01

The education of doctoral chemists contributes to the chemical research enterprise and thus to innovation as an engine of the economy. This quantitative analysis describes trends in the production and diversity of chemistry Ph.D. degrees in the top-50 U.S. Ph.D.-granting departments in the past two decades. Time series data for individual…

Kinetics and equilibrium modelling of lead uptake by algae Gelidium and algal waste from agar extraction industry.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2007-05-08

Pb(II) biosorption onto algae Gelidium, algal waste from agar extraction industry and a composite material was studied. Discrete and continuous site distribution models were used to describe the biosorption equilibrium at different pH (5.3, 4 and 3), considering competition among Pb(II) ions and protons. The affinity distribution function of Pb(II) on the active sites was calculated by the Sips distribution. The Langmuir equilibrium constant was compared with the apparent affinity calculated by the discrete model, showing higher affinity for lead ions at higher pH values. Kinetic experiments were conducted at initial Pb(II) concentrations of 29-104 mgl(-1) and data fitted to pseudo-first Lagergren and second-order models. The adsorptive behaviour of biosorbent particles was modelled using a batch mass transfer kinetic model, which successfully predicts Pb(II) concentration profiles at different initial lead concentration and pH, and provides significant insights on the biosorbents performance. Average values of homogeneous diffusivity, D(h), are 3.6 x 10(-8); 6.1 x 10(-8) and 2.4 x 10(-8)cm(2)s(-1), respectively, for Gelidium, algal waste and composite material. The concentration of lead inside biosorbent particles follows a parabolic profile that becomes linear near equilibrium.

Poly(methacrylic acid)-grafted chitosan microspheres via surface-initiated ATRP for enhanced removal of Cd(II) ions from aqueous solution.

PubMed

Huang, Liqiang; Yuan, Shaojun; Lv, Li; Tan, Guangqun; Liang, Bin; Pehkonen, S O

2013-09-01

Cross-linked chitosan (CCS) microspheres tethered with pH-sensitive poly(methacrylic acid) (PMAA) brushes were developed for the efficient removal of Cd(II) ions from aqueous solutions. Functional PMAA brushes containing dense and active carboxyl groups (COOH) were grafted onto the CCS microsphere surface via surface-initiated atom transfer radical polymerization (ATRP). Batch adsorption results showed that solution pH values had a major impact on cadmium adsorption by the PMAA-grafted CCS microspheres with the optimal removal observed above pH 5. The CCS-g-PMAA microsphere was found to achieve the adsorption equilibrium of Cd(II) within 1 h, much faster than about 7 h on the CCS microsphere. At pH 5 and with an initial concentration 0.089-2.49 mmol dm(-3), the maximum adsorption capacity of Cd(II), derived from the Langmuir fitting on the PMAA-grafted microspheres was around 1.3 mmol g(-1). Desorption and adsorption cycle experimental results revealed that the PMAA-grafted CCS microspheres loaded with Cd(II) can be effectively regenerated in a dilute HNO3 solution, and the adsorption capacity remained almost unchanged upon five cycle reuse. Copyright © 2013 Elsevier Inc. All rights reserved.

Redox Reactions between Mn(II) and Hexagonal Birnessite Change Its Layer Symmetry.

PubMed

Zhao, Huaiyan; Zhu, Mengqiang; Li, Wei; Elzinga, Evert J; Villalobos, Mario; Liu, Fan; Zhang, Jing; Feng, Xionghan; Sparks, Donald L

2016-02-16

Birnessite, a phyllomanganate and the most common type of Mn oxide, affects the fate and transport of numerous contaminants and nutrients in nature. Birnessite exhibits hexagonal (HexLayBir) or orthogonal (OrthLayBir) layer symmetry. The two types of birnessite contain contrasting content of layer vacancies and Mn(III), and accordingly have different sorption and oxidation abilities. OrthLayBir can transform to HexLayBir, but it is still vaguely understood if and how the reverse transformation occurs. Here, we show that HexLayBir (e.g., δ-MnO2 and acid birnessite) transforms to OrthLayBir after reaction with aqueous Mn(II) at low Mn(II)/Mn (in HexLayBir) molar ratios (5-24%) and pH ≥ 8. The transformation is promoted by higher pH values, as well as smaller particle size, and/or greater stacking disorder of HexLayBir. The transformation is ascribed to Mn(III) formation via the comproportionation reaction between Mn(II) adsorbed on vacant sites and the surrounding layer Mn(IV), and the subsequent migration of the Mn(III) into the vacancies with an ordered distribution in the birnessite layers. This study indicates that aqueous Mn(II) and pH are critical environmental factors controlling birnessite layer structure and reactivity in the environment.

Extraction and separation of tungsten (VI) from aqueous media with Triton X-100-ammonium sulfate-water aqueous two-phase system without any extractant.

PubMed

Yongqiang Zhang; Tichang Sun; Tieqiang Lu; Chunhuan Yan

2016-11-25

An aqueous two-phase system composed of Triton X-100-(NH 4 ) 2 SO 4 -H 2 O was proposed for extraction and separation of tungsten(VI) from aqueous solution without using any extractant. The effects of aqueous pH, concentration of ammonium sulfate, Triton X-100 and tungsten, extracting temperature on the extraction of tungsten were investigated. The extraction of tungsten has remarkable relationship with aqueous pH and are to above 90% at pH=1.0-3.0 under studied pH range (pH=1.0-7.0) and increases gradually with increasing Triton X-100 concentration, but decreases slightly with increasing ammonium sulfate concentration. The extraction percentage of tungsten is hardly relevant to temperature but its distribution coefficient linearly increases with increasing temperature within 303.15-343.15K. The distribution coefficient of tungsten increases with the increase of initial tungsten concentration (0.1-3%) and temperature (303.15 K-333.15K). The solubilization capacity of tungsten in Triton X-100 micellar phase is independent of temperature. FT-IR analysis reveals that there is no evident interaction between polytungstate anion and ether oxygen unit in Triton X-100, and DLS analysis indicates that zeta potential of Triton X-100 micellar phase have a little change from positive to negative after extracting tungsten. Based on the above-mentioned results, it can be deduced that polytungstate anions are solubilized in hydrophilic outer shell of Triton X-100 micelles by electrostatic attraction depending on its relatively high hydrophobic nature. The stripping of tungsten is mainly influenced by temperature and can be easily achieved to 95% in single stage stripping. The tungsten (VI) is separated out from solution containing Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Al(III), Cr(III) and Mn(II) under the suitable conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines

NASA Astrophysics Data System (ADS)

Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee

2017-01-01

The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic brine lakes and acid mine drainage locations that contain precipitated iron oxyhydroxides.

Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

NASA Astrophysics Data System (ADS)

van der Grift, B.; Behrends, T.; Osté, L. A.; Schot, P. P.; Wassen, M. J.; Griffioen, J.

2016-08-01

Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition, reaction kinetics, and the characteristics of the produced Fe hydroxyphosphate precipitates in a series of aeration experiments with anoxic synthetic water and natural groundwater. A pH stat device was used to maintain constant pH and to record the H+ production during Fe(II) oxidation in the aeration experiments in which the initial aqueous P/Fe ratios ((P/Fe)ini), oxygen concentration and pH were varied. In general, Fe(II) oxidation proceeded slower in the presence of PO4 but the decrease of the PO4 concentration during Fe(II) oxidation due to the formation of Fe hydroxyphosphates caused additional deceleration of the reaction rate. The progress of the reaction could be described using a pseudo-second-order rate law with first-order dependencies on PO4 and Fe(II) concentrations. After PO4 depletion, the Fe(II) oxidation rates increased again and the kinetics followed a pseudo-first-order rate law. The first-order rate constants after PO4 depletion, however, were lower compared to the Fe(II) oxidation in a PO4-free solution. Hence, the initially formed Fe hydroxyphosphates also affect the kinetics of continuing Fe(II) oxidation after PO4 depletion. Presence of aqueous PO4 during oxidation of Fe(II) led to the formation of Fe hydroxyphosphates. The P/Fe ratios of the precipitates ((P/Fe)ppt) and the recorded ratio of H+ production over decrease in dissolved Fe(II) did not change detectably throughout the reaction despite a changing P/Fe ratio in the solution. When (P/Fe)ini was 0.9, precipitates with a (P/Fe)ppt ratio of about 0.6 were formed. In experiments with (P/Fe)ini ratios below 0.6, the (P/Fe)ppt decreased with decreasing (P/Fe)ini and pH value. Aeration experiments with natural groundwater showed no principal differences in Fe(II) oxidation kinetics and in PO4 immobilisation dynamics compared with synthetic solutions with corresponding P/Fe ratio, pH and oxygen pressure. However, aeration of groundwater with relative high DOC concentrations and a low salinity lead to P-rich Fe colloids that were colloidally stable. The formation of a Fe hydroxyphosphate phase with a molar P/Fe ratio of 0.6 can be used for predictive modelling of PO4 immobilisation upon aeration of pH-neutral natural groundwater with an (P/Fe)ini ratio up to 1.5. These findings provide a solid basis for further studies on transport and bioavailability of phosphorus in streams, ditches and channels that receive anoxic Fe-rich groundwater.

pH optimization for a reliable quantification of brain tumor cell and tissue extracts with (1)H NMR: focus on choline-containing compounds and taurine.

PubMed

Robert, O; Sabatier, J; Desoubzdanne, D; Lalande, J; Balayssac, S; Gilard, V; Martino, R; Malet-Martino, M

2011-01-01

The aim of this study was to define the optimal pH for (1)H nuclear magnetic resonance (NMR) spectroscopy analysis of perchloric acid or methanol-chloroform-water extracts from brain tumor cells and tissues. The systematic study of the proton chemical shift variations as a function of pH of 13 brain metabolites in model solutions demonstrated that recording (1)H NMR spectra at pH 10 allowed resolving resonances that are overlapped at pH 7, especially in the 3.2-3.3 ppm choline-containing-compounds region. (1)H NMR analysis of extracts at pH 7 or 10 showed that quantitative measurements of lactate, alanine, glutamate, glutamine (Gln), creatine + phosphocreatine and myo-inositol (m-Ino) can be readily performed at both pHs. The concentrations of glycerophosphocholine, phosphocholine and choline that are crucial metabolites for tumor brain malignancy grading were accurately measured at pH 10 only. Indeed, the resonances of their trimethylammonium moieties are cleared of any overlapping signal, especially those of taurine (Tau) and phosphoethanolamine. The four non-ionizable Tau protons resonating as a singlet in a non-congested spectral region permits an easier and more accurate quantitation of this apoptosis marker at pH 10 than at pH 7 where the triplet at 3.43 ppm can be overlapped with the signals of glucose or have an intensity too low to be measured. Glycine concentration was determined indirectly at both pHs after subtracting the contribution of the overlapped signals of m-Ino at pH 7 or Gln at pH 10.

Evaluation of a hollow fiber supported liquid membrane device as a chemical surrogate for the measurements of zinc (II) bioavailability using two microalgae strains as biological references.

PubMed

Rodríguez-Morales, Erik A; Rodríguez de San Miguel, Eduardo; de Gyves, Josefina

2017-03-01

The environmental bioavailability of zinc (II), i.e., the uptake of the element by an organism, was determined using two microalgae species, Scenedesmus acutus and Pseudokirchneriella subcapitata, and estimated using hollow fiber supported liquid membrane (HF-SLM) device as the chemical surrogate. Several experimental conditions were studied including the presence of organic matter, inorganic anions and concomitant cations and pH. The results show strong positive correlation coefficients between the responses given by the HF-SLM and the microalgae species (r = 0.900 for S. acutus and r = 0.876 for P. subcapitata) in multivariate environments (changes in pH, calcium, humic and citrate concentrations). The maximum amount of zinc (II) retained by the HF-SLM (4.7 × 10 -8  mol/cm 2 ) was higher than those for P. subcapitata and S. acutus (9.4 × 10 -11  mol/cm 2 and 6.2 × 10 -11  mol/cm 2 , respectively). The variation in pH (pH 5.5-9) was the variable with the greatest effect on zinc internalization in all systems, increasing approximately 2.5 times for P. subcapitata and 5.5 times for S. acutus respect to pH = 5.5, while the presence of humic acids did not affect the response. The species' concentration analysis of the experimental design at pH = 5.5 indicated that the amount of internalized zinc (II) by the HF-SLM and both microalgae species is strongly dependent on the free zinc concentration (r = 0.910 for the HF-SLM, r = 0.922 for S. acutus and r = 0.954 for P. subcapitata); however, at pH = 9.0, the amount of internalized zinc (II) is strongly dependent on the sum of free zinc and labile species (r = 0.912 for the HF-SLM, r = 0.947 for S. acutus and r = 0.900 for P. subcapitata). The presence of inorganic ligands (chloride, sulfate, phosphate, carbonate, and nitrate) and metal ions (cobalt (II), copper (II), nickel (II), chromium (VI), lead (II) and cadmium (II)) produced different behaviors both in the chemical surrogate and the biological references. The results showed that the synthetic device can mimic biological uptake in the presence of humic acids, nitrate, sulfate, and phosphate, and pH within the range 5.5-9 when S. acutus was used as the biological reference, considering the simultaneous contribution of the Zn 2+ and ZnOH + labile species depending on the chemical composition of the medium. Copyright © 2016 Elsevier Ltd. All rights reserved.

21 CFR 514.1 - Applications.

Code of Federal Regulations, 2011 CFR

2011-04-01

... post office address of, and must be countersigned by, an authorized attorney, agent, or official... pharmacologically related drugs. (c) Description of dosage form and quantitative composition. (ii) Scientific... quantitative statement of composition. Reasonable alternatives for any listed component may be specified. (ii...

21 CFR 514.1 - Applications.

Code of Federal Regulations, 2010 CFR

2010-04-01

... post office address of, and must be countersigned by, an authorized attorney, agent, or official... pharmacologically related drugs. (c) Description of dosage form and quantitative composition. (ii) Scientific... quantitative statement of composition. Reasonable alternatives for any listed component may be specified. (ii...

21 CFR 514.1 - Applications.

Code of Federal Regulations, 2012 CFR

2012-04-01

... post office address of, and must be countersigned by, an authorized attorney, agent, or official... pharmacologically related drugs. (c) Description of dosage form and quantitative composition. (ii) Scientific... quantitative statement of composition. Reasonable alternatives for any listed component may be specified. (ii...

21 CFR 514.1 - Applications.

Code of Federal Regulations, 2014 CFR

2014-04-01

... post office address of, and must be countersigned by, an authorized attorney, agent, or official... pharmacologically related drugs. (c) Description of dosage form and quantitative composition. (ii) Scientific... quantitative statement of composition. Reasonable alternatives for any listed component may be specified. (ii...

21 CFR 514.1 - Applications.

Code of Federal Regulations, 2013 CFR

2013-04-01

... post office address of, and must be countersigned by, an authorized attorney, agent, or official... pharmacologically related drugs. (c) Description of dosage form and quantitative composition. (ii) Scientific... quantitative statement of composition. Reasonable alternatives for any listed component may be specified. (ii...

pH-Dependent spin state population and 19F NMR chemical shift via remote ligand protonation in an iron(ii) complex.

PubMed

Gaudette, Alexandra I; Thorarinsdottir, Agnes E; Harris, T David

2017-11-30

An Fe II complex that features a pH-dependent spin state population, by virtue of a variable ligand protonation state, is described. This behavior leads to a highly pH-dependent 19 F NMR chemical shift with a sensitivity of 13.9(5) ppm per pH unit at 37 °C, thereby demonstrating the potential utility of the complex as a 19 F chemical shift-based pH sensor.

Polarographic study of cadmium 5-hydroxy 2-(hydroxymethyl) 4H-pyran-4-one complex

NASA Technical Reports Server (NTRS)

Wilson, Ray F.; Daniels, Robert C.

1989-01-01

A polarographic study was performed on the products formed in the interaction of cadmium (II) with a 5-hydroxy 2-(hydroxymethyl) 4H-Pyran-4-one, using varying conditions of pH, supporting electrolytes, and concentrations. Measurements using the differential pulse method show that cadmium (II) exhibits a molar combining ratio of complexing agents to cation ranging from 1 to 1 to 3 to 1 depending on the pH and the supporting electrolyte employed.

Comparison of nickel biosorption properties of living and dead Rhizopus arrhizus biosorbent

NASA Astrophysics Data System (ADS)

Silah, Hülya; Gül, Ülküye Dudu

2017-04-01

The passive removal of commonly used heavy metal Ni(II), from aqueous solutions by inexpensive biomaterial, fungi Rhizopus arrhizus biomass, termed biosorption, was studied in this study. The effects of biomass type (living and dead) and pH (2-6) on metal removal by fungus were investigated. The dead biomass (44.2%) exhibited higher uptake ability of Ni(II) than living biomass (40.5%) at 100 mg/L heavy metal after 6 h. Optimal pH for biosorption was 6.

Speedy Alchemy.

ERIC Educational Resources Information Center

Deininger, Rolf A.; Berger, Carl F., Jr.

1983-01-01

Provides instructions for interfacing a pH meter directly to an Apple II microcomputer without an analog-to-digital converter. Includes program listing (with enough remark statements to make it self-documenting) in Integer Basic to display the pH readings. (Author/JN)

An extended model based on the modified Nernst-Planck equation for describing transdermal iontophoresis of weak electrolytes.

PubMed

Imanidis, Georgios; Luetolf, Peter

2006-07-01

An extended model for iontophoretic enhancement of transdermal drug permeation under constant voltage is described based on the previously modified Nernst-Planck equation, which included the effect of convective solvent flow. This model resulted in an analytical expression for the enhancement factor as a function of applied voltage, convective flow velocity due to electroosmosis, ratio of lipid to aqueous pathway passive permeability, and weighted average net ionic valence of the permeant in the aqueous epidermis domain. The shift of pH in the epidermis compared to bulk caused by the electrical double layer at the lipid-aqueous domain interface was evaluated using the Poisson-Boltzmann equation. This was solved numerically for representative surface charge densities and yielded pH differences between bulk and epidermal aqueous domain between 0.05 and 0.4 pH units. The developed model was used to analyze the experimental enhancement of an amphoteric weak electrolyte measured in vitro using human cadaver epidermis and a voltage of 250 mV at different pH values. Parameter values characterizing the involved factors were determined that yielded the experimental enhancement factors and passive permeability coefficients at all pH values. The model provided a very good agreement between experimental and calculated enhancement and passive permeability. The deduced parameters showed (i) that the pH shift in the aqueous permeation pathway had a notable effect on the ionic valence and the partitioning of the drug in this domain for a high surface charge density and depending on the pK(a) and pI of the drug in relation to the bulk pH; (ii) the magnitude and the direction of convective transport due to electroosmosis typically reflected the density and sign, respectively, of surface charge of the tissue and its effect on enhancement was substantial for bulk pH values differing from the pI of epidermal tissue; (iii) the aqueous pathway predominantly determined passive permeability of the studied compound despite its measurable lipophilicity and therefore the lipid pathway did not notably affect enhancement. Hence, the proposed model can provide a good quantitative insight into the interplay between different phenomena and permeant properties influencing iontophoresis and can potentially be used as a predictive tool of the process.

Bovine serum albumin-Cu(II) hybrid nanoflowers: An effective adsorbent for solid phase extraction and slurry sampling flame atomic absorption spectrometric analysis of cadmium and lead in water, hair, food and cigarette samples.

PubMed

Yilmaz, Erkan; Ocsoy, Ismail; Ozdemir, Nalan; Soylak, Mustafa

2016-02-04

Herein, the synthesis of bovine serum albumin-Cu(II) hybrid nanoflowers (BSA-NFs) through the building blocks of bovine serum albumin (BSA) and copper(II) ions in phosphate buffered saline (PBS) and their use as adsorbent for cadmium and lead ions are reported. The BSA-NFs, for the first time, were efficiently utilized as novel adsorbent for solid phase extraction (SPE) of cadmium and lead ions in water, food, cigarette and hair samples. The method is based on the separation and pre-concentration of Cd(II) and Pb(II) by BSA-NFs prior to determination by slurry analysis via flame atomic absorption spectrometry (FAAS). The analytes were adsorbed on BSA-NFs under the vortex mixing and then the ion-loaded slurry was separated and directly introduced into the flame AAS nebulizer by using a hand-made micro sample introduction system to eliminate a number of drawbacks. The effects of analytical key parameters, such as pH, amount of BSA-NFs, vortexing time, sample volume, and matrix effect of foreign ions on adsorbing of Cd(II) and Pb(II) were systematically investigated and optimized. The limits of detection (LODs) for Cd(II) and Pb(II) were calculated as 0.37 μg L(-)(1) and 8.8 μg L(-)(1), respectively. The relative standard deviation percentages (RSDs) (N = 5) for Cd(II) and Pb(II) were 7.2%, and 5.0%, respectively. The accuracy of the developed procedure was validated by the analysis of certified reference materials (TMDA-53.3 Fortified Water, TMDA-70 Fortified Water, SPS-WW2 Waste Water, NCSDC-73349 Bush Branches and Leaves) and by addition/recovery analysis. The quantitative recoveries were obtained for the analysis of certified reference materials and addition/recovery tests. The method was successfully applied to the analysis of cadmium and lead in water, food, cigarette and hair samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Linkage of iron elution and dissolved oxygen consumption with removal of organic pollutants by nanoscale zero-valent iron: Effects of pH on iron dissolution and formation of iron oxide/hydroxide layer.

PubMed

Fujioka, Nanae; Suzuki, Moe; Kurosu, Shunji; Kawase, Yoshinori

2016-02-01

The iron elution and dissolved oxygen (DO) consumption in organic pollutant removal by nanoscale zero-valent iron (nZVI) was examined in the range of solution pH from 3.0 to 9.0. Their behaviors were linked with the removal of organic pollutant through the dissolution of iron and the formation of iron oxide/hydroxide layer affected strongly by solution pH and DO. As an example of organic pollutants, azo-dye Orange II was chosen in this study. The chemical composition analyses before and after reaction confirmed the corrosion of nZVI into ions, the formation of iron oxide/hydroxide layer on nZVI surface and the adsorption of the pollutant and its intermediates. The complete decolorization of Orange II with nZVI was accomplished very quickly. On the other hand, the total organic carbon (TOC) removal was considerably slow and the maximum TOC removal was around 40% obtained at pH 9.0. The reductive cleavage of azo-bond by emitted electrons more readily took place as compared with the cleavage of aromatic rings of Orange II leading to the degradation to smaller molecules and subsequently the mineralization. A reaction kinetic model based on the Langmuir-Hinshelwood/Eley-Rideal approach was developed to elucidate mechanisms for organic pollutant removal controlled by the formation of iron oxide/hydroxide layer, the progress of which could be characterized by considering the dynamic concentration changes in Fe(2+) and DO. The dynamic profiles of Orange II removal linked with Fe(2+) and DO could be reasonably simulated in the range of pH from 3.0 to 9.0. Copyright © 2015 Elsevier Ltd. All rights reserved.

Quantitative analysis of autophagic flux by confocal pH-imaging of autophagic intermediates

PubMed Central

Maulucci, Giuseppe; Chiarpotto, Michela; Papi, Massimiliano; Samengo, Daniela; Pani, Giovambattista; De Spirito, Marco

2015-01-01

Although numerous techniques have been developed to monitor autophagy and to probe its cellular functions, these methods cannot evaluate in sufficient detail the autophagy process, and suffer limitations from complex experimental setups and/or systematic errors. Here we developed a method to image, contextually, the number and pH of autophagic intermediates by using the probe mRFP-GFP-LC3B as a ratiometric pH sensor. This information is expressed functionally by AIPD, the pH distribution of the number of autophagic intermediates per cell. AIPD analysis reveals how intermediates are characterized by a continuous pH distribution, in the range 4.5–6.5, and therefore can be described by a more complex set of states rather than the usual biphasic one (autophagosomes and autolysosomes). AIPD shape and amplitude are sensitive to alterations in the autophagy pathway induced by drugs or environmental states, and allow a quantitative estimation of autophagic flux by retrieving the concentrations of autophagic intermediates. PMID:26506895

AT2 DS II - Accelerator System Design (Part II) - CCC Video Conference

ScienceCinema

None

2017-12-09

Discussion Session - Accelerator System Design (Part II) Tutors: C. Darve, J. Weisend II, Ph. Lebrun, A. Dabrowski, U. Raich Video Conference with the CERN Control Center. Experts in the field of Accelerator science will be available to answer the students questions. This session will link the CCC and SA (using Codec VC).

Separation, preconcentration and inductively coupled plasma-mass spectrometric (ICP-MS) determination of thorium(IV), titanium(IV), iron(III), lead(II) and chromium(III) on 2-nitroso-1-naphthol impregnated MCI GEL CHP20P resin.

PubMed

Aydin, Funda Armagan; Soylak, Mustafa

2010-01-15

A simple and effective method is presented for the separation and preconcentration of Th(IV), Ti(IV), Fe(III), Pb(II) and Cr(III) by solid phase extraction on 2-nitroso-1-naphthol impregnated MCI GEL CHP20P resin prior to their inductively coupled plasma-mass spectrometric determinations. The influence of analytical parameters including pH of the aqueous solution, flow rates of sample and eluent solutions and sample volume on the quantitative recoveries of analyte ions was investigated. Matrix effects caused by the presence of alkali, earth alkali and some metal ions in the analyzed solutions were investigated. The presented solid phase extraction method was applied to BCR-144R Sewage Sludge (domestic origin), BCR-141R Calcareous Loam Soil, NIST 1568a Rice Flour and NIST 1577b Bovine Liver certified reference materials (CRMs) for the determination of analyte ions and the results were in good agreement with the certified values. The separation procedure presented was also applied to the various natural water samples collected from Turkey with satisfactory results.

Determination and reoxidation of the disulfide bridges of a squash-type trypsin inhibitor from Sechium edule seeds.

PubMed

Faça, Vitor M; Pereira, Sandra R; Laure, Hélen J; Greene, Lewis J

2004-07-01

The determination of the disulfide pairings of SETI-II, a trypsin inhibitor isolated from Sechium edule, is described herein. The inhibitor contains 31 amino acid residues per mol, 6 of which are cysteine. Forty-five nmol (160 microg) of SETI-II was hydrolyzed with 20 microg thermolysin for 48 hr at 45 degrees C, and peptides were separated by reverse phase high performance liquid chromatography (RP-HPLC). The major products were identified by amino acid composition, Edman degradation, and on the basis of the sequence of the inhibitor. The disulfide bridge pairings and (yields) are: Cys1-Cys4 (79%), Cys2-Cys5 (21%) and Cys3-Cys6 (43%). When the reduced inhibitor was reoxidized with glutathione reduced form (GSH)/glutathione oxidized form (GSSG) at pH 8.5 for 3 hr, full activity was recovered. These data show that disulfide bridge pairing and oxidation can be determined at nanomole levels and that sensitive and quantitative Edman degradation can eliminate the final time- and material-consuming step of disulfide determinations by eliminating the need to purify and cleave each peptide containing a disulfide bridge.

Pharyngeal airway space and frontal and sphenoid sinus changes after maxillomandibular advancement with counterclockwise rotation for class II anterior open bite malocclusions

PubMed Central

Prado, FB; Rossi, AC; Freire, AR; Groppo, FC; De Moraes, M; Caria, PHF

2012-01-01

Objectives The purpose of this study was to cephalometrically evaluate the pharyngeal airway space and frontal and sphenoid sinus changes after maxillomandibular advancement counterclockwise rotation for class II anterior open bite malocclusion. Methods The study included 49 patients (98 lateral teleradiographs; 36 females and 13 males) who were analysed in the pre-operative (1 week before surgery) and post-operative (6 months after surgery) periods. In each lateral teleradiography, the dimensions of the inferior and superior pharyngeal airway space, TB-PhW1 [the point between the posterior aspect of the tongue to the dorsal pharyngeal wall (oropharynx) (TB) and the point on the dorsal pharyngeal wall closest to TB (PhW1)] and UP-PhW2 [and the point between the posterior aspect of the soft palate to the dorsal pharyngeal wall (nasopharynx) (UP) (PhW2)] measurements were evaluated, as well as the dimensions of the frontal and sphenoid sinuses. The differences between the two operative times were evaluated by Student's t-test. Results All measurements showed excellent reproducibility for the intraclass correlation coefficient (ICC > 0.9; p < 0.0001). There was an increase in the measurements TB-PhW1 and UP-PhW2 and a decrease in the dimensions of the frontal and sphenoid sinuses after orthognathic surgery. Conclusions The morphology of the superior and inferior pharyngeal airway space and frontal and sphenoid sinuses changes after 6 months of maxillomandibular advancement counterclockwise rotation for class II anterior open bite malocclusion. PMID:22116128

Pro-hormone Secretogranin II Regulates Dense Core Secretory Granule Biogenesis in Catecholaminergic Cells*

PubMed Central

Courel, Maïté; Soler-Jover, Alex; Rodriguez-Flores, Juan L.; Mahata, Sushil K.; Elias, Salah; Montero-Hadjadje, Maïté; Anouar, Youssef; Giuly, Richard J.; O'Connor, Daniel T.; Taupenot, Laurent

2010-01-01

Processes underlying the formation of dense core secretory granules (DCGs) of neuroendocrine cells are poorly understood. Here, we present evidence that DCG biogenesis is dependent on the secretory protein secretogranin (Sg) II, a member of the granin family of pro-hormone cargo of DCGs in neuroendocrine cells. Depletion of SgII expression in PC12 cells leads to a decrease in both the number and size of DCGs and impairs DCG trafficking of other regulated hormones. Expression of SgII fusion proteins in a secretory-deficient PC12 variant rescues a regulated secretory pathway. SgII-containing dense core vesicles share morphological and physical properties with bona fide DCGs, are competent for regulated exocytosis, and maintain an acidic luminal pH through the V-type H+-translocating ATPase. The granulogenic activity of SgII requires a pH gradient along this secretory pathway. We conclude that SgII is a critical factor for the regulation of DCG biogenesis in neuroendocrine cells, mediating the formation of functional DCGs via its pH-dependent aggregation at the trans-Golgi network. PMID:20061385

Pro-hormone secretogranin II regulates dense core secretory granule biogenesis in catecholaminergic cells.

PubMed

Courel, Maïté; Soler-Jover, Alex; Rodriguez-Flores, Juan L; Mahata, Sushil K; Elias, Salah; Montero-Hadjadje, Maïté; Anouar, Youssef; Giuly, Richard J; O'Connor, Daniel T; Taupenot, Laurent

2010-03-26

Processes underlying the formation of dense core secretory granules (DCGs) of neuroendocrine cells are poorly understood. Here, we present evidence that DCG biogenesis is dependent on the secretory protein secretogranin (Sg) II, a member of the granin family of pro-hormone cargo of DCGs in neuroendocrine cells. Depletion of SgII expression in PC12 cells leads to a decrease in both the number and size of DCGs and impairs DCG trafficking of other regulated hormones. Expression of SgII fusion proteins in a secretory-deficient PC12 variant rescues a regulated secretory pathway. SgII-containing dense core vesicles share morphological and physical properties with bona fide DCGs, are competent for regulated exocytosis, and maintain an acidic luminal pH through the V-type H(+)-translocating ATPase. The granulogenic activity of SgII requires a pH gradient along this secretory pathway. We conclude that SgII is a critical factor for the regulation of DCG biogenesis in neuroendocrine cells, mediating the formation of functional DCGs via its pH-dependent aggregation at the trans-Golgi network.

Biosorption of Nickel from Industrial Wastewater using Zygnema sp.

NASA Astrophysics Data System (ADS)

Sivaprakash, Kanchana; Blessi T. L., Adlin; Madhavan, Jeyanthi

2015-12-01

Contamination of water sources with heavy metals is a very important pollution problem in the current scenario. Biosorption is an effective method for the removal of heavy metal ions from wastewaters. In this study, the removal of Nickel(II) ions from electroplating industrial wastewater using biosorbent prepared from fresh water algal biomass Zygnema was investigated under batch mode. The sorption efficiency of nickel on Zygnema sp. was evaluated as a function of time, pH and sorbent dosage. The Nickel(II) uptake was dependent on initial pH with pH 3 being the optimum value. For 100 mg/L initial Nickel(II) concentration, sorption equilibrium was attained at a contact time of 100 min. The sorbent dosage affected the biosorption efficiency and maximum removal of 76.4 % was obtained at a dosage of 7.5 g/L. From the performance studies, algal biosorbent Zygnema is found to be a valuable material for the removal of Nickel from industrial wastewater and a better substitute for the conventional adsorbents.

Active-Site Environment of Copper-Bound Human Amylin Relevant to Type 2 Diabetes.

PubMed

Seal, Manas; Dey, Somdatta Ghosh

2018-01-02

Type 2 diabetes mellitus (T2Dm) is characterized by reduced β cell mass and amyloid deposits of human islet amyloid polypeptide (hIAPP) or amylin, a 37 amino acid containing peptide around pancreatic β cells. The interaction of copper (Cu) with amylin and its mutants has been studied in detail using absorption, circular dichroism, electron paramagnetic resonance spectroscopy, and cyclic voltammetry. Cu binds amylin in a 1:1 ratio, and the binding domain lies within the first 19 amino acid residues of the peptide. Depending on the pH of the medium, Cu-amylin shows the formation of five pH-dependent components (component IV at pH 4.0, component III at pH 5.0, component II at pH 6.0, component I at pH 8.0, and another higher pH component above pH 9.0). The terminal amine, His18, and amidates are established as key residues in the peptide that coordinate the Cu center. The physiologically relevant components I and II can generate H 2 O 2 , which can possibly account for the enhanced toxicity of amylin in the presence of Cu, causing damage of the β cells of the pancreas via oxidative stress.

The effect of biogenic Fe(II) on the stability and sorption of Co(II)EDTA 2- to goethite and a subsurface sediment

NASA Astrophysics Data System (ADS)

Zachara, John M.; Smith, Steven C.; Fredrickson, James K.

2000-04-01

Laboratory experiments were conducted with suspensions of goethite (α-FeOOH) and a subsurface sediment to assess the influence of bacterial iron reduction on the fate of Co(II)EDTA 2-, a representative metal-ligand complex of intermediate stability (log K Co(II)EDTA = 17.97). The goethite was synthetic (ca. 55 m 2/g) and the sediment was a Pleistocene age, Fe(III) oxide-containing material from the Atlantic coastal plain (Milford). Shewanella alga strain BrY, a dissimilatory iron reducing bacterium (DIRB), was used to promote Fe(III) oxide reduction. Sorption isotherms and pH adsorption edges were measured for Co 2+, Fe 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- on the two sorbents in 0.001 mol/L Ca(ClO 4) 2 to aid in experiment interpretation. Anoxic suspensions of the sorbents in PIPES buffer at pH 6.5-7.0 were spiked with Co(II)EDTA 2- (10 -5 mol/L, 60Co and 14EDTA labeled), inoculated with BrY (1-6 × 10 8 organisms/mL), and the headspace filled with a N 2/H 2 gas mix. The experiments were conducted under non-growth conditions. The medium did not contain PO 43- (with one exception), trace elements, or vitamins. The tubes were incubated under anoxic conditions at 25°C for time periods in excess of 100 d. Replicate tubes were sacrificed and analyzed at desired time periods for pH, Fe(II) TOT, Fe (aq)2+, 60Co, and 14EDTA. Abiotic analogue experiments were conducted where Fe (aq)2+ was added in increasing concentration to Co(II)EDTA 2-/mineral suspensions to simulate the influence of bacterial Fe(II) evolution. The DIRB generated Fe(II) from both goethite and the Milford sediment that was strongly sorbed by mineral surfaces. Aqueous Fe 2+ increased during the experiment as surfaces became saturated; Fe (aq)2+ induced the dissociation of Co(II)EDTA 2- into a mixture of Co 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- (log K Fe(II)EDTA = 15.98). The extent of dissociation of Co(II)EDTA 2- was greater in the subsurface sediment because it sorbed Fe(II) less strongly than did goethite. The post dissociation sorption behavior of Co 2+ was dependent on pH and the intrinsic sorptivity of the solid phases. Dissociation generally lead to an increase in the sorption (e.g., K d) of Co 2+ relative to EDTA 4- (form unspecified). Sorbed biogenic Fe(II) competed with free Co (aq)2+and reduced its sorption relative to unreduced material. It is concluded that cationic radionuclides such as 60Co or 239/240Pu, which may be mobilized from disposed wastes by complexation with EDTA 4-, may become immobilized in groundwater zones where dissimilatory bacterial iron reduction is operative.

Extraction of trace amounts of mercury with sodium dodecyle sulphate-coated magnetite nanoparticles and its determination by flow injection inductively coupled plasma-optical emission spectrometry.

PubMed

Faraji, Mohammad; Yamini, Yadollah; Rezaee, Mohammad

2010-05-15

A new method for solid-phase extraction and preconcentration of trace amounts Hg(II) from environmental samples was developed by using sodium dodecyle sulphate-coated magnetite nanoparticles (SDS-coated Fe(3)O(4) NPs) as a new extractant. The procedure is based on the adsorption of the analyte, as mercury-Michler's thioketone [Hg(2)(TMK)(4)](2+) complex on the negatively charged surface of the SDS-coated Fe(3)O(4) NPs and then elution of the preconcentrated mercury from the surface of the SDS-coated Fe(3)O(4) NPs prior to its determination by flow injection inductively coupled plasma-optical emission spectrometry. The effects of pH, TMK concentration, SDS and Fe(3)O(4) NPs amounts, eluent type, sample volume and interfering ions on the recovery of the analyte were investigated. Under optimized conditions, the calibration curve was linear in the range of 0.2-100ngmL(-1) with r(2)=0.9994 (n=8). The limit of detection for Hg(II) determination was 0.04ngmL(-1). Also, relative standard deviation (R.S.D.) for the determination of 2 and 50ngmL(-1) of Hg(II) was 5.2 and 4.7% (n=6), respectively. Due to the quantitative extraction of Hg(II) from 1000mL of the sample solution an enhancement factor as large as 1230-fold can be obtained. The proposed method has been validated using a certified reference materials, and also the method has been applied successfully for the determination of Hg(II) in aqueous samples.

Ultrasonically assisted solvothermal synthesis of novel Ni/Al layered double hydroxide for capturing of Cd(II) from contaminated water

NASA Astrophysics Data System (ADS)

Rahmanian, Omid; Maleki, Mohammad Hassan; Dinari, Mohammad

2017-11-01

A novel adsorbent of nickel aluminum layered double hydroxide (Ni/Al-LDH) was prepared through the precipitation of metal nitrates by ultrasonically assisted solvothermal method. The surface morphology, chemical structure and thermal properties of this compound were examined by X-ray diffraction (XRD), Fourier Transform Infrared (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) techniques. The XRD, TEM and FE-SEM results established that the synthesized LDH have a well-ordered layer structure with good crystalline nature. Then it was applied to remove excessive Cd(II) ions from water and the effects of contact time, pH and adsorbent dose were examined at initial Cd(II) concentration of 10 mg/L. Results show that the time required to reach equilibrium was fast (40 min) and working pH solution was neutral (pH 7). Langmuir and Freundlich model of adsorption isotherms were explored; the results show that the Freundlich model was better fitted than that Langmuir model. This results predicting a multilayer adsorption of Cd(II) on LDH. The equilibrium kinetic adsorption data were fixed to the pseudo-second order kinetic equation.

Strong copper(II) species in estuarine and sea waters investigated by a method with high detection window.

PubMed

Alberti, Giancarla; Biesuz, Raffaela; D'Agostino, Girolamo; Scarponi, Giuseppe; Pesavento, Maria

2007-02-15

The distribution of copper(II) in species of different stability in some estuarine and sea water samples (Adriatic Sea) was investigated by a method based on the sorption of the metal ion on a strongly sorbing resin, Chelex 100, whose sorbing properties have been previously characterized. From them, it is possible to predict very high values of detection windows at the considered conditions, for example side reaction coefficient as high as 10(10) at pH 7.5. Strong copper(II) species in equilibrium with Chelex 100 were detected, at concentration 2-20nM, with a reaction coefficient approximately 10(10.6) at pH 7.45 in sea water, strictly depending on the acidity. They represent 50-70% of the total metal ion and are the strongest copper(II) complexes found in sea water. Weak complexes too were detected in all the samples, with reaction coefficient lower than ca. 10(9) at the same pH. The method applied, named resin titration (RT), was described in a previous investigation, and is here modified in order to be carried out on oceanographic boat during a cruise in the Adriatic Sea.

Anti-aggregation-based spectrometric detection of Hg(II) at physiological pH using gold nanorods.

PubMed

Rajeshwari, A; Karthiga, D; Chandrasekaran, Natarajan; Mukherjee, Amitava

2016-10-01

An efficient detection method for Hg (II) ions at physiological pH (pH7.4) was developed using tween 20-modified gold nanorods (NRs) in the presence of dithiothreitol (DTT). Thiol groups (-SH) at the end of DTT have a higher affinity towards gold atoms, and they can covalently interact with gold NRs and leads to their aggregation. The addition of Hg(II) ions prevents the aggregation of gold NRs due to the covalent bond formation between the -SH group of DTT and Hg(II) ions in the buffer system. The changes in the longitudinal surface plasmon resonance peak of gold NRs were characterized using a UV-visible spectrophotometer. The absorption intensity peak of gold NRs at 679nm was observed to reduce after interaction with DTT, and the absorption intensity was noted to increase by increasing the concentration of Hg(II) ions. The TEM analysis confirms the morphological changes of gold NRs before and after addition of Hg(II) ions in the presence of DTT. Further, the aggregation and disaggregation of gold NRs were confirmed by particle size and zeta potential analysis. The developed method shows an excellent linearity (y=0.001x+0.794) for the graph plotted between the absorption ratio and Hg(II) concentration (1 to 100pM) under the optimized conditions. The limit of detection was noted to be 0.42pM in the buffer system. The developed method was tested in simulated body fluid, and it was found to have a good recovery rate. Copyright © 2016 Elsevier B.V. All rights reserved.

Isolation of Alkaline and Neutral Proteases from Aspergillus flavus var. columnaris, a Soy Sauce Koji Mold

PubMed Central

Impoolsup, Attawut; Bhumiratana, Amaret; Flegel, Timothy W.

1981-01-01

Two different extracellular proteases, protease I (P-I), an alkaline protease, and protease II (P-II) a neutral protease, from Aspergillus flavus var. columnaris were partially purified by using (NH4)2SO4 precipitation, diethylaminoethyl-Sephadex A-50 chromatography, carboxymethylcellulose CM-52 chromatography, and Sephadex G-100 gel filtration. The degree of purity was followed using polyacrylamide gel electrophoresis. The activity of P-I was completely inhibited by 0.1 mM phenylmethylsulfonyl fluoride, and that of P-II was completely inhibited by 1 mM ethylenediaminetetraacetate. By using these inhibitors with extracts of wheat bran koji, the proportions of total activity that could be assigned to P-I and P-II were 80 and 20%, respectively. This compared favorably with activities estimated by using polyacrylamide gel electrophoresis slices (82 and 18%, respectively). Extracts from factory-run soybean koji gave comparable results. Both enzymes demonstrated maximum activity at 50 to 55°C and only small changes in activity between pH 6 and 11. For P-I, activity was somewhat higher from pH 8.0 to 11.0, whereas for P-II it was somewhat higher from pH 6 to 9. In the presence of 18% NaCl, the activities of both P-I and P-II dropped by approximately 90 and 85%, respectively. P-I was inferred to possess aminopeptidase activity since it could hydrolyze l-leucyl-p-nitroanilide hydrochloride. P-II was devoid of such activity. The ramifications of the results for factory-produced soy sauce koji are discussed. Images PMID:16345858

Speciation study in the sulfamethoxazole-copper-pH-soil system: implications for retention prediction.

PubMed

Morel, Marie-Christine; Spadini, Lorenzo; Brimo, Khaled; Martins, Jean M F

2014-05-15

Sulfamethoxazole (SMX) is a persistent sulfonamide antibiotic drug used in the veterinary and human medical sectors and is widely detected in natural waters. To better understand the reactive transport of this antibiotic in soil, the speciation of the SMX-Cu(II)-H(+) system in solution and the combined sorption of these components in a natural vineyard soil were investigated by acid-base titrimetry and infrared spectroscopy. Cu(II) is considered to represent a strongly complexing trace element cation (such as Cd(2+), Zn(2+), Pb(2+), Ni(2+), etc.) in comparison to more prevalent but more weakly binding cations (such as Ca(2+) and Mg(2+)). Titrimetric studies showed that, relative to other antibiotics, such as tetracycline, SMX is a weak copper chelating agent and a weak soil sorbent at the soil pH (pH6). However, the sorption of SMX in soil increases strongly (by a factor of 6) in the presence of copper. This finding strongly supports the hypothetical formation of ternary SMX-Cu-soil complexes, especially considering that copper is dominantly sorbed in a state at pH6. The data were successfully modelled with PhreeqC assuming the existence of binary and ternary surface complexes in equilibrium with aqueous Cu, SMX and Cu-SMX complexes. It is thought that other strongly complexing cations present on the surface of reactive organic and mineral soil phases, such as Cd(II), Ni(II), Zn(II), Pb(II), Fe(II/III), Mn(II/IV) and Al(III), affect the solid/solution partitioning of SMX. This study thus suggests that surface-adsorbed cations significantly increase the sorption of SMX. Copyright © 2014 Elsevier B.V. All rights reserved.

Optimization study for Pb(II) and COD sequestration by consortium of sulphate-reducing bacteria

NASA Astrophysics Data System (ADS)

Verma, Anamika; Bishnoi, Narsi R.; Gupta, Asha

2017-09-01

In this study, initial minimum inhibitory concentration (MIC) of Pb(II) ions was analysed to check optimum concentration of Pb(II) ions at which the growth of sulphate-reducing consortium (SRC) was found to be maximum. 80 ppm of Pb(II) ions was investigated as minimum inhibitory concentration for SRC. Influence of electron donors such as lactose, sucrose, glucose and sodium lactate was examined to investigate best carbon source for growth and activity of sulphate-reducing bacteria. Sodium lactate was found to be the prime carbon source for SRC. Later optimization of various parameters was executed using Box-Behnken design model of response surface methodology to explore the effectiveness of three independent operating variables, namely, pH (5.0-9.0), temperature (32-42 °C) and time (5.0-9.0 days), on dependent variables, i.e. protein content, precipitation of Pb(II) ions, and removal of COD by SRC biomass. Maximum removal of COD and Pb(II) was observed to be 91 and 98 %, respectively, at pH 7.0 and temperature 37 °C and incubation time 7 days. According to response surface analysis and analysis of variance, the experimental data were perfectly fitted to the quadratic model, and the interactive influence of pH, temperature and time on Pb(II) and COD removal was highly significant. A high regression coefficient between the variables and response ( r 2 = 0.9974) corroborate eminent evaluation of experimental data by second-order polynomial regression model. SEM and Fourier transform infrared analysis was performed to investigate morphology of PbS precipitates, sorption mechanism and involved functional groups in metal-free and metal-loaded biomass of SRC for Pb(II) binding.

Importance of allochthonous and autochthonous dissolved organic matter in Fe(II) oxidation: A case study in Shizugawa Bay watershed, Japan.

PubMed

Lee, Ying Ping; Fujii, Manabu; Kikuchi, Tetsuro; Natsuike, Masafumi; Ito, Hiroaki; Watanabe, Toru; Yoshimura, Chihiro

2017-08-01

Ferrous iron (Fe[II]) oxidation by dissolved oxygen was investigated in the Shizugawa Bay watershed with particular attention given to the effect of dissolved organic matter (DOM) properties on Fe(II) oxidation. To cover a wide spectrum of DOM composition, water samples were collected from various water sources including freshwater (e.g., river water and wastewater effluent) and coastal seawater. Measurement of nanomolar Fe(II) oxidation by using luminol chemiluminescence under dark, air-saturated conditions at 25 °C indicated that spatio-temporal variation of the second-order rate constant (6.7-74.5 M -1  s -1 ) was partially explained by the variation of the sample pH (7.5-8.6). However, at comparable pH values, the oxidation rates for freshwater were generally greater than those for coastal seawater. The substantial decline in oxidation rate constant after the removal of humic-type (allochthonous) DOM suggested that this hydrophobic DOM is a key factor that accelerates the Fe(II) oxidation in the freshwater samples. Observed lower oxidation rates for coastal seawater compared with freshwater and organic ligand-free seawater were likely associated with microbially derived autochthonous DOM, and the variation of Fe(II) oxidation at a fixed pH was best described by fluorescence index that represents the proportion of autochthonous and allochthonous DOM in natural waters. Consistently, Fe(II) oxidation was found to be slower in the presence of cellular exudates from phytoplankton. The present study highlighted the significant effect of DOM composition on the Fe(II) oxidation in inland and coastal waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of divalent metals to metal oxide nanoparicles: Competitive and temperature effects

NASA Astrophysics Data System (ADS)

Grover, Valerie Ann

The presence of metals in natural waters is becoming a critical environmental and public health concern. Emerging nanotechnology and the use of metal oxide nanoparticles has been identified as a potential remediation technique in removing metals from water. However, practical applications are still being explored to determine how to apply their unique chemical and physical properties for full scale remediation projects. This thesis investigates the sorption properties of Cd(II), Cu(II), Pb(II) and Zn(II) to hematite (alpha-Fe2O3) and titanium dioxide (TiO2) nanoparticles in single- and binary-adsorbate systems. Competitive sorption was evaluated in 1L batch binary-metal systems with 0.05g/L nano-hematite at pH 8.0 and pH 6.0. Results indicate that the presence of a secondary metal can affect the sorption process depending upon the molar ratios, such as increased or reduced adsorption. Thermodynamic properties were also studied in order to better understand the effects of temperature on equilibrium and kinetic adsorption capabilities. Understanding the thermodynamic properties can also give insight to determine if the sorption process is a physical, chemical or ion exchange reaction. Thermodynamic parameters such as enthalpy (DeltaH), entropy (DeltaS), and Gibbs free energy (DeltaG) were evaluated as a function of temperature, pH, and metal concentration. Results indicate that Pb(II) and Cu(II) adsorption to nano-hematite was an endothermic and physical adsorption process, while Zn(II) and Cd(II) adsorption was dependent upon the adsorbed concentration evaluated. However, metal adsorptions to nano-titanium dioxide were all found to be endothermic and physical adsorption processes; the spontaneity of metal adsorption was temperature dependent for both metal oxide nanoparticles.

Chemical catalysis of nitrate reduction by iron (II)

NASA Astrophysics Data System (ADS)

Ottley, C. J.; Davison, W.; Edmunds, W. M.

1997-05-01

Experiments have been conducted to investigate the chemical reduction of nitrate under conditions relevant to the often low organic carbon environment of groundwaters. At pH 8 and 20 ± 2°C, in the presence of Cu(II), NO 3- was chemically reduced by Fe(II) to NH 4+ with an average stoichiometric liberation of 8 protons. The rate of the reaction systematically increased with pH in the range pH 7-8.5. The half-life for nitrate reduction, t 1/2, was inversely related to the total molar copper concentration, [Cu T], by the equation log t 1/2 = -1.35 log [Cu T] -2.616, for all measured values of t 1/2 from 23 min to 15 days. At the Cu(II) concentrations used of 7 × 10 -6 -10 -3 M, Cu was present mainly as a solid phase, either adsorbed to the surfaces of precipitated iron oxides or as a saturated solid. It is this solid phase copper rather than CU 2+ in solution which is catalytically active. Neither magnetite, which was formed as a product of the reaction, nor freshly prepared lepidocrocite catalysed the reaction, but goethite did. Although traces of oxygen accelerated the reaction, at higher partial pressures (>0.01 atm) the reduction of nitrate was inhibited, probably due to competition between NO 3- and O 2 for Fe(II). Appreciable catalytic effects were also observed for solid phase forms of Ag(I), Cd(H), Ni(H), Hg(II), and Pb(II). Mn(II) enhanced the rate slightly, and there was evidence for slow abiotic reduction in the absence of any added metal catalysts. These results suggest that the chemical reduction of nitrate at catalytic concentrations and temperatures appropriate to groundwater conditions is feasible on a timescale of months to years.

Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems

PubMed Central

Lewis, Scott; Lynch, Andrew; Bachas, Leonidas; Hampson, Steve; Ormsbee, Lindell; Bhattacharyya, Dibakar

2009-01-01

Abstract The primary objective of this research was to model and understand the chelate-modified Fenton reaction for the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. The addition of a nontoxic chelate (L), such as citrate or gluconic acid, allows for operation at near-neutral pH and controlled release of Fe(II)/Fe(III). For the standard Fenton reaction at low pH in two-phase systems, an optimum H2O2:Fe(II) molar ratio was found to be between 1:1 and 2:1. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinated TCE in both the aqueous and organic phases at pH 6–7 using low H2O2:Fe(II) molar ratios (4:1 to 8:1). Increasing the L:Fe ratio was found to decrease the rate of H2O2 degradation in both Fe(II) and Fe(III) systems at near-neutral pH. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using literature-reported hydroxyl radical reaction kinetics and mass transfer relationships. Additional aspects of this work include the reusability of the Fe–citrate complex under repeated H2O2 injections in real water systems as well as packed column studies for simulated groundwater injection. PMID:20418966

Spectrophotometric determination of flucloxacillin in pharmaceutical preparations using some nitrophenols as a complexing agent

NASA Astrophysics Data System (ADS)

El-Mammli, Magda Y.

2003-03-01

Some nitrophenols are proposed as chromogenic reagents for the spectrophotometric determination of flucloxacillin. The reagent forms a greenish yellow 1:1 complex with flucloxacillin at pH 9.0. This complex is stable for at least 3.0 h after its formation. The greenish yellow charge transfer complex species has an absorption maximum at 446, 435, 442, 473 and 439 nm for p-nitrophenol (I), 2,4-dinitrophenol (II), 3,5-dinitrosalycilic acid (III), picramic acid (IV) and picric acid (V), respectively, with a molar absorptivity between 1.43×10 4 and 2.59×10 4 l mol -1 cm -1. Beer's low is valid over the concentration range 2.0-40 μg ml -1 of flucloxacillin. The detection and quantitation limits as well as relative standard deviation were also calculated. The reagents have been successfully used for the spectrophotometric determination of flucloxacillin in pure form and in pharmaceutical preparations.

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

PubMed

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

2013-01-01

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

Efficient adsorption of Hg (II) ions in water by activated carbon modified with melamine

NASA Astrophysics Data System (ADS)

Qin, Hangdao; Meng, Jingling; Chen, Jing

2018-04-01

Removal of Hg (II) ions from industrial wastewater is important for the water treatment, and adsorption is an efficient treatment process. Activated carbon (AC) was modified with melamine, which introduced nitrogen-containing functional groups onto AC surface. Original AC and melamine modified activated carbon (ACM) were characterized by elemental analysis, N2 adsorption-desorption, determination of the pH of the point of zero charge (pHpzc) and X-ray photoelectron spectroscopy (XPS) and their performance in the adsorption of Hg(II) ions was investigated. Langmuir model fitted the experimental data of equilibrium isotherms well. ACM showed the higher Hg (II) ions adsorption capacity, increasing more than more than 1.8 times compared to the original one. Moreover, ACM showed a wider pH range for the maximum adsorption than the parent AC.

The effects of Wechsler Intelligence Scale for Children-Fourth Edition cognitive abilities on math achievement.

PubMed

Parkin, Jason R; Beaujean, A Alexander

2012-02-01

This study used structural equation modeling to examine the effect of Stratum III (i.e., general intelligence) and Stratum II (i.e., Comprehension-Knowledge, Fluid Reasoning, Short-Term Memory, Processing Speed, and Visual Processing) factors of the Cattell-Horn-Carroll (CHC) cognitive abilities, as operationalized by the Wechsler Intelligence Scale for Children, Fourth Edition (WISC-IV; Wechsler, 2003a) subtests, on Quantitative Knowledge, as operationalized by the Wechsler Individual Achievement Test, Second Edition (WIAT-II; Wechsler, 2002) subtests. Participants came from the WISC-IV/WIAT-II linking sample (n=550). We compared models that predicted Quantitative Knowledge using only Stratum III factors, only Stratum II factors, and both Stratum III and Stratum II factors. Results indicated that the model with only the Stratum III factor predicting Quantitative Knowledge best fit the data. Copyright © 2011 Society for the Study of School Psychology. Published by Elsevier Ltd. All rights reserved.

Analysis of in vitro interactions of protein tyrosine phosphatase 1B with insulin receptors.

PubMed

Wang, X Y; Bergdahl, K; Heijbel, A; Liljebris, C; Bleasdale, J E

2001-02-28

One strategy to treat the insulin resistance that is central to type II diabetes mellitus may be to maintain insulin receptors (IR) in the active (tyrosine phosphorylated) form. Because protein tyrosine phosphatase 1B (PTP1B) binds and subsequently dephosphorylates IR, inhibitors of PTP1B-IR binding are potential insulin 'sensitizers.' A Scintillation Proximity Assay (SPA) was developed to characterize and quantitate PTP1B-IR binding. Human IR were solubilized and captured on wheat germ agglutinin (WGA)-coated SPA beads. Subsequent binding of human, catalytically inactive [35S] PTP1B Cys(215)/Ser (PTP1B(C215S)) to the lectin-anchored IR results in scintillation from the SPA beads that can be quantitated. Binding of PTP1B to IR was pH- and divalent cation-sensitive. Ca(2+) and Mn(2+), but not Mg(2+), dramatically attenuated the loss of PTP1B-IR binding observed when pH was raised from 6.2 to 7.8. PTP1B binding to IR from insulin-stimulated cells was much greater than to IR from unstimulated cells and was inhibited by either an antiphosphotyrosine antibody or treatment of IR with alkaline phosphatase, suggesting that tyrosine phosphorylation of IR is required for PTP1B binding. Phosphopeptides modeled after various IR phosphotyrosine domains each only partially inhibited PTP1B-IR binding, indicating that multiple domains of IR are likely involved in binding PTP1B. However, competitive displacement of [35S]PTP1B(C215S) by PTP1B(C215S) fitted best to a single binding site with a K(d) in the range 100-1000 nM, depending upon pH and divalent cations. PNU-200898, a potent and selective inhibitor of PTP1B whose orientation in the active site of PTP1B has been solved, competitively inhibited catalysis and PTP1B-IR binding with equal potency. The results of this novel assay for PTP1B-IR binding suggest that PTP1B binds preferentially to tyrosine phosphorylated IR through its active site and that binding may be susceptible to therapeutic disruption by small molecules.

Plasma proteomics for biomarker discovery: a study in blue.

PubMed

Di Girolamo, Francesco; Righetti, Pier Giorgio

2011-12-01

The performance of Cibacron Blue dye (HiTrapBlue or Affigel Blue) in depleting albumin from plasma, as a pre-treatment for biomarker searching in the low-abundance proteome, is here assessed. It is shown that (i) co-depletion of non-albumin species is an ever-present hazard; (ii) the only proper eluant able to release quantitatively the proteins bound to the dye is boiling 4% SDS-25 mM DTT, an ion shock (2 M NaCl) being quite ineffective in releasing the low-abundance species tightly bound to the dye moiety; (iii) the mechanism of dye-protein interaction, after an initial ion-ion docking, is a robust hydrophobic interaction, which progressively augments at lower and lower pH values; (iv) at pH 2.2 in the presence of 0.1% TFA, the blue resin behaves, for all practical purposes, just as a reverse-phase chromatography column, since all residual proteins present in plasma are completely harvested. However Cibacron Blue technology should not necessarily be discarded: As long as also the plasma fraction adsorbed is properly released and analyzed, together with the flow through, one should be able to perform a viable analysis of the low-abundance proteome. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Full-scale simulation of seawater reverse osmosis desalination processes for boron removal: Effect of membrane fouling.

PubMed

Park, Pyung-Kyu; Lee, Sangho; Cho, Jae-Seok; Kim, Jae-Hong

2012-08-01

The objective of this study is to further develop previously reported mechanistic predictive model that simulates boron removal in full-scale seawater reverse osmosis (RO) desalination processes to take into account the effect of membrane fouling. Decrease of boron removal and reduction in water production rate by membrane fouling due to enhanced concentration polarization were simulated as a decrease in solute mass transfer coefficient in boundary layer on membrane surface. Various design and operating options under fouling condition were examined including single- versus double-pass configurations, different number of RO elements per vessel, use of RO membranes with enhanced boron rejection, and pH adjustment. These options were quantitatively compared by normalizing the performance of the system in terms of E(min), the minimum energy costs per product water. Simulation results suggested that most viable options to enhance boron rejection among those tested in this study include: i) minimizing fouling, ii) exchanging the existing SWRO elements to boron-specific ones, and iii) increasing pH in the second pass. The model developed in this study is expected to help design and optimization of the RO processes to achieve the target boron removal at target water recovery under realistic conditions where membrane fouling occurs during operation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Influence of edaphic and management factors on the diversity and abundance of ammonia-oxidizing thaumarchaeota and bacteria in soils of bioenergy crop cultivars.

PubMed

Bertagnolli, Anthony D; Meinhardt, Kelley A; Pannu, Manmeet; Brown, Sally; Strand, Stuart; Fransen, Steven C; Stahl, David A

2015-04-01

Ammonia-oxidizing thaumarcheota (AOA) and ammonia-oxidizing bacteria (AOB) differentially influence soil and atmospheric chemistry, but soil properties that control their distributions are poorly understood. In this study, the ammonia monooxygenase gene (amoA) was used to identify and quantify presumptive AOA and AOB and relate their distributions to soil properties in two experimental fields planted with different varieties of switchgrass (Panicum virgatum), a potential bioenergy feedstock. Differences in ammonia oxidizer diversity were associated primarily with soil properties of the two field sites, with pH displaying significant correlations with both AOA and AOB population structure. Percent nitrogen (%N), carbon to nitrogen ratios (C : N), and pH were also correlated with shifts nitrifier population structure. Nitrosotalea-like and Nitrosospira cluster II populations were more highly represented in acidic soils, whereas populations affiliated with Nitrososphaera and Nitrosospira cluster 3A.1 were relatively more abundant in alkaline soils. AOA were the dominant functional group in all plots based on quantitative polymerase chain reaction and high-throughput sequencing analyses. These data suggest that AOA contribute significantly to nitrification rates in carbon and nitrogen rich soils influenced by perennial grasses. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

O2-dependent Aliphatic Carbon-carbon Bond Cleavage Reactivity in a Ni(II) Enolate Complex Having a Hydrogen Bond Donor Microenvironment; Comparison with a Hydrophobic Analog

PubMed Central

Grubel, Katarzyna; Fuller, Amy L.; Chambers, Bonnie M.; Arif, Atta M.; Berreau, Lisa M.

2010-01-01

A mononuclear Ni(II) complex having an acireductone type ligand, and supported by the bnpapa (N,N-bis((6-neopentylamino-2-pyridyl)methyl-N-((2-pyridyl)methyl)amine ligand, [(bnpapa)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (14), has been prepared and characterized by elemental analysis, 1H NMR, FTIR, and UV-vis. To gain insight into the 1H NMR features of 14, the air stable analog complexes [(bnpapa)Ni(CH3C(O)CHC(O)CH3)]ClO4 (16) and [(bnpapa)Ni(ONHC(O)CH3)]ClO4 (17) were prepared and characterized by X-ray crystallography, 1H NMR, FTIR, UV-vis, mass spectrometry, and solution conductivity measurements. Compounds 16 and 17 are 1:1 electrolyte species in CH3CN. 1H and 2H NMR studies of 14, 16, and 17 and deuterated analogs revealed that the complexes having six-membered chelate rings for the exogenous ligand (14 and 16) do not have a plane of symmetry within the solvated cation and thus exhibit more complicated 1H NMR spectra. Compound 17, as well as other simple Ni(II) complexes of the bnpapa ligand (e.g. [(bnpapa)Ni(ClO4)(CH3CN)]ClO4 (18) and [(bnpapaNi)2(μ-Cl)2](ClO4)2 (19)), exhibit 1H NMR spectra consistent with the presence of a plane of symmetry within the cation. Treatment of [(bnpapa)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (14) with O2 results in aliphatic carbon-carbon bond cleavage within the acireductone-type ligand and the formation of [(bnpapa)Ni(O2CPh)]ClO4 (9), benzoic acid, benzil, and CO. Use of 18O2 in the reaction gives high levels of incorporation (>80%) of one labeled oxygen atom into 9 and benzoic acid. The product mixture and level of 18O incorporation in this reaction is different than that exhibited by the analog supported the hydrophobic 6-Ph2TPA ligand, [(6-Ph2TPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO4 (2). We propose that this difference is due to variations in the reactivity of bnpapa- and 6-Ph2TPA-ligated Ni(II) complexes with triketone and/or peroxide species produced in the reaction pathway. PMID:20039645

Fine-particle water and pH in the southeastern United States

EPA Science Inventory

Particle water and pH are predicted using meteorological observations (relative humidity (RH), temperature (T)), gas/particle composition, and thermodynamic modeling (ISORROPIA-II). A comprehensive uncertainty analysis is included, and the model is validated. We investigate mass ...

Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity.

PubMed

Semin, B К; Davletshina, L N; Seibert, M; Rubin, A B

2018-01-01

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2 Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH5.7) than at neutral pH (3Mn/RC are extracted at pH6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H 2 Q action, since H 2 Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H 2 Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O 2 at a low rate in the presence of exogenous Ca 2+ (at about 27% of the rate of O 2 evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O 2 by the 3Mn/1Fe cluster or apparent O 2 evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes) is discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

pH & Rate of Enzymatic Reactions.

ERIC Educational Resources Information Center

Clariana, Roy B.

1991-01-01

A quantitative and inexpensive way to measure the rate of enzymatic reaction is provided. The effects of different pH levels on the reaction rate of an enzyme from yeast are investigated and the results graphed. Background information, a list of needed materials, directions for preparing solutions, procedure, and results and discussion are…

Synthesis and Characterization of a Series of Structurally and Electronically Diverse Fe(II) Complexes Featuring a Family of Triphenylamido-Amine Ligands

PubMed Central

Paraskevopoulou, Patrina; Ai, Lin; Wang, Qiuwen; Pinnapareddy, Devender; Acharyya, Rama; Dinda, Rupam; Das, Purak; Çelenligil-Çetin, Remle; Floros, Georgios; Sanakis, Yiannis; Choudhury, Amitava; Rath, Nigam P.; Stavropoulos, Pericles

2009-01-01

A family of triphenylamido-amine ligands of the general stoichiometry LxH3 = [R-NH-(2-C6H4)]3N (R = 4-t-BuPh (L1H3), 3,5-t-Bu2Ph (L2H3), 3,5-(CF3)2Ph (L3H3), CO-t-Bu (L4H3) 3,5-Cl2Ph (L5H3), COPh (L6H3), CO-i-Pr (L7H3), COCF3 (L8H3), i-Pr (L9H3)) has been synthesized and characterized, featuring a rigid triphenylamido-amine scaffold and an array of stereoelectronically diverse aryl, acyl and alkyl substituents (R). These ligands are deprotonated by potassium hydride in THF or DMA and reacted with anhydrous FeCl2 to afford a series of ferrous complexes, exhibiting stoichiometric variation and structural complexity. The prevalent [(Lx)Fe(II)–solv]− structures (Lx = L1, L2, L3, L5, solv = THF; Lx = L8, solv = DMA; Lx = L6, L8, solv = MeCN), reveal a distorted trigonal bipyramidal geometry, featuring ligand-derived [N3,amidoNamine] coordination and solvent attachment trans to the Namine atom. Specifically for [(L8)Fe(II)–DMA]−, an Namido residue is coordinated as the corresponding Nimino moiety (Fe–N(Ar)=C(CF3)–O−). In contrast, compounds [(L4)Fe(II)] −, [(L6)2Fe(II)2]2−, [K(L7)2Fe(II)2]22− and [K(L9)Fe]2 are all solvent-free in their coordination sphere and exhibit four-coordinate geometries of significant diversity. In particular, [(L4)Fe(II)]− demonstrates coordination of one amidato residue via the O-atom end (Fe–O–C(t-Bu)=N(Ar)). Furthermore, [(L6)2Fe(II)2]2− and [K(L7)2Fe(II)2]22− are similar structures exhibiting bridging amidato residues (Fe–N(Ar)–C(R)=O–Fe) in dimeric structural units. Finally the structure of [K(L9)Fe]2 is the only example featuring a minimal [N3,amidoNamine] coordination sphere around each Fe(II) site. All compounds have been characterized by a variety of physicochemical techniques, including Mössbauer spectroscopy and electrochemistry, to reveal electronic attributes that are responsible for a range of Fe(II)/Fe(III) redox potentials exceeding 1.0 V. PMID:19950956

Ferrate(VI) oxidation of zinc-cyanide complex.

PubMed

Yngard, Ria; Damrongsiri, Seelawut; Osathaphan, Khemarath; Sharma, Virender K

2007-10-01

Zinc-cyanide complexes are found in gold mining effluents and in metal finishing rinse water. The effect of Zn(II) on the oxidation of cyanide by ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was thus investigated by studying the kinetics of the reaction of Fe(VI) with cyanide present in a potassium salt of a zinc cyanide complex (K(2)Zn(CN)(4)) and in a mixture of Zn(II) and cyanide solutions as a function of pH (9.0-11.0). The rate-law for the oxidation of Zn(CN)(4)(2-) by Fe(VI) was found to be -d[Fe(VI)]/dt=k[Fe(VI)][Zn(CN)(4)(2-)](0.5). The rate constant, k, decreased with an increase in pH. The effect of temperature (15-45 degrees C) on the oxidation was studied at pH 9.0, which gave an activation energy of 45.7+/-1.5kJmol(-1). The cyanide oxidation rate decreased in the presence of the Zn(II) ions. However, Zn(II) ions had no effect on the cyanide removal efficiency by Fe(VI) and the stoichiometry of Fe(VI) to cyanide was approximately 1:1; similar to the stoichiometry in absence of Zn(II) ions. The destruction of cyanide by Fe(VI) resulted in cyanate. The experiments on removal of cyanide from rinse water using Fe(VI) demonstrated complete conversion of cyanide to cyanate.

Enamel demineralization and remineralization under plaque fluid-like conditions: a quantitative light-induced fluorescence study.

PubMed

Lippert, F; Butler, A; Lynch, R J M

2011-01-01

The present study investigated de- and remineralization in enamel lesions under plaque fluid (PF)-like conditions using quantitative light-induced fluorescence (QLF). Preformed lesions were exposed to partially saturated lactic acid solutions, varying in pH and fluoride concentration ([F]) based on a 5 × 3 factorial study design (0/0.1/0.5/1.5/4 ppm F; pH 4.9/5.2/5.5). Average fluorescence loss (ΔF) was monitored for 11 days. Subsequently, lesions were demineralized in a partially saturated acetic acid solution for two 24-hour periods. Data were analyzed using repeated measures analysis of covariance. Lesions exposed to PF at 4 ppm F and pH 5.5 showed not only the most remineralization (ΔΔF = 28.2 ± 14.0%) for all groups after 11 days, but also the most demineralization (ΔΔF = -19.3 ± 13.5%) after subsequent acetic acid exposure. Increased [F] resulted in more remineralization, regardless of pH. Higher pH values resulted in more remineralization. No remineralization was observed in lesions exposed to F-free solutions, regardless of pH. Remineralization was noticeable under the following conditions: pH 4.9 - [F] = 4 ppm, pH 5.2 - [F] ≥ 1.5 ppm, and pH 5.5 - [F] ≥ 0.5 ppm. Overall, [F] had a stronger effect on remineralization than pH. Subsequent demineralization showed that little protection was offered by PF-like solutions, and further demineralization compared with baseline was observed on lesions not remineralized initially. [F] had a stronger effect on net mineral change than pH. The present study has shown that QLF is a valuable tool in studying lesion de- and remineralization under PF-like conditions, where [F] was shown to be more important than pH. Copyright © 2011 S. Karger AG, Basel.

Interactions of Zn(II) Ions with Humic Acids Isolated from Various Type of Soils. Effect of pH, Zn Concentrations and Humic Acids Chemical Properties.

PubMed

Boguta, Patrycja; Sokołowska, Zofia

2016-01-01

The main aim of this study was the analysis of the interaction between humic acids (HAs) from different soils and Zn(II) ions at wide concentration ranges and at two different pHs, 5 and 7, by using fluorescence and FTIR spectroscopy, as well as potentiometric measurements. The presence of a few areas of HAs structures responsible for Zn(II) complexing was revealed. Complexation at α-sites (low humified structures of low-molecular weight and aromatic polycondensation) and β-sites (weakly humified structures) was stronger at pH 7 than 5. This trend was not observed for γ-sites (structures with linearly-condensed aromatic rings, unsaturated bonds and large molecular weight). The amount of metal complexed at pH5 and 7 by α and γ-structures increased with a decrease in humification and aromaticity of HAs, contrary to β-areas where complexation increased with increasing content of carboxylic groups. The stability of complexes was higher at pH 7 and was the highest for γ-structures. At pH 5, stability decreased with C/N increase for α-areas and -COOH content increase for β-sites; stability increased with humification decrease for γ-structures. The stability of complexes at α and β-areas at pH 7 decreased with a drop in HAs humification. FTIR spectra at pH 5 revealed that the most-humified HAs tended to cause bidentate bridging coordination, while in the case of the least-humified HAs, Zn caused bidentate bridging coordination at low Zn additions and bidentate chelation at the highest Zn concentrations. Low Zn doses at pH 7 caused formation of unidentate complexes while higher Zn doses caused bidentate bridging. Such processes were noticed for HAs characterized by high oxidation degree and high oxygen functional group content; where these were low, HAs displayed bidentate bridging or even bidentate chelation. To summarize, the above studies have showed significant impact of Zn concentration, pH and some properties of HAs on complexation reactions of humic acids with zinc.

Interactions of Zn(II) Ions with Humic Acids Isolated from Various Type of Soils. Effect of pH, Zn Concentrations and Humic Acids Chemical Properties

PubMed Central

Boguta, Patrycja; Sokołowska, Zofia

2016-01-01

The main aim of this study was the analysis of the interaction between humic acids (HAs) from different soils and Zn(II) ions at wide concentration ranges and at two different pHs, 5 and 7, by using fluorescence and FTIR spectroscopy, as well as potentiometric measurements. The presence of a few areas of HAs structures responsible for Zn(II) complexing was revealed. Complexation at α-sites (low humified structures of low-molecular weight and aromatic polycondensation) and β-sites (weakly humified structures) was stronger at pH 7 than 5. This trend was not observed for γ-sites (structures with linearly-condensed aromatic rings, unsaturated bonds and large molecular weight). The amount of metal complexed at pH5 and 7 by α and γ-structures increased with a decrease in humification and aromaticity of HAs, contrary to β-areas where complexation increased with increasing content of carboxylic groups. The stability of complexes was higher at pH 7 and was the highest for γ-structures. At pH 5, stability decreased with C/N increase for α-areas and -COOH content increase for β-sites; stability increased with humification decrease for γ-structures. The stability of complexes at α and β-areas at pH 7 decreased with a drop in HAs humification. FTIR spectra at pH 5 revealed that the most-humified HAs tended to cause bidentate bridging coordination, while in the case of the least-humified HAs, Zn caused bidentate bridging coordination at low Zn additions and bidentate chelation at the highest Zn concentrations. Low Zn doses at pH 7 caused formation of unidentate complexes while higher Zn doses caused bidentate bridging. Such processes were noticed for HAs characterized by high oxidation degree and high oxygen functional group content; where these were low, HAs displayed bidentate bridging or even bidentate chelation. To summarize, the above studies have showed significant impact of Zn concentration, pH and some properties of HAs on complexation reactions of humic acids with zinc. PMID:27077915

Sensing of biologically relevant d-metal ions using a Eu(III)-cyclen based luminescent displacement assay in aqueous pH 7.4 buffered solution.

PubMed

Kotova, Oxana; Comby, Steve; Gunnlaugsson, Thorfinnur

2011-06-28

1·Eu·BPS was developed as a luminescent lanthanide sensor for use in displacement assays for detection of d-metal ions by monitoring the changes in the europium emission, which was quenched for iron(II), with a detection limit of ∼10 pM (0.002 μg L(-1)) for Fe(II) in buffered pH 7.4 solution. This journal is © The Royal Society of Chemistry 2011

Reductive Dissolution of PuO2(am): The Effect of Fe(II) and Hydroquinone

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

Rai, Dhanpat; Gorby, Yuri A.; Fredrickson, Jim K.

2002-06-01

SYNOPIS-Reducing agents commonly present in geologic environments can increase solubility of PuO2(am), which is otherwise very insoluble, by many orders of magnitude through reduction of Pu(IV) to Pu(III). The reduction reactions involving Fe(II) and hydroquinone, hitherto unquantified under environmental pH values, were found to be relatively fast and controlled the extent of PuO2(am) dissolution: a decrease in redox potential (pe + pH) resulted in concomitant increase in PuO2(am) solubility.

The life story of hydrogen peroxide II: a periodic pH and thermochemical drive for the RNA world

PubMed Central

Ball, Rowena; Brindley, John

2015-01-01

It is now accepted that primordial non-cellular RNA communities must have been subject to a periodic drive in order to replicate and prosper. We have proposed the oxidation of thiosulfate by hydrogen peroxide as this drive. This reaction system behaves as (i) a thermochemical and (ii) a pH oscillator, and in this work, we unify (i) and (ii) for the first time. We report thermally self-consistent, dynamical simulations in which the system transitions smoothly from nearly isothermal pH to fully developed thermo-pH oscillatory regimes. We use this oscillator to drive simulated replication of a 39-bp RNA species. Production of replicated duplex under thermo-pH drive was significantly enhanced compared with that under purely thermochemical drive, effectively allowing longer strands to replicate. Longer strands are fitter, with more potential to evolve enzyme activity and resist degradation. We affirm that concern over the alleged toxicity of hydrogen peroxide to life is largely misplaced in the current context, we survey its occurrence in the solar system to motivate its inclusion as a biosignature in the search for life on other worlds and highlight that pH oscillations in a spatially extended, bounded system manifest as the fundamental driving force of life: a proton gradient. PMID:26202683

Effect of Humic Acid on the Removal of Chromium(VI) and the Production of Solids in Iron Electrocoagulation.

PubMed

Pan, Chao; Troyer, Lyndsay D; Liao, Peng; Catalano, Jeffrey G; Li, Wenlu; Giammar, Daniel E

2017-06-06

Iron-based electrocoagulation can be highly effective for Cr(VI) removal from water supplies. However, the presence of humic acid (HA) inhibited the rate of Cr(VI) removal in electrocoagulation, with the greatest decreases in Cr(VI) removal rate at higher pH. This inhibition was probably due to the formation of Fe(II) complexes with HA that are more rapidly oxidized than uncomplexed Fe(II) by dissolved oxygen, making less Fe(II) available for reduction of Cr(VI). Close association of Fe(III), Cr(III), and HA in the solid products formed during electrocoagulation influenced the fate of both Cr(III) and HA. At pH 8, the solid products were colloids (1-200 nm) with Cr(III) and HA concentrations in the filtered fraction being quite high, while at pH 6 these concentrations were low due to aggregation of small particles. X-ray diffraction and X-ray absorption fine structure spectroscopy indicated that the iron oxides produced were a mixture of lepidocrocite and ferrihydrite, with the proportion of ferrihydrite increasing in the presence of HA. Cr(VI) was completely reduced to Cr(III) in electrocoagulation, and the coordination environment of the Cr(III) in the solids was similar regardless of the humic acid loading, pH, and dissolved oxygen level.

Revisiting the pH Effect on Orthophosphate Control of Plumbosolvency

EPA Science Inventory

Although solubility models for Pb(II) have largely been successful for giving corrosion control treatment guidance for over 2 decades, very little systematic research has been done to precisely define plumbosolvency responses to changes in pH, carbonate and phosphate concentratio...

Applications of organo-silica nanocomposites for SPNE of Hg(II)

NASA Astrophysics Data System (ADS)

Kaur, Anupreet

2016-02-01

An analytical method using modified SiO2 nanoparticles as solid-phase extractant has been developed for the preconcentration of trace amounts of Hg(II) in different water samples. Conditions of the analysis such as preconcentration factor, effect of pH, sample volume, shaking time, elution conditions and effects of interfering ions for the recovery of analyte were investigated. The adsorption capacity of nanometer SiO2-APTMS was found to be 181.42 µmol g-1 at optimum pH and the detection limit (3σ) was 0.45 µg L-1. The extractant showed rapid kinetic sorption. The adsorption equilibrium of Hg(II) on nanometer SiO2-APTMS was achieved just in 15 min. Adsorbed Hg(II) was easily eluted with 4 mL of 2.0 M hydrochloric acid. The maximum preconcentration factor was 75. The method was applied for the determination of trace amounts of Hg(II) in various synthetic samples and water samples.

Elementary sulfur in effluent from denitrifying sulfide removal process as adsorbent for zinc(II).

PubMed

Chen, Chuan; Zhou, Xu; Wang, Aijie; Wu, Dong-hai; Liu, Li-hong; Ren, Nanqi; Lee, Duu-Jong

2012-10-01

The denitrifying sulfide removal (DSR) process can simultaneously convert sulfide, nitrate and organic compounds into elementary sulfur (S(0)), di-nitrogen gas and carbon dioxide, respectively. However, the S(0) formed in the DSR process are micro-sized colloids with negatively charged surface, making isolation of S(0) colloids from other biological cells and metabolites difficult. This study proposed the use of S(0) in DSR effluent as a novel adsorbent for zinc removal from wastewaters. Batch and continuous tests were conducted for efficient zinc removal with S(0)-containing DSR effluent. At pH<7.5, removal rates of zinc(II) were increased with increasing pH. The formed S(0) colloids carried negative charge onto which zinc(II) ions could be adsorbed via electrostatic interactions. The zinc(II) adsorbed S(0) colloids further enhanced coagulation-sedimentation efficiency of suspended solids in DSR effluents. The DSR effluent presents a promising coagulant for zinc(II) containing wastewaters. Copyright © 2012 Elsevier Ltd. All rights reserved.

In vivo pH monitoring using boron doped diamond microelectrode and silver needles: Application to stomach disorder diagnosis

NASA Astrophysics Data System (ADS)

Fierro, Stéphane; Seishima, Ryo; Nagano, Osamu; Saya, Hideyuki; Einaga, Yasuaki

2013-11-01

This study presents the in vivo electrochemical monitoring of pH using boron doped diamond (BDD) microelectrode and silver needles for potential application in medical diagnosis. Accurate calibration curve for pH determination were obtained through in vitro electrochemical measurements. The increase induced in stomach pH by treatment with pantoprazole was used to demonstrate that it is possible to monitor the pH in vivo using the simple and noninvasive system proposed herein. Using the results of the in vivo and in vitro experiments, a quantitative analysis of the increase in stomach pH is also presented. It is proposed that the catheter-free pH monitoring system presented in this study could be potentially employed in any biological environment.

In vivo pH monitoring using boron doped diamond microelectrode and silver needles: application to stomach disorder diagnosis.

PubMed

Fierro, Stéphane; Seishima, Ryo; Nagano, Osamu; Saya, Hideyuki; Einaga, Yasuaki

2013-11-19

This study presents the in vivo electrochemical monitoring of pH using boron doped diamond (BDD) microelectrode and silver needles for potential application in medical diagnosis. Accurate calibration curve for pH determination were obtained through in vitro electrochemical measurements. The increase induced in stomach pH by treatment with pantoprazole was used to demonstrate that it is possible to monitor the pH in vivo using the simple and noninvasive system proposed herein. Using the results of the in vivo and in vitro experiments, a quantitative analysis of the increase in stomach pH is also presented. It is proposed that the catheter-free pH monitoring system presented in this study could be potentially employed in any biological environment.

Optical measurement of acidification of human dental plaque in vitro

NASA Astrophysics Data System (ADS)

Graham, Jasmine Y.; Nelson, Leonard Y.; Seibel, Eric J.

2018-02-01

A pH measurement of oral biofilms is helpful for monitoring the impact of acidogenic bacteria in the caries process. Demineralization of dental enamel is closely related to the time dependent pH of human plaque. Therefore, providing a means to easily measure the local pH of biofilms is a useful clinical diagnostic in the arsenal of caries prevention tools. Optical measurement methods of plaque metabolism can use intrinsic fluorescence or extrinsic fluorescence from added dyes. Autofluorescence spectral features of human oral biofilms at green (500 nm) and red (634 nm) fluorescence wavelengths using 405 nm excitation did not demonstrate a spectral or intensity shift between neutral and acidic conditions. Chlorin e6, an ingredient in chlorophyllin food supplement, exhibited a spectral and intensity shift of fluorescence emission in buffered solutions, but this quantitative pH-dependence was not transferable to a human plaque environment. Finally, a ratiometric quantitative pH measure was achieved by exciting (405 nm laser) a mixture of two dyes, fluorescein and rhodamine B. This two-dye mixture produced two strong fluorescent bands centered at 515 nm (fluorescein) and 580 nm (rhodamine B), where the 515 nm band was pH sensitive and the 580 nm band served as a pH insensitive reference. This dual-dye fluorescence ratio exhibited a linear response over pH 7 to 5 in human oral biofilms during a sugar challenge. We have explored methods to use non-contact, optical measures of local acidity levels in difficult to access dental locations such as occlusal fissures using various pH sensitive fluorescent dye systems.

Preparation and characterization of trihydroxamic acid functionalized carbon materials for the removal of Cu(II) ions from aqueous solution

NASA Astrophysics Data System (ADS)

Godino-Salido, M. Luz; Santiago-Medina, Antonio; López-Garzón, Rafael; Gutiérrez-Valero, María D.; Arranz-Mascarós, Paloma; López de la Torre, M. Dolores; Domingo-García, María; López-Garzón, F. Javier

2016-11-01

The main objective of this study is to prepare and characterize two functionalizated carbon materials with enhanced adsorptive properties for Cu(II). Thus, two novel hybrid materials have been prepared by a non-covalent functionalization method based on the adsorption of a pyrimidine-desferrioxamine-B conjugate compound (H4L) on two activated carbons, ACs (labelled Merck and F). The adsorption of H4L on the ACs is pH-dependent and highly irreversible. This is due to strong π-π interactions between the arene centers of the ACs and the pyrimidine moiety of H4L. The textural characterization of the AC/H4L hybrids shows large decreases of their surface areas. Thus the values of Merck and F are 1031 and 1426 m2/g respectively, while these of Merck/H4L and F/H4L hybrids are 200 and 322 m2/g. An important decrease in the micropore volumes is also found, due to the blockage of narrow porosity produced by the adsorption of H4L molecules. The ACs/H4L hybrids show larger adsorption capacities for Cu(II) (0.105(4) and 0.13(2) mmol/g, at pH 2.0, and 0.20(3) and 0.242(9) mmol/g, at pH 5.5, for Merck/H4L and F/H4L, respectively) than those of the ACs (0.024(6) and 0.096(9) mmol/g, at pH 2.0, and 0.10(2) and 0.177(8) mmol/g, at pH 5.5, for Merck and F respectively), which is explained on the basis of the complexing ability of the trihydroxamic acid functions. The desorption of Cu(II) from the ACs/H4L/Cu(II) materials in acid solution allows the regeneration of most active sites (78.5% in the case of Merck/H4L/Cu(II) and 83.0% in the case of F/H4L/Cu(II)).

Multilayer adsorption of Cu(II) and Cd(II) over Brazilian Orchid Tree (Pata-de-vaca) and its adsorptive properties

NASA Astrophysics Data System (ADS)

Jorgetto, Alexandre de O.; da Silva, Adrielli C. P.; Wondracek, Marcos H. P.; Silva, Rafael I. V.; Velini, Edivaldo D.; Saeki, Margarida J.; Pedrosa, Valber A.; Castro, Gustavo R.

2015-08-01

Through very simple and inexpensive processes, pata-de-vaca leaves were turned into a powder and applied as an adsorbent for the uptake of Cu(II) and Cd(II) from water. The material was characterized through SEM, EDX, FTIR and surface area measurement. The material had its point of zero charge determined (5.24), and its adsorption capacity was evaluated as a function of time, pH and metal concentration. The material presented fast adsorption kinetics, reaching adsorption equilibrium in less than 5 min and it had a good correlation with the pseudo-second order kinetic model. Optimum pH for the adsorption of Cu(II) and Cd(II) were found to be in the range from 4 to 5, approximately. In the experiment as a function of the analyte concentration, analogously to gas adsorption, the material presented a type II isotherm, indicating the formation of multilayers for both species. Such behavior was explained with basis in the alternation between cations and anions over the material's surface, and the maximum adsorption capacity, considering the formation of the multilayers were found to be 0.238 mmol L-1 for Cu(II) and 0.113 mmol L-1 for Cd(II).

Extraction and separation of Co(II) and Ni(II) from acidic sulfate solutions using Aliquat 336.

PubMed

Nayl, A A

2010-01-15

Extraction and separation of Co(II) and Ni(II) from acidic sulfate solutions by solvent extraction technique were studied using different forms of Aliquat 336 diluted with kerosene. The extraction percent of each metal ion was found to increase with increasing pH and extractant concentration. Co(II) was preferentially extracted by different forms of Aliquat 336 over Ni(II) under the same extraction conditions. From analysis of the experimental results, the extraction mechanism of R(4)N-forms was proposed with Co(II). It was found that the highest separation factor (S(Co/Ni)) value of 606.7 was obtained with 0.36 M R(4)N-SCN in kerosene from 2.0M H(2)SO(4) solution at pH 4.8 and shaking time of 20 min. Stripping of the two metal ions from the organic phase was also investigated. Based on the experimental results, a separation method was developed and tested to separate high purity Co(II), Ni(II) and Ln(III) from Ni-MH batteries leached by 2.0M H(2)SO(4). Based on the experimental results, a flow sheet was developed and tested and 0.34 g Co, 1.39 g Ln and 5.2g Ni were obtained from the leaching process.

TRANSFORMATION OF NITROSOBENZENES AND HYDROXYLANILINES BY FE (II) SPECIES: ELUCIDATION OF MECHANISM, EFFECT OF FERRIC OXIDES AND PH

EPA Science Inventory

The purpose of this work was to (i) study the effect of structure composition on the reactivity of a series of N-hydroxylaniline and nitrosobenzene compounds toward their reduction by Fe(II) species, (ii) evaluate the usefulness of several chemical parameters for predicting the r...

2,4-Dinitrophenylhydrazine functionalized sodium dodecyl sulfate-coated magnetite nanoparticles for effective removal of Cd(II) and Ni(II) ions from water samples.

PubMed

Sobhanardakani, Soheil; Zandipak, Raziyeh

2015-07-01

2,4-Dinitrophenylhydrazine immobilized on sodium dodecyl sulfate (SDS)-coated magnetite and was used for removal of Cd(II) and Ni(II) ions from aqueous solution. The prepared product was characterized by X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The size of the nanoparticles according to SEM was obtained around 20-35 nm. In batch tests, the effects of pH, contact time, initial metal concentration, and temperature were studied. The kinetic and equilibrium data were modeled with recently developed models. The adsorption kinetics and isotherms were well fitted by the fractal-like pseudo-second-order model and Langmuir-Freundlich model, respectively. Maximum adsorption capacity by this adsorbent is 255.1 mg g(-1) for Cd(II) ion and 319.6 mg g(-1) for Ni(II) ion at pH 7.0 and 25 °C. The method was successfully applied to the removal of metal cations in real samples (tap water, river water, and petrochemical wastewater).

Mercury(II) and methyl mercury determinations in water and fish samples by using solid phase extraction and cold vapour atomic absorption spectrometry combination.

PubMed

Tuzen, Mustafa; Karaman, Isa; Citak, Demirhan; Soylak, Mustafa

2009-07-01

A method has been developed for mercury(II) and methyl mercury speciation on Staphylococcus aureus loaded Dowex Optipore V-493 micro-column in the presented work, by using cold vapour atomic absorption spectrometry. Selective and sequential elution with 0.1 molL(-1) HCl for methyl mercury and 2 molL(-1) HCl for mercury(II) were performed at the pH range of 2-6. Optimal analytical conditions including pH, amounts of biosorbent, sample volumes were investigated. The detection limits of the analytes were 2.5 ngL(-1) for Hg(II) and 1.7 ngL(-1) for methyl mercury. The capacity of biosorbent for mercury(II) and methyl mercury was 6.5 and 5.4 mgg(-1), respectively. The validation of the presented procedure is performed by the analysis of standard reference material. The speciation procedure established was successfully applied to the speciation of mercury(II) and methyl mercury in natural water and microwave digested fish samples.

pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

PubMed

Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

2008-09-21

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

Use of Eichhornia crassipes modified Nano-chitosan as a biosorbent for lead (II), cadmium (II), and copper (II) ion removal from aqueous solutions

NASA Astrophysics Data System (ADS)

Alkaff, A. H.; Hendri, H.; Farozy, I. H.; Annisa, M.; Aritonang, R. P.

2018-01-01

Industrial waste in a major city poses a considerable threat to water environment from the accumulation of heavy metals. Additionally, uncontrolled growth of Eichhornia crassipes will also damage the water environment by lowering the levels of dissolved oxygen. Therefore, we conduct research to not only treat industrial waste in water but also reduce the population of E. crassipes in water. We made this biosorbent by mixing E. crassipes with nano-chitosan in various compositions. Its absorptivity was tested against single metal solutions of lead (II), cadmium (II), and copper (II) to get the best biosorbent composition. The chosen biosorbent then went through an adsorptivity test against a mixture of three solutions, with each test was carried at various pH. The best biosorbent composition is the mixture of 1 g of E. crassipes with 30 mL of nano-chitosan 0.01%, while adsorption tests in single or three metals solution show that the biosorbent performs better in neutral pH.

pH determines the energetic efficiency of the cyanobacterial CO2 concentrating mechanism.

PubMed

Mangan, Niall M; Flamholz, Avi; Hood, Rachel D; Milo, Ron; Savage, David F

2016-09-06

Many carbon-fixing bacteria rely on a CO2 concentrating mechanism (CCM) to elevate the CO2 concentration around the carboxylating enzyme ribulose bisphosphate carboxylase/oxygenase (RuBisCO). The CCM is postulated to simultaneously enhance the rate of carboxylation and minimize oxygenation, a competitive reaction with O2 also catalyzed by RuBisCO. To achieve this effect, the CCM combines two features: active transport of inorganic carbon into the cell and colocalization of carbonic anhydrase and RuBisCO inside proteinaceous microcompartments called carboxysomes. Understanding the significance of the various CCM components requires reconciling biochemical intuition with a quantitative description of the system. To this end, we have developed a mathematical model of the CCM to analyze its energetic costs and the inherent intertwining of physiology and pH. We find that intracellular pH greatly affects the cost of inorganic carbon accumulation. At low pH the inorganic carbon pool contains more of the highly cell-permeable H2CO3, necessitating a substantial expenditure of energy on transport to maintain internal inorganic carbon levels. An intracellular pH ≈8 reduces leakage, making the CCM significantly more energetically efficient. This pH prediction coincides well with our measurement of intracellular pH in a model cyanobacterium. We also demonstrate that CO2 retention in the carboxysome is necessary, whereas selective uptake of HCO3 (-) into the carboxysome would not appreciably enhance energetic efficiency. Altogether, integration of pH produces a model that is quantitatively consistent with cyanobacterial physiology, emphasizing that pH cannot be neglected when describing biological systems interacting with inorganic carbon pools.

pH determines the energetic efficiency of the cyanobacterial CO2 concentrating mechanism

PubMed Central

Flamholz, Avi; Hood, Rachel D.; Milo, Ron

2016-01-01

Many carbon-fixing bacteria rely on a CO2 concentrating mechanism (CCM) to elevate the CO2 concentration around the carboxylating enzyme ribulose bisphosphate carboxylase/oxygenase (RuBisCO). The CCM is postulated to simultaneously enhance the rate of carboxylation and minimize oxygenation, a competitive reaction with O2 also catalyzed by RuBisCO. To achieve this effect, the CCM combines two features: active transport of inorganic carbon into the cell and colocalization of carbonic anhydrase and RuBisCO inside proteinaceous microcompartments called carboxysomes. Understanding the significance of the various CCM components requires reconciling biochemical intuition with a quantitative description of the system. To this end, we have developed a mathematical model of the CCM to analyze its energetic costs and the inherent intertwining of physiology and pH. We find that intracellular pH greatly affects the cost of inorganic carbon accumulation. At low pH the inorganic carbon pool contains more of the highly cell-permeable H2CO3, necessitating a substantial expenditure of energy on transport to maintain internal inorganic carbon levels. An intracellular pH ≈8 reduces leakage, making the CCM significantly more energetically efficient. This pH prediction coincides well with our measurement of intracellular pH in a model cyanobacterium. We also demonstrate that CO2 retention in the carboxysome is necessary, whereas selective uptake of HCO3− into the carboxysome would not appreciably enhance energetic efficiency. Altogether, integration of pH produces a model that is quantitatively consistent with cyanobacterial physiology, emphasizing that pH cannot be neglected when describing biological systems interacting with inorganic carbon pools. PMID:27551079

Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides.

PubMed

Bilyachenko, Alexey N; Yalymov, Alexey I; Shul'pina, Lidia S; Mandelli, Dalmo; Korlyukov, Alexander A; Vologzhanina, Anna V; Es'kova, Marina A; Shubina, Elena S; Levitsky, Mikhail M; Shul'pin, Georgiy B

2016-05-19

New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)₆(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)₆(NaCl)(C₄H₈O₂)13(PhCN)₂(H₂O)₂ and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers.

Electrogenerated chemiluminescence of tris(2,2' bipyridine)ruthenium(II) using common biological buffers as co-reactant, pH buffer and supporting electrolyte.

PubMed

Kebede, Noah; Francis, Paul S; Barbante, Gregory J; Hogan, Conor F

2015-11-07

A series of aliphatic tertiary amines (HEPES, POPSO, EPPS and BIS-TRIS) commonly used to buffer the pH in biological experiments, were examined as alternative, non-toxic co-reactants for the electrogenerated chemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) ([Ru(bpy)3](2+)). These were found to be very attractive as "multi-tasking" reagents, serving not only as co-reactants, but also fulfiling the roles of pH buffer and supporting electrolyte within an aqueous environment; thus significantly simplifying the overall ECL analysis. Sub-nanomolar detection limits were obtained for [Ru(bpy)3](2+) in the presence of BIS-TRIS, making this species an valuable option for co-reactant ECL-based bioanalytical applications.

Iron oxidation stimulates organic matter decomposition in humid tropical forest soils.

PubMed

Hall, Steven J; Silver, Whendee L

2013-09-01

Humid tropical forests have the fastest rates of organic matter decomposition globally, which often coincide with fluctuating oxygen (O2 ) availability in surface soils. Microbial iron (Fe) reduction generates reduced iron [Fe(II)] under anaerobic conditions, which oxidizes to Fe(III) under subsequent aerobic conditions. We demonstrate that Fe (II) oxidation stimulates organic matter decomposition via two mechanisms: (i) organic matter oxidation, likely driven by reactive oxygen species; and (ii) increased dissolved organic carbon (DOC) availability, likely driven by acidification. Phenol oxidative activity increased linearly with Fe(II) concentrations (P < 0.0001, pseudo R(2)  = 0.79) in soils sampled within and among five tropical forest sites. A similar pattern occurred in the absence of soil, suggesting an abiotic driver of this reaction. No phenol oxidative activity occurred in soils under anaerobic conditions, implying the importance of oxidants such as O2 or hydrogen peroxide (H2 O2 ) in addition to Fe(II). Reactions between Fe(II) and H2 O2 generate hydroxyl radical, a strong nonselective oxidant of organic compounds. We found increasing consumption of H2 O2 as soil Fe(II) concentrations increased, suggesting that reactive oxygen species produced by Fe(II) oxidation explained variation in phenol oxidative activity among samples. Amending soils with Fe(II) at field concentrations stimulated short-term C mineralization by up to 270%, likely via a second mechanism. Oxidation of Fe(II) drove a decrease in pH and a monotonic increase in DOC; a decline of two pH units doubled DOC, likely stimulating microbial respiration. We obtained similar results by manipulating soil acidity independently of Fe(II), implying that Fe(II) oxidation affected C substrate availability via pH fluctuations, in addition to producing reactive oxygen species. Iron oxidation coupled to organic matter decomposition contributes to rapid rates of C cycling across humid tropical forests in spite of periodic O2 limitation, and may help explain the rapid turnover of complex C molecules in these soils. © 2013 John Wiley & Sons Ltd.

Removal of Cd (II) from water using the waste of jatropha fruit ( Jatropha curcas L.)

NASA Astrophysics Data System (ADS)

Nacke, Herbert; Gonçalves, Affonso Celso; Coelho, Gustavo Ferreira; Schwantes, Daniel; Campagnolo, Marcelo Angelo; Leismann, Eduardo Ariel Völz; Junior, Élio Conradi; Miola, Alisson Junior

2017-10-01

The aim of this work was to evaluate the removal of Cd (II) from water using three biosorbents originated from the biomass of jatropha (bark, endosperm, and endosperm + tegument). For that, batch tests were performed to verify the effect of solution pH, adsorbent mass, contact time, initial concentration of Cd (II), and the temperature of the process. The adsorption process was evaluated by the studies of kinetics, isotherms, and thermodynamics. The ideal conditions of solution pH were 5.5 and 8 g L-1 of adsorbent mass of biosorbents by solution volume, with an equilibrium time of 60 min. According to the Langmuir model, the maximum adsorption capacity for bark, endosperm, and bark + endosperm of jatropha was, respectively, 29.665, 19.562, and 34.674 mg g-1, predominating chemisorption in monolayers. The biosorbents presented potential for the remediation of waters contaminated with Cd (II).

Sorption and desorption of lead (II) from wastewater by green algae Cladophora fascicularis.

PubMed

Deng, Liping; Su, Yingying; Su, Hua; Wang, Xinting; Zhu, Xiaobin

2007-05-08

Biosorption is an effective method to remove heavy metals from wastewater. In this work, adsorption features of Cladophora fascicularis were investigated as a function of time, initial pH, initial Pb(II) concentrations, temperature and co-existing ions. Kinetics and equilibria were obtained from batch experiments. The biosorption kinetics followed the pseudo-second order model. Adsorption equilibria were well described by the Langmuir and Freundlich isotherm models. The maximum adsorption capacity was 198.5 mg/g at 298K and pH 5.0. The adsorption processes were endothermic and the biosorption heat was 29.6 kJ/mol. Desorption experiments indicated that 0.01 mol/L Na(2)EDTA was an efficient desorbent for the recovery of Pb(II) from biomass. IR spectrum analysis suggested amido or hydroxy, CO and C-O could combine intensively with Pb(II).

The Importance of pH, Oxygen, and Bitumen on the Oxidation and Precipitation of Fe(III)-(oxy)hydroxides during Hydraulic Fracturing of Oil/Gas Shales

NASA Astrophysics Data System (ADS)

Jew, A. D.; Dustin, M. K.; Harrison, A. L.; Joe-Wong, C. M.; Thomas, D.; Maher, K.; Brown, G. E.; Bargar, J.

2016-12-01

Due to the rapid growth of hydraulic fracturing in the United States, understanding the cause for the rapid production drop off of new wells over the initial months of production is paramount. One possibility for the production decrease is pore occlusion caused by the oxidation of Fe(II)-bearing phases resulting in Fe(III) precipitates. To understand the release and fate of Fe in the shale systems, we reacted synthesized fracture fluid at 80oC with shale from four different geological localities (Marcellus Fm., Barnett Fm., Eagle Ford Fm., and Green River Fm.). A variety of wet chemical and synchrotron-based techniques (XRF mapping and x-ray absorption spectroscopy) were used to understand Fe release and solid phase Fe speciation. Solution pH was found to be the greatest factor for Fe release. Carbonate-poor Barnett and Marcellus shale showed rapid Fe release into solution followed by a plateau or significant drop in Fe concentrations indicating mineral precipitation. Conversely, in high carbonate shales, Eagle Ford and Green River, no Fe was detected in solution indicating fast Fe oxidation and precipitation. For all shale samples, bulk Fe EXAFS data show that a significant amount of Fe in the shales is bound directly to organic carbon. Throughout the course of the experiments inorganic Fe(II) phases (primarily pyrite) reacted while Fe(II) bound to C showed no indication of reaction. On the micron scale, XRF mapping coupled with μ-XANES spectroscopy showed that at pH < 4.0, Fe(III) bearing phases precipitated as diffuse surface precipitates of ferrihydrite, goethite, and magnetite away from Fe(II) point sources. In near circum-neutral pH systems, Fe(III)-bearing phases (goethite and hematite) form large particles 10's of μm's in diameter near Fe(II) point sources. Idealized systems containing synthesized fracturing fluid, dissolved ferrous chloride, and bitumen showed that bitumen released during reaction with fracturing fluids is capable of oxidizing Fe(II) to Fe(III) at pH's 2.0 and 7.0. This indicates that bitumen can play a large role in Fe oxidation and speciation in the subsurface. This work shows that shale mineralogy has a significant impact on the morphology and phases of Fe(III) precipitates in the subsurface which in turn can significantly impact subsurface solution flow.

Copper(II) ions interactions in the systems with triamines and ATP. Potentiometric and spectroscopic studies.

PubMed

Hoffmann, S K; Goslar, J; Bregier-Jarzebowska, R; Gasowska, A; Zalewska, A; Lomozik, L

2017-12-01

The mode of interaction and thermodynamic stability of complexes formed in binary and ternary Cu(II)/ATP/triamines systems were studied using potentiometric and spectroscopic (NMR, EPR, UV-Vis) methods. It was found that in binary metal-free systems ATP/H x PA species are formed (PA: Spd=spermidine or 3,3-tri=1,7-diamino-4-azaheptane) where the phosphate groups from nucleotides are preferred negative centers and protonated amine groups of amines are positive centers of reaction. In the ternary systems Cu/ATP/H x (PA) as well as Cu/(ATP)(PA) species are formed. The type of the formed Cu(II) complexes depends on pH of the solution. For a low pH value the complexation appears between Cu(II) and ATP molecules via oxygen atoms of phosphate groups. For a very high pH value, where ATP is hydrolyzed, the Cu(II) ions are bound to the nitrogen atoms of polyamine molecules. We did not detect any direct coordination of the N7 nitrogen atom of adenosine to Cu(II) ions. It means that the CuN7 interaction is an indirect type and can be due to noncovalent interplay including water molecule. EPR studies were performed at glassy state (77K) after a fast freezing both for binary and ternary systems. The glassy state EPR spectra do not reflect species identified in titration studies indicating significant effect of rapid temperature decrease on equilibrium of Cu(II) complexes. We propose the molecular structure of all the studied complexes at the glassy state deduced from EPR and optical spectroscopy results. Copyright © 2017 Elsevier Inc. All rights reserved.

Synthesis, structure, theoretical studies, and Ligand exchange reactions of monomeric, T-shaped arylpalladium(II) halide complexes with an additional, weak agostic interaction.

PubMed

Stambuli, James P; Incarvito, Christopher D; Bühl, Michael; Hartwig, John F

2004-02-04

A series of monomeric arylpalladium(II) complexes LPd(Ph)X (L = 1-AdPtBu2, PtBu3, or Ph5FcPtBu2 (Q-phos); X = Br, I, OTf) containing a single phosphine ligand have been prepared. Oxidative addition of aryl bromide or aryl iodide to bis-ligated palladium(0) complexes of bulky, trialkylphosphines or to Pd(dba)2 (dba = dibenzylidene acetone) in the presence of 1 equiv of phosphine produced the corresponding arylpalladium(II) complexes in good yields. In contrast, oxidative addition of phenyl chloride to the bis-ligated palladium(0) complexes did not produce arylpalladium(II) complexes. The oxidative addition of phenyl triflate to PdL2 (L = 1-AdPtBu2, PtBu3, or Q-phos) also did not form arylpalladium(II) complexes. The reaction of silver triflate with (1-AdPtBu2)Pd(Ph)Br furnished the corresponding arylpalladium(II) triflate in good yield. The oxidative addition of phenyl bromide and iodide to Pd(Q-phos)2 was faster than oxidative addition to Pd(1-AdPtBu2)2 or Pd(PtBu3)2. Several of the arylpalladium complexes were characterized by X-ray diffraction. All of the arylpalladium(II) complexes are T-shaped monomers. The phenyl ligand, which has the largest trans influence, is located trans to the open coordination site. The complexes appear to be stabilized by a weak agostic interaction of the metal with a ligand C-H bond positioned at the fourth-coordination site of the palladium center. The strength of the Pd.H bond, as assessed by tools of density functional theory, depended upon the donating properties of the ancillary ligands on palladium.

Determination of Cu Environments in the Cyanobacterium Anabaena flos-aquae by X-Ray Absorption Spectroscopy

PubMed Central

Kretschmer, X. C.; Meitzner, G.; Gardea-Torresdey, J. L.; Webb, R.

2004-01-01

Whole cells and peptidoglycan isolated from cell walls of the cyanobacterium Anabaena flos-aquae were lyophilized and used at pH 2 and pH 5 in Cu(II) binding studies. X-ray absorption spectra measured at the Cu K-edge were used to determine the oxidation states and chemical environments of Cu species in the whole-cell and peptidoglycan samples. In the whole-cell samples, most of the Cu retained at both pH values was coordinated by phosphate ligands. The whole-cell fractions contained significant concentrations of Cu(I) as well as Cu(II). An X-ray absorption near-edge spectrum analysis suggested that Cu(I) was coordinated by amine and thiol ligands. An analysis of the peptidoglycan fractions found that more Cu was adsorbed by the peptidoglycan fraction prepared at pH 5, due to increased chelation by amine and carboxyl ligands. The peptidoglycan fractions, also referred to as the cell wall fractions, contained little or no Cu(I). The Cu loading level was 30 times higher in the cell wall sample prepared at pH 5 than in the sample prepared at pH 2. Amine and bidentate carboxyl ligands had similar relative levels of importance in cell wall peptidoglycan samples prepared at both pH values, but phosphate coordination was insignificant. PMID:14766554

Identification of Mn(II)-oxidizing bacteria from a low-pH contaminated former uranium mine.

PubMed

Akob, Denise M; Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-08-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Identification of Mn(II)-Oxidizing Bacteria from a Low-pH Contaminated Former Uranium Mine

PubMed Central

Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A.; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-01-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments. PMID:24928873

Identification of Mn(II)-oxidizing bacteria from a low-pH contaminated former uranium mine

USGS Publications Warehouse

Akob, Denise M.; Bohu, Tsing; Beyer, Andrea; Schäffner, Franziska; Händel, Matthias; Johnson, Carol A.; Merten, Dirk; Büchel, Georg; Totsche, Kai Uwe; Küsel, Kirsten

2014-01-01

Biological Mn oxidation is responsible for producing highly reactive and abundant Mn oxide phases in the environment that can mitigate metal contamination. However, little is known about Mn oxidation in low-pH environments, where metal contamination often is a problem as the result of mining activities. We isolated two Mn(II)-oxidizing bacteria (MOB) at pH 5.5 (Duganella isolate AB_14 and Albidiferax isolate TB-2) and nine strains at pH 7 from a former uranium mining site. Isolate TB-2 may contribute to Mn oxidation in the acidic Mn-rich subsoil, as a closely related clone represented 16% of the total community. All isolates oxidized Mn over a small pH range, and isolates from low-pH samples only oxidized Mn below pH 6. Two strains with different pH optima differed in their Fe requirements for Mn oxidation, suggesting that Mn oxidation by the strain found at neutral pH was linked to Fe oxidation. Isolates tolerated Ni, Cu, and Cd and produced Mn oxides with similarities to todorokite and birnessite, with the latter being present in subsurface layers where metal enrichment was associated with Mn oxides. This demonstrates that MOB can be involved in the formation of biogenic Mn oxides in both moderately acidic and neutral pH environments.

A Novel Pb-Resistant Bacillus subtilis Bacterium Isolate for Co-Biosorption of Hazardous Sb(III) and Pb(II): Thermodynamics and Application Strategy

PubMed Central

Cai, Yue; Liu, Dongying; Xu, Changlin; Ai, Yuwei; Sun, Xuemeng; Zhang, Meng; Gao, Yu; Zhang, Yuchao; Yang, Tao; Wang, Jingzhi; Wang, Lijun; Li, Xiaoyun; Yu, Hongtao

2018-01-01

The present work is the first to study co-biosorption of Pb(II) and Sb(III) by a novel bacterium and its application strategy. The biosorption characteristics of Pb(II) and Sb(III) ions from aqueous solution using B. subtilis were investigated. Optimum pH, biomass dosage, contact time and temperature were determined to be 5.00, 6.00 mg/L, 45 min and 35 °C, respectively. Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by B. subtilis. Results showed that Langmuir model fitted the equilibrium data of Pb(II) better than others, while biosorption of Sb(III) obeyed the Freundlich model well. The biosorption capacity of B. subtilis biomass for Pb(II) and Sb(III) ions was found to be 17.34 ± 0.14 and 2.32 ± 0.30 mg/g, respectively. Kinetic data showed the biosorption process of Pb(II) and Sb(III) ions both followed the pseudo-second-order kinetic model, with R2 ranging from 0.974 to 0.999 for Pb(II) and from 0.967 to 0.979 for Sb(III). The calculated thermodynamic parameters, negative ∆G and positive ∆H and ∆S values, indicated the biosorption of Pb(II) and Sb(III) ions onto B. subtilis biomass in water was feasible, endothermic, and spontaneous. Bacterial bioleaching experiment revealed B. subtilis can increase the mobility of Pb(II) and Sb(III) in polluted soil when pH was close to 6 at low temperature. Consequently, B. subtilis, as a cheap and original bacterial material, could be a promising biomass to remove Pb or isolate Sb from industrial wastewater and to assist phytoremediation of Pb and Sb from weak acid or near neutral pH polluted soils at low temperature. PMID:29642529

A Novel Pb-Resistant Bacillus subtilis Bacterium Isolate for Co-Biosorption of Hazardous Sb(III) and Pb(II): Thermodynamics and Application Strategy.

PubMed

Cai, Yue; Li, Xiaoping; Liu, Dongying; Xu, Changlin; Ai, Yuwei; Sun, Xuemeng; Zhang, Meng; Gao, Yu; Zhang, Yuchao; Yang, Tao; Wang, Jingzhi; Wang, Lijun; Li, Xiaoyun; Yu, Hongtao

2018-04-09

The present work is the first to study co-biosorption of Pb(II) and Sb(III) by a novel bacterium and its application strategy. The biosorption characteristics of Pb(II) and Sb(III) ions from aqueous solution using B. subtilis were investigated. Optimum pH, biomass dosage, contact time and temperature were determined to be 5.00, 6.00 mg/L, 45 min and 35 °C, respectively. Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by B. subtilis . Results showed that Langmuir model fitted the equilibrium data of Pb(II) better than others, while biosorption of Sb(III) obeyed the Freundlich model well. The biosorption capacity of B. subtilis biomass for Pb(II) and Sb(III) ions was found to be 17.34 ± 0.14 and 2.32 ± 0.30 mg/g, respectively. Kinetic data showed the biosorption process of Pb(II) and Sb(III) ions both followed the pseudo-second-order kinetic model, with R² ranging from 0.974 to 0.999 for Pb(II) and from 0.967 to 0.979 for Sb(III). The calculated thermodynamic parameters, negative ∆ G and positive ∆ H and ∆ S values, indicated the biosorption of Pb(II) and Sb(III) ions onto B. subtilis biomass in water was feasible, endothermic, and spontaneous. Bacterial bioleaching experiment revealed B. subtilis can increase the mobility of Pb(II) and Sb(III) in polluted soil when pH was close to 6 at low temperature. Consequently, B. subtilis , as a cheap and original bacterial material, could be a promising biomass to remove Pb or isolate Sb from industrial wastewater and to assist phytoremediation of Pb and Sb from weak acid or near neutral pH polluted soils at low temperature.

Quantum Search and Beyond

DTIC Science & Technology

2008-07-02

an N-atom system. II. Calculation of the eigenstates Terry Rudolph, Itay Yavin and Helen Freedhoff, quant-ph/0206067 Phys. Rev. A. 69, 013815 (2004...Calculation of the eigenstates Terry Rudolph, Itay Yavin and Helen Freedhoff, quant-ph/0206067 Phys. Rev. A. 69, 013815 (2004). 13. Quantum searching a

Damage and protection of the photosynthetic apparatus from UV-B radiation. II. Effect of quercetin at different pH.

PubMed

Dobrikova, Anelia G; Apostolova, Emilia L

2015-07-20

The effect of the exogenously added quercetin against the UV-B inhibition of the photosystem II (PSII) functions in isolated pea thylakoid membranes suspended at different pH of the medium (6.5, 7.6 and 8.4) was investigated. The data revealed that the interaction of this flavonoid with the membranes depends on the pH and influences the initial S0-S1 state distribution of PSII in the dark, the energy transfer between pigment-protein complexes of the photosynthetic apparatus and the membrane fluidity. Quercetin also displays a different UV-protective effect depending on its location in the membranes, as the effect is more pronounced at pH 8.4 when it is located at the membrane surface. The results suggest that quercetin induces structural changes in thylakoid membranes, one of the possible reasons for its protection of the photosynthetic apparatus. Copyright © 2015 Elsevier GmbH. All rights reserved.

Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

PubMed

Norkus, E; Vaskelis, A; Zakaite, I

1996-03-01

D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

Quantitative and simultaneous detection of four foodborne bacterial pathogens with a multi-channel SPR sensor.

PubMed

Taylor, Allen D; Ladd, Jon; Yu, Qiuming; Chen, Shengfu; Homola, Jirí; Jiang, Shaoyi

2006-12-15

We report the quantitative and simultaneous detection of four species of bacteria, Escherichia coli O157:H7, Salmonella choleraesuis serotype typhimurium, Listeria monocytogenes, and Campylobacter jejuni, using an eight-channel surface plasmon resonance (SPR) sensor based on wavelength division multiplexing. Detection curves showing SPR response versus analyte concentration were established for each species of bacteria in buffer at pH 7.4, apple juice at native pH 3.7, and apple juice at an adjusted pH of 7.4, as well as for a mixture containing all four species of bacteria in buffer. Control experiments were performed to show the non-fouling characteristics of the sensor surface as well as the specificity of the amplification antibodies used in this study. The limit of detection (LOD) for each of the four species of bacteria in the tested matrices ranges from 3.4 x 10(3) to 1.2 x 10(5) cfu/ml. Detection curves in buffer of an individual species of bacteria in a mixture of all four species of bacteria correlated well with detection curves of the individual species of bacteria alone. SPR responses were higher for bacteria in apple juice at pH 7.4 than in apple juice at pH 3.7. This difference in sensor response could be partly attributed to the pH dependence of antibody-antigen binding.

Interactions of diamines with adenosine-5'-triphosphate (ATP) in the systems including copper(II) ions.

PubMed

Bregier-Jarzebowska, R; Gasowska, A; Hoffmann, S K; Lomozik, L

2016-09-01

Interactions were studied in the systems ATP/tn and ATP/Put (tn=1,3-diaminopropane, Put=putrescine) whereas the complexation reactions in ternary systems Cu(II)/ATP/tn and Cu(II)/ATP/Put. Results of the potentiometric and spectroscopic studies evidenced the formation of adducts of the type (ATP)H x (PA), where PA=diamine. The thermodynamic stability of the complexes and the mode of interactions were determined. On the basis of analysis of changes in the positions of NMR signals, in the pH range of (ATP)H 3 (Put) formation, the preferred centres of the interaction between ATP and Put are the endocyclic nitrogen atoms from the nucleotide. On the other hand, the shorter diamine tn in the entire pH range reacts with the phosphate groups from ATP. The positive centres of noncovalent interactions are the protonated NH x + groups from amines. In both complexes Cu(ATP)H 2 (tn) and Cu(ATP)H 3 (Put) formed in ternary systems at pH<6.5, the amines are in the outer sphere of coordination with the noncovalent interaction with anchoring Cu(ATP). Only the phosphate groups from the nucleotide take part in metalation. At higher pH in the range of Cu(ATP)(PA) complex formation, significant differences in the reactions of the two amines appear. The shorter one (tn) binds Cu(II) ions with two nitrogen atoms, while putrescine coordinates in the monofunctional mode, which is undoubtedly related to the differences in lengths of methylene chain. This explains the considerable differences in the stability of Cu(ATP)(tn) and Cu(ATP)(Put). In both complexes the nucleotide is coordinated through phosphate groups. As a result of noncovalent interactions ATP forms molecular complexes with 1,3-diaminopropane and 1,4-diaminobutane (putrescine). Significant differences in the mode of interactions between the two diamines were observed in ATP/diamine binary systems and in ternary systems Cu(II)/ATP/diamine, at high pH. Copyright © 2016 Elsevier Inc. All rights reserved.

[Adsorption behavior of copper ion and methylene blue on citric acid- esterified wheat straw].

PubMed

Sun, Jin; Zhong, Ke-Ding; Feng, Min; Liu, Xing-Yan; Gong, Ren-Min

2008-03-01

A cationic adsorbent with carboxyl groups derived from citric acid- esterified wheat straw (EWS) was prepared by the method of solid phase preparation, and a batch experiment was conducted to study the adsorption behaviors of Cu (II) and methylene blue (MB) in aqueous solution on the EWS under conditions of different initial pH, adsorbent dosage, adsorbate concentration, and contact time. The results showed that the maximum adsorption of Cu (II) and MB was obtained when the initial solution pH was > or = 4.0. 96% of Cu (II) in 100 mg x L(-1) Cu solution and 99% of MB in 250 mg x L(-1) dye solution could be removed by > or = 2.0 g x L(-1) of EWS. The adsorption of Cu (II) and MB fitted the Langmuir sorption isothermal model. The maximum removal capacity (Qm) of EWS was 79.37 mg x g(-1) for Cu (II) and 312.50 mg x g(-1) for MB, and the adsorption equilibrium of Cu (II) and MB was reached within 75 min and 5 h, respectively. The adsorption processes of Cu (II) and MB could be described by pseudo-first order and pseudo-second order kinetic functions, respectively.

Formation of tyrosine radicals in photosystem II under far-red illumination.

PubMed

Ahmadova, Nigar; Mamedov, Fikret

2018-04-01

Photosystem II (PS II) contains two redox-active tyrosine residues on the donor side at symmetrical positions to the primary donor, P 680 . Tyr Z , part of the water-oxidizing complex, is a preferential fast electron donor while Tyr D is a slow auxiliary donor to P 680 + . We used PS II membranes from spinach which were depleted of the water oxidation complex (Mn-depleted PS II) to study electron donation from both tyrosines by time-resolved EPR spectroscopy under visible and far-red continuous light and laser flash illumination. Our results show that under both illumination regimes, oxidation of Tyr D occurs via equilibrium with Tyr Z • at pH 4.7 and 6.3. At pH 8.5 direct Tyr D oxidation by P 680 + occurs in the majority of the PS II centers. Under continuous far-red light illumination these reactions were less effective but still possible. Different photochemical steps were considered to explain the far-red light-induced electron donation from tyrosines and localization of the primary electron hole (P 680 + ) on the Chl D1 in Mn-depleted PS II after the far-red light-induced charge separation at room temperature is suggested.

Synthesis of Copper-Chelates Derived from Amino Acids and Evaluation of Their Efficacy as Copper Source and Growth Stimulator for Lactuca sativa in Nutrient Solution Culture.

PubMed

Kaewchangwat, Narongpol; Dueansawang, Sattawat; Tumcharern, Gamolwan; Suttisintong, Khomson

2017-11-15

Five tetradentate ligands were synthesized from l-amino acids and utilized for the synthesis of Cu(II)-chelates 1-5. The efficacy of Cu(II)-chelates as copper (Cu) source and growth stimulator in hydroponic cultivation was evaluated with Lactuca sativa. Their stability test was performed at pH 4-10. The results suggested that Cu(II)-chelate 3 is the most pH tolerant complex. Levels of Cu, Zn, and Fe accumulated in plants supplied with Cu(II)-chelates were compared with those supplied with CuSO 4 at the same Cu concentration of 8.0 μM. The results showed that Cu(II)-chelate 3 significantly enhanced Cu, Zn, and Fe content in shoot by 35, 15, and 48%, respectively. Application of Cu(II)-chelate 3 also improved plant dry matter yield by 54%. According to the results, Cu(II)-chelate 3 demonstrated the highest stimulating effect on plant growth and plant mineral accumulation so that it can be used as an alternative to CuSO 4 for supplying Cu in nutrient solutions and enhancing the plant growth.

A dip-and-read test strip for the determination of mercury(II) ion in aqueous samples based on urease activity inhibition.

PubMed

Shi, Guo-Qing; Jiang, Guibin

2002-11-01

A sensitive dip-and-read test strip for the determination of mercury in aqueous samples based on the inhibition of urease reaction by the ion has been developed. The strip has a circular sensing zone that containing two layers: the top layer is a cellulose acetate membrane where urease is immobilized on it; the bottom layer is a pH indicator wafer that is impregnated with urea. The principle of the measurement is based on the disappearance of a yellow spot on the pH indicator wafer. The elapsing time until the disappearance of the spot which depends on the concentration of mercury(II) ion is measured with a stopwatch. Under the experimental conditions, as low as 0.2 ng/ml mercury can be observed with the detection range from 0.2 to 200 ng/ml in water. Organomercury compounds give essentially the same response as inorganic mercury. Heavy-metal ions such as Ag(I), Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) as well as other sample matrixes basically do not interfere with the mercury measurement.

Validation of a method for the quantitation of ghrelin and unacylated ghrelin by HPLC.

PubMed

Staes, Edith; Rozet, Eric; Ucakar, Bernard; Hubert, Philippe; Préat, Véronique

2010-02-05

An HPLC/UV method was first optimized for the separation and quantitation of human acylated and unacylated (or des-acyl) ghrelin from aqueous solutions. This method was validated by an original approach using accuracy profiles based on tolerance intervals for the total error measurement. The concentration range that achieved adequate accuracy extended from 1.85 to 59.30microM and 1.93 to 61.60microM for acylated and unacylated ghrelin, respectively. Then, optimal temperature, pH and buffer for sample storage were determined. Unacylated ghrelin was found to be stable in all conditions tested. At 37 degrees C acylated ghrelin was stable at pH 4 but unstable at pH 7.4, the main degradation product was unacylated ghrelin. Finally, this validated HPLC/UV method was used to evaluate the binding of acylated and unacylated ghrelin to liposomes.

Educational Training and Careers of Ph.D. Holders: An Exploratory Empirical Study. Planning Paper 27.

ERIC Educational Resources Information Center

Morris, Jeffrey

This study analyzes the occupational mobility of individuals who hold the Ph.D. degree. Drawing upon data contained in the National Register of Scientific and Technical Personnel compiled by the National Science Foundation, this paper presents the quantitative relationships between educational background, occupational mobility, and salaries. Based…

Bacterial Formation of As(V) and As(III) Ferric Oxyhydroxides in Acid Mine Drainage.

NASA Astrophysics Data System (ADS)

Morin, G.; Juillot, F.; Lebrun, S.; Casiot, C.; Elbaz-Poulichet, F.; Bruneel, O.; Personne, J.; Leblanc, M.; Ildefonse, P.; Calas, G.

2002-12-01

The oxidation of dissolved Fe(II) which is often promoted by acidophilic bacteria in acid mine drainage (AMD) and some hot springs, leads to the precipitation of Fe(III) oxy-hydroxides which incorporate toxic elements within their structure or adsorb them at their surface, thus limiting their mobility. In such complex natural systems, synchrotron-based techniques as X-ray absorption spectroscopy offer the opportunity to monitor surface/solution interactions as well as redox changes affecting the mobility and toxicity of trace elements as arsenic. Spatial and seasonal variations of the (bio-) oxidation of Fe(II) and As(III), and the subsequent precipitation of As-Fe gels, were followed by XANES, XRD, and SEM along the CarnoulŠs AMD (Gard, France). Chemical and mineralogical data collected on sediments, stromatolite, and bioassay samples showed that some indigenous bacteria living in the As-rich CarnoulŠs water ([As] = up to 350 mg.l-1) play an important role in the nature and composition of the solid phases that sequester arsenic at the site. The formation of nano-crystalline and amorphous As(III) ferric oxy-hydroxides has been related to the presence of bacteria able to oxidize Fe(II) but not As(III), which are only present in winter in the upstream area. A rare ferric arsenite sulfate oxy-hydroxide mineral was discovered in this context. Other types of bacteria, occurring in the downstream area whatever the season, are able to catalyze As(III) to As(V) oxidation and, provided that enough Fe(II) oxidizes, promote the formation of amorphous As(V) rich ferric oxy-hydroxides. These bacterially mediated reactions significantly reduce the concentration of dissolved As(III), which is more toxic and mobile than As(V), and might thus be helpful for designing As-removal processes. This work was supported by the French PEVS and ACI Ecologie Quantitative Programs and the PIRAMID EC program. ?Deceased, 26 October 1999 Juillot F., Ildefonse Ph., Morin G., Calas G., De Kersabiec A.M. and Benedetti M. Applied Geochemistry 8, 1031-1048 (1999). Morin G., Lecocq D., Juillot F., Ildefonse Ph., Calas Bull. Soc. Géol. Fr. 173, 281-291 (2002). Morin G., Juillot F., Casiot C., Bruneel O., Personné J-C., Elbaz-Poulichet F., Leblanc M., Ildefonse P. and Calas G. Environ. Sci. Technol (in review.)

Platinum(II) 1,10-phenanthroline complexes of acetylides containing redox-active groups.

PubMed

Siemeling, Ulrich; Bausch, Kirstin; Fink, Heinrich; Bruhn, Clemens; Baldus, Marc; Angerstein, Brigitta; Plessow, Regina; Brockhinke, Andreas

2005-07-21

The new diimine ligand 3,8-di-n-pentyl-4,7-di(phenylethynyl)-1,10-phenanthroline (1) was used for the synthesis of a range of Pt(II) complexes, viz.[Pt(1)Cl2], [Pt(1)(C triple bond C-Ph)2], [Pt(1)(C triple bond C-Fc)2] and [Pt(1)(C triple bond C-p-C6H4-C triple bond C-Fc)2](Fc = ferrocenyl). Crystal structure analyses were performed for [Pt(1)Cl2] and [Pt(1)(C triple bond C-Ph)2] and revealed that the di(acetylide)pi-tweezer of the latter binds a molecule of chloroform through C-H...pi hydrogen bonds. The redox and optical properties of 1 and its complexes were investigated by (spectro-)electrochemistry, UV-Vis and luminescence spectroscopy, and an energy level diagram was derived for [Pt(1)(C triple bond C-Fc)2] and related compounds on the basis of the data collected. The ferrocenyl-substituted Pt(II) complexes are donor-sensitiser assemblies. Intramolecular quenching of the photoexcited Pt(II) diimine unit leads to very short luminescence lifetimes for [Pt(1)(C triple bond C-p-C(6)H(4)-C triple bond C-Fc)2](2 ns) and [Pt(1)(C triple bond C-Fc)2](0.3 ns), as opposed to [Pt(1)(C triple bond C-Ph)2](0.7 micros). Excimer formation has been observed for [Pt(1)(C triple bond C-Ph)(2)] at room temperature in dichloromethane and at low temperatures in frozen glassy dichloromethane and 2-methyltetrahydrofuran solution, but not in the solid state.

Redox reactions of selenium as catalyzed by magnetite: Lessons learned from using electrochemistry and spectroscopic methods

NASA Astrophysics Data System (ADS)

Kim, YoungJae; Yuan, Ke; Ellis, Brian R.; Becker, Udo

2017-02-01

Although previous studies have demonstrated redox transformations of selenium (Se) in the presence of Fe-bearing minerals, the specific mechanism of magnetite-mediated Se electron transfer reactions are poorly understood. In this study, the redox chemistry of Se on magnetite is investigated over an environmentally relevant range of Eh and pH conditions (+0.85 to -1.0 V vs. Ag/AgCl; pH 4.0-9.5). Se redox peaks are found via cyclic voltammetry (CV) experiments at pH conditions of 4.0-8.0. A broad reduction peak centered at -0.5 V represents a multi-electron transfer process involving the transformation of selenite to Se(0) and Se(-II) and the comproportionation reaction between Se(-II) and Se(IV). Upon anodic scans, the oxidation peak centered at -0.25 V is observed and is attributed to the oxidation of Se(-II) to higher oxidation states. Deposited Se(0) may be oxidized at +0.2 V when pH is below 7.0. Over a pH range of 4.0-8.0, the pH dependence of peak potentials is less pronounced than predicted from equilibrium redox potentials. This is attributed to pH gradients in the microporous media of the cavity where the rate of proton consumption by the selenite reduction is faster relative to mass transfer from the solution. In chronoamperometry measurements at potentials ⩾-0.6 V, the current-time transients show good linearity between the current and time in a log-log scale. In contrast, deviation from the linear trend is observed at more negative potentials. Such a trend is indicative of Se(0) nucleation and growth on the magnetite surface, which can be theoretically explained by the progressive nucleation model. XPS analysis reveals the dominance of elemental selenium at potentials ⩽-0.5 V, in good agreement with the peak assignment on the cyclic voltammograms and the nucleation kinetic results.

Heterogeneous selenite reduction by zero valent iron steel wool.

PubMed

Li, Ziyan; Huang, Donglin; McDonald, Louis M

2017-02-01

Mine drainage from the low-sulfur surface coal mines in southern West Virginia, USA, is circumneutral (pH > 6) but contains elevated selenium (Se) concentrations. Removal of selenite ions from aqueous solutions under anoxic condition at pH 6-8.5 by zero valent iron steel wool (ZVI-SW) was investigated in bench-scale kinetic experiments using wet chemical, microscopic and spectroscopic techniques (X-ray photoelectron spectroscopy). ZVI-SW could effectively and efficiently remove Se IV from solution with pH 6-8.5. A two-step removal mechanism was identified for Se IV reduction by ZVI-SW. The proposed mechanism was electrochemical reduction of Se IV by Fe 0 in an initial lag stage, followed by a faster heterogeneous reduction, mediated by an Fe II -bearing phase (hydroxide or green rust). Solution pH was a critical factor for the kinetic rate in the lag stage (0.33 h -1 for pH > 8 and 0.10 h -1 for pH 6-8). The length of lag stage was 20-30 min as determined by the time for dissolved Fe II concentration to reach 0.30 ± 0.04 mg L -1 which was critical for induction of the faster stage. About 65% of the initial Se IV was reduced to Se 0 , the primary reductive product in both stages.

beta-Citryl-L-glutamate is an endogenous iron chelator that occurs naturally in the developing brain.

PubMed

Hamada-Kanazawa, Michiko; Kouda, Makiko; Odani, Akira; Matsuyama, Kaori; Kanazawa, Kiyoka; Hasegawa, Tatsuya; Narahara, Masanori; Miyake, Masaharu

2010-01-01

The compound beta-citryl-L-glutamate (beta-CG) was initially isolated from developing brains, while it has also been found in high concentrations in testes and eyes. However, its functional roles are unclear. To evaluate its coordination with metal ions, we performed pH titration experiments. The stability constant, logbeta(pqr) for M(p)(beta-CG)(q)H(r) was calculated from pH titration data, which showed that beta-CG forms relatively strong complexes with Fe(III), Cu(II), Fe(II) and Zn(II). beta-CG was also found able to solubilize Fe more effectively from Fe(OH)(2) than from Fe(OH)(3). Therefore, we examined the effects of beta-CG on Fe-dependent reactive oxygen species (ROS)-generating systems, as well as the potential ROS-scavenging activities of beta-CG and metal ion-(beta-CG) complexes. beta-CG inhibited the Fe-dependent degradation of deoxyribose and Fe-dependent damage to DNA or plasmid DNA in a dose-dependent manner, whereas it had no effect on Cu-mediated DNA damage. In addition, thermodynamic data showed that beta-CG in a physiological pH solution is an Fe(II) chelator rather than an Fe(III) chelator. Taken together, these findings suggest that beta-CG is an endogenous low molecular weight Fe chelator.

Trichoderma harzianum Produces a New Thermally Stable Acid Phosphatase, with Potential for Biotechnological Application

PubMed Central

Souza, Amanda Araújo; Leitão, Vanessa Oliveira; Ramada, Marcelo Henrique; Mehdad, Azadeh; Georg, Raphaela de Castro; Ulhôa, Cirano José; de Freitas, Sonia Maria

2016-01-01

Acid phosphatases (ACPases) are produced by a variety of fungi and have gained attention due their biotechnological potential in industrial, diagnosis and bioremediation processes. These enzymes play a specific role in scavenging, mobilization and acquisition of phosphate, enhancing soil fertility and plant growth. In this study, a new ACPase from Trichoderma harzianum, named ACPase II, was purified and characterized as a glycoprotein belonging to the acid phosphatase family. ACPase II presents an optimum pH and temperature of 3.8 and 65°C, respectively, and is stable at 55°C for 120 min, retaining 60% of its activity. The enzyme did not require metal divalent ions, but was inhibited by inorganic phosphate and tungstate. Affinity for several phosphate substrates was observed, including phytate, which is the major component of phosphorus in plant foods. The inhibition of ACPase II by tungstate and phosphate at different pH values is consistent with the inability of the substrate to occupy its active site due to electrostatic contacts that promote conformational changes, as indicated by fluorescence spectroscopy. A higher affinity for tungstate rather than phosphate at pH 4.0was observed, in accordance with its highest inhibitory effect. Results indicate considerable biotechnological potential of the ACPase II in soil environments. PMID:26938873

Application of principal component analysis for the optimisation of lead(II) biosorption.

PubMed

Wajda, Łukasz; Duda-Chodak, Aleksandra; Tarko, Tomasz; Kamiński, Paweł

2017-10-03

Current study was focused on optimising lead(II) biosorption carried out by living cells of Arthrospira platensis using Principal Component Analysis. Various experimental conditions were considered: initial metal concentration (50 and 100 mg/l), solution pH (4.0, 4.5, 5.0, 5.5) and contact time (10, 20, 30, 40, 50 and 60 min) at constant rotary speed 200 rpm. It was found that when the biomass was separated from experimental solutions by the filtration, almost 50% of initial metal dose was removed by the filter paper. Moreover, pH was the most important parameter influencing examined processes. The Principal Component Analysis indicated that the most optimum conditions for lead(II) biosorption were metal initial concentration 100 mg/l, pH 4.5 and time 60 min. According to the analysis of the first component it might be stated that the lead(II) uptake increases in time. In overall, it was found to be useful for analysing data obtained in biosorption experiments and eliminating insignificant experimental conditions. Experimental data fitted Langmuir and Dubinin-Radushkevich models indicating that physical and chemical absorption take place at the same time. Further studies are necessary to verify how sorption-desorption cycles affect A. platensis cells.

Trichoderma harzianum Produces a New Thermally Stable Acid Phosphatase, with Potential for Biotechnological Application.

PubMed

Souza, Amanda Araújo; Leitão, Vanessa Oliveira; Ramada, Marcelo Henrique; Mehdad, Azadeh; Georg, Raphaela de Castro; Ulhôa, Cirano José; de Freitas, Sonia Maria

2016-01-01

Acid phosphatases (ACPases) are produced by a variety of fungi and have gained attention due their biotechnological potential in industrial, diagnosis and bioremediation processes. These enzymes play a specific role in scavenging, mobilization and acquisition of phosphate, enhancing soil fertility and plant growth. In this study, a new ACPase from Trichoderma harzianum, named ACPase II, was purified and characterized as a glycoprotein belonging to the acid phosphatase family. ACPase II presents an optimum pH and temperature of 3.8 and 65 °C, respectively, and is stable at 55 °C for 120 min, retaining 60% of its activity. The enzyme did not require metal divalent ions, but was inhibited by inorganic phosphate and tungstate. Affinity for several phosphate substrates was observed, including phytate, which is the major component of phosphorus in plant foods. The inhibition of ACPase II by tungstate and phosphate at different pH values is consistent with the inability of the substrate to occupy its active site due to electrostatic contacts that promote conformational changes, as indicated by fluorescence spectroscopy. A higher affinity for tungstate rather than phosphate at pH 4.0 was observed, in accordance with its highest inhibitory effect. Results indicate considerable biotechnological potential of the ACPase II in soil environments.

Umbilical Cord Blood pH in Intrapartum Hypoxia.

PubMed

Perveen, Fouzia; Khan, Ayesha; Ali, Tahmina; Rabia, Syeda

2015-09-01

To determine the association of cord arterial blood pH with neonatal outcome in cases of intrapartum fetal hypoxia. Descriptive analytical study. Gynaecology Unit-II, Civil Hospital, Karachi, from September 2011 to November 2012. All singleton cephalic fetuses at term gestation were included in the study. Those with any anomaly, malpresentation, medical disorders, maternal age < 18 years, multiple gestation and ruptured membranes were excluded. Patients with abnormal cardiotocography and/or meconium stained liquor were enrolled as index case and immediate next delivery with no such signs as a control. Demographic characteristics, pH level < or > 7.25, neonatal outcome measures (healthy, NICU admission or neonatal death), color of liquor and mode of delivery recorded on predesigned proforma. Statistical analysis performed by SPSS 16 by using independent-t test or chi-square test and ANOVA test as needed. A total of 204 newborns were evaluated. The mean pH level was found to be significantly different (p=0.007) in two groups. The pH value 7.25 had significant association (p < 0.001) with the neonatal outcome. However, the association of neonatal outcome with severity of acidemia was not found to be significant. Grading of Meconium Stained Liquor (MSL) also did not relate positively with pH levels as 85.7% of grade I, 68.9% of grade II and 59.4% of grade III MSLhad pH > 7.25. Majority (63.6%) cases needed caesarean section as compared to 31.4% controls. There is a significant association of cord arterial blood pH at birth with neonatal outcome at pH < or > 7.25; but below the level of pH 7.25 it is still inconclusive.

Synthesis and Structure of Vanadium Halide Complexes Containing Diphosphine Ligands with Pendant Amines

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

Egbert, Jonathan D.; Labios, Liezel A.; Darmon, Jonathan M.

2016-02-18

A series of vanadium(III) diiodide complexes of the formula CpV(P RN R'P R)I 2 (Cp = 5-C 5H 5; P RN R'P R = (R 2PCH 2) 2N(R)), where R = Et, R = Me (1a), R = Ph (1b); R = Ph, R = Me (1c)) is reported. The corresponding vanadium(II) monoiodide complexes of the formula CpV(P RN R' PR)I, where R = Et, R = Me (2a), R = Ph (2b); R = Ph, R = Me (2c)) were prepared in THF by reduction of 1a-c with Zn powder. The paramagnetic complexes 1a-c and 2a-c are characterized bymore » elemental analysis, 1H NMR spectroscopy, and by cyclic voltammetry for complexes 2b and 4b. Complexes 1c and 2a-c were also characterized in the single crystal by X-ray crystallography. We report the preparation of the vanadium(II) complexes CpV(P Ph 2N Ph 2)I (3) (P Ph 2N Ph 2 = 1,5-diphenyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) and trans-[VCl 2(PEtNMePEt)2] (4a) and trans-[VCl 2(PEtNPhPEt) 2] (4b). These complexes represent initial coordination chemistry of vanadium complexes with P RN R'P R and P Ph 2N Ph 2 diphosphine ligands, which contain a pendant amine in the second coordination sphere. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Carbon-Based Solid-State Calcium Ion-Selective Microelectrode and Scanning Electrochemical Microscopy: A Quantitative Study of pH-Dependent Release of Calcium Ions from Bioactive Glass.

PubMed

Ummadi, Jyothir Ganesh; Downs, Corey J; Joshi, Vrushali S; Ferracane, Jack L; Koley, Dipankar

2016-03-15

Solid-state ion-selective electrodes are used as scanning electrochemical microscope (SECM) probes because of their inherent fast response time and ease of miniaturization. In this study, we report the development of a solid-state, low-poly(vinyl chloride), carbon-based calcium ion-selective microelectrode (Ca(2+)-ISME), 25 μm in diameter, capable of performing an amperometric approach curve and serving as a potentiometric sensor. The Ca(2+)-ISME has a broad linear response range of 5 μM to 200 mM with a near Nernstian slope of 28 mV/log[a(Ca(2+))]. The calculated detection limit for Ca(2+)-ISME is 1 μM. The selectivity coefficients of this Ca(2+)-ISME are log K(Ca(2+),A) = -5.88, -5.54, and -6.31 for Mg(2+), Na(+), and K(+), respectively. We used this new type of Ca(2+)-ISME as an SECM probe to quantitatively map the chemical microenvironment produced by a model substrate, bioactive glass (BAG). In acidic conditions (pH 4.5), BAG was found to increase the calcium ion concentration from 0.7 mM ([Ca(2+)] in artificial saliva) to 1.4 mM at 20 μm above the surface. In addition, a solid-state dual SECM pH probe was used to correlate the release of calcium ions with the change in local pH. Three-dimensional pH and calcium ion distribution mapping were also obtained by using these solid-state probes. The quantitative mapping of pH and Ca(2+) above the BAG elucidates the effectiveness of BAG in neutralizing and releasing calcium ions in acidic conditions.

The effect of antioxidants on quantitative changes of lysine and methionine in linoleic acid emulsions at different pH conditions.

PubMed

Hęś, Marzanna; Gliszczyńska-Świgło, Anna; Gramza-Michałowska, Anna

2017-01-01

Plants are an important source of phenolic compounds. The antioxidant capacities of green tea, thyme and rosemary extracts that contain these compounds have been reported earlier. However, there is a lack of accessible information about their activity against lipid oxidation in emulsions and inhibit the interaction of lipid oxidation products with amino acids. Therefore, the influence of green tea, thyme and rosemary extracts and BHT (butylated hydroxytoluene) on quantitative changes in lysine and methionine in linoleic acid emulsions at a pH of isoelectric point and a pH lower than the isoelectric point of amino acids was investigated. Total phenolic contents in plant extracts were determined spectrophotometrically by using Folin-Ciocalteu's reagent, and individual phenols by using HPLC. The level of oxidation of emulsion was determined using the measurement of peroxides and TBARS (thiobarbituric acid reactive substances). Methionine and lysine in the system were reacted with sodium nitroprusside and trinitrobenzenesulphonic acid respectively, and the absorbance of the complexes was measured. Extract of green tea had the highest total polyphenol content. The system containing antioxidants and amino acid protected linoleic acid more efficiently than by the addition of antioxidants only. Lysine and methionine losses in samples without the addition of antioxidants were lower in their isoelectric points than below these points. Antioxidants decrease the loss of amino acids. The protective properties of antioxidants towards methionine were higher in a pH of isoelectric point whereas towards lysine in pH below this point. Green tea, thyme and rosemary extracts exhibit antioxidant activity in linoleic acid emulsions. Moreover, they can be utilized to inhibit quantitative changes in amino acids in lipid emulsions. However, the antioxidant efficiency of these extracts seems to depend on pH conditions. Further investigations should be carried out to clarify this issue.

Note: In vivo pH imaging system using luminescent indicator and color camera

NASA Astrophysics Data System (ADS)

Sakaue, Hirotaka; Dan, Risako; Shimizu, Megumi; Kazama, Haruko

2012-07-01

Microscopic in vivo pH imaging system is developed that can capture the luminescent- and color-imaging. The former gives a quantitative measurement of a pH distribution in vivo. The latter captures the structural information that can be overlaid to the pH distribution for correlating the structure of a specimen and its pH distribution. By using a digital color camera, a luminescent image as well as a color image is obtained. The system uses HPTS (8-hydroxypyrene-1,3,6-trisulfonate) as a luminescent pH indicator for the luminescent imaging. Filter units are mounted in the microscope, which extract two luminescent images for using the excitation-ratio method. A ratio of the two images is converted to a pH distribution through a priori pH calibration. An application of the system to epidermal cells of Lactuca Sativa L is shown.

Calibration of diatom-pH-alkalinity methodology for the interpretation of the sedimentary record in Emerald Lake Integrated watershed study. Final report, 6 May 1985-10 October 1986

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

Holmes, R.W.

1986-10-10

The present study was designed to establish quantitative relationships between lake air-equilibrated pH, alkalinity, and diatoms occurring in the surface sediments in high-elevation Sierra Nevada Lakes. These relationships provided the necessary information to develop predictive equations relating lake pH to the composition of surface-sediment diatom assemblages in 27 study lakes. Using the Hustedt diatom pH classification system, Index B of Renberg and Hellberg, and multiple linear regression analysis, two equations were developed which predict lake pH from the relative abundance of sediment diatoms occurring in each of four diatom pH groupings.

Adsorption studies of Cd(II) onto Al 2O 3/Nb 2O 5 mixed oxide dispersed on silica matrix and its on-line preconcentration and determination by flame atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Mendonça Costa, Lucimara; Ribeiro, Emerson Schwingel; Segatelli, Mariana Gava; do Nascimento, Danielle Raphael; de Oliveira, Fernanda Midori; Tarley, César Ricardo Teixeira

2011-05-01

The present study describes the adsorption characteristic of Cd(II) onto Nb 2O 5/Al 2O 3 mixed oxide dispersed on silica matrix. The characterization of the adsorbent has been carried out by infrared spectroscopy (IR), scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), energy dispersive X-ray fluorescence analysis (EDXRF) and specific surface area ( SBET). From batch experiments, adsorption kinetic of Cd(II) was described by a pseudo-second-order kinetic model. The Langmuir linear isotherm fitted to the experimental adsorption isotherm very well, and the maximum adsorption capacity was found to be 17.88 mg g -1. Using the effective material, a method for Cd(II) preconcentration at trace level was developed. The method was based on on-line adsorption of Cd(II) onto SiO 2/Al 2O 3/Nb 2O 5 at pH 8.64, in which the quantitative desorption occurs with 1.0 mol L -1 hydrochloric acid towards FAAS detector. The experimental parameters related to the system were studied by means of multivariate analysis, using 2 4 full factorial design and Doehlert matrix. The effect of SO 42-, Cu 2+, Zn 2+ and Ni 2+ foreign ions showed no interference at 1:100 analyte:interferent proportion. Under the most favorable experimental conditions, the preconcentration system provided a preconcentration factor of 18.4 times, consumption index of 1.08 mL, sample throughput of 14 h -1, concentration efficiency of 4.35 min -1, linear range from 5.0 up to 35.0 μg L -1 and limits of detection and quantification of 0.19 and 0.65 μg L -1 respectively. The feasibility of the proposed method for Cd(II) determination was assessed by analysis of water samples, cigarette sample and certified reference materials TORT-2 (Lobster hepatopancreas) and DOLT-4 (Dogfish liver).

Surgery in World War II. Orthopedic Surgery in the Zone of Interior

DTIC Science & Technology

1970-01-01

General Reference and Research Branch ROSE C. ENGELMAN, Ph. D., Chief, Historians Branch GERALDINE B. SITES, Chief, Information Activities Branch Major...SERIES Internal Medicine in World War II: Vol. I. Activities of Medical Consultants Vol. II. Infectious Diseases Vol. III. Infectious Diseases and General...Arthropodborne Diseases Other Than Malaria Vol. IX. Special Fields Surgery in World War II: Activities of Surgical Consultants, vol. I Activities of Surgical

Iron(II)-Catalyzed Iron Atom Exchange and Mineralogical Changes in Iron-rich Organic Freshwater Flocs: An Iron Isotope Tracer Study.

PubMed

ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben

2017-06-20

In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57 Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57 Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short-term Fe(III)-reducing conditions facilitating the fast attainment of solid-solution equilibria (e.g., in stagnant waters), Fe-rich freshwater flocs are expected to remain an effective sink for trace elements.

Mn(II) Oxidation by the Multicopper Oxidase Complex Mnx: A Binuclear Activation Mechanism.

PubMed

Soldatova, Alexandra V; Tao, Lizhi; Romano, Christine A; Stich, Troy A; Casey, William H; Britt, R David; Tebo, Bradley M; Spiro, Thomas G

2017-08-23

The bacterial protein complex Mnx contains a multicopper oxidase (MCO) MnxG that, unusually, catalyzes the two-electron oxidation of Mn(II) to MnO 2 biomineral, via a Mn(III) intermediate. Although Mn(III)/Mn(II) and Mn(IV)/Mn(III) reduction potentials are expected to be high, we find a low reduction potential, 0.38 V (vs Normal Hydrogen Electrode, pH 7.8), for the MnxG type 1 Cu 2+ , the electron acceptor. Indeed the type 1 Cu 2+ is not reduced by Mn(II) in the absence of molecular oxygen, indicating that substrate oxidation requires an activation step. We have investigated the enzyme mechanism via electronic absorption spectroscopy, using chemometric analysis to separate enzyme-catalyzed MnO 2 formation from MnO 2 nanoparticle aging. The nanoparticle aging time course is characteristic of nucleation and particle growth; rates for these processes followed expected dependencies on Mn(II) concentration and temperature, but exhibited different pH optima. The enzymatic time course is sigmoidal, signaling an activation step, prior to turnover. The Mn(II) concentration and pH dependence of a preceding lag phase indicates weak Mn(II) binding. The activation step is enabled by a pK a > 8.6 deprotonation, which is assigned to Mn(II)-bound H 2 O; it induces a conformation change (consistent with a high activation energy, 106 kJ/mol) that increases Mn(II) affinity. Mnx activation is proposed to decrease the Mn(III/II) reduction potential below that of type 1 Cu(II/I) by formation of a hydroxide-bridged binuclear complex, Mn(II)(μ-OH)Mn(II), at the substrate site. Turnover is found to depend cooperatively on two Mn(II) and is enabled by a pK a 7.6 double deprotonation. It is proposed that turnover produces a Mn(III)(μ-OH) 2 Mn(III) intermediate that proceeds to the enzyme product, likely Mn(IV)(μ-O) 2 Mn(IV) or an oligomer, which subsequently nucleates MnO 2 nanoparticles. We conclude that Mnx exploits manganese polynuclear chemistry in order to facilitate an otherwise difficult oxidation reaction, as well as biomineralization. The mechanism of the Mn(III/IV) conversion step is elucidated in an accompanying paper .

Evaluation of calcium alginate beads for Ce, La and Nd preconcentration from groundwater prior to ICP OES analysis.

PubMed

Arantes de Carvalho, Gabriel G; Kondaveeti, Stalin; Petri, Denise F S; Fioroto, Alexandre M; Albuquerque, Luiza G R; Oliveira, Pedro V

2016-12-01

Analytical methods for the determination of rare earth elements (REE) in natural waters by plasma spectrochemical techniques often require sample preparation procedures for analytes preconcentration as well as for removing matrix constituents, that may interfere on the analytical measurements. In the present work, calcium alginate (CA) beads were used for the first time aiming at Ce, La and Nd preconcentration from groundwater samples for further determination by inductively coupled plasma optical emission spectrometry (ICP OES). Test samples were analyzed in batch mode by transferring a 40mL test portion (pH=5±0.2) into a 50mL polyethylene flask containing 125mg CA beads. After 15min contact, the analytes were quantitatively extracted from the loaded CA beads with 2.0mL of 1.0molL -1 HCl solution for further determination by ICP OES, using Ce (II) 456.236, La (II) 379.478 and Nd (II) 430.358nm emission lines. The proposed approach is a reliable alternative for REE single-stage preconcentration from aqueous samples, as it provided accurate results based on the addition and recovery analysis of groundwater. The results obtained by the proposed method were also compared with those from reference method based on inductively coupled plasma mass spectrometry (ICP-MS) and no significant differences were observed after applying the Student's t-test at 95% confidence level. Copyright © 2016 Elsevier B.V. All rights reserved.

Multi-spectroscopic and molecular modeling approaches to elucidate the binding interaction between bovine serum albumin and darunavir, a HIV protease inhibitor

NASA Astrophysics Data System (ADS)

Shi, Jie-Hua; Zhou, Kai-Li; Lou, Yan-Yue; Pan, Dong-Qi

2018-01-01

Darunavir (DRV), a second-generation HIV protease inhibitor, is widely used across the world as an important component of HIV therapy. The interaction of DRV with bovine serum albumin (BSA), a major carrier protein, has been studied under simulated physiological conditions (pH 7.4) by multi-spectroscopic techniques in combination with molecular modeling. Fluorescence data revealed that the intrinsic fluorescence of BSA was quenched by DRV in terms of a static quenching procedure due to the formation of the DRV-BSA complex. The results indicated the presence of single weak affinity binding site ( 103 M- 1, 310 K) on protein. The thermodynamic parameters, namely enthalpy change (ΔH0), entropy change (ΔS0) and Gibbs free energy change (ΔG0) were calculated, which signified that the binding reaction was spontaneous, the main binding forces were hydrogen bonding and van der Waals forces. Importantly, competitive binding experiments with three site probes, phenylbutazone (in sub-domain IIA, site I), ibuprofen (in sub-domain IIIA, site II) and artemether (in the interface between sub-domain IIA and IIB, site II'), suggested that DRV was preferentially bound to the hydrophobic cavity in site II' of BSA, and this finding was validated by the docking results. Additionally, synchronous fluorescence, three-dimensional fluorescence and Resonance Rayleigh Scattering (RRS) spectroscopy gave qualitative information on the conformational changes of BSA upon adding DRV, while quantitative data were obtained with Fourier transform infrared spectroscopy (FT-IR).

The pH-dependent Structures of the Manganese Binding Sites in Oxalate Decarboxylase as Revealed by High-Field Electron Paramagnetic Resonance

PubMed Central

Tabares, Leandro C.; Gätjens, Jessica; Hureau, Christelle; Burrell, Matthew R.; Bowater, Laura; Pecoraro, Vincent L.; Bornemann, Stephen; Un, Sun

2009-01-01

A high-field electron paramagnetic resonance (HFEPR) study of oxalate decarboxylase (OxdC) is reported. OxdC breaks down oxalate to carbon dioxide and formate and possesses two distinct manganese(II) binding sites, referred to as site-1 and -2. The Mn(II) zero-field interaction was used to probe the electronic state of the metal ion and to examine chemical/mechanistic roles of each of the Mn(II) centers. High magnetic-fields were exploited not only to resolve the two sites, but also to measure accurately the Mn(II) zero-field parameters of each of the sites. The spectra exhibited surprisingly complex behavior as a function of pH. Six different species were identified based on their zero-field interactions, two corresponding to site-1 and four states to site-2. The assignments were verified using a mutant that only affected site-1. The speciation data determined from the HFEPR spectra for site -2 was consistent with a simple triprotic equilibrium model, while the pH dependence of site-1 could be described by a single pKa. This pH dependence was independent of the presence of the His-tag and of whether the preparations contained 1.2 or 1.6 Mn per subunit. Possible structures of the six species are proposed based on spectroscopic data from model complexes and existing protein crystallographic structures obtained at pH 8 are discussed. Although site-1 has been identified as the active site and no role has been assigned to site-2, the pronounced changes in the electronic structure of the latter and its pH behavior, which also matches the pH-dependent activity of this enzyme, suggests that even if the conversion of oxalate to formate is carried out at site-1, site-2 likely plays a catalytically relevant role. PMID:19505123

Development of quantitative methods for the detection of enteroviruses in sewage sludges during activation and following land disposal.

PubMed Central

Hurst, C J; Farrah, S R; Gerba, C P; Melnick, J L

1978-01-01

The development and evaluation of methods for the quantitative recovery of enteroviruses from sewage sludge are reported. Activated sewage sludge solids were collected by centrifugation, and elution of the solid-associated virus was accomplished by mechanical agitation in glycine buffer at pH 11.0. Eluted viruses were concentrated either onto an aluminum hydroxide floc or by association with a floc which formed de novo upon adjustment of the glycine eluate to pH 3.5. Viruses which remained in the liquid phase after lowering the pH of glycine eluate were concentrated by adsorption to and elution from membrane filters. The method of choice included high pH glycine elution and subsequent low pH concentration; it yielded an efficiency of recovery from activated sludge of 80% for poliovirus type 1, 68% for echovirus type 7, and 75% for coxsackievirus B3. This method was used to study the survival of naturally occurring virus in sludge at a sewage treatment plant and after subsequent land disposal of the solids after aerobic digestion. Reduction of enterovirus titers per gram (dry weight) of solids were modest during sludge activation but increased to a rate of 2 log 10/week after land disposal. PMID:29559

Development of quantitative methods for the detection of enteroviruses in sewage sludges during activation and following land disposal.

PubMed

Hurst, C J; Farrah, S R; Gerba, C P; Melnick, J L

1978-07-01

The development and evaluation of methods for the quantitative recovery of enteroviruses from sewage sludge are reported. Activated sewage sludge solids were collected by centrifugation, and elution of the solid-associated virus was accomplished by mechanical agitation in glycine buffer at pH 11.0. Eluted viruses were concentrated either onto an aluminum hydroxide floc or by association with a floc which formed de novo upon adjustment of the glycine eluate to pH 3.5. Viruses which remained in the liquid phase after lowering the pH of glycine eluate were concentrated by adsorption to and elution from membrane filters. The method of choice included high pH glycine elution and subsequent low pH concentration; it yielded an efficiency of recovery from activated sludge of 80% for poliovirus type 1, 68% for echovirus type 7, and 75% for coxsackievirus B3. This method was used to study the survival of naturally occurring virus in sludge at a sewage treatment plant and after subsequent land disposal of the solids after aerobic digestion. Reduction of enterovirus titers per gram (dry weight) of solids were modest during sludge activation but increased to a rate of 2 log 10/week after land disposal.

Watershed scale fungal community characterization along a pH gradient in a subsurface environment co-contaminated with uranium and nitrate

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

Jasrotia, Puja; Green, Stefan; Canion, Andy

2014-01-01

The objective of this study was to characterize fungal communities in a subsurface environment co-contaminated with uranium and nitrate at the watershed scale, and to determine the potential contribution of fungi to contaminant transformation (nitrate attenuation). The abundance, distribution and diversity of fungi in subsurface groundwater samples were determined using quantitative and semi-quantitative molecular techniques, including quantitative PCR of eukaryotic SSU rRNA genes and pyrosequencing of fungal internal transcribed spacer (ITS) regions. Potential bacterial and fungal denitrification was assessed in sediment-groundwater slurries amended with antimicrobial compounds and in fungal pure cultures isolated from subsurface. Our results demonstrate that subsurface fungalmore » communities are dominated by members of the phylum Ascomycota, and a pronounced shift in fungal community composition occurs across the groundwater pH gradient at the field site, with lower diversity observed under acidic (pH < 4.5) conditions. Fungal isolates recovered from subsurface sediments were shown to reduce nitrate to nitrous oxide, including cultures of the genus Coniochaeta that were detected in abundance in pyrosequence libraries of site groundwater samples. Denitrifying fungal isolates recovered from the site were classified, and found to be distributed broadly within the phylum Ascomycota, and within a single genus within the Basidiomycota. Potential denitrification rate assays with sediment-groundwater slurries showed the potential for subsurface fungi to reduce nitrate to nitrous oxide under in situ acidic pH conditions.« less

Acid-tolerant microaerophilic Fe(II)-oxidizing bacteria promote Fe(III)-accumulation in a fen.

PubMed

Lüdecke, Claudia; Reiche, Marco; Eusterhues, Karin; Nietzsche, Sandor; Küsel, Kirsten

2010-10-01

The ecological importance of Fe(II)-oxidizing bacteria (FeOB) at circumneutral pH is often masked in the presence of O(2) where rapid chemical oxidation of Fe(II) predominates. This study addresses the abundance, diversity and activity of microaerophilic FeOB in an acidic fen (pH ∼ 5) located in northern Bavaria, Germany. Mean O(2) penetration depth reached 16 cm where the highest dissolved Fe(II) concentrations (up to 140 µM) were present in soil water. Acid-tolerant FeOB cultivated in gradient tubes were most abundant (10(6) cells g(-1) peat) at the 10-20 cm depth interval. A stable enrichment culture was active at up to 29% O(2) saturation and Fe(III) accumulated 1.6 times faster than in abiotic controls. An acid-tolerant, microaerophilic isolate (strain CL21) was obtained which was closely related to the neutrophilic, lithoautotrophic FeOB Sideroxydans lithotrophicus strain LD-1. CL21 oxidized Fe(II) between pH 4 and 6.0, and produced nanoscale-goethites with a clearly lower mean coherence length (7 nm) perpendicular to the (110) plane than those formed abiotically (10 nm). Our results suggest that an acid-tolerant population of FeOB is thriving at redox interfaces formed by diffusion-limited O(2) transport in acidic peatlands. Furthermore, this well-adapted population is successfully competing with chemical oxidation and thereby playing an important role in the microbial iron cycle. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

Bimodal MR-PET agent for quantitative pH imaging

PubMed Central

Frullano, Luca; Catana, Ciprian; Benner, Thomas; Sherry, A. Dean; Caravan, Peter

2010-01-01

Activatable or “smart” magnetic resonance contrast agents have relaxivities that depend on environmental factors such as pH or enzymatic activity, but the MR signal depends on relaxivity and agent concentration – two unknowns. A bimodal approach, incorporating a positron emitter, solves this problem. Simultaneous positron emission tomography (PET) and MR imaging with the biomodal, pH-responsive MR-PET agent GdDOTA-4AMP-F allows direct determination of both concentration (PET) and T1 (MRI), and hence pH. PMID:20191650

Linking Mn(II)-oxidizing bacteria to natural attenuation at a former U mining site

NASA Astrophysics Data System (ADS)

Akob, D.; Bohu, T.; Beyer, A.; Schäffner, F.; Händel, M.; Johnson, C.; Merten, D.; Büchel, G.; Totsche, K.; Küsel, K.

2012-04-01

Uranium mining near Ronneburg, Germany resulted in widespread environmental contamination with acid mine drainage (AMD) and high concentrations of heavy metals and radionuclides. Despite physical remediation of the area, groundwater is still a source of heavy metal contaminants, e.g., Cd, Ni, Co, Cu and Zn, to nearby ecosystems. However, natural attenuation of heavy metals is occurring in Mn oxide rich soils and sediments ranging in pH from 5 to 7. While microorganisms readily oxidize Mn(II) and precipitate Mn oxides at pH ~7 under oxic conditions, few studies describe Mn(II)-oxidizing bacteria (MOB) at pH ~5 and/or in the presence of heavy metals. In this study we (1) isolated MOB from the contaminated Ronneburg area at pH 5.5 and 7 and (2) evaluated the biological formation of Mn oxides. We isolated nine MOB strains at pH 7 (members of the Proteobacteria, Actinobacteria, Bacteroidetes, and Firmicutes phyla) and a single isolate at pH 5.5 (Oxalobacteraceae isolate AB_14, within the β-Proteobacteria). LA-ICP-MS showed that all isolates accumulated Mn and Fe in their biomass. However, the Oxalobacteraceae isolate AB_14 oxidizes more Mn without additional Fe in the medium. Preliminary FTIR analysis indicated that all isolates formed precipitates, which showed absorption bands that were characteristic for birnessite. High resolution TEM showed variable morphology of precipitates and EDS confirmed the presence of Mn oxides. Isolate AB_14 was not surrounded with precipitates whereas our Actinobacteria isolate AB_18 was encrusted with Mn oxides. Electron diffraction is currently being used to confirm the presence of birnessite and other Mn oxide phases. This, the first known report of any organism capable of Mn oxidation at low pH, demonstrated that MOB can be involved in the natural attenuation of both moderately acidic and neutral pH soils and sediments via the formation of biogenic Mn oxides. Future work will fully evaluate the minerals formed in this process as well as their interactions with contaminating heavy metals and radionuclides.

Zinc(II) complexation by some biologically relevant pH buffers.

PubMed

Wyrzykowski, D; Tesmar, A; Jacewicz, D; Pranczk, J; Chmurzyński, L

2014-12-01

The isothermal titration calorimetry (ITC) technique supported by potentiometric titration data was used to study the interaction of zinc ions with pH buffer substances, namely 2-(N-morpholino)ethanesulfonic acid (Mes), piperazine-N,N'-bis(2-ethanesulfonic acid) (Pipes), and dimethylarsenic acid (Caco). The displacement ITC titration method with nitrilotriacetic acid as a strong, competitive ligand was applied to determine conditional-independent thermodynamic parameters for the binding of Zn(II) to Mes, Pipes, and Caco. Furthermore, the relationship between the proposed coordination mode of the buffers and the binding enthalpy has been discussed. Copyright © 2014 John Wiley & Sons, Ltd.

United States Air Force Summer Research Program -- 1993. Volume 6. Arnold Engineering Development Center, Frank J. Seiler Research Laboratory, Wilford Hall Medical Center

DTIC Science & Technology

1993-12-01

where negative charge state. The local symmetry of the Ge(I) and Ge(II) centers are CI and C2 respectively. (See also Fig. 1.) q=- 1 Ge(I) Ge(II) s p...Raymond Field: Dept. of Computer Science Dept, CEM. M•e s , PhD Laboratory: / 3200 Willow Creek Road zmbry-Riddle Aeronautical Univ Vol-Page No: 0- 0...Field: Electrical Engineering Assistant Professor, PhD Laboratory: PL/WS 2390 S . York Street University of Denver Vol-Page No: 3-35 Denver, CO 80209-0177

Accumulation of metal ions by pectinates

NASA Astrophysics Data System (ADS)

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

2009-04-01

The knowledge of the mechanisms which regulate the interactions of metal ions with partially methyl esterified linear polymers of α-1,4 linked D-galacturonic acid units (pectinates), well represented in the root inner and outer apoplasm, is of great relevance to understand the processes which control their accumulation at the soil-root interface as well as their mobilization by plant metabolites. Accumulation of a metal by pectinates can be affected by the presence of other metals so that competition or distribution could be expected depending on the similar or different affinity of the metal ions towards the binding sites, mainly represented by the carboxylate groups. In order to better understand the mechanism of accumulation in the apoplasm of several metal ions, the sorption of Cd(II), Zn(II), Cu(II), Pb(II) and Cr(III) by a Ca-polygalacturonate gel, used as model of the soil-root interface, with a degree of esterification of 18% (PGAE1) and 65% (PGAE2) was studied at pH 3.0, 4.0, 5.0 and 6.0 in the presence of CaCl2 2.5 mM.. The results show that sorption increases with increasing both the initial metal concentration and pH. A similar sorption trend was evidenced for Cu(II) and Pb(II) and for Zn(II) and Cd(II), indicating that the mechanism of sorption for these two ionic couples is quite different. As an example, at pH 6.0 and an initial metal concentration equal to 2.0 mM, the amount of Cu(II) and Pb(II) sorbed was about 1.98 mg-1 of PGAE1 while that of Cd(II) and Zn(II) was about 1.2 mg-1. Cr(III) showed a rather different sorption trend and a much higher amount (2.8 mg-1of PGAE1 at pH 6.0) was recorded. The higher affinity of Cr(III) for the polysaccharidic matrix is attributable to the formation of Cr(III) polynuclear species in solution, as shown by the distribution diagrams obtained through the MEDUSA software. On the basis of these findings, the following affinity towards the PGAE1 can be assessed: Cr(III) > Cu(II) ? Pb(II) > Zn (II) ? Cd(II). Surprisingly, simultaneous sorption tests and SEM analyses indicate that a different mechanism regulates the sorption of Cu(II) and Pb(II) by PGAE1. In fact, the amount of Pb(II) sorbed (0.92 moles mg-1of PGAE1) by PGAE1 was nearly independent by the presence of Cu(II) ions, at least at the three different concentrations tested, that indicates a higher affinity of Pb(II). Such an aspect was further confirmed by exchange experiments. Samples of PGAE1 saturated with 1.96 moles mg-1of Cu(II) or 2.01 moles mg-1of Pb(II) were put in contact with 100 mL of solutions containing 97.3 moles of Pb(II) or 99.4 moles Cu(II), respectively. The exchange kinetics show that about 80% of Cu(II) was stochiometrically exchanged by Pb(II). In contrast, only about 10% of Pb(II) complexed by PGAE1 was exchanged by Cu(II). The kinetics of simultaneous sorption of all the metal ions tested indicate that Pb(II) is selectively sorbed by the PGAE1 gels. Cd(II) and Zn(II) show a similar affinity towards PGAE1. Thus, in the simultaneous presence of these ions, their selectivity towards this matrix follows the order: Pb > Cu > Cd ? Zn. Sorption of Cr(III) in the presence of the ions considered was not possible to carry out due to interference phenomena. The sorption of the same ions by 50 mg of PGAE2 evidences that the amount of Cu(II), Pb(II), and Cr(III) sorbed is markedly lower than that found for PGAE1. By considering that two carboxylic groups are involved in the complexation of a metal ion, the data show that such a stoichiometry is respected only for Pb(II). The amount of Cu(II) sorbed is about 50% lower than that of Pb(II) at all the pH values tested whereas those of Zn(II) and Cd(II) are negligible whereas that of Cr(III) is the highest. The different behaviour of Cu(II) compared to Pb(II) can be explained taking into account for both hydrophobic and steric effects of the methyl groups as well as to their different charge density. Thus, it can be concluded that the accumulation of metals at the soil-root interface strictly depends on the esterification degree of the root pectinates which, even highly esterified, do not loose the ability to accumulate metals, mainly Pb(II) and Cr(III).

Pd(II)/PhI(OAc)2 promoted direct cross coupling of glucals with aromatic acids.

PubMed

Begum, Zubeda; Shankar, G; Sirisha, K; Reddy, B V Subba

2018-05-22

A highly efficient oxidative C2-aroyloxylation of D-glucal with aromatic carboxylic acids has been achieved for the first time using 5 mol% Pd(OAc) 2 and 1 equiv of PhI(OAc) 2 to produce C2-aroyloxyglycals in good yields. The use of excess of PhI(OAc) 2 (2 equiv) provides C2-acyloxyglycal exclusively. Copyright © 2018 Elsevier Ltd. All rights reserved.

Experimental and computational study of the bonding properties of mixed bis-ylides of phosphorus and sulfur.

PubMed

Serrano, Elena; Navarro, Rafael; Soler, Tatiana; Carbó, Jorge J; Lledós, Agustí; Urriolabeitia, Esteban P

2009-07-20

The reactivity of the known ylide-sulfonium salt [Ph(3)P=CHC(O)CH(2)SMe(2)]Br 1 and the new ylide-sulfide [Ph(3)P=CHC-(O)CH(2)SMe] 2 toward Pd(II) complexes has been studied. Compound 1 reacts with PdCl(2)(NCMe)(2) and NEt(3) to give cis-[PdCl(2)[Ph(3)PCHC(O)CHSMe(2)-kappa-C,C

THE EFFECT OF PH AND DISSOLVED INORGANIC CARBON ON THE PROPERTIES OF IRON COLLOIDAL SUSPENSIONS

EPA Science Inventory

Discolored water resulting from suspended iron particles is a relatively common drinking water consumer complaint. These particles result from the oxygenation of Fe(II), and this study shows that pH and dissolved inorganic carbon (DIC) have important effects on their properties....

A solid phase extraction procedure for the determination of Cd(II) and Pb(II) ions in food and water samples by flame atomic absorption spectrometry.

PubMed

Daşbaşı, Teslima; Saçmacı, Şerife; Ülgen, Ahmet; Kartal, Şenol

2015-05-01

A relatively rapid, accurate and precise solid phase extraction method is presented for the determination of cadmium(II) and lead(II) in various food and water samples. Quantitation is carried out by flame atomic absorption spectrometry (FAAS). The method is based on the retention of the trace metal ions on Dowex Marathon C, a strong acid cation exchange resin. Some important parameters affecting the analytical performance of the method such as pH, flow rate and volume of the sample solution; type, concentration, volume, flow rate of the eluent; and matrix effects on the retention of the metal ions were investigated. Common coexisting ions did not interfere on the separation and determination of the analytes. The detection limits (3 σb) for Cd(II) and Pb(II) were found as 0.13 and 0.18 μg L(-1), respectively, while the limit of quantification values (10 σb) were computed as 0.43 and 0.60 μg L(-1) for the same sequence of the analytes. The precision (as relative standard deviation was lower than 4% at 5 μg L(-1) Cd(II) and 10 μg L(-1) Pb(II) levels, and the preconcentration factor was found to be 250. The accuracy of the proposed procedure was verified by analysing the certified reference materials, SPS-WW2 Batch 108 wastewater level 2 and INCT-TL-1 tea leaves, with the satisfactory results. In addition, for the accuracy of the method the recovery studies (⩾ 95%) were carried out. The method was applied to the determination of the analytes in the various natural waters (lake water, tap water, waste water with boric acid, waste water with H2SO4) and food samples (pomegranate flower, organic pear, radish leaf, lamb meat, etc.), and good results were obtained. While the food samples almost do not contain cadmium, they have included lead at low levels of 0.13-1.12 μg g(-1). Copyright © 2014 Elsevier Ltd. All rights reserved.

Genetic and Physiological Characterization of Two Clusters of Quantitative Trait Loci Associated With Seed Dormancy and Plant Height in Rice

PubMed Central

Ye, Heng; Beighley, Donn H.; Feng, Jiuhuan; Gu, Xing-You

2013-01-01

Seed dormancy and plant height have been well-studied in plant genetics, but their relatedness and shared regulatory mechanisms in natural variants remain unclear. The introgression of chromosomal segments from weedy into cultivated rice (Oryza sativa) prompted the detection of two clusters (qSD1-2/qPH1 and qSD7-2/qPH7) of quantitative trait loci both associated with seed dormancy and plant height. Together, these two clusters accounted for >96% of the variances for plant height and ~71% of the variances for germination rate in an isogenic background across two environments. On the initial introgression segments, qSD1-2/qPH1 was dissected genetically from OsVp1 for vivipary and qSD7-2/qPH7 separated from Sdr4 for seed dormancy. The narrowed qSD1-2/qPH1 region encompasses the semidwarf1 (sd1) locus for gibberellin (GA) biosynthesis. The qSD1-2/qPH1 allele from the cultivar reduced germination and stem elongation and the mutant effects were recovered by exogenous GA, suggesting that sd1 is a candidate gene of the cluster. In contrast, the effect-reducing allele at qSD7-2/qPH7 was derived from the weedy line; this allele was GA-insensitive and blocked GA responses of qSD1-2/qPH1, including the transcription of a GA-inducible α-amylase gene in imbibed endosperm, suggesting that qSD7-2/qPH7 may work downstream from qSD1-2/qPH1 in GA signaling. Thus, this research established the seed dormancy-plant height association that is likely mediated by GA biosynthesis and signaling pathways in natural populations. The detected association contributed to weed mimicry for the plant stature in the agro-ecosystem dominated by semidwarf cultivars and revealed the potential benefit of semidwarf genes in resistance to preharvest sprouting. PMID:23390608

Genetic and physiological characterization of two clusters of quantitative trait Loci associated with seed dormancy and plant height in rice.

PubMed

Ye, Heng; Beighley, Donn H; Feng, Jiuhuan; Gu, Xing-You

2013-02-01

Seed dormancy and plant height have been well-studied in plant genetics, but their relatedness and shared regulatory mechanisms in natural variants remain unclear. The introgression of chromosomal segments from weedy into cultivated rice (Oryza sativa) prompted the detection of two clusters (qSD1-2/qPH1 and qSD7-2/qPH7) of quantitative trait loci both associated with seed dormancy and plant height. Together, these two clusters accounted for >96% of the variances for plant height and ~71% of the variances for germination rate in an isogenic background across two environments. On the initial introgression segments, qSD1-2/qPH1 was dissected genetically from OsVp1 for vivipary and qSD7-2/qPH7 separated from Sdr4 for seed dormancy. The narrowed qSD1-2/qPH1 region encompasses the semidwarf1 (sd1) locus for gibberellin (GA) biosynthesis. The qSD1-2/qPH1 allele from the cultivar reduced germination and stem elongation and the mutant effects were recovered by exogenous GA, suggesting that sd1 is a candidate gene of the cluster. In contrast, the effect-reducing allele at qSD7-2/qPH7 was derived from the weedy line; this allele was GA-insensitive and blocked GA responses of qSD1-2/qPH1, including the transcription of a GA-inducible α-amylase gene in imbibed endosperm, suggesting that qSD7-2/qPH7 may work downstream from qSD1-2/qPH1 in GA signaling. Thus, this research established the seed dormancy-plant height association that is likely mediated by GA biosynthesis and signaling pathways in natural populations. The detected association contributed to weed mimicry for the plant stature in the agro-ecosystem dominated by semidwarf cultivars and revealed the potential benefit of semidwarf genes in resistance to preharvest sprouting.

Role of oxidants in enhancing dewaterability of anaerobically digested sludge through Fe (II) activated oxidation processes: hydrogen peroxide versus persulfate

PubMed Central

Song, Kang; Zhou, Xu; Liu, Yiqi; Gong, Yanyan; Zhou, Beibei; Wang, Dongbo; Wang, Qilin

2016-01-01

Improving dewaterability of sludge is important for the disposal of sludge in wastewater treatment plants (WWTPs). This study, for the first time, investigated the Fe(II) activated oxidization processes in improving anaerobically digested sludge (ADS) dewaterability. The combination of Fe(II) (0–100 mg/g total solids (TS)) and persulfate (0–1,000 mg/g TS) under neutral pH as well as the combination of Fe(II) (0–100 mg/g TS) and hydrogen peroxide (HP) (0–1,000 mg/g TS) under pH 3.0 were used to examine and compare their effect on the ADS dewaterability enhancement. The highest ADS dewaterability enhancement was attained at 25 mg Fe(II)/g TS and 50 mg HP/g TS, when the CST (CST: the capillary suction time, a sludge dewaterability indicator) was reduced by 95%. In contrast, the highest CST reduction in Fe(II)-persulfate conditioning was 90%, which was obtained at 50 mg Fe(II)/g TS and 250 mg persulfate/g TS. The results showed that Fe(II)-HP conditioning was comparable with Fe(II)-persulfate conditioning in terms of highest CST reduction. Economic analysis suggested that the Fe(II)-HP conditioning was more promising for improving ADS dewaterability compared with Fe(II)-persulfate conditioning, with the saving being up to $65,000 per year in a WWTP with a population equivalent of 100,000. PMID:27109500

Pb(II) removal from water using Fe-coated bamboo charcoal with the assistance of microwaves.

PubMed

Zhang, Zengsheng; Wang, Xuejiang; Wang, Yin; Xia, Siqing; Chen, Ling; Zhang, Yalei; Zhao, Jianfu

2013-05-01

Bamboo charcoal (BC) was used as starting material to prepare iron-modified bamboo charcoal (Fe-MBC) by its impregnation in FeCl3 and HNO3 solutions simultaneously, followed by microwave heating. The material can be used as an adsorbent for Pb(II) contaminants removal in water. The composites were prepared with Fe molar concentration of 0.5, 1.0 and 2.0 mol/L and characterized by means of N2 adsorption-desorption isotherms, X-ray diffraction spectroscopy (XRD), scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM-EDS), Fourier transform infrared (FT-IR) and point of zero charge (pH(pzc)) measurements. Nitrogen adsorption analyses showed that the BET specific surface area and total pore volume increased with iron impregnation. The adsorbent with Fe molar concentration of 2 mol/L (2Fe-MBC) exhibited the highest surface area and produced the best pore structure. The Pb(II) adsorption process of 2Fe-MBC and BC were evaluated in batch experiments and 2Fe-MBC showed an excellent adsorption capability for removal Pb(II). The adsorption of Pb(II) strongly depended on solution pH, with maximum values at pH 5.0. The ionic strength had a significant effect on the adsorption at pH < 6.0. The adsorption isotherms followed the Langmuir isotherm model well, and the maximum adsorption capacity for Pb(II) was 200.38 mg/g for 2Fe-MBC. The adsorption processes were well fitted by a pseudo second-order kinetic model. Thermodynamic parameters showed that the adsorption of Pb(II) onto Fe-MBC was feasible, spontaneous, and exothermic under the studied conditions, and the ion exchange mechanism played an significant role. These results have important implications for the design of low-cost and effective adsorbents in the removal of Pb(II) from wastewater.

Glutathione Complex Formation With Mercury(Ii) in Aqueous Solution at Physiological Ph

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

Mah, V.; Jalilehvand, F.; /SLAC

2012-08-23

The mercury(II) complexes formed in neutral aqueous solution with glutathione (GSH, here denoted AH{sub 3} in its triprotonated form) were studied using Hg L{sub III}-edge extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy, complemented with electrospray ionization mass spectrometric (ESI-MS) analyses. The [Hg(AH){sub 2}]{sup 2-} complex, with the Hg-S bond distances at 2.325 {+-} 0.01 {angstrom} in linear S-Hg-S coordination, and the {sup 199}Hg NMR chemical shift at -984 ppm, dominates except at high excess of glutathione. In a series of solutions with C{sub Hg(II)} {approx} 17 mM and GSH/Hg(II) mole ratios rising from 2.4 to 11.8,more » the gradually increasing mean Hg-S bond distance corresponds to an increasing amount of the [Hg(AH){sub 3}]{sup 4-} complex. ESI-MS peaks appear at -m/z values of 1208 and 1230 corresponding to the [Na{sub 4}Hg(AH){sub 2}(A)]{sup -} and [Na{sub 5}Hg(AH)(A){sub 2}]{sup -} species, respectively. In another series of solutions at pH 7.0 with CHg(II) 50 mM and GSH/Hg(II) ratios from 2.0 to 10.0, the Hg L{sub III}-edge EXAFS and {sup 199}Hg NMR spectra show that at high excess of glutathione (0.35 M) about 70% of the total mercury(II) concentration is present as the [Hg(AH){sub 3}]4- complex, with the average Hg-S bond distance 2.42 {+-} 0.02 {angstrom} in trigonal HgS{sub 3} coordination. The proportions of HgSn species, n = 2, 3, and 4, quantified by fitting linear combinations of model EXAFS oscillations to the experimental EXAFS data in our present and previous studies were used to obtain stability constants for the [Hg(AH){sub 3}]{sup 4-} complex and also for the [Hg(A){sub 4}]{sup 10-} complex that is present at high pH. For Hg(II) in low concentration at physiological conditions (pH 7.4, C{sub GSH} = 2.2 mM), the relative amounts of the HgS{sub 2} species [Hg(AH){sub 2}]{sup 2-}, [Hg(AH)(A)]{sup 3-}, and the HgS{sub 3} complex [Hg(AH){sub 3}]{sup 4-} were calculated to be 95:2:3. Our results are not consistent with the formation of dimeric Hg(II)-GSH complexes proposed in a recent EXAFS study.« less

Effects of inorganic electrolyte anions on enrichment of Cu(II) ions with aminated Fe3O4/graphene oxide: Cu(II) speciation prediction and surface charge measurement.

PubMed

Hu, Xin-jiang; Liu, Yun-guo; Zeng, Guang-ming; Wang, Hui; You, Shao-hong; Hu, Xi; Tan, Xiao-fei; Chen, An-wei; Guo, Fang-ying

2015-05-01

The present work evaluated the effects of six inorganic electrolyte anions on Cu(II) removal using aminated Fe3O4/graphene oxide (AMGO) in single- and multi-ion systems. A 2(6-2) fractional factorial design (FFD) was employed for assessing the effects of multiple anions on the adsorption process. The results indicated that the Cu(II) adsorption was strongly dependent on pH and could be significantly affected by inorganic electrolyte anions due to the changes in Cu(II) speciation and surface charge of AMGO. In the single-ion systems, the presence of monovalent anions (Cl(-), ClO4(-), and NO3(-)) slightly increased the Cu(II) adsorption onto AMGO at low pH, while the Cu(II) adsorption was largely enhanced by the presence of SO4(2-), CO3(2-), and HPO4(2-). Based on the estimates of major effects and interactions from FFD, the factorial effects of the six selected species on Cu(II) adsorption in multi-ion system were in the following sequence: HPO4(2-)>CO3(2-)>Cl(-)>SO4(2-)>NO3(-)=ClO4(-), and the combined factors of AD (Cl(-)×SO4(2-)) and EF (Cl(-)×SO4(2-)) had significant effects on Cu(II) removal. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nickel(II) biosorption by Rhodotorula glutinis.

PubMed

Suazo-Madrid, Alicia; Morales-Barrera, Liliana; Aranda-García, Erick; Cristiani-Urbina, Eliseo

2011-01-01

The present study reports the feasibility of using Rhodotorula glutinis biomass as an alternative low-cost biosorbent to remove Ni(II) ions from aqueous solutions. Acetone-pretreated R. glutinis cells showed higher Ni(II) biosorption capacity than untreated cells at pH values ranging from 3 to 7.5, with an optimum pH of 7.5. The effects of other relevant environmental parameters, such as initial Ni(II) concentration, shaking contact time and temperature, on Ni(II) biosorption onto acetone-pretreated R. glutinis were evaluated. Significant enhancement of Ni(II) biosorption capacity was observed by increasing initial metal concentration and temperature. Kinetic studies showed that the kinetic data were best described by a pseudo-second-order kinetic model. Among the two-, three-, and four-parameter isotherm models tested, the Fritz-Schluender model exhibited the best fit to experimental data. Thermodynamic parameters (activation energy, and changes in activation enthalpy, activation entropy, and free energy of activation) revealed that the biosorption of Ni(II) ions onto acetone-pretreated R. glutinis biomass is an endothermic and non-spontaneous process, involving chemical sorption with weak interactions between the biosorbent and Ni(II) ions. The high sorption capacity (44.45 mg g(-1) at 25°C, and 63.53 mg g(-1) at 70°C) exhibited by acetone-pretreated R. glutinis biomass places this biosorbent among the best adsorbents currently available for removal of Ni(II) ions from aqueous effluents.

Role of hydrous iron oxide formation in attenuation and diel cycling of dissolved trace metals in a stream affected by acid rock drainage

USGS Publications Warehouse

Parker, S.R.; Gammons, C.H.; Jones, Clain A.; Nimick, D.A.

2007-01-01

Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column. ?? 2006 Springer Science+Business Media B.V.

An enzyme kinetics study of the pH dependence of chloride activation of oxygen evolution in photosystem II.

PubMed

Baranov, Sergei; Haddy, Alice

2017-03-01

Oxygen evolution by photosystem II (PSII) involves activation by Cl - ion, which is regulated by extrinsic subunits PsbQ and PsbP. In this study, the kinetics of chloride activation of oxygen evolution was studied in preparations of PSII depleted of the PsbQ and PsbP subunits (NaCl-washed and Na 2 SO 4 /pH 7.5-treated) over a pH range from 5.3 to 8.0. At low pH, activation by chloride was followed by inhibition at chloride concentrations >100 mM, whereas at high pH activation continued as the chloride concentration increased above 100 mM. Both activation and inhibition were more pronounced at lower pH, indicating that Cl - binding depended on protonation events in each case. The simplest kinetic model that could account for the complete data set included binding of Cl - at two sites, one for activation and one for inhibition, and four protonation steps. The intrinsic (pH-independent) dissociation constant for Cl - activation, K S , was found to be 0.9 ± 0.2 mM for both preparations, and three of the four pK a s were determined, with the fourth falling below the pH range studied. The intrinsic inhibition constant, K I , was found to be 64 ± 2 and 103 ± 7 mM for the NaCl-washed and Na 2 SO 4 /pH7.5-treated preparations, respectively, and is considered in terms of the conditions likely to be present in the thylakoid lumen. This enzyme kinetics analysis provides a more complete characterization of chloride and pH dependence of O 2 evolution activity than has been previously presented.

Arsenic removal from acidic solutions with biogenic ferric precipitates.

PubMed

Ahoranta, Sarita H; Kokko, Marika E; Papirio, Stefano; Özkaya, Bestamin; Puhakka, Jaakko A

2016-04-05

Treatment of acidic solution containing 5g/L of Fe(II) and 10mg/L of As(III) was studied in a system consisting of a biological fluidized-bed reactor (FBR) for iron oxidation, and a gravity settler for iron precipitation and separation of the ferric precipitates. At pH 3.0 and FBR retention time of 5.7h, 96-98% of the added Fe(II) precipitated (99.1% of which was jarosite). The highest iron oxidation and precipitation rates were 1070 and 28mg/L/h, respectively, and were achieved at pH 3.0. Subsequently, the effect of pH on arsenic removal through sorption and/or co-precipitation was examined by gradually decreasing solution pH from 3.0 to 1.6 (feed pH). At pH 3.0, 2.4 and 1.6, the highest arsenic removal efficiencies obtained were 99.5%, 80.1% and 7.1%, respectively. As the system had ferric precipitates in excess, decreased arsenic removal was likely due to reduced co-precipitation at pH<2.4. As(III) was partially oxidized to As(V) in the system. In shake flask experiments, As(V) sorbed onto jarosite better than As(III). Moreover, the sorption capacity of biogenic jarosite was significantly higher than that of synthetic jarosite. The developed bioprocess simultaneously and efficiently removes iron and arsenic from acidic solutions, indicating potential for mining wastewater treatment. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of gastric pH on the pharmacokinetics of a BCS class II compound in dogs: utilization of an artificial stomach and duodenum dissolution model and GastroPlus,™ simulations to predict absorption.

PubMed

Bhattachar, Shobha N; Perkins, Everett J; Tan, Jeffrey S; Burns, Lee J

2011-11-01

Dogs are one of the most commonly used non-rodent species in toxicology studies and are known to have basal stomach pH ranging from 2 to 7 in the fasted state. Thus absorption and resulting plasma exposure of weakly basic compounds administered as crystalline suspensions to dogs are often variable. LY2157299 is a potent and selective transforming growth factor (TGF)-beta receptor type 1 kinase (TGF-βRI) inhibitor that displayed variable absorption in early dog studies. This molecule is a weakly basic Biopharmaceutics Classification System (BCS)Class II compound, and depends on the rate and extent of dissolution to drive oral absorption. An artificial stomach and duodenum (ASD) dissolution model was utilized to evaluate potential effect of gastric pH on the absorption of suspension and buffered solution formulations. GastroPlus™ was also employed to predict the magnitude of gastric pH changes on LY2157299 absorption. The ASD experiments demonstrated that administration of a buffered acidic solution could improve the potential for absorption by normalizing gastric pH and enabling supersaturation in the duodenum. GastroPlus™ modeling suggested that direct modulation of gastric pH could lead to marked changes in bioavailability. Pharmacokinetic experiments were conducted in dogs to evaluate the effect of gastric pH modification on plasma exposure. The data were qualitatively consistent with the predictions. Copyright © 2011 Wiley-Liss, Inc.

Identification, characterization, and quantitation of soluble HLA antigens in the circulation and peritoneal dialysate of renal patients.

PubMed Central

Gelder, F B; McDonald, J C; Landreneau, M D; McMillan, R M; Aultman, D F

1991-01-01

Human lymphocyte antigen (HLA) class I and class II antigens and beta 2 microglobulin (B2M) were identified in peritoneal dialysate (PD) and serum from patients with end-stage renal disease (ESRD) using monoclonal antibodies in an enzyme-linked immunoassay. The HLA class I and class II antigens each exhibited approximate molecular weights of 50,000 to 60,000 daltons by chromatography on Sepharose CL 6B. Class I antigens in serum and PD fluid were associated with B2M. Free B2M (Mr 11,500) also was detected in both sera and PD fluids. Unlike class I antigens, class II antigens were not found to have attached B2M. Class I and class II antigens eluted from 2-diethylaminoethanol ion exchange gradient columns at 0.07 mol/L (molar) phosphate buffer pH 7.2 and migrated with alpha 2-beta 1 mobility in agarose electrophoresis. Class I antigens were purified from ESRD patients' PD fluid by solid-phase immunoaffinity chromatography. Enzyme-linked immunoassay demonstrated that this purified protein was composed of a class I heavy chain and B2M. Class I allospecificity was confirmed by neutralization on known HLA typing antisera in a microcytotoxicity assay. Soluble HLA class I antigen preparations specifically inhibited blast transformation of responder lymphocytes in mixed lymphocyte culture reactions. Inhibition was dose dependent and ranged from 0% to 95%. The presence of soluble HLA antigens in body fluids may play an important part in the immunologic tolerance to self. This study demonstrates a ready source of large quantities of soluble HLA for detailed analysis. Images Fig. 1. PMID:2039290

Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: the role of Fe(II) and Fe(III).

PubMed

Yan, Sen; Chen, Yongheng; Xiang, Wu; Bao, Zhengyu; Liu, Chongxuan; Deng, Baolin

2014-12-01

The role of Fe(II) and Fe(III) in U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed that U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.9 to 9.0. For instance, at pH 6.9 the observed U(VI) reduction rates decreased by 81% and 82% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can be enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) possibly acted as an electron shuttle to ferry the electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 could facilitate U(VI) reductive immobilization in the contaminated groundwater.

Competitive Adsorption of Metals onto Magnetic Graphene Oxide: Comparison with Other Carbonaceous Adsorbents

PubMed Central

Hur, Jin; Shin, Jaewon; Yoo, Jeseung; Seo, Young-Soo

2015-01-01

Competitive adsorption isotherms of Cu(II), Pb(II), and Cd(II) were examined on a magnetic graphene oxide (GO), multiwalled carbon nanotubes (MWCNTs), and powered activated carbon (PAC). A series of analyses confirmed the successful synthesis of the magnetic GO based on a simple ultrasonification method. Irrespective of the adsorbents, the adsorption was highly dependent on pH, and the adsorption was well described by the Langmuir isotherm model. The maximum adsorption capacities of the adsorbents were generally higher in the order of Pb(II) > Cu(II) > Cd(II), which is the same as the degree of the electronegativity and the hydrated radius of the metals, suggesting that the metal adsorption may be governed by an ion exchange between positively charged metals and negatively charged surfaces, as well as diffusion of metals into the surface layer. The adsorption of each metal was mostly lower for multi- versus single-metal systems. The antagonistic effects were influenced by solution pH as well as the type of metals, and they were higher in the order of the magnetic GO > MWCNT > PAC. Dissolved HS played a greater role than HS adsorbed onto the adsorbents, competing with the adsorption sites for metal complexation. PMID:25861683

Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: The role of Fe(II) and Fe(III)

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

Yan, Sen; Chen, Yongheng; Xiang, Wu

2014-12-01

The role of Fe(II) and Fe(III) on U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.92 to 9.03. For instance, at pH 6.92 the observed U(VI) reduction rates decreased by 80.7% and 82.3% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can bemore » enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) probably acted as an electron shuttle to mediate the transfer of electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 can facilitate the U(VI) reductive immobilization in the contaminated groundwater.« less