Sample records for solution ph anion
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Relationship of Cell Sap pH to Organic Acid Change During Ion Uptake 1
Hiatt, A. J.
1967-01-01
Excised roots of barley (Hordeum vulgare, var. Campana) were incubated in KCl, K2SO4, CaCl2, and NaCl solutions at concentrations of 10−5 to 10−2 n. Changes in substrate solution pH, cell sap pH, and organic acid content of the roots were related to differences in cation and anion absorption. The pH of expressed sap of roots increased when cations were absorbed in excess of anions and decreased when anions were absorbed in excess of cations. The pH of the cell sap shifted in response to imbalances in cation and anion uptake in salt solutions as dilute as 10−5 n. Changes in cell sap pH were detectable within 15 minutes after the roots were placed in 10−3 n K2SO4. Organic acid changes in the roots were proportional to expressed sap pH changes induced by unbalanced ion uptake. Changes in organic acid content in response to differential cation and anion uptake appear to be associated with the low-salt component of ion uptake. PMID:16656506
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NASA Astrophysics Data System (ADS)
Wiśniewska, Małgorzata; Chibowski, Stanisław; Urban, Teresa
2016-05-01
The adsorption mechanism of anionic polyacrylamide (PAM) on the nanozirconia surface was examined. The effects of solution pH, carboxyl groups content in macromolecules and anionic surfactant (sodium dodecyl sulfate-SDS) addition were determined. The more probable structure of polymer adsorption layer was characterized based on the data obtained from spectrophotometry, viscosimetry and potentiometric titration methods. The adsorbed amount of polymer, size of macromolecules in the solution and surface charge density of ZrO2 particles in the absence and presence of PAM were assessed, respectively. Analysis of these results indicated that the increase of solution pH and content of carboxyl groups in the polymeric chains lead to more expanded conformations of adsorbing macromolecules. As a result, the adsorption of anionic polyacrylamide decreased. The SDS presence caused the significant increase of PAM adsorbed amount at pH 3, whereas at pH 6 and 9 the surfactant addition resulted in reduction of polymer adsorption level.
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Electronic structures and spectra of two antioxidants: uric acid and ascorbic acid
NASA Astrophysics Data System (ADS)
Shukla, M. K.; Mishra, P. C.
1996-04-01
Electronic absorption and fluorescence spectra of aqueous solutions of two well known antioxidants, uric acid and ascorbic acid (vitamin C), have been studied at different pH. The observed spectra have been interpreted in terms of neutral and anionic forms of the molecules with the help of molecular orbital calculations. The N 3 site of uric acid has been shown to be the most acidic. Fluorescence of uric acid seems to originate from an anion of the molecule in a wide pH range. Around pH 3, both the neutral and anionic forms of ascorbic acid appear to be present in aqueous solutions. In aqueous media, ascorbic acid appears to get converted easily to its dehydro form and this conversion does not seem to be reversible. An anion of dehydroascorbic acid seems to be formed on heating dehydroascorbic acid in aqueous solutions.
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NASA Astrophysics Data System (ADS)
Yaremko, Z. M.; Fedushinskaya, L. B.; Burka, O. A.; Soltys, M. N.
2014-09-01
The role of hydrophobic interaction in the development of associative processes is demonstrated, based on the concentration dependences of the viscosity and pH of binary solutions of polymethacrylic acid as an anionic polyelectrolyte and sodium laureth sulfate as an anionic surfactant. It is found that the inflection point on the dependence of the difference between the pH values of binary solutions of polymethacrylic acid and sodium laureth sulfate on the polyelectrolyte concentration is a criterion for determining the predominant contribution from hydrophobic interaction, as is the inflection point on the dependence of pH of individual solutions of polymethacrylic acid on the polyelectrolyte concentration.
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Nuclear reactor cooling system decontamination reagent regeneration. [PWR; BWR
Anstine, L.D.; James, D.B.; Melaika, E.A.; Peterson, J.P. Jr.
1980-06-06
An improved method for decontaminating the coolant system of water-cooled nuclear power reactors and for regenerating the decontamination solution is described. A small amount of one or more weak-acid organic complexing agents is added to the reactor coolant, and the pH is adjusted to form a decontamination solution which is circulated throughout the coolant system to dissolve metal oxides from the interior surfaces and complex the resulting metal ions and radionuclide ions. The coolant containing the complexed metal ions and radionuclide ions is passed through a strong-base anion exchange resin bed which has been presaturated with a solution containing the complexing agents in the same ratio and having the same pH as the decontamination solution. As the decontamination solution passes through the resin bed, metal-complexed anions are exchanged for the metal-ion-free anions on the bed, while metal-ion-free anions in the solution pass through the bed, thus removing the metal ions and regenerating the decontamination solution.
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Nuclear reactor cooling system decontamination reagent regeneration
Anstine, Larry D.; James, Dean B.; Melaika, Edward A.; Peterson, Jr., John P.
1985-01-01
An improved method for decontaminating the coolant system of water-cooled nuclear power reactors and for regenerating the decontamination solution. A small amount of one or more weak-acid organic complexing agents is added to the reactor coolant, and the pH is adjusted to form a decontamination solution which is circulated throughout the coolant system to dissolve metal oxides from the interior surfaces and complex the resulting metal ions and radionuclide ions. The coolant containing the complexed metal ions and radionuclide ions is passed through a strong-base anion exchange resin bed which has been presaturated with a solution containing the complexing agents in the same ratio and having the same pH as the decontamination solution. As the decontamination solution passes through the resin bed, metal-complexed anions are exchanged for the metal-ion-free anions on the bed, while metal-ion-free anions in the solution pass through the bed, thus removing the metal ions and regenerating the decontamination solution.
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The decomposition of peroxynitrite to nitroxyl anion (NO−) and singlet oxygen in aqueous solution
Khan, Ahsan Ullah; Kovacic, Dianne; Kolbanovskiy, Alexander; Desai, Mehul; Frenkel, Krystyna; Geacintov, Nicholas E.
2000-01-01
The mechanism of decomposition of peroxynitrite (OONO−) in aqueous sodium phosphate buffer solution at neutral pH was investigated. The OONO− was synthesized by directly reacting nitric oxide with superoxide anion at pH 13. The hypothesis was explored that OONO−, after protonation at pH 7.0 to HOONO, decomposes into 1O2 and HNO according to a spin-conserved unimolecular mechanism. Small aliquots of the concentrated alkaline OONO− solution were added to a buffer solution (final pH 7.0–7.2), and the formation of 1O2 and NO− in high yields was observed. The 1O2 generated was trapped as the transannular peroxide (DPAO2) of 9,10-diphenylanthracene (DPA) dissolved in carbon tetrachloride. The nitroxyl anion (NO−) formed from HNO (pKa 4.5) was trapped as nitrosylhemoglobin (HbNO) in an aqueous methemoglobin (MetHb) solution. In the presence of 25 mM sodium bicarbonate, which is known to accelerate the rate of decomposition of OONO−, the amount of singlet oxygen trapped was reduced by a factor of ≈2 whereas the yield of trapping of NO− by methemoglobin remained unaffected. Because NO3− is known to be the ultimate decomposition product of OONO−, these results suggest that the nitrate anion is not formed by a direct isomerization of OONO−, but by an indirect route originating from NO−. PMID:10716721
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Suzuki, Yuji
2006-06-01
In a dye-binding method using a pH indicator, color development has reportedly been affected by the kind of buffer solution used in the color reagent. This phenomenon was analyzed by using a calculation based on the assumption that the anion of the buffer solution also reacts with protein. Color development decreases with increases in the anion concentration of the buffer solution and in the equilibrium constant of the reaction between the anion and protein. The differences in color development due to the kind of buffer solution can be attributed to differences in the equilibrium constant of the reaction forming the anion-protein complex and to the concentration of the anion between the buffer solutions.
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Mulugeta, Mesay; Wibetoe, Grethe; Engelsen, Christian J; Lund, Walter
2009-05-15
A simple and versatile solid phase extraction (SPE) method has been developed to determine the anionic species of As, Cr, Mo, Sb, Se and V in leachates of cement mortar and concrete materials in the pH range 3-13. The anionic fractions of these elements were extracted using a strong anion exchanger (SAX) and their concentrations were determined as the difference in element concentration between the sample and the SAX effluent. Inductively coupled plasma mass spectrometry (ICP-MS) was used off-line to analyse solutions before and after passing through the SAX. The extraction method has been developed by optimizing sorbent type, sorbent conditioning and sample percolation rate. Breakthrough volumes and effect of matrix constituents were also studied. It was found that a polymer-based SAX conditioned with a buffer close to the sample pH or in some cases deionised water gave the best retention of the analytes. Optimal conditions were also determined for the quantitative elution of analytes retained on the SAX. Extraction of the cement mortar and concrete leachates showed that most of the elements had similar distribution of anions in both leachate types, and that the distribution was strongly pH dependent. Cr, Mo and V exist in anionic forms in strongly basic leachates (pH>12), and significant fractions of anionic Se were also detected in these solutions. Cr, Mo, Se and V were not determined as anions by the present method in the leachates of pH<12. Anionic As and Sb were found in small fractions in most of the leachates.
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Production of high specific activity silicon-32
Phillips, Dennis R.; Brzezinski, Mark A.
1994-01-01
A process for preparation of silicon-32 is provide and includes contacting an irradiated potassium chloride target, including spallation products from a prior irradiation, with sufficient water, hydrochloric acid or potassium hydroxide to form a solution, filtering the solution, adjusting pH of the solution to from about 5.5 to about 7.5, admixing sufficient molybdate-reagent to the solution to adjust the pH of the solution to about 1.5 and to form a silicon-molybdate complex, contacting the solution including the silicon-molybdate complex with a dextran-based material, washing the dextran-based material to remove residual contaminants such as sodium-22, separating the silicon-molybdate complex from the dextran-based material as another solution, adding sufficient hydrochloric acid and hydrogen peroxide to the solution to prevent reformation of the silicon-molybdate complex and to yield an oxidization state of the molybdate adapted for subsequent separation by an anion exchange material, contacting the solution with an anion exchange material whereby the molybdate is retained by the anion exchange material and the silicon remains in solution, and optionally adding sufficient alkali metal hydroxide to adjust the pH of the solution to about 12 to 13. Additionally, a high specific activity silicon-32 product having a high purity is provided.
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High specific activity silicon-32
Phillips, Dennis R.; Brzezinski, Mark A.
1996-01-01
A process for preparation of silicon-32 is provided and includes contacting an irradiated potassium chloride target, including spallation products from a prior irradiation, with sufficient water, hydrochloric acid or potassium hydroxide to form a solution, filtering the solution, adjusting pH of the solution to from about 5.5 to about 7.5, admixing sufficient molybdate-reagent to the solution to adjust the pH of the solution to about 1.5 and to form a silicon-molybdate complex, contacting the solution including the silicon-molybdate complex with a dextran-based material, washing the dextran-based material to remove residual contaminants such as sodium-22, separating the silicon-molybdate complex from the dextran-based material as another solution, adding sufficient hydrochloric acid and hydrogen peroxide to the solution to prevent reformation of the silicon-molybdate complex and to yield an oxidization state of the molybdate adapted for subsequent separation by an anion exchange material, contacting the solution with an anion exchange material whereby the molybdate is retained by the anion exchange material and the silicon remains in solution, and optionally adding sufficient alkali metal hydroxide to adjust the pH of the solution to about 12 to 13. Additionally, a high specific activity silicon-32 product having a high purity is provided.
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High specific activity silicon-32
Phillips, D.R.; Brzezinski, M.A.
1996-06-11
A process for preparation of silicon-32 is provided and includes contacting an irradiated potassium chloride target, including spallation products from a prior irradiation, with sufficient water, hydrochloric acid or potassium hydroxide to form a solution, filtering the solution, adjusting pH of the solution from about 5.5 to about 7.5, admixing sufficient molybdate-reagent to the solution to adjust the pH of the solution to about 1.5 and to form a silicon-molybdate complex, contacting the solution including the silicon-molybdate complex with a dextran-based material, washing the dextran-based material to remove residual contaminants such as sodium-22, separating the silicon-molybdate complex from the dextran-based material as another solution, adding sufficient hydrochloric acid and hydrogen peroxide to the solution to prevent reformation of the silicon-molybdate complex and to yield an oxidation state of the molybdate adapted for subsequent separation by an anion exchange material, contacting the solution with an anion exchange material whereby the molybdate is retained by the anion exchange material and the silicon remains in solution, and optionally adding sufficient alkali metal hydroxide to adjust the pH of the solution to about 12 to 13. Additionally, a high specific activity silicon-32 product having a high purity is provided.
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Formation of hydrotalcite in aqueous solutions and intercalation of ATP by anion exchange.
Tamura, Hiroki; Chiba, Jun; Ito, Masahiro; Takeda, Takashi; Kikkawa, Shinichi; Mawatari, Yasuteru; Tabata, Masayoshi
2006-08-15
The formation reaction and the intercalation of adenosine triphosphate (ATP) were studied for hydrotalcite (HT), a layered double hydroxide (LDH) of magnesium and aluminum. Hydrotalcite with nitrate ions in the interlayer (HT-NO(3)) was formed (A) by dropwise addition of a solution of magnesium and aluminum nitrates (pH ca. 3) to a sodium hydroxide solution (pH ca. 14) until the pH decreased from 14 to 10 and (B) by dropwise addition of the NaOH solution to the solution of magnesium and aluminum nitrates with pH increasing from 3 to 10. The precipitate obtained with method B was contaminated with aluminum hydroxide and the crystallinity of the product was low, possibly because aluminum hydroxide precipitates at pH 4 or 5 and remains even after HT-NO(3) forms at pH above 8. With method A, however, the precipitate was pure HT-NO(3) with increased crystallinity, since the solubility of aluminum hydroxide at pH above and around 10 is high as dissolved aluminate anions are stable in this high pH region, and there was no aluminum hydroxide contamination. The formed HT-NO(3) had a composition of [Mg(0.71)Al(0.29)(OH)(2)](NO(3))(0.29).0.58H(2)O. To intercalate ATP anions into the HT-NO(3), HT-NO(3) was dispersed in an ATP solution at pH 7. It was found that the interlayer nitrate ions were completely exchanged with ATP anions by ion exchange, and the interlayer distance expanded almost twice with a free space distance of 1.2 nm. The composition of HT-ATP was established as [Mg(0.68)Al(0.32)(OH)(2)](ATP)(0.080)0.88H(2)O. The increased distance could be explained with a calculated molecular configuration of the ATP as follows: An ATP molecule is bound to an interlayer surface with the triphosphate group, the adenosine group bends owing to its bond angles and projects into the interlayer to a height of 1 nm, and the adenosine groups aligned in the interlayer support the interlayer distance.
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Esaka, Yukihiro; Okumura, Noriko; Uno, Bunji; Goto, Masashi
2003-05-01
We have investigated analysis of anion radicals of phenanthrenequinone (PhQ) and anthraquinone (AQ) using acetonitrile-capillary electrophoresis (CE) under anaerobic conditions. PhQ and AQ have relatively high negative reduction potentials meaning that their anion radicals are re-oxidized quite readily by the surrounding O(2) to disappear during analysis and we failed to detect them with our previous system. In this work, we have developed an on-line system combining a unique electrolysis cell for generation of the radicals and a CE unit to keep the analysis system free from external O(2) molecules and to reduce analysis time remarkably. As a result, electrophoretic detection of the anion radicals of PhQ and AQ has been achieved. Furthermore, we have observed hydrogen-bonding interaction between the anion radicals and dimethylurea (DMU) using the present system and have indicated a characteristic interaction of the anion radical of PhQ as an ortho-quinone with DMU.
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NASA Astrophysics Data System (ADS)
Putschögl, M.; Zirak, P.; Penzkofer, A.
2008-01-01
The absorption and fluorescence behaviour of trans- p-coumaric acid ( trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form ( p-CAH 2) and the single anionic form ( p-CAH -) at low pH (p Kna ≈ 4.9), and between the single anionic and the double anionic form ( p-CA 2-) at high pH (p Kaa ≈ 9.35). In the organic solvents studied trans- p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans- p-coumaric acid in aqueous solution is ϕF ≈ 1.4 × 10 -4 for the neutral and the single anionic form, while it is ϕF ≈ 1.3 × 10 -3 for the double anionic form. For trans- p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 × 10 -5 (acetonitrile) to 1.5 × 10 -4 (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm -1 Stokes shifted in aqueous solution, and 5400-8200 cm -1 Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA 2-, solvent-assisted intra-molecular charge-transfer or ππ ∗ to nπ ∗ transfer and internal conversion for p-CAH 2 and p-CAH -). The solvent dependence of the first ππ ∗ electronic transition frequency and of the fluorescence Stokes shift of p-CAH 2 is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted.
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Zhang, Le; Zhang, Jifeng
2012-09-04
The perturbation of salt ions on the solubility of a monoclonal antibody was systematically studied at various pHs in Na(2)SO(4), NaNO(3), NaCl, NaF, MgSO(4), Mg(NO(3))(2) and MgCl(2) solutions below 350 mM. At pH 7.1, close to the pI, all of the salts increased the solubility of the antibody, following the order of SO(4)(2-) > NO(3)(-) > Cl(-) > F(-) for anions and Mg(2+) > Na(+) for cations. At pH 5.3 where the antibody had a net positive charge, the anions initially followed the order of SO(4)(2-) > NO(3)(-) > Cl(-) > F(-) for effectiveness in reducing the solubility and then switched to increasing the solubility retaining the same order. Furthermore, the antibody was more soluble in the Mg(2+) salt solutions than in the corresponding Na(+) salt solutions with the same anion. At pH 9.0 where the antibody had a net negative charge, an initial decrease in the protein solubility was observed in the solutions of the Mg(2+) salts and NaF, but not in the rest of the Na(+) salt solutions. Then, the solubility of the antibody was increased by the anions in the order of SO(4)(2-) > NO(3)(-) > Cl(-) > F(-). The above complex behavior is explained based on the ability of both cation and anion from a salt to modulate protein-protein interactions through their specific binding to the protein surface.
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Brdicka, R
1936-07-20
1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions.
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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.
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Li, Ming; Fan, Hua; Liu, Jiahua; Wang, Minhong; Wang, Lili; Wang, Chaozhan
2012-03-01
Recombinant human granulocyte colony-stimulating factor (rhG-CSF) is a very efficient therapeutic protein drug which has been widely used in human clinics to treat cancer patients suffering from chemotherapy-induced neutropenia. In this study, rhG-CSF was solubilized from inclusion bodies by using a high-pH solution containing low concentration of urea. It was found that solubilization of the rhG-CSF inclusion bodies greatly depended on the buffer pH employed; alkalic pH significantly favored the solubilization. In addition, when small amount of urea was added to the solution at high pH, the solubilization was further enhanced. After solubilization, the rhG-CSF was renatured with simultaneous purification by using weak anion exchange, strong anion exchange, and hydrophobic interaction chromatography, separately. The results indicated that the rhG-CSF solubilized by the high-pH solution containing low concentration of urea had much higher mass recovery than the one solubilized by 8 M urea when using anyone of the three refolding methods employed in this work. In the case of weak anion exchange chromatography, the high pH solubilized rhG-CSF could get a mass recovery of 73%. The strategy of combining solubilization of inclusion bodies at high pH with refolding of protein using liquid chromatography may become a routine method for protein production from inclusion bodies.
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Tautomeric equilibria of 5-fluorouracil anionic species in water.
Markova, Nadezhda; Enchev, Venelin; Ivanova, Galya
2010-12-23
It has long been postulated that rare tautomeric or ionized forms of nucleic acid bases may play a role in mispair formation. Therefore, ab initio quantum chemical investigations on the tautomeric equilibrium in 5-fluorouracil (5FU) and its anions (deprotonated from N1, AN1, and from N3, AN3) and their tautomeric forms in water were performed. The effect of the water as solvent was introduced using solute-solvent clusters (four water molecules). The influence of the water molecules on the tautomeric reactions between different forms was considered by multiple proton transfer mechanisms. We show that when a water dimer is located in the reaction site between the two pairs of N-H and C═O groups, the assistive effect of the water molecules is strengthened. All calculations of the solute-water complexes were carried out at an MP2 level of theory and supplemented with correction for higher order correlation terms at CCSD(T) level, using the 6-31+G(d,p) basis set. The ab initio calculated frequencies and Raman intensities of 5FU and its anions AN1, AN3, and dianion are in good agreement with the experimental Raman frequencies in aqueous solution at different pH. In order to establish the pH-induced structural transformation in the molecule of 5FU, further (1)H, (19)F, and (13)C NMR spectra in water solution for pH = 6.9-13.8 were acquired and the chemical shift alterations were determined as a function of pH. On the basis of NMR spectroscopic data obtained for 5FU in aqueous solution at alkaline pH, we suggest the existence of a mixture of the anionic tautomeric forms predicted by our theoretical calculations.
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Brdička, R.
1936-01-01
1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions. PMID:19872968
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Bray, Lane Allan; DesChane, Jaquetta R.
1998-01-01
A method for separating .sup.213 Bi from a solution of radionuclides wherein the solution contains a concentration of the chloride ions and hydrogen ions adjusted to allow the formation of a chloride complex. The solution is then brought into contact with an anion exchange resin, whereupon .sup.213 Bi is absorbed from the solution and adhered onto the anion exchange resin in the chloride complex. Other non-absorbing radionuclides such as .sup.225 Ra, .sup.225 Ac, and .sup.221 Fr, along with HCl are removed from the anion exchange resin with a scrub solution. The .sup.213 Bi is removed from the anion exchange resin by washing the anion exchange resin with a stripping solution free of chloride ions and with a reduced hydrogen ion concentration which breaks the chloride anionic complex, releasing the .sup.213 Bi as a cation. In a preferred embodiment of the present invention, the anion exchange resin is provided as a thin membrane, allowing for extremely rapid adherence and stripping of the .sup.213 Bi. A preferred stripping solution for purification of .sup.213 Bi for use in medical applications includes sodium acetate, pH 5.5. A protein conjugated with bifunctional chelating agents in vivo with the NaOAc, to receive the .sup.213 Bi as it is being released from the anion exchange resin.
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Bray, L.A.; DesChane, J.R.
1998-05-05
A method is described for separating {sup 213}Bi from a solution of radionuclides wherein the solution contains a concentration of the chloride ions and hydrogen ions adjusted to allow the formation of a chloride complex. The solution is then brought into contact with an anion exchange resin, whereupon {sup 213}Bi is absorbed from the solution and adhered onto the anion exchange resin in the chloride complex. Other non-absorbing radionuclides such as {sup 225}Ra, {sup 225}Ac, and {sup 221}Fr, along with HCl are removed from the anion exchange resin with a scrub solution. The {sup 213}Bi is removed from the anion exchange resin by washing the anion exchange resin with a stripping solution free of chloride ions and with a reduced hydrogen ion concentration which breaks the chloride anionic complex, releasing the {sup 213}Bi as a cation. In a preferred embodiment of the present invention, the anion exchange resin is provided as a thin membrane, allowing for extremely rapid adherence and stripping of the {sup 213}Bi. A preferred stripping solution for purification of {sup 213}Bi for use in medical applications includes sodium acetate, pH 5.5. A protein conjugated with bifunctional chelating agents in vivo with the NaOAc receives the {sup 213}Bi as it is being released from the anion exchange resin. 10 figs.
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Action of some foreign cations and anions on the chloride permeability of frog muscle
Hutter, O. F.; Warner, Anne E.
1967-01-01
1. Evidence for the existence in skeletal muscle of a specific cation binding system capable of lowering the chloride permeability was obtained by testing the effect of several metal ion species upon the efflux of 36Cl from frog muscles equilibrated in high-KCl solution. 2. Cu2+, Zn2+ and UO22+ ions, when present in concentrations of approximately 10-4 M in inactive wash solution at pH 7·4 slowed the efflux of 36Cl to half its original value. At pH 5·0, when the chloride permeability was already low as a consequence of hydrogen ion binding, these metal ions had little further effect. 3. Presence of Ni2+, Co2+, Pb2+, Ce3+ and La3+ in 10-4 M or higher concentrations had no detectable influence on the 36Cl efflux. Wide variations in Ca2+ concentration were similarly ineffective. 4. The influence of more adsorbable anions on the chloride permeability was examined at different pH values. Extracellular iodide greatly slowed the rapid efflux of 36Cl into alkaline solution. In acid solutions, when the chloride permeability was already low, the effect of iodide was less pronounced, but still demonstrable. The chloride permeability was consequently increased to a lesser extent by a rise in pH in the presence of iodide. 5. The efflux of iodide and bromide was measured at different pH values under conditions of self exchange. In alkaline solution the permeabilities to iodide and bromide were considerably lower than that to chloride. In acid solution the membrane differentiated less between anion species of different adsorbability. PMID:6040156
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Anion-exchange resins (AERs) separate As(V) and As(lIl) in solution by retaining As(V) and allowing As(lIl) to pass through. AERs offer several advantages including portability, ease of use, and affordability (relative to other As speciation methods). The use of AERs for the inst...
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Yang, Senpei; Li, Lingyi; Chen, Tao; Han, Lujia; Lian, Guoping
2018-05-14
Sebum is an important shunt pathway for transdermal permeation and targeted delivery, but there have been limited studies on its permeation properties. Here we report a measurement and modelling study of solute partition to artificial sebum. Equilibrium experiments were carried out for the sebum-water partition coefficients of 23 neutral, cationic and anionic compounds at different pH. Sebum-water partition coefficients not only depend on the hydrophobicity of the chemical but also on pH. As pH increases from 4.2 to 7.4, the partition of cationic chemicals to sebum increased rapidly. This appears to be due to increased electrostatic attraction between the cationic chemical and the fatty acids in sebum. Whereas for anionic chemicals, their sebum partition coefficients are negligibly small, which might result from their electrostatic repulsion to fatty acids. Increase in pH also resulted in a slight decrease of sebum partition of neutral chemicals. Based on the observed pH impact on the sebum-water partition of neutral, cationic and anionic compounds, a new quantitative structure-property relationship (QSPR) model has been proposed. This mathematical model considers the hydrophobic interaction and electrostatic interaction as the main mechanisms for the partition of neutral, cationic and anionic chemicals to sebum.
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Corrosion Control through a Better Understanding of the Metallic Substrate/Organic Coating Interface
1990-03-16
electrically coupling steel electrodes in different pH solutions. Anodic and cathodic sites beneath a coating are known to produce acidic and alkaline...9,16]. Lead-steel couples were used to model the interactions between metallic lead and steel. Both acidic and alkaline solutions were used because the...acetate solution can be altered by the addition of acid or base without precipitation of the anion. Other anions such as chlorides and sulfates are
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Songlin, Wang; Ning, Zhou; Si, Wu; Qi, Zhang; Zhi, Yang
2015-03-01
Ultrasound degradation of humic acid has been investigated in the presence of persulfate anions at ultrasonic frequency of 40 kHz. The effects of persulfate anion concentration, ultrasonic power input, humic acid concentration, reaction time, solution pH and temperature on humic acid removal efficiency were studied. It is found that up to 90% humic acid removal efficiency was achieved after 2 h reaction. In this system, sulfate radicals (SO₄⁻·) were considered to be the mainly oxidant to mineralize humic acid while persulfate anion can hardly react with humic acid directly. A novel kinetic model based on sulfate radicals (SO₄⁻·) oxidation was established to describe the humic acid mineralization process mathematically and chemically in sono-activated persulfate system. According to the new model, ultrasound power, persulfate dosage, solution pH and reaction temperature have great influence on humic acid degradation. Different initial concentration of persulfate anions and humic acid, ultrasonic power, initial pH and reaction temperature have been discussed to valid the effectiveness of the model, and the simulated data showed new model had good agreement with the experiments data.
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NASA Astrophysics Data System (ADS)
Gryff-Keller, A.; Kraska-Dziadecka, A.
2011-12-01
13C NMR spectra of 1,3-dimethylbarbituric acid in aqueous solutions of various acidities and for various solute concentrations have been recorded and interpreted. The spectra recorded at pH = 2 and below contain the signals of the neutral solute molecule exclusively, while the ones recorded at pH = 7 and above only the signals of the appropriate anion, which has been confirmed by theoretical GIAO-DFT calculations. The signals in the spectra recorded for solutions of pH < 7 show dynamic broadenings. The lineshape analysis of these signals has provided information on the kinetics of the processes running in the dynamic acid-base equilibrium. The kinetic data determined this way have been used to clarify the mechanisms of these processes. The numerical analysis has shown that under the investigated conditions deprotonation of the neutral solute molecules undergoes not only via a simple transfer of the C-H proton to water molecules but also through a process with participation of the barbiturate anions. Moreover, the importance of tautomerism, or association, or both these phenomena for the kinetics of the acid-base transformations in the investigated system has been shown. Qualitatively similar changes of 13C NMR spectra with the solution pH variation have been observed for the parent barbituric acid.
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Yang, Xiaoxia; Li, Yanhui; Du, Qiuju; Sun, Jiankun; Chen, Long; Hu, Song; Wang, Zonghua; Xia, Yanzhi; Xia, Linhua
2015-09-01
Novel anionic polyacrylamide/graphene oxide aerogels were prepared by a freeze drying method and used to remove basic fuchsin from aqueous solutions. These aerogels were sponge-like solid with lightweight, fluffy and porous structure. The batch adsorption experiments were carried out to study the effect of various parameters, such as the solution pH, adsorbent dose, contact time and temperature on adsorption properties of basic fuchsin onto anionic polyacrylamide/graphene oxide aerogels. The kinetics of adsorption corresponded to the pseudo-second-order kinetic model. The Langmuir adsorption isotherm was suitable to describe the equilibrium adsorption process. The maximum adsorption capacity was up to 1034.3 mg/g, which indicated that anionic polyacrylamide/graphene oxide aerogels were promising adsorbents for removing dyes pollutants from aqueous solution. Copyright © 2015 Elsevier Inc. All rights reserved.
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NASA Astrophysics Data System (ADS)
Peng, Jiaoyu; Chen, Jing; Dong, Yaping; Li, Wu
2018-06-01
Raman spectra of boron-concentrated, diluted, and corresponding mother solutions of brine were recorded at 298.15 K. The main polyborate anions present and their interactions in brine during evaporation and dilution were proposed according to the Raman spectra. The polyborate anions B(OH)3, B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- were found to be the main forms in boron-concentrated brine with B3O3(OH)4- ion being the principal form. Diluting brines with water accelerated depolymerization of B5O6(OH)4- and B6O7(OH)62- anions into B(OH)3 and B3O3(OH)4- ions and generated OH- ions, causing the pH of the solutions to increase from 4.2 to almost 8.0. Mg-borates precipitated from all diluted solutions could be classified as either hexaborates or triborates. A mechanism of solid phase transformation was also proposed and discussed based on Raman spectra analysis and solid species and solution pH data.
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Chakraborty, Subhashis; Shukla, Dali; Jain, Achint; Mishra, Brahmeshwar; Singh, Sanjay
2009-07-15
The effect of surfactants on the solubility of a new phosphate salt of carvedilol was investigated at different biorelevent pH to evaluate their solubilization capacity. Solutions of different classes of surfactants viz., anionic-sodium dodecyl sulfate (SDS) and sodium taurocholate (STC), cationic-cetyltrimethylammonium bromide (CTAB) and non-ionic-Tween 80 (T80) were prepared in the concentration range of 5-35 mmol dm(-3) in buffer solutions of pH 1.2, 3.0, 4.5, 5.8, 6.8 and 7.2. The solubility data were used to calculate the solubilization characteristics viz. molar solubilization capacity, water micelle partition coefficient, free energy of solubilization and binding constant. Solubility enhancement in basic pH was in following order: CTAB>T80>SDS>STC. CTAB and T80 showed remarkable solubility enhancement in acidic pH as well. Among the anionic surfactants, solubility in acidic medium was retarded except at pH 1.2 in case of SDS. Cationic and non-ionic surfactants were found to be suitable for enhancing the solubility of CP which can be employed for maintaining the in vitro sink condition in the basic dissolution medium. While anionic surfactants showed solubility retardant behavior which may be exploited in increasing the drug entrapment efficiency of a colloidal drug delivery system formulated by emulsification technique.
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1992-02-04
D& similar to those formed by ph3phatidyl choline (pc, egg lecithin vesicles). They are large, unilamellar systems about 3000A in diameter. Their...S S (sodium S dodecylsulfate, anionic), DTINS (di-/iisopropyl naphthalene sulfonate, anionic), C18DMB I (octadecyl dimethyl betaine , zwitterionic
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Aqueous pyrite oxidation by dissolved oxygen and by ferric iron
Moses, Carl O.; Nordstrom, D. Kirk; Herman, Janet S.; Mills, Aaron L.
1987-01-01
Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.
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Li, Ronghua; Wang, Jim J; Zhou, Baoyue; Awasthi, Mukesh Kumar; Ali, Amjad; Zhang, Zengqiang; Gaston, Lewis A; Lahori, Altaf Hussain; Mahar, Amanullah
2016-07-15
Mg/Al ratio plays a significant role for anion adsorption by Mg/Al-layered double hydroxides (Mg/Al-LDHs) modified biochar. In this study, Mg/Al-LDHs biochar with different Mg/Al ratios (2, 3, 4) were prepared by co-precipitation for phosphate removal from aqueous solution. Factors on phosphate adsorption including Mg/Al ratio, pH, and the presence of other inorganic anions were investigated through batch experiments. Increasing Mg/Al ratio in the Mg/Al-LDHs biochar composites generally enhanced phosphate adsorption with Langmuir adsorption maximum calculated at 81.83mg phosphorous (P) per gram of 4:1Mg/Al-LDHs biochar at pH3.0. The adsorption process was best described by the pseudo-second-order kinetic model. Solution pH had greater effects on the phosphate adsorption by Mg/Al LDHs biochar composites with lower Mg/Al ratios. The presence of other inorganic anions decreased the phosphate adsorption efficiency in the order of F(-) > SO4(2-) > NO2(-) >Cl(-). Phosphate adsorption mechanism involves ion exchange, electrostatic attraction and surface inner-sphere complex formation. Overall, Mg/Al-LDHs biochar composites offer a potential alternative of carbon-based adsorbent for phosphate removal from aqueous solution. Copyright © 2016 Elsevier B.V. All rights reserved.
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Diffusion of water-soluble sorptive drugs in HEMA/MAA hydrogels.
Liu, D E; Dursch, T J; Taylor, N O; Chan, S Y; Bregante, D T; Radke, C J
2016-10-10
We measure and, for the first time, theoretically predict four prototypical aqueous-drug diffusion coefficients in five soft-contact-lens material hydrogels where solute-specific adsorption is pronounced. Two-photon fluorescence confocal microscopy and UV/Vis-absorption spectrophotometry assess transient solute concentration profiles and concentration histories, respectively. Diffusion coefficients are obtained for acetazolamide, riboflavin, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA) copolymer hydrogels as functions of composition, equilibrium water content (30-90%), and aqueous pH (2 and 7.4). At pH2, MAA chains are nonionic, whereas at pH7.4, MAA chains are anionic (pKa≈5.2). All studied prototypical drugs specifically interact with HEMA and nonionic MAA (at pH2) moieties. Conversely, none of the prototypical drugs adsorb specifically to anionic MAA (at pH7.4) chains. As expected, diffusivities of adsorbing solutes are significantly diminished by specific interactions with hydrogel strands. Despite similar solute size, relative diffusion coefficients in the hydrogels span several orders of magnitude because of varying degrees of solute interactions with hydrogel-polymer chains. To provide a theoretical framework for the new diffusion data, we apply an effective-medium model extended for solute-specific interactions with hydrogel copolymer strands. Sorptive-diffusion kinetics is successfully described by local equilibrium and Henry's law. All necessary parameters are determined independently. Predicted diffusivities are in good agreement with experiment. Copyright © 2016 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
King, P. L.; De Deckker, P.
2012-12-01
On Mars, limited solutions (water/brine) were likely present episodically. Gradients in solution abundance may have caused salt precipitation and re-solution, brine reflux, pH gradients, and cycling of anions and cations; we provide an example of such processes in a playa lake. We propose that on Mars, the limited, episodic solutions, pH and abundant Fe-O(-H) phases are significant factors in salt precipitation and in promoting adsorption/desorption of anions and cations. FACTORS LEADING TO EPISODIC SOLUTIONS: Episodic movement of solutions may be driven by punctuated processes that 1) remove surface materials (e.g., impact and sedimentary mass wasting and deflation); 2) add surface materials (e.g., impact, volcanic and sedimentary processes); and 3) increase temperature and/or decrease atmospheric pressure (e.g., seasons, diurnal cycles, variation in obliquity). Removal and addition of surface materials results in topographic gradients that change pressure gradients of any potential groundwater, films, or buried ground ice. For example, episodic fluid flow and salt precipitation/re-solution may occur at topographic discontinuities like craters/basins, channel walls, mounds and dunes. Such areas provide the opportunity to sample multiple fluid sources (with different pH, Eh and total dissolved solids, TDS) and they may be the foci of subsurface solution flow and surface transport. EARTH ANALOG: Interplay of the three processes above is seen in Lake Tyrrell (playa), western Victoria, Australia (McCumber, P, 1991 http://vro.dpi.vic.gov.au). During wetter periods, springs from the regional groundwater (low pH, oxidized, mod-high TDS) mix with lake waters and saline 'reflux' brines (mod. pH, reduced, high TDS) at the lake edge at the base of higher ground. The Br/Cl of the reflux brines indicates mineral re-solution. Gypsum and Fe-O(-H) phases precipitate near the lake edge. During hot, dry climate episodes the lake precipitates gypsum and carbonate, efflorescent salts are common, and these salts may form eolian dunes with fine particles. We may expect similar processes and mineral and chemical gradients in craters/basins on Mars like Gale Crater, the site of the Mars Science Laboratory mission. ROLE OF Fe-O(-H) PHASES: Nanophase Fe-O(-H)-phases are abundant on Mars and their precipitation results in an Fe-poor solution and salts (like Lake Tyrrell). Fe-O(-H) phases precipitate most readily at near-neutral pH; however, the high Fe of Mars' surface allows for pH>1. Nanophase Fe-O(-H)-phases have surface species that promote adsorption; which may be important in dry conditions like Mars. If we take goethite (FeO(OH)), the surface species and aqueous ions in solution are Fe3+ (pH<~2); Fe(OH)2+ (pH~2-3.5); Fe(OH)2+ (pH~3.5-~8); and FeOH4- (pH>~8). Other Fe-O(-H) phases have slightly different pH limits. Thus, at pH<~8, Fe-O(-H) surfaces sequester anions in surface complexes or in Fe-bearing salts (e.g. Fe3+-phosphate and sulfates, especially at pH<4). PO43- species have high adsorption affinity, followed by SO42-, Cl-(O) and Br-(O) species. At pH>~8, adsorption and exchange of cations are likely. These chemical variations may provide us with clues of the past pH on Mars.
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Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua
2008-11-01
Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.
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Solution chemistry effects on orthophosphate adsorption by cationized solid wood residues
K.G. Karthikeyan; Mandla A. Tshabalala; D. Wang; M. Kalbasi
2004-01-01
Adsorption of orthophosphate anions in aqueous solution by cationized milled solid wood residues was characterized as a function of sorbate-to- sorbent ratio (=0.001-2.58 mmol of P/g substrate), pH (3-9), ionic strength, I (no I control; 0.001 and 0.01 M NaCl), reaction time (4 min to 24 h), and in the presence of other competing anions (0.08-50 mM SO4 2-; 0.08-250 mM...
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Nesterenko, Ekaterina P; Nesterenko, Pavel N; Paull, Brett
2008-12-05
The retention and separation selectivity of inorganic anions and on-column derivatised negatively charged citrate or oxalate metal complexes on reversed-phase stationary phases dynamically coated with N-(dodecyl-N,N-dimethylammonio)undecanoate (DDMAU) has been investigated. The retention mechanism for the metal-citrate complexes was predominantly anion exchange, although the amphoteric/zwitterionic nature of the stationary phase coating undoubtedly also contributed to the unusual separation selectivity shown. A mixture of 10 inorganic anions and metal cations was achieved using a 20 cm monolithic DDMAU modified column and a 1 mM citrate eluent, pH 4.0, flow rate equal to 0.8 mL/min. Selectivity was found to be strongly pH dependent, allowing additional scope for manipulation of solute retention, and thus application to complex samples. This is illustrated with the analysis of an acidic mine drainage sample with a range of inorganic anions and transition metal cations, varying significantly in their concentrations levels.
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METHOD OF RECOVERING URANIUM COMPOUNDS
Poirier, R.H.
1957-10-29
S>The recovery of uranium compounds which have been adsorbed on anion exchange resins is discussed. The uranium and thorium-containing residues from monazite processed by alkali hydroxide are separated from solution, and leached with an alkali metal carbonate solution, whereby the uranium and thorium hydrorides are dissolved. The carbonate solution is then passed over an anion exchange resin causing the uranium to be adsorbed while the thorium remains in solution. The uranium may be recovered by contacting the uranium-holding resin with an aqueous ammonium carbonate solution whereby the uranium values are eluted from the resin and then heating the eluate whereby carbon dioxide and ammonia are given off, the pH value of the solution is lowered, and the uranium is precipitated.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Fan; Parker, Jack C.; Luo, Wensui
2008-01-01
Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less
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Evaluating of arsenic(V) removal from water by weak-base anion exchange adsorbents.
Awual, M Rabiul; Hossain, M Amran; Shenashen, M A; Yaita, Tsuyoshi; Suzuki, Shinichi; Jyo, Akinori
2013-01-01
Arsenic contamination of groundwater has been called the largest mass poisoning calamity in human history and creates severe health problems. The effective adsorbents are imperative in response to the widespread removal of toxic arsenic exposure through drinking water. Evaluation of arsenic(V) removal from water by weak-base anion exchange adsorbents was studied in this paper, aiming at the determination of the effects of pH, competing anions, and feed flow rates to improvement on remediation. Two types of weak-base adsorbents were used to evaluate arsenic(V) removal efficiency both in batch and column approaches. Anion selectivity was determined by both adsorbents in batch method as equilibrium As(V) adsorption capacities. Column studies were performed in fixed-bed experiments using both adsorbent packed columns, and kinetic performance was dependent on the feed flow rate and competing anions. The weak-base adsorbents clarified that these are selective to arsenic(V) over competition of chloride, nitrate, and sulfate anions. The solution pH played an important role in arsenic(V) removal, and a higher pH can cause lower adsorption capacities. A low concentration level of arsenic(V) was also removed by these adsorbents even at a high flow rate of 250-350 h(-1). Adsorbed arsenic(V) was quantitatively eluted with 1 M HCl acid and regenerated into hydrochloride form simultaneously for the next adsorption operation after rinsing with water. The weak-base anion exchange adsorbents are to be an effective means to remove arsenic(V) from drinking water. The fast adsorption rate and the excellent adsorption capacity in the neutral pH range will render this removal technique attractive in practical use in chemical industry.
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Phosphate Removal by Anion Binding on Functionalized Nanoporous Sorbents
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chouyyok, Wilaiwan; Wiacek, Robert J.; Pattamakomsan, Kanda
2010-03-26
Phosphate was captured from aqueous solutions by cationic metal-EDA complexes anchored inside mesoporous silica MCM-41 supports (Cu(II)-EDA-SAMMS and Fe(III)-EDA-SAMMS). Fe-EDA-SAMMS was more effective at capturing phosphate than the Cu-EDA-SAMMS and was further studied for matrix effects (e.g., pH, ionic strength, and competing anions) and sorption performance (e.g., capacity and rate). The adsorption of phosphate was highly pH dependent; it increased with increasing pH from 1.0 to 6.5, and decreased above pH 6.5. The adsorption was affected by high ionic strength (0.1 M of NaCl). In the presence of 1000-fold molar excess of chloride and nitrate anions, phosphate removal by Fe-EDA-SAMMSmore » was not affected. Slight, moderate and large impacts were seen with bicarbonate, sulfate and citrate anions, respectively. The phosphate adsorption data on Fe-EDA-SAMMS agreed well with the Langmuir model with the estimated maximum capacity of 43.3 mg/g. The material displayed rapid sorption rate (99% of phosphate removal within 1 min) and lowering the phosphate content to ~ 10 µg/L of phosphorus, which is lower than the EPA’s established freshwater contaminant level for phosphorous (20 µg/L).« less
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Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions
NASA Technical Reports Server (NTRS)
Nadarajah, Arunan
1996-01-01
Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.
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Malá, Zdena; Gebauer, Petr
2018-01-15
This work describes for the first time a functional electrolyte system setup for anionic isotachophoresis (ITP) with electrospray-ionization mass-spectrometric (ESI-MS) detection in the neutral to medium-alkaline pH range. So far no application was published on the analysis of very weak acids by anionic ITP-MS although there is a broad spectrum of potential analytes with pK a values in the range 5-10, where application of this technique promises interesting gains in both sensitivity and specificity. The problem so far was the lack of anionic ESI-compatible ITP systems in the mentioned pH range as all typical volatile anionic system components are fully ionized at neutral and alkaline pH and thus too fast to suit as terminators. We propose an original solution of the problem based on the combination of two ITP methods: (i) use of the hydroxyl ion as a natural and ESI-compatible terminator, and (ii) use of configurations based on moving-boundary ITP. The former method ensures effective stacking of analytes by an alkaline terminator of sufficiently low mobility and the latter offers increased flexibility for tuning of the separation window and selectivity according to actual needs. A theoretical description of the proposed model is presented and applied to the design of very simple functional electrolyte configurations. The properties of example systems are demonstrated by both computer simulation and experiments with a group of model analytes. Potential effects of carbon dioxide present in the solutions are demonstrated for particular systems. Experimental results confirm that the proposed methodology is well capable of performing sensitive and selective ITP-MS analyses of very weak acidic analytes (e.g. sulfonamides or chlorophenols). Copyright © 2017 Elsevier B.V. All rights reserved.
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Hagiwara, S; Takahashi, K
1974-04-01
1. Properties of anion permeation through the membrane of skeletal muscle fibres of the stingray, Taeniura lymma, were studied with intracellular recording and polarization techniques.2. The Cl conductance of the resting membrane in the normal stingray saline at pH 7.7 is 8-10 times greater than the K conductance.3. The Cl conductance decreases with decreasing external pH, with an apparent pK of 5.3, whereas the K conductance is independent of pH between 4 and 9.4. The Q(10) of the Cl conductance is about 2.0, compared with a value of 1.2-1.4 for the K conductance.5. The Cl conductance is proportional to the external Cl concentration when observed after the fibre is equilibrated in the test solution.6. The permeability sequence obtained by potential measurement is SCN > NO(3) > Cl = Br > I > ClO(3) and the permeability ratio is independent of the mole fraction of anions.7. The conductance sequence determined by total replacement of the external Cl with other anion species differs from the permeability sequence and the conductance observed for partial replacement deviates significantly from that expected from the independence principle.8. Possible mechanisms of anion permeation are discussed.
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Hagiwara, Susumu; Takahashi, Kunitaro
1974-01-01
1. Properties of anion permeation through the membrane of skeletal muscle fibres of the stingray, Taeniura lymma, were studied with intracellular recording and polarization techniques. 2. The Cl conductance of the resting membrane in the normal stingray saline at pH 7·7 is 8-10 times greater than the K conductance. 3. The Cl conductance decreases with decreasing external pH, with an apparent pK of 5·3, whereas the K conductance is independent of pH between 4 and 9. 4. The Q10 of the Cl conductance is about 2·0, compared with a value of 1·2-1·4 for the K conductance. 5. The Cl conductance is proportional to the external Cl concentration when observed after the fibre is equilibrated in the test solution. 6. The permeability sequence obtained by potential measurement is SCN > NO3 > Cl = Br > I > ClO3 and the permeability ratio is independent of the mole fraction of anions. 7. The conductance sequence determined by total replacement of the external Cl with other anion species differs from the permeability sequence and the conductance observed for partial replacement deviates significantly from that expected from the independence principle. 8. Possible mechanisms of anion permeation are discussed. PMID:4838800
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Functional magnetic microspheres
NASA Technical Reports Server (NTRS)
Rembaum, Alan (Inventor); Landel, Robert F. (Inventor); Yen, Shiao-Ping S. (Inventor)
1981-01-01
Functional magnetic particles are formed by dissolving a mucopolysaccharide such as chitosan in acidified aqueous solution containing a mixture of ferrous chloride and ferric chloride. As the pH of the solution is raised magnetite is formed in situ in the solution by raising the pH. The dissolved chitosan is a polyelectrolyte and forms micelles surrounding the granules at pH of 8-9. The chitosan precipitates on the granules to form microspheres containing the magnetic granules. On addition of the microspheres to waste aqueous streams containing dissolved ions, the hydroxyl and amine functionality of the chitosan forms chelates binding heavy metal cations such as lead, copper, and mercury and the chelates in turn bind anions such as nitrate, fluoride, phosphate and borate.
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Effect of pH, competitive anions and NOM on the leaching of arsenic from solid residuals.
Ghosh, Amlan; Sáez, A Eduardo; Ela, Wendell
2006-06-15
Implementation of the new arsenic MCL in 2006 will lead to the generation of an estimated 6 million pounds of arsenic-bearing solid residuals (ABSRs) every year, which will be disposed predominantly in non-hazardous landfills. The Toxicity Characteristic Leaching Procedure (TCLP) is typically used to assess whether a waste is hazardous and most solid residuals pass the TCLP. However, recent research shows the TCLP significantly underestimates arsenic mobilization in landfills. A variety of compositional dissimilarities between landfill leachates and the TCLP extractant solution likely play a role. Among the abiotic factors likely to play a key role in arsenic remobilization/leaching from solid sorbents are pH, and the concentrations of natural organic matter (NOM) and anions like phosphate, bicarbonate, sulfate and silicate. This study evaluates the desorption of arsenic from actual treatment sorbents, activated alumina (AA) and granular ferric hydroxide (GFH), which are representative of those predicted for use in arsenic removal processes, and as a function of the specific range of pH and concentrations of the competitive anions and NOM found in landfills. The influence of pH is much more significant than that of competing anions or NOM. An increase in one unit of pH may increase the fraction of arsenic leached by 3-4 times. NOM and phosphate replace arsenic from sorbent surface sites up to three orders of magnitude more than bicarbonate, sulfate and silicate, on a per mole basis. Effects of anions are neither additive nor purely competitive. Leaching tests, which compare the fraction of arsenic mobilized by the TCLP vis-a-vis an actual or more realistic synthetic landfill leachate, indicate that higher pH, and greater concentrations of anions and NOM are all factors, but of varying significance, in causing higher extraction in landfill and synthetic leachates than the TCLP.
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Anion-exchange behavior of several alkylsilica reversed-phase columns.
Marchand, D H; Snyder, L R
2008-10-31
Some alkylsilica columns carry a positive charge at low pH, as determined by anion-exchange with nitrate ion. In the present study, the relative positive charge for 14 alkylsilica columns was measured for a mobile-phase pH 3.0. All but 3 of these columns were found to carry a significant positive charge under these conditions. The relative positive charge on these columns was found to correlate approximately with two other column characteristics: relative cation-exchange behavior as measured by the hydrophobic-subtraction model (values of C-2.8), and slow equilibration of the column to changes in the mobile-phase-as evidenced by a slow change in the retention of anionic and cationic solutes with time. The origin of this positive charge may arise from the bonding process, with incorporation of some cationic entity into the stationary phase.
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The effects of ion identity and ionic strength on the dissolution rate of a gibbsitic bauxite
NASA Astrophysics Data System (ADS)
Mogollón, José Luis; Pérez-Diaz, Alberto; Lo Monaco, Salvador
2000-03-01
The influence of cation and anion identity and concentration, on the far from equilibrium dissolution rate of gibbsite, was studied at 298°K. Input solutions, with initial pH = 3.5 and variable salt type and concentration, were flowed at different rates, through columns packed with a unconsolidated gibbsitic bauxite from Los Pijigüaos-Venezuela ore deposit. It was observed cations Na +, K +, Mg 2+ and Ca2+ have no influence on the far from equilibrium dissolution rate. Anions have two different effects: concentration increases of monovalent anions (Cl -, NO 3- and ClO 4-) causes a decrease in the rate, as a function of [anion] (-0.11 ± 0.01); and increases of sulfate concentration causes an increase in the rate as a function of [SO 4=] (0.4 ± 0.1). According to our calculations, these two effects have a remarkable influence upon the lifetime of gibbsite under weathering conditions. Based on Transition State Theory, it is proposed the experimental observations are due to an electrostatic effect on the activated complex (AC ♯) of the gibbsite dissolution reaction. For this AC ♯ the product of the charge of the involved chemical entities is negative. When SO 4= participates in the AC ♯ the product of the charges switches to positive and therefore, the electrostatic interaction increase the dissolution rate. The dissolution rates are independent of the solution saturation degree below ΔGr = - 0.74 kcal/mol. It is inferred that the critical ΔGr is a constant of the solid, not affected by the solution characteristics, e.g., pH, ionic strength, cation and anion identities.
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NASA Astrophysics Data System (ADS)
Chao, Jianbin; Liu, Yuhong; Zhang, Yan; Zhang, Yongbin; Huo, Fangjun; Yin, Caixia; Wang, Yu; Qin, Liping
2015-07-01
A new fluorescent enhanced probe based on (E)-9-(2-nitrovinyl)-anthracene is developed, which shows high selectivity and sensitivity for the detection of bisulfite anions at Na2HPO4 citric acid buffer solutions (pH 5.0). When addition of HSO3-, the fluorescence intensity is significantly enhanced and the probe displays apparent fluorescence color changes from non-fluorescence to blue under a UV lamp illumination, the solution color also changes from yellow to colorless. The detection limit is determined to be as low as 6.30 μM. This offers another specific colorimetric and fluorescent probe for bisulfite anions detection, furthermore it is applied in detecting the level of bisulfite in sugar samples.
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NASA Astrophysics Data System (ADS)
Suhartana; Sukmasari, Emmanuella; Azmiyawati, Choiril
2018-04-01
The aim of the research is to natural zeolite with Fe(III) using anion exchange process to improve the anion exchange capacity. Natural zeolite was activated using HNO3 1 N and then mixed with FeCl3 solution and refluxed followed by oven and calcination at a temperature of 550°C. The influence of Fe(III) to zeolite was characterized by FTIR while presence of Fe in zeolite characterized by AAS. Zeolite and Zeolite-Fe adsorption capacity of chloride and carbonate anions were determined through adsorption test by variation of pH and contact time. In advanced, and then to determining the Fe adsorbed concentration at Zeolite using UV-Vis spectrophotometer. FTIR analysis result showed that the addition of Fe does not affect the zeolite’s structure but change the intensity of the zeolite spectra. The Fe concentration in Zeolite-Fe of 714 mg L-1, indicate that Fe was present in the zeolite. Both Zeolite and Zeolite-Fe adsorbtion results showed that optimum pH of Chloride anion is 2, with adsorption capacity 2,33 x 10-3 gg-1 and optimum contact time is 8 minutes. While Zeolite and Zeolite-Fe adsorbtion results showed that optimum pH of Carbonate anion is 5, with adsorption capacity 5,31 x 10-3 gg-1 and optimum contact time is 8 minutes.
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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.
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Beaton, R.H.
1960-06-28
A process is given for separating tri- or tetravalent plutonium from fission products in an aqueous solution by complexing the fission products with oxalate, tannate, citrate, or tartrate anions at a pH value of at least 2.4 (preferably between 2.4 and 4), and contacting a cation exchange resin with the solution whereby the plutonium is adsorbed while the complexed fission products remain in solution.
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NASA Astrophysics Data System (ADS)
Fu, Jingni; Zhang, Luning
2018-03-01
The protonation/deprotonation equilibrium of a fluorescent pH probe (carboxy-seminaphthorhodafluor-1, SNARF-1) within the nanoscale water layer confined in common black films (CBFs) has been studied. We find that SNARF-1 molecules feel a more acidic environment in CBFs than when they are in the bulk micellar solution, using the base/acid peak area ratio of the dye to indicate its microenvironment pH. Three surfactants are used to study the dependence of the pH drop versus charge: cationic (cetyltrimethylammonium bromide, CTAB), anionic (sodium dodecylsulphate, SDS) and nonionic (Triton X-100) species. The decrease of CBFs pH versus the pH of the micellar solution is the following: ΔpH ≈ 1.5 for CTAB (pH: 7.0-9.0), ΔpH ≈ 0.8 for SDS, and ΔpH ≈ 0.4 for Triton X-100. With the addition of electrolyte in CBFs, we observe large decrease the amplitude of the pH anomaly, thus suggesting an electrostatic origin of the pH change at nanoscale environment.
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RECOVERY OF URANIUM FROM CARBONATE LEACH LIQUORS
Wilson, H.F.
1958-07-01
An improved process is described for the recovery of uranium from vanadifrous ores. In the prior art such ores have been digested with alkali carbonate solutions at a pH of less than 10 and then contacted with a strong base anion exchange resin to separate uranium from vanadium. It has been found that if the exchamge resin feed solution has its pH adjusted to the range 10.8 to 11.8, that vanadium adsorption on the resin is markedly decreased and the separation of uranium from the vanadium is thereby improved.
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Interfacial activity in alkaline flooding enhanced oil recovery
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chan, M.K.
1981-01-01
The ionization of long-chained organic acids in the crude oil to form soaps was shown to be primarily responsible for the lowering of oil-water interfacial tension at alkaline pH. These active acids can be concentrated by silica gel chromatography into a minor polar fraction. An equilibrium chemical model was proposed based on 2 competing reactions: the ionization of acids to form active anions, and the formation of undissociated soap between acid anions and sodium ions. It correlates the interfacial activity with the interfacial concentration of active acid anions which is expressed in terms of the concentrations of the chemical speciesmore » in the system. The model successfully predicts the observed oil-alkaline solution interfacial phenomenon, including its dependence on pH, alkali and salt concentrations, type of acid present and type of soap formed. Flooding at different alkali concentrations to activate different acid species present in the crude was shown to give better recovery than flooding at a single high alkali concentration. Treating the crude oil with a dilute solution of mineral acids liberates additional free active acids and yields better interfacial activity during subsequent alkali contact.« less
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Zhang, Caihong; Wen, Haifeng; Huang, Yingying; Shi, Wenjian
2017-04-01
High content of primary amino crosslinked chitosan microspheres (ACCMs) were synthesized and characterized with IR, XRD and SEM technologies. Subsequently, ACCMs were adopted to adsorb three common anionic surfactants from aqueous solution: sodium dodecyl benzene sulfonate (SDBS), sodium lauryl sulfate (SLS), and sodium dodecyl sulfonate (SDS). The adsorption performances were evaluated based on different variables such as the pH, contact time, temperature and initial concentration of the anionic surfactants. Moreover, the adsorption were investigated with kinetic models, equilibrium isotherms and thermodynamic models. The experimental results indicated that the adsorption processes were fitted very well with a pseudo-second-order model. The adsorption isotherms could be better described by Langmuir model rather than Freundlich model. The adsorption of SDBS was a spontaneous, exothermic process. While the adsorption of SLS and SDS were spontaneous, endothermic. The adsorption processes were complex physical-chemistry adsorption models, which are dominated by physisorption. Furthermore, this study found that the material had strong absorption abilities for anionic surfactants, the saturation adsorption capacity of ACCMs were 1220mg/g for SDBS, 888mg/g for SLS, and 825mg/g for SDS at pH 3.0 and 298K, respectively. The adsorption capacity was reduced only 5.7% after 8 cycles of the adsorption-desorption processes. Copyright © 2017 Elsevier B.V. All rights reserved.
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Prado-Gotor, R; López-Pérez, G; Martín, M J; Cabrera-Escribano, F; Franconetti, A
2014-06-01
A systematic study of the interaction between free anionic gold nanoparticles and chitosan in a solution is presented. A spectroscopic study of the interaction between 10nm gold nanoparticles and low molecular weight chitosan is reported as a function of the concentration and pH of the polymer in a solution. Zeta potential measurements and TEM images indicate the effective aggregation of the nanoparticles in the presence of chitosan. At the same time, anionic gold nanoparticles act as crosslink agents to form chitosan nanocapsules with an average molecular size of 260nm. The changes of the surface plasmon band due to the adsorption of the polymer on the nanoparticle surface allow using of the citrate gold nanoparticles as sensors of the polymer for analytical purposes. The limit of detection for chitosan biopolymer is 69nM. The optimum pH for the interaction between the biopolymer and the nanoparticles is found at a value of 6.4, obtained from spectrophotometric measurements and applying a deconvolution analysis of the experimental data. A simple model based on molecular surface electrostatic interactions is proposed to understand the pH dependence of the investigated system. Copyright © 2014 Elsevier Inc. All rights reserved.
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Sun, Chencheng; Xiong, Bowen; Pan, Yang; Cui, Hao
2017-02-01
Polyaniline (PANI) prepared by chemical oxidation was studied for adsorption removal of tannic acid (TA) from aqueous solution. Batch adsorption studies were carried out under different adsorbent dosages, pH, ionic strength, initial TA concentration and coexisting anions. Solution pH had an important impact on TA adsorption onto PANI with optimal removal in the pH range of 8-11. TA adsorption on PANI at three ionic strength levels (0.02, 0.2 and 2molL -1 NaCl) could be well described by Langmuir model (monolayer adsorption process) and the maximum adsorption capacity was 230, 223 and 1023mgg -1 , respectively. Kinetic data showed that TA adsorption on PANI fitted well with pseudo-second-order model (controlled by chemical process). Among the coexisting anions tested, PO 4 3- significantly inhibited TA adsorption due to the enhancement of repulsive interaction. Continuous flow adsorption studies indicated good flexibility and adaptability of the PANI adsorbent under different flow rates and influent TA concentrations. The mechanism controlling TA adsorption onto PANI under different operating conditions was analyzed with the combination of electrostatic interactions, hydrogen bonding, π-π interactions and Van der Waals interactions. Copyright © 2016 Elsevier Inc. All rights reserved.
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Hernández-Soriano, Maria del Carmen; Peña, Aránzazu; Dolores Mingorance, Ma
2010-01-01
Anionic surfactants, mainly sulfosuccinamates, can be found in soils as the result of sludge application, wastewater irrigation, and remediation processes. Relatively high concentrations of surfactants together with multimetals can represent an environmental risk. A study was performed to assess the potential of the anionic surfactant Aerosol 22 (A22) for release of Cd, Cu, Pb, and Zn from a metal-amended soil representative of a Mediterranean area. Metal desorption was performed by batch experiments and release kinetics were assessed. Response surface methodology was applied to determine the influence of A22 concentration and the surfactant/soil ratio, as extraction key factors. An increase in solution/soil ratio to 100 (mL g(-1)) caused higher metal release. Leaching predictions found Pb to have the lowest and Cd the highest hazard. Metal release was highly dependent on pH. When extraction was made at pH less than 7, low or negligible amounts of metals were leached, whereas an increase to pH 7 caused desorption rates of 50 to 55% for Cd, Cu, and Zn but only 35% for Pb. Complexed metal-carboxylic groups from A22 were mainly responsible for its higher extractive capacity, especially of Cd and Cu.
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Jia, Hanzhong; Gu, Cheng; Li, Hui; Fan, Xiaoyun; Li, Shouzhu; Wang, Chuanyi
2012-09-01
Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.
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The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C
Bennett, P.C.; Melcer, M.E.; Siegel, D.I.; Hassett, J.P.
1988-01-01
The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH.The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.
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A hybrid sorption - Spectrometric method for determination of synthetic anionic dyes in foodstuffs.
Tikhomirova, Tatyana I; Ramazanova, Gyulselem R; Apyari, Vladimir V
2017-04-15
A sorption-spectrometric method for determination of the anionic synthetic dyes based on their sorption on silica sorbent modified with hexadecyl groups (C16) followed by measuring the diffuse reflectance spectra on the surface of the sorbent has been proposed. Adsorption of sulfonated azo dyes Tartrazine (E102), Sunset Yellow FCF (E110), Ponceau 4R (E124) reaches maximum in acidic medium (1M HCl - pH 1). For the quinophthalone type dye Quinoline Yellow (E104), the adsorption is also maximal in an acidic medium (1M HCl - pH 2). The triphenylmethane dye Fast Green FCF (E143) is absorbed in the wider area of pH (1M HCl - pH 6). Increasing concentration of the dyes in a solution led to the increase in absorption band intensity in diffuse reflectance spectra of the adsorbent, which was used for their direct determination. The proposed method was applied to the determination of dyes in beverages and pharmaceuticals. Copyright © 2016 Elsevier Ltd. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Basame, S.B.; White, H.S.
2000-04-01
The potential-dependent breakdown of the native oxide film ({approximately}20 {angstrom} thick) on titanium has been investigated in aqueous Br{sup {minus}} solutions and in solutions that contain a mixture of Br{sup {minus}} and anions that inhibit oxide breakdown (i.e., Cl{sup {minus}}, I{sup {minus}}, SO{sub 4}{sup 2{minus}}, Fe(CN){sub 6}{sup 4{minus}}, and Fe(CN){sub 6}{sup 3{minus}}). The oxide film is unstable in neutral pH solutions containing only Br{sup {minus}}, resulting in the formation of stable corrosion pits at relatively low potentials ({approximately}1.4 V vs. Ag/AgCl). The pitting potential, E{sub p}, is strongly dependent upon the concentration of Br{sup {minus}}, and can be modeled usingmore » a Langmuir isotherm to describe the adsorption of Br{sup {minus}} at the oxide film/electrolyte interface. Addition of a second anion inhibits oxide film breakdown, as indicated by a large positive shift in E{sub p} and a decrease in the number of stable corrosion pits. The dependence of E{sub p} on the relative concentrations of Br{sup {minus}} and the inhibitor anion is consistent with competitive adsorption of the anions. Equilibrium adsorption coefficients for I{sup {minus}}, Br{sup {minus}}, and Cl{sup {minus}} are estimated from the dependence of E{sub p} on anion concentration. The results are used to establish a physical basis for the anomalously low pitting potential for titanium in aqueous Br{sup {minus}} solutions.« less
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Iggy, Litaor M.; Thurman, E.M.
1988-01-01
Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai-, derived from DOC at sample pH and the concentration of organic anion, Ax- at the equivalence point were calculated using carboxyl contents from isolated and purified humic material from soil solutions. Subtracting Ax- from Ai- yields the contribution of humic substances to the buffering capacity (Aequiv.-). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado. ?? 1988.
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Osmotic pressures and second virial coefficients for aqueous saline solutions of lysozyme
Moon, Y. U.; Anderson, C. O.; Blanch, H. W.; ...
2000-03-27
Experimental data at 25 °C are reported for osmotic pressures of aqueous solutions containing lysozyme and any one of the following salts: ammonium sulfate, ammonium oxalate and ammonium phosphate at ionic strength 1 or 3M. Data were obtained using a Wescor Colloid Membrane Osmometer at lysozyme concentrations from about 4 to 20 grams per liter at pH 4, 7 or 8. Osmotic second virial coefficients for lysozyme were calculated from the osmotic-pressure data. All coefficients were negative, increasing in magnitude with ionic strength. Furthermore, tesults are insensitive to the nature of the anion, but rise slightly in magnitude as themore » size of the anion increases.« less
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Ion and solute transport by prestin in Drosophila and Anopheles
Hirata, Taku; Czapar, Anna; Brin, Lauren R.; Haritonova, Alyona; Bondeson, Daniel P.; Linser, Paul J.; Cabrero, Pablo; Dow, Julian A. T.; Romero, Michael F.
2012-01-01
The gut and Malpighian tubules of insects are the primary sites of active solute and water transport for controlling hemolymph and urine composition, pH, and osmolarity. These processes depend on ATPase (pumps), channels and solute carriers (Slc proteins). Maturation of genomic databases enables us to identify the putative molecular players for these processes. Anion transporters of the Slc4 family, AE1 and NDAE1, have been reported as HCO3− transporters, but are only part of the story. Here we report Dipteran (Drosophila melanogaster (d) and Anopheles gambiae (Ag)) anion exchangers, belonging to the Slc26 family, which are multi-functional anion exchangers. One Drosophila and two Ag homologues of mammalian Slc26a5 (prestin) and Slc26a6 (aka, PAT1, CFEX) were identified and designated dPrestin, AgPrestinA and AgPrestinB. dPrestin and AgPrestinB show electrogenic anion exchange (Cl−/nHCO3−, Cl−/SO42− and Cl−/oxalate2−) in an oocyte expression system. Since these transporters are the only Dipteran Slc26 proteins whose transport is similar to mammalian Slc26a6, we submit that Dipteran Prestin are functional and even molecular orthologues of mammalian Slc26a6. OSR1 kinase increases dPrestin ion transport, implying another set of physiological processes controlled by WNK/SPAK signaling in epithelia. All of these mRNAs are highly expressed in the gut and Malpighian tubules. Dipteran Prestin proteins appear suited for central roles in bicarbonate, sulfate and oxalate metabolism including generating the high pH conditions measured in the Dipteran midgut lumen. Finally, we present and discuss Drosophila genetic models that integrate these processes. PMID:22321763
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Deng, Shubo; Ting, Yen Peng
2005-11-01
Heavy metal pollution in the aqueous environment is a problem of global concern. Biosorption has been considered as a promising technology for the removal of low levels of toxic metals from industrial effluents and natural waters. A modified fungal biomass of Penicillium chrysogenum with positive surface charges was prepared by grafting polyethylenimine (PEI) onto the biomass surface in a two-step reaction. The presence of PEI on the biomass surface was verified by FTIR and X-ray photoelectron spectroscopy (XPS) analyses. Due to the high density of amine groups in the long chains of PEI molecules on the surface, the modified biomass was found to possess positive zeta potential at pH below 10.4 as well as high sorption capacity for anionic Cr(VI). Using the Langmuir adsorption isotherm, the maximum sorption capacity for Cr(VI) at a pH range of 4.3-5.5 was 5.37 mmol/g of biomass dry weight, the highest sorption capacity for Cr(VI) compared to other sorbents reported in the literature. Scanning electronic microscopy (SEM) provided evidence of chromium aggregates formed on the biomass surface. XPS results verified the presence of Cr(III) on the biomass surface in the pH range 2.5-10.5, suggesting that some Cr(VI) anions were reduced to Cr(III) during the sorption. The sorption kinetics indicated that redox reaction occurred on the biomass surface, and whether the converted Cr(III) ions were released to solution or adsorbed on the biomass depended on the solution pH. Sorption mechanisms including electrostatic interaction, chelation, and precipitation were found to be involved in the complex sorption of chromium on the PEI-modified biomass.
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Anionic pH-Sensitive Lipoplexes.
Mignet, Nathalie; Scherman, Daniel
2017-01-01
To provide long circulating nanoparticles able to carry a gene to tumors, we have designed anionic pegylated lipoplexes which are pH sensitive. Anionic pegylated lipoplexes have been prepared from the combined formulation of cationic lipoplexes and pegylated anionic liposomes. The neutralization of the particle surface charge as a function of the pH was monitored by light scattering in order to determine the ratio between anionic and cationic lipids that would give pH sensitive complexes. This ratio has been optimized to form particles sensitive to pH change in the range 5.5-6.5. Compaction of DNA into these newly formed anionic complexes is checked by DNA accessibility to picogreen. The transfection efficiency and pH sensitive property of these formulations has been shown in vitro using bafilomycin, a vacuolar H + -ATPase inhibitor.
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Tellurate and periodate solutions as media for paper electrophoresis of carbohydrates.
Alesofie, B M; Popiel, W J
1973-02-01
Electrophoretic separations of sugars and other polyhydroxy compounds may be performed in 0.2M telluric acid media adjusted to pH 10 with sodium hydroxide, and in 0.07M sodium metaperiodate at pH 11. Oxidation by periodate appears to be only slight under these conditions. Migration rates of 21 compounds are reported relative to the movement of d-ribose. In both electrolytes the compounds form anionic complexes.
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NASA Astrophysics Data System (ADS)
Dai, Yanpeng; Wang, Peng; Fu, Jiaxin; Yao, Kun; Xu, Kuoxi; Pang, Xiaobin
2017-08-01
A quinaldine functionalized probe QP has been designed and synthesized. It exhibited selective turn-off fluorescence response toward Cu2 + ion over most of the biologically important ions at physiological pH. The binding ratio of the probe QP and Cu2 + ion was determined to be 1:1 through fluorescence titration, Job's plot and ESI-MS. The binding constant (K) of Cu2 + to probe QP was found to be 2.12 × 104 M- 1. Further, the Cu2 + ensemble of probe QP was found to respond H2PO4- and HPO42 - among other important biological anions via fluorescence turn-on response at physiological pH. Fluorescence microscopy imaging using living Hela cells showed that probe QP could be used as an effective fluorescent probe for detecting Cu2 + cation and H2PO4- and HPO42 - anions in living cells.
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Perchlorate adsorption and desorption on activated carbon and anion exchange resin.
Yoon, In-Ho; Meng, Xiaoguang; Wang, Chao; Kim, Kyoung-Woong; Bang, Sunbaek; Choe, Eunyoung; Lippincott, Lee
2009-05-15
The mechanisms of perchlorate adsorption on activated carbon (AC) and anion exchange resin (SR-7 resin) were investigated using Raman, FTIR, and zeta potential analyses. Batch adsorption and desorption results demonstrated that the adsorption of perchlorate by AC and SR-7 resin was reversible. The reversibility of perchlorate adsorption by the resin was also proved by column regeneration test. Solution pH significantly affected perchlorate adsorption and the zeta potential of AC, while it did not influence perchlorate adsorption and the zeta potential of resin. Zeta potential measurements showed that perchlorate was adsorbed on the negatively charged AC surface. Raman spectra indicated the adsorption resulted in an obvious position shift of the perchlorate peak, suggesting that perchlorate was associated with functional groups on AC at neutral pH through interactions stronger than electrostatic interaction. The adsorbed perchlorate on the resin exhibited a Raman peak at similar position as the aqueous perchlorate, indicating that perchlorate was adsorbed on the resin through electrostatic attraction between the anion and positively charged surface sites.
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Dai, Yanpeng; Wang, Peng; Fu, Jiaxin; Yao, Kun; Xu, Kuoxi; Pang, Xiaobin
2017-08-05
A quinaldine functionalized probe QP has been designed and synthesized. It exhibited selective turn-off fluorescence response toward Cu 2+ ion over most of the biologically important ions at physiological pH. The binding ratio of the probe QP and Cu 2+ ion was determined to be 1:1 through fluorescence titration, Job's plot and ESI-MS. The binding constant (K) of Cu 2+ to probe QP was found to be 2.12×10 4 M -1 . Further, the Cu 2+ ensemble of probe QP was found to respond H 2 PO 4 - and HPO 4 2- among other important biological anions via fluorescence turn-on response at physiological pH. Fluorescence microscopy imaging using living Hela cells showed that probe QP could be used as an effective fluorescent probe for detecting Cu 2+ cation and H 2 PO 4 - and HPO 4 2- anions in living cells. Copyright © 2017 Elsevier B.V. All rights reserved.
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Sun, Min; Qiu, Hongdeng; Wang, Licheng; Liu, Xia; Jiang, Shengxiang
2009-05-01
A new specific stationary phase based on poly(1-allylimidazole)-grafted silica has been synthesized and characterized, by infrared spectra, elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. The results of test showed that poly(1-allylimidazole) can effectively mask the residual silanol groups and reduce the adverse effect of residual silanol. Using this stationary phase, phenol compounds, aniline compounds, and polycyclic aromatic hydrocarbons were successfully separated with symmetric peak shapes in the reversed-phase chromatography. Inorganic anions (IO(3)(-), BrO(3)(-), Br(-), NO(3)(-), I(-), SCN(-)) were also separated completely in the anion-exchange chromatography using sodium chloride solution as the mobile phase. The effects of pH and the concentration of eluent on the separation of inorganic anions were studied. The separation mechanism appears to involve the mixed interactions of hydrogen bonding, hydrophobic, pi-pi, electrostatic, and anion-exchange interactions.
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Qiu, Hongdeng; Zhang, Qinghua; Chen, Limei; Liu, Xia; Jiang, Shengxiang
2008-08-01
Separations of common inorganic anions were carried out on ODS columns coated with two long-chain alkylimidazolium ionic liquids ([C(12)MIm]Br and [C(14)MIm]Br) as new cationic surfactants for ion chromatography. With phthalate buffer solution as the mobile phases and non-suppressed conductivity detection, high column efficiencies and excellent selectivity were obtained in the separation of inorganic anions. Chromatographic parameters are calculated and the results show that the coated column possesses significant potential for the analysis of some inorganic anions such as CH(3)COO(-), IO(3)(-), Cl(-), BrO(3)(-), NO(2)(-), Br(-), NO(3)(-), SO(4)(2-), I(-), BF(4)(-), and SCN(-). The effect of eluent pH values on the separation of anions has been studied on the column coated with [C(12)MIm]Br. The stability of the coated columns was also examined.
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NASA Astrophysics Data System (ADS)
Wang, Wenxia; Huang, Guohe; An, Chunjiang; Xin, Xiaying; Zhang, Yan; Liu, Xia
2017-05-01
From the viewpoint of sustainability, biomass adsorbent has a high potential in pollution control and there is an emerging interest to investigate the behaviors of pollutants at the interface between biomass adsorbent and solution. This study investigated the performance of cetyltrimethylammonium bromide surfactant-modified flax shives (MFS) for removal of anionic azo dyes from aqueous solution. The equilibrium and kinetic analysis for the adsorption of Acid Orange 7 (AO-7), Acid Red 18 (AR-18) and Acid Black 1 (AB-1) on MFS were conducted. The surface of MFS was characterized by synchrotron infrared and SEM analysis. The absorbed amount of three anionic azo dyes varied with the change of adsorbent dosage, pH and ionic strength. The adsorption isotherm data well fit to the Langmuir model. The adsorption process followed the pseudo-second-order kinetics and the liquid film diffusion models. Thermodynamic studies indicated that the adsorption of three anionic azo dyes was spontaneous. The adsorption of AR-18 and AB-1 onto MFS was endothermic while the adsorption of AO-7 was exothermic. The results can help better understand the behaviors of organic pollutants at biomass adsorbent-water interface. They also present the potential of using MFS as a suitable adsorbent for the removal of anionic azo dyes from wastewater.
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Takayanagi, Akari; Kobayashi, Maki; Kawase, Yoshinori
2017-03-01
Mechanisms for removal of anionic surfactant sodium dodecyl benzene sulfonate (SDBS) in wastewaters by zero-valent iron (ZVI) were systematically examined. The contributions of four removal mechanisms, i.e., reductive degradation, oxidative degradation, adsorption, and precipitation, changed significantly with solution pH were quantified and the effective removal of SDBS by ZVI was found to be attributed to the adsorption capability of iron oxides/hydroxides on ZVI surface at nearly neutral pH instead of the degradation at acidic condition. The fastest SDBS removal rate and the maximum TOC (total organic carbon) removal efficiency were obtained at pH 6.0. The maximum TOC removal at pH 6.0 was 77.8%, and the contributions of degradation, precipitation, and adsorption to TOC removal were 4.6, 14.9, and 58.3%, respectively. At pH 3.0, which is an optimal pH for oxidative degradation by the Fenton reaction, the TOC removal was only 9.8% and the contributions of degradation, precipitation, and adsorption to TOC removal were 2.3, 4.6, and 2.9%, respectively. The electrostatic attraction between dodecyl benzene sulfate anion and the iron oxide/hydroxide layer controlled the TOC removal of SDBS. The kinetic model based on the Langmuir-Hinshelwood/Eley-Rideal approach could successfully describe the experimental results for SDBS removal by ZVI with the averaged correlation coefficient of 0.994. ZVI was found to be an efficient material toward the removal of anionic surfactant at nearly neutral pH under the oxic condition.
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The Al(I) molecule, Ph2COAl and its anion
NASA Astrophysics Data System (ADS)
Zhang, Xinxing; Eichhorn, Bryan; Schnöckel, Hansgeorg; Bowen, Kit
2016-08-01
We have formed the Al(I)-containing molecule, benzophenone-aluminum, i.e., Ph2COAl, and studied it by conducting density functional theory calculations on both its neutral and anionic forms and by measuring the photoelectron spectrum of its anion. Our calculations identified two nearly iso-energetic anion isomers, (Ph2COAl)-, the vertical detachment energies (VDE) of which are in excellent agreement with our photoelectron spectrum. Natural population analysis (NPA) of Ph2COAl found the Al moiety to be positively charged by +0.81 e, indicating a strongly ionic bond between Al and Ph2CO, i.e., Ph2CO-Al+.
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Reaction behaviors of decomposition of monocrotophos in aqueous solution by UV and UV/O processes.
Ku, Y; Wang, W; Shen, Y S
2000-02-01
The decomposition of monocrotophos (cis-3-dimethoxyphosphinyloxy-N-methyl-crotonamide) in aqueous solution by UV and UV/O(3) processes was studied. The experiments were carried out under various solution pH values to investigate the decomposition efficiencies of the reactant and organic intermediates in order to determine the completeness of decomposition. The photolytic decomposition rate of monocrotophos was increased with increasing solution pH because the solution pH affects the distribution and light absorbance of monocrotophos species. The combination of O(3) with UV light apparently promoted the decomposition and mineralization of monocrotophos in aqueous solution. For the UV/O(3) process, the breakage of the >C=C< bond of monocrotophos by ozone molecules was found to occur first, followed by mineralization by hydroxyl radicals to generate CO(3)(2-), PO4(3-), and NO(3)(-) anions in sequence. The quasi-global kinetics based on a simplified consecutive-parallel reaction scheme was developed to describe the temporal behavior of monocrotophos decomposition in aqueous solution by the UV/O(3) process.
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Hirsh, Allen G; Tsonev, Latchezar I
2017-04-28
This paper details the use of a method of creating controlled pH gradients (pISep) to improve the separation of protein isoforms on ion exchange (IEX) stationary phases in the presence of various isocratic levels of urea. The pISep technology enables the development of computer controlled pH gradients on both cationic (CEX) and anionic (AEX) IEX stationary phases over the very wide pH range from 2 to 12. In pISep, titration curves generated by proportional mixing of the acidic and basic pISep working buffers alone, or in the presence of non-buffering solutes such as the neutral salt NaCl (0-1M), polar organics such as urea (0-8M) or acetonitrile (0-80 Vol%), can be fitted with high fidelity using high order polynomials which, in turn allows construction of a mathematical manifold %A (% acidic pISep buffer) vs. pH vs. [non-buffering solute], permitting precise computer control of pH and the non-buffering solute concentration allowing formation of dual uncoupled liquid chromatographic (LC) gradients of arbitrary shape (Hirsh and Tsonev, 2012 [1]). The separation of protein isoforms examined in this paper by use of such pH gradients in the presence of urea demonstrates the fractionation power of a true single step two dimensional liquid chromatography which we denote as Stability-Influenced Ion Exchange Chromatography (SIIEX). We present evidence that SIIEX is capable of increasing the resolution of protein isoforms difficult to separate by ordinary pH gradient IEX, and potentially simplifying the development of laboratory and production purification strategies involving on-column simultaneous pH and urea unfolding or refolding of targeted proteins. We model some of the physics implied by the dynamics of the observed protein fractionations as a function of both urea concentration and pH assuming that urea-induced native state unfolding competes with native state electrostatic interaction binding to an IEX stationary phase. Implications for in vivo protein-membrane interactions are discussed. Copyright © 2017 Elsevier B.V. All rights reserved.
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Oxidation of aqueous polyselenide solutions. A mechanistic pulse radiolysis study
DOE Office of Scientific and Technical Information (OSTI.GOV)
Goldbach, A.; Saboungi, M.L.; Johnson, J.A.
2000-05-04
The oxidation of aqueous polyselenide solutions was studied by pulse radiolysis in the presence of N{sub 2}O at pH 12.3; the hydroxyl radical OH was the predominant oxidant, while hydrogen selenide anions HSe{sup {minus}} and triselenide dianions Se{sub 3}{sup 2{minus}} were the major selenide species in the starting solution. The progress of the oxidation was monitored by optical spectroscopy. Transient polyselenides appeared immediately after the electron pulse and rapidly proceeded to form adducts with HSe{sup {minus}}, i.e., HSe{sub 2}{sup 2{minus}} and H{sub 2}Se{sub 2}{sup {minus}}, and a fairly long-lived intermediate that was identified as the diselenide radical anion Se{sub 2}{supmore » {minus}}. These radicals recombine to give eventually the tetraselenide dianion, Se{sub 4}{sup 2{minus}}.« less
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Water-soluble drug partitioning and adsorption in HEMA/MAA hydrogels.
Dursch, Thomas J; Taylor, Nicole O; Liu, David E; Wu, Rong Y; Prausnitz, John M; Radke, Clayton J
2014-01-01
Two-photon confocal microscopy and back extraction with UV/Vis-absorption spectrophotometry quantify equilibrium partition coefficients, k, for six prototypical drugs in five soft-contact-lens-material hydrogels over a range of water contents from 40 to 92%. Partition coefficients were obtained for acetazolamide, caffeine, hydrocortisone, Oregon Green 488, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA, pKa≈5.2) copolymer hydrogels as functions of composition, aqueous pH (2 and 7.4), and salinity. At pH 2, the hydrogels are nonionic, whereas at pH 7.4, hydrogels are anionic due to MAA ionization. Solute adsorption on and nonspecific electrostatic interaction with the polymer matrix are pronounced. To express deviation from ideal partitioning, we define an enhancement or exclusion factor, E ≡ k/φ1, where φ1 is hydrogel water volume fraction. All solutes exhibit E > 1 in 100 wt % HEMA hydrogels owing to strong specific adsorption to HEMA strands. For all solutes, E significantly decreases upon incorporation of anionic MAA into the hydrogel due to lack of adsorption onto charged MAA moieties. For dianionic sodium fluorescein and Oregon Green 488, and partially ionized monoanionic acetazolamide at pH 7.4, however, the decrease in E is more severe than that for similar-sized nonionic solutes. Conversely, at pH 2, E generally increases with addition of the nonionic MAA copolymer due to strong preferential adsorption to the uncharged carboxylic-acid group of MAA. For all cases, we quantitatively predict enhancement factors for the six drugs using only independently obtained parameters. In dilute solution for solute i, Ei is conveniently expressed as a product of individual enhancement factors for size exclusion (Ei(ex)), electrostatic interaction (Ei(el)), and specific adsorption (Ei(ad)):Ei≡Ei(ex)Ei(el)Ei(ad). To obtain the individual enhancement factors, we employ an extended Ogston mesh-size distribution for Ei(ex); Donnan equilibrium for Ei(el); and Henry's law characterizing specific adsorption to the polymer chains for Ei(ad). Predicted enhancement factors are in excellent agreement with experiment. Copyright © 2013 Elsevier Ltd. All rights reserved.
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The stability of 6-mercaptopurine riboside in neutral and basic medium.
Jelińska, A; Magdziarz, M
2000-01-01
The kinetics of hydrolysis of 6-mercaptopurine riboside (R-6-MP) was studied in aqueous solutions over the pH range of 6.11-12.13 at 353 K. The decomposition was investigated by HPLC method. At the pH range from 6.11 to 12.13 hydrolysis of 6-mercaptopurine riboside includes: spontaeous hydrolysis of non-protonated R-6-MP molecules mono- and di-anions R-6-MP molecules under the effect of water.
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Cao, Wei; Dang, Zhi; Yia, Xiao-Yun; Yang, Chen; Lu, Gui-Ning; Liu, Yun-Feng; Huang, Se-Yan; Zheng, Liu-Chun
2013-01-01
An anion exchanger from rice straw was used to remove Cr (VI) from synthetic wastewater and electroplating effluent. The exchanger was characterized using Fourier transform infrared (FTIR) spectrum and scanning electron microscopy (SEM), and it was found that the quaternary amino group and hydroxyl group are the main functional groups on the fibrous surface of the exchanger. The effect of contact time, initial concentration and pH on the removal of Cr (VI), and adsorption isotherms at different temperature, was investigated. The results showed that the removal of Cr (VI) was very rapid and was significantly affected by the initial pH of the solution. Although acidic conditions (pH = 2-6) facilitated Cr (VI) adsorption, the exchanger was effective in neutral solution and even under weak base conditions. The equilibrium data fitted well with Langmuir adsorption model, and the maximum Cr (VI) adsorption capacities at pH 6.4 were 0.35, 0.36 and 0.38 mmol/g for 15, 25 and 35 degrees C, respectively. The exchanger was finally tested with real electroplating wastewater, and at sorbent dosage of 10 g/L, the removal efficiencies for Cr (VI) and total Cr were 99.4% and 97.8%, respectively. In addition, the positive relationship between adsorbed Cr (VI) and desorbed Cl- suggested that Cr (VI) was mainly removed by ion exchange with chlorine.
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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.
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NASA Astrophysics Data System (ADS)
Ebrahimi-Gatkash, Mehdi; Younesi, Habibollah; Shahbazi, Afsaneh; Heidari, Ava
2017-07-01
In the present study, amino-functionalized Mobil Composite Material No. 41 (MCM-41) was used as an adsorbent to remove nitrate anions from aqueous solutions. Mono-, di- and tri-amino functioned silicas (N-MCM-41, NN-MCM-41 and NNN-MCM-41) were prepared by post-synthesis grafting method. The samples were characterized by means of X-ray powder diffraction, FTIR spectroscopy, thermogravimetric analysis, scanning electron microscopy and nitrogen adsorption-desorption. The effects of pH, initial concentration of anions, and adsorbent loading were examined in batch adsorption system. Results of adsorption experiments showed that the adsorption capacity increased with increasing adsorbent loading and initial anion concentration. It was found that the Langmuir mathematical model indicated better fit to the experimental data than the Freundlich. According to the constants of the Langmuir equation, the maximum adsorption capacity for nitrate anion by N-MCM-41, NN-MCM-41 and NNN-MCM-41 was found to be 31.68, 38.58 and 36.81 mg/g, respectively. The adsorption kinetics were investigated with pseudo-first-order and pseudo-second-order model. Adsorption followed the pseudo-second-order rate kinetics. The coefficients of determination for pseudo-second-order kinetic model are >0.99. For continuous adsorption experiments, NNN-MCM-41 adsorbent was used for the removal of nitrate anion from solutions. Breakthrough curves were investigated at different bed heights, flow rates and initial nitrate anion concentrations. The Thomas and Yan models were utilized to calculate the kinetic parameters and to predict the breakthrough curves of different bed height. Results from this study illustrated the potential utility of these adsorbents for nitrate removal from water solution.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Bortolaz de Oliveira, Henrique; Wypych, Fernando, E-mail: wypych@ufpr.br
Layered zinc hydroxide nitrate (ZnHN) and Zn/Ni layered double hydroxide salts were synthesized and used to remove chromate ions from solutions at pH 8.0. The materials were characterized by many instrumental techniques before and after chromate ion removal. ZnHN decomposed after contact with the chromate solution, whereas the layered structure of Zn/Ni hydroxide nitrate (Zn/NiHN) and Zn/Ni hydroxide acetate (Zn/NiHA) remained their layers intact after the topotactic anionic exchange reaction, only changing the basal distances. ZnHN, Zn/NiHN, and Zn/NiHA removed 210.1, 144.8, and 170.1 mg of CrO{sub 4}{sup 2−}/g of material, respectively. Although the removal values obtained for Zn/NiHN andmore » Zn/NiHA were smaller than the values predicted for the ideal formulas of the solids (194.3 and 192.4 mg of CrO{sub 4}{sup 2−}/g of material, respectively), the measured capacities were higher than the values achieved with many materials reported in the literature. Kinetic experiments showed the removal reaction was fast. To facilitate the solid/liquid separation process after chromium removal, Zn/Ni layered double hydroxide salts with magnetic supports were also synthesized, and their ability to remove chromate was evaluated. - Highlights: • Zinc hydroxide nitrate and Zn/Ni hydroxide nitrate or acetate were synthesized. • The interlayer anions were replaced by chromate anions at pH=8.0. • Only Zn/Ni hydroxide nitrate or acetate have the structure preserved after exchange. • Fast exchange reaction and high capacity of chromate removal were observed. • Magnetic materials were obtained to facilitate the solids removal the from solutions.« less
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The hydrothermolysis of the picrate anion: Kinetics and mechanism
Ross, D.S.; Jayaweera, I.
2002-01-01
The hydrothermolysis of the picrate anion in aqueous solution has been studied at 260-325??C in liquid water. At starting pH values above 12, the disappearance of picrate begins immediately and is first order in OH-. At lower pH, there is an induction period preceding the disappearance, and over the pH range 6.7-11.9 there is no pH dependence in the developed reaction phase. Added borate and silicate salts promote the reaction, suggesting their acting as nucleophiles at hydrothermal conditions. Nitrite is an initial product, while acetate is a final product and reflective of a vigorous oxidative sequence consuming the intermediate products. A reaction sequence consistent with the results at the lower pH includes initiation of a chain process by displacement of nitrite by water, followed by nucleophilic displacement of nitrite by nitrite such that a nitro group is replaced by an O-N=O group. The ester then rapidly hydrolyzes, and the net reaction is the production of an additional nitrite with each cycle. A simple modeling of this system satisfactorily fits the experimental findings. ?? 2002 Elsevier Science B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Aksu, Z.; Calik, A.
1999-03-01
In this study a comparative biosorption of iron(III)-cyanide complex anions from aqueous solutions to Rhizopus arrhizus and Chlorella vulgaris was investigated. The iron(III)-cyanide complex ion-binding capacities of the biosorbents were shown as a function of initial pH, initial iron(III)-cyanide complex ion, and biosorbent concentrations. The results indicated that a significant reduction of iron(III)-cyanide complex ions was achieved at pH 13, a highly alkaline condition for both the biosorbents. The maximum loading capacities of the biosorbents were found to be 612.2 mg/g for R.arrhizus at 1,996.2 mg/L initial iron(III)-cyanide complex ion concentration and 387.0 mg/g for C. vulgaris at 845.4 mg/Lmore » initial iron(III)-cyanide complex ion concentration at this pH. The Freundlich, Langmuir, and Redlich-Peterson adsorption models were fitted to the equilibrium data at pH 3, 7, and 13. The equilibrium data of the biosorbents could be best fitted by all the adsorption models over the entire concentration range at pH 13.« less
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Photochemical reduction of cytochrome c by a 1,4,5,8-naphthalenediimide radical anion.
Campos, Ivana B; Nantes, Iseli L; Politi, Mario J; Brochsztain, Sergio
2004-01-01
Steady-state UV irradiation of aqueous solutions containing cytochrome c (cyt c) and N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (BPNDI), a water-soluble aromatic imide, resulted in the reduction of the heme iron from the Fe(III) to the Fe(II) oxidation state. The reaction kinetics were followed by the increase of the ferrocytochrome c absorbance band at 549 nm. The rate of the photochemical reaction was pH dependent, reaching its maximum values over the pH range 4-7. Addition of electrolyte (NaCl) at pH 5 resulted in a decrease in the reaction rate, as expected for reactions between oppositely charged species. Flash photolysis studies revealed that the actual reductant in the reaction was a photogenerated BPNDI radical anion, which transferred an electron to the cyt c heme iron. The participation of imide radicals in the process was confirmed by the ready reduction of cyt c by BPNDI radicals chemically generated with sodium dithionite.
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NASA Astrophysics Data System (ADS)
Lafhaj, Z.; Filippov, L. O.; Filippova, I. V.
2017-07-01
The flotation separation of salt type calcium minerals is problematic, due to the similarities in their same active Ca2+ related site for interaction with anionic collectors and similar physicochemical characteristics such as solubility, zero-point charge, surface speciation and Ca-site density. The work was performed to achieve effective and selective separation of the calcium-minerals using pure minerals samples: orange calcite with Mg impurities, optic calcite with impurities level and an apatite. The pure samples surface was examined using techniques sensitive near-surface like infrared spectroscopy (FTIR) and chemical composition was obtained by ICPMS. The isoelectric point (IEP) and point of zero charge (PZC) in electrolyte were recorded using electrophoresis method at different ionic strengths of the solution. Mechanisms of charge development at the mineral-water interface are discussed. The time of contact as important parameter for the charge equilibrium was deduced from kinetics study and fixed to 30 minutes. The difference in the values obtained between IEP and PZSE can be explained by the presence of a specific adsorption of cations and anions on the surface. The effect of pure anionic collectors such as oleic and linoleic acid were studied. At low pH, both collectors lead to a good recovery for the calcites. The flotation recovery of optic calcite at pH 9 with sodium oleate is higher than with sodium linoleate. At alkaline pH, apatite showed a better recovery with sodium linoleate.
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Enrichment of copper and recycling of cyanide from copper-cyanide waste by solvent extraction
NASA Astrophysics Data System (ADS)
Gao, Teng-yue; Liu, Kui-ren; Han, Qing; Xu, Bin-shi
2016-11-01
The enrichment of copper from copper-cyanide wastewater by solvent extraction was investigated using a quaternary ammonium salt as an extractant. The influences of important parameters, e.g., organic-phase components, aqueous pH values, temperature, inorganic anion impurities, CN/Cu molar ratio, and stripping reagents, were examined systematically, and the optimal conditions were determined. The results indicated that copper was effectively concentrated from low-concentration solutions using Aliquat 336 and that the extraction efficiency increased linearly with increasing temperature. The aqueous pH value and concentrations of inorganic anion impurities only weakly affected the extraction process when varied in appropriate ranges. The CN/Cu molar ratio affected the extraction efficiency by changing the distribution of copper-cyanide complexes. The difference in gold leaching efficiency between using raffinate and fresh water was negligible.
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Rouster, Paul; Pavlovic, Marko; Szilagyi, Istvan
2017-07-13
Ion specific effects on colloidal stability of titania nanosheets (TNS) were investigated in aqueous suspensions. The charge of the particles was varied by the pH of the solutions, therefore, the influence of mono- and multivalent anions on the charging and aggregation behavior could be studied when they were present either as counter or co-ions in the systems. The aggregation processes in the presence of inorganic salts were mainly driven by interparticle forces of electrostatic origin, however, chemical interactions between more complex ions and the surface led to additional attractive forces. The adsorption of anions significantly changed the surface charge properties and hence, the resistance of the TNS against salt-induced aggregation. On the basis of their ability in destabilization of the dispersions, the monovalent ions could be ordered according to the Hofmeister series in acidic solutions, where they act as counterions. However, the behavior of the biphosphate anion was atypical and its adsorption induced charge reversal of the particles. The multivalent anions destabilized the oppositely charged TNS more effectively and the aggregation processes followed the Schulze-Hardy rule. Only weak or negligible interactions were observed between the anions and the particles in alkaline suspensions, where the TNS possessed negative charge.
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Rodríguez, Araceli; García, Juan; Ovejero, Gabriel; Mestanza, María
2009-12-30
Activated carbon was utilized as adsorbent to remove anionic dye, Orange II (OII), and cationic dye, Methylene blue (MB), from aqueous solutions by adsorption. Batch experiments were conducted to study the effects of temperature (30-65 degrees C), initial concentration of adsorbate (300-500 mg L(-1)) and pH (3.0-9.0) on dyes adsorption. Equilibrium adsorption isotherms and kinetics were investigated. The equilibrium experimental data were analyzed by the Langmuir, Freundlich, Toth and Redlich-Peterson models. The kinetic data obtained with different carbon mass were analyzed using a pseudo-first order, pseudo-second order, intraparticle diffusion, Bangham and Chien-Clayton equations. The best results were achieved with the Langmuir isotherm equilibrium model and with the pseudo-second order kinetic model. The activated carbon was found to be very effective as adsorbent for MB and OII from aqueous solutions.
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NASA Astrophysics Data System (ADS)
Areibat, Lila Elamari Mohamed; Kamari, Azlan
2017-05-01
Wastewater originating from industrial effluents contains many types of pollutants including dyes. Anionic and cationic dyes are very toxic and they can cause several problems to aquatic system. In present study, razor clam shell was used as a potential adsorbent to remove two classes of dyes, namely anionic (Congo red, CR) and cationic (Rhodamine B, RB) dyes from aqueous solution. Batch adsorption experiments were performed to study the effects of three experimental parameters, namely solution pH, adsorbent dosage and initial dye concentration, on adsorption capacity of CR and RB onto razor clam shell. Results indicated that pH 2.0 was optimum pH for adsorbent to adsorb both CR and RB. At an initial concentration of 20 mg/L, the removal percentages of CR and RB were 97% and 38%, respectively. The Freundlich and Langmuir isotherm models were used to describe adsorption behaviour of CR and RB, as well as the relationship between adsorbent and adsorbate. The adsorption equilibrium data were well fitted to Freundlich isotherm model. The separation factor (RL) constants suggest that both CR and RB were favourably adsorbed by razor clam shell. Razor clam shell was characterised by using two techniques, namely Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectrometry (FTIR). Overall, this study suggests that razor clam shell has great potential to be an alternative to expensive adsorbents.
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Use of metallurgical dust for removal chromium ions from aqueous solutions
NASA Astrophysics Data System (ADS)
Pająk, Magdalena; Dzieniszewska, Agnieszka; Kyzioł-Komosińska, Joanna; Chrobok, Michał
2018-01-01
The aim of the study was to determine the potential for the application of dust from steel plant as an effective sorbent for removing Cr(III) and Cr(VI) in the form of simple and complex ions - Acid Blue 193 dye from aqueous solutions. Three isotherms models were used to interpret the experimental results namely: Langmuir, Freundlich, and Dubinin-Radushkevich. Estimated equations parameters allowed to determine the binding mechanism. Based on laboratory studies it was found that the dust was characterized by high sorption capacities for Cr ions and dye from the aqueous solution. The sorption capacity of the dust for Cr(III) and Cr(VI) ions depended on the degree of oxidation, pH of solution and kind of anion and changed in series: Cr(III)-Cl pH=5.0> Cr(III)-SO4 pH=5.0> Cr(III)-Cl pH=3.0> Cr(III)-SO4 pH=3.0> Cr(VI) pH=5.0> Cr(VI) pH=3.0. Dust was also characterized by a high maximum sorption capacity of dye at a range of 38.2 - 91.7 mg/g, depending on the dose of dust. Based on the study it was found that dust from a steel plant, containing iron oxides, can be used as low-cost and effective sorbent to remove pollutions containing chromium ions, especially from acidic wastewater.
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Halloysite nanotubule clay for efficient water purification.
Zhao, Yafei; Abdullayev, Elshad; Vasiliev, Alexandre; Lvov, Yuri
2013-09-15
Halloysite clay has chemical structure similar to kaolinite but it is rolled in tubes with diameter of 50 nm and length of ca. 1000 nm. Halloysite exhibits higher adsorption capacity for both cationic and anionic dyes because it has negative SiO2 outermost and positive Al2O3 inner lumen surface; therefore, these clay nanotubes have efficient bivalent adsorbancy. An adsorption study using cationic Rhodamine 6G and anionic Chrome azurol S has shown approximately two times better dye removal for halloysite as compared to kaolin. Halloysite filters have been effectively regenerated up to 50 times by burning the adsorbed dyes. Overall removal efficiency of anionic Chrome azurol S exceeded 99.9% for 5th regeneration cycle of halloysite. Chrome azurol S adsorption capacity decreases with the increase of ionic strength, temperature and pH. For cationic Rhodamine 6G, higher ionic strength, temperature and initial solution concentration were favorable to enhanced adsorption with optimal pH 8. The equilibrium adsorption data were described by Langmuir and Freundlich isotherms. Copyright © 2013 Elsevier Inc. All rights reserved.
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Tajmir-Riahi, H A
1990-10-01
The interaction of L-ascorbic acid with alkaline earth metal ions has been investigated in aqueous solution at pH 6-7. The solid salts of the type Mg(L-ascorbate)2.4H2O, Ca(L-ascorbate)2.2H2O, Sr(L-ascorbate)2.2H2O and Ba(L-ascorbate)2.2H2O were isolated and characterized by means of 13C NMR and FT-IR spectroscopy. Spectroscopic and other evidence suggested that in aqueous solution, the binding of the alkaline earth metal ions is through the O-3 atom of the ascorbate anion, while in the solid state the binding of the Mg(II) is different from those of the other alkaline earth metal ion salts. The Mg(II) ion binds to the O-3, O-1 atom of the two ascorbate anions and to two H2O molecules, while the eight-coordination around the Ca(II), Sr(II), and Ba(II) ions would be completed by the coordination of three acid anions, through O-5, O-6 of the first, O-3, O-5, O-6 of the second and O-1 of the third anion as well as to two H2O molecules. The structural properties of the alkaline earth metal-ascorbate salts are different in the solid and aqueous solution.
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Polanams, Jup; Ray, Alisha D; Watt, Richard K
2005-05-02
Nanoparticles of iron phosphate, iron arsenate, iron molybdate, and iron vanadate were synthesized within the 8 nm interior of ferritin. The synthesis involved reacting Fe(II) with ferritin in a buffered solution at pH 7.4 in the presence of phosphate, arsenate, vanadate, or molybdate. O2 was used as the oxidant to deposit the Fe(III) mineral inside ferritin. The rate of iron incorporation into ferritin was stimulated when oxo-anions were present. The simultaneous deposition of both iron and the oxo-anion was confirmed by elemental analysis and energy-dispersive X-ray analysis. The ferritin samples containing iron and one of the oxo-anions possessed different UV/vis spectra depending on the anion used during mineral formation. TEM analysis showed mineral cores with approximately 8 nm mineral particles consistent with the formation of mineral phases inside ferritin.
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Synthesis, purification, and structural characterization of the dimethyldiselenoarsinate anion.
Gailer, Jürgen; George, Graham N; Harris, Hugh H; Pickering, Ingrid J; Prince, Roger C; Somogyi, Arpad; Buttigieg, Gavin A; Glass, Richard S; Denton, M Bonner
2002-10-21
A novel arsenic-selenium solution species was synthesized by reacting equimolar sodium selenite and sodium dimethylarsinate with 10 mol equiv of glutathione (pH 7.5) in aqueous solution. The solution species showed a single (77)Se NMR resonance at 112.8 ppm. Size-exclusion chromatography (SEC) using an inductively coupled plasma atomic emission spectrometer (ICP-AES) as the simultaneous arsenic-, selenium-, sulfur-, and carbon-specific detector revealed an arsenic-selenium moiety with an As:Se molar ratio of 1:2. Electrospray ionization mass spectrometry (ESI-MS) of the chromatographically purified compound showed a molecular mass peak at m/z 263 in the negative ion mode. Fragmentation of the parent ion (ESI-MS-MS) produced (CH(3))(2)As(-) and Se(2)(-) fragments. Arsenic and selenium extended X-ray absorption fine structure spectroscopy (EXAFS) of the purified species revealed two As-C interactions at 1.943 A and two As-Se interactions at 2.279 A. On the basis of these results this novel solution species is identified as the dimethyldiselenoarsinate anion.
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Colcombet, Jean; Lelièvre, Françoise; Thomine, Sébastien; Barbier-Brygoo, Hélène; Frachisse, Jean-Marie
2005-07-01
Variations in both intracellular and extracellular pH are known to be involved in a wealth of physiological responses. Using the patch-clamp technique on Arabidopsis hypocotyl cells, it is shown that rapid-type and slow-type anion channels at the plasma membrane are both regulated by pH via distinct mechanisms. Modifications of pH modulate the voltage-dependent gating of the rapid channel. While intracellular alkalinization facilitates channel activation by shifting the voltage gate towards negative potentials, extracellular alkalinization shifts the activation threshold to more positive potentials, away from physiological resting membrane potentials. By contrast, pH modulates slow anion channel activity in a voltage-independent manner. Intracellular acidification and extracellular alkalinization increase slow anion channel currents. The possible role of these distinct modulations in physiological processes involving anion efflux and modulation of extracellular and/or intracellular pH, such as elicitor and ABA signalling, are discussed.
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Stevens, Joanna S; Gainar, Adrian; Suljoti, Edlira; Xiao, Jie; Golnak, Ronny; Aziz, Emad F; Schroeder, Sven L M
2015-05-04
Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO-LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs and σ* shape resonances in the NEXAFS spectra. This provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute-solvent interactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Conte, Leandro O; Schenone, Agustina V; Giménez, Bárbara N; Alfano, Orlando M
2018-04-05
The effects of four inorganic anions (Cl - , SO 4 2 -, HCO 3 - , NO 3 - ) usually present in groundwater were investigated on the photo-Fenton degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). A kinetic model derived from a reaction sequence is proposed using the ferrioxalate complex as iron source at pH close to natural conditions (pH = 5). It was demonstrated that oxalate not only maintained iron in solution for the natural groundwater system, but also increased the photochemical activation of the process. Results showed that the minimum conversion of 2,4-D for the simulated groundwater after 180 min was 63.80%. This value was only 14.1% lower than the conversion achieved without anions. However, with all anions together, the consumption of hydrogen peroxide (HP) per mole of herbicide showed an increase with respect to the test without anions. Only one kinetic parameter was estimated for each anion applying a nonlinear regression method. Subsequently, these optimized kinetic constants were used to simulate the system behaviour, considering the influence of all the studied anions together. A good agreement between kinetic model predictions and experimental data was observed, with the following errors: RMSE 2,4-D = 3.98 × 10 -3 mM, RMSE HP = 1.83 × 10 -1 mM, RMSE OX = 1.39 × 10 -2 mM, and RMSE 2,4-DCP = 5.59 × 10 -3 mM. Copyright © 2018 Elsevier B.V. All rights reserved.
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Kim, Kyung Hyun; Jia, Baolei; Jeon, Che Ok
2017-01-01
Halobacillus halophilus , a moderately halophilic bacterium, accumulates a variety of compatible solutes including glycine betaine, glutamate, glutamine, proline, and ectoine to cope with osmotic stress. Non-targeted analysis of intracellular organic compounds using 1 H-NMR showed that a large amount of trans-4-hydroxy-L-proline (Hyp), which has not been reported as a compatible solute in H. halophilus , was accumulated in response to high NaCl salinity, suggesting that Hyp may be an important compatible solute in H. halophilus . Candidate genes encoding proline 4-hydroxylase (PH-4), which hydroxylates L-proline to generate Hyp, were retrieved from the genome of H. halophilus through domain searches based on the sequences of known PH-4 proteins. A gene, HBHAL_RS11735, which was annotated as a multidrug DMT transporter permease in GenBank, was identified as the PH-4 gene through protein expression analysis in Escherichia coli . The PH-4 gene constituted a transcriptional unit with a promoter and a rho-independent terminator, and it was distantly located from the proline biosynthetic gene cluster ( pro operon). Transcriptional analysis showed that PH-4 gene expression was NaCl concentration-dependent, and was specifically induced by chloride anion, similar to the pro operon. Accumulation of intracellular Hyp was also observed in other bacteria, suggesting that Hyp may be a widespread compatible solute in halophilic and halotolerant bacteria.
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Kim, Kyung Hyun; Jia, Baolei; Jeon, Che Ok
2017-01-01
Halobacillus halophilus, a moderately halophilic bacterium, accumulates a variety of compatible solutes including glycine betaine, glutamate, glutamine, proline, and ectoine to cope with osmotic stress. Non-targeted analysis of intracellular organic compounds using 1H-NMR showed that a large amount of trans-4-hydroxy-L-proline (Hyp), which has not been reported as a compatible solute in H. halophilus, was accumulated in response to high NaCl salinity, suggesting that Hyp may be an important compatible solute in H. halophilus. Candidate genes encoding proline 4-hydroxylase (PH-4), which hydroxylates L-proline to generate Hyp, were retrieved from the genome of H. halophilus through domain searches based on the sequences of known PH-4 proteins. A gene, HBHAL_RS11735, which was annotated as a multidrug DMT transporter permease in GenBank, was identified as the PH-4 gene through protein expression analysis in Escherichia coli. The PH-4 gene constituted a transcriptional unit with a promoter and a rho-independent terminator, and it was distantly located from the proline biosynthetic gene cluster (pro operon). Transcriptional analysis showed that PH-4 gene expression was NaCl concentration-dependent, and was specifically induced by chloride anion, similar to the pro operon. Accumulation of intracellular Hyp was also observed in other bacteria, suggesting that Hyp may be a widespread compatible solute in halophilic and halotolerant bacteria. PMID:29104571
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Stevens, Joanna S.; Gainar, Adrian; Suljoti, Edlira; ...
2015-03-18
Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO–LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs andmore » σ* shape resonances in the NEXAFS spectra. Finally, this provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute–solvent interactions.« less
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NASA Astrophysics Data System (ADS)
Dyatlenko, L. M.; Lobachev, V. L.; Bezbozhnaya, T. V.
2018-07-01
The kinetics of oxidation of diethyl sulfide (Et2S) is studied in aqueous solutions of hydrogen peroxide and sodium peroxoborate (Na2[B2(O2)2(OH)4]) in the presence of bicarbonate ions by means of gas-liquid distribution. The kinetics is investigated in a broad range of pH. Data show that the oxidation of Et2S by sodium peroxoborate in the range of pH 6-12 is mediated by such reactive species as hydrogen peroxide, hydrogen peroxide anions, and mono (B(O2H)(OH)3^{ - }) and diperoxoborate (B(O2H)2(OH)2^{ - }) anions. The rate of Et2S oxidation increases in the presence of bicarbonate, due to the additional reaction pathways mediated by monoperoxocarbonate species.
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Removal of trivalent and hexavalent chromium by seaweed biosorbent
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kratochvil, D.; Volesky, B.; Pimentel, P.
1998-09-15
Protonated or Ca-form Sargassum seaweed biomass bound up to 40 mg/g of Cr(III) by ion exchange at pH 4. An ion-exchange model assuming that the only species taken up by the biomass was Cr(OH){sup 2+} successfully fitted the experimental biosorption data for Cr(III). The maximum uptake of Cr(VI) by protonated Sargassum biomass at pH 2 was explained by simultaneous anion exchange and Cr(VI) to Cr(III) reduction. At pH <2.0, the reduction of Cr(VI) to Cr(III) dominated the equilibrium behavior of the batch systems, which was explained by the dependence of the reduction potential of HCrO{sub 4}{sup {minus}} ions on themore » pH. At pH >2.0, the removal of Cr(VI) was linked to the depletion of protons in equilibrium batch systems via an anion-exchange reaction. The optimum pH for Cr(VI) removal by sorption lies in the region where the two mechanisms overlap, which for Sargassum biomass is in the vicinity of pH 2. The existence of the optimum pH for the removal of Cr(VI) may be explained by taking into account (a) the desorption of Cr(III) from biomass at low pH and (b) the effect of pH on the reduction potential of Cr(VI) in aqueous solutions. Seventy percent of Cr(VI) bound to the seaweed at pH 2 can be desorbed with 0.2 M H{sub 2}SO{sub 4} via reduction to Cr(III).« less
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Removal of phosphate from aqueous solutions and sewage using natural and surface modified coir pith.
Krishnan, K Anoop; Haridas, Ajit
2008-04-01
Iron impregnated coir pith (CP-Fe-I) can be effectively used for the removal of phosphate from aqueous streams and sewage. Iron impregnation on natural coir pith was carried out by drop by drop addition method. The effect of various factors such as pH, initial concentration of phosphate, contact time and adsorbent dose on phosphate adsorption was studied by batch technique. The pH at 3.0 favored the maximum adsorption of phosphate from aqueous solutions. The effect of pH on phosphate adsorption was explained by pH(zpc), phosphate speciation in solution and affinity of anions towards the adsorbent sites. A comparative study of the adsorption of phosphate using CP-Fe-I and CP (coir pith) was made and results show that the former one is five to six times more effective than the latter. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Adsorption followed Langmuir isotherm model. Column studies were conducted to examine the utility of the investigated adsorbent for the removal of phosphate from continuously flowing aqueous solutions.
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Factors affecting UV/H2O2 inactivation of Bacillus atrophaeus spores in drinking water.
Zhang, Yongji; Zhang, Yiqing; Zhou, Lingling; Tan, Chaoqun
2014-05-05
This study aims at estimating the performance of the Bacillus atrophaeus spores inactivation by the UV treatment with addition of H2O2. The effect of factors affecting the inactivation was investigated, including initial H2O2 dose, UV irradiance, initial cell density, initial solution pH and various inorganic anions. Under the experimental conditions, the B. atrophaeus spores inactivation followed both the modified Hom Model and the Chick's Model. The results revealed that the H2O2 played dual roles in the reactions, while the optimum reduction of 5.88lg was received at 0.5mM H2O2 for 10min. The inactivation effect was affected by the UV irradiance, while better inactivation effect was achieved at higher irradiance. An increase in the initial cell density slowed down the inactivation process. A slight acid condition at pH 5 was considered as the optimal pH value. The inactivation effect within 10min followed the order of pH 5>pH 7>pH 9>pH 3>pH 11. The effects of three added inorganic anions were investigated and compared, including sulfate (SO4(2)(-)), nitrate (NO3(-)) and carbonate (CO3(2)(-)). The sequence of inactivation effect within 10min followed the order of control group>SO4(2)(-)>NO3(-)>CO3(2)(-). Copyright © 2014 Elsevier B.V. All rights reserved.
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Hutta, Milan; Ráczová, Janka; Góra, Róbert; Pessl, Juraj
2015-08-21
Novel anion-exchange liquid chromatographic method with step gradient of aqueous EDTA(4-) based mobile phase elution has been developed to profile available Slovak soil humic substances and alkaline extracts of various soils. The method utilize short glass column (30mm×3mm) filled in with hydrolytically stable particles (60μm diameter) Separon HEMA-BIO 1000 having (diethylamino)ethyl functional groups. Step gradient was programmed by mixing mobile phase composed of aqueous solution of sodium EDTA (pH 12.0; 5mmolL(-1)) and mobile phase constituted of aqueous solution of sodium EDTA (pH 12.0, 500mmolL(-1)). The FLD of HSs was set to excitation wavelength 480nm and emission wavelength 530nm (λem). Separation mechanism was studied by use of selected aromatic acids related to humic acids with the aid of UV spectrophotometric detection at 280nm. The proposed method benefits from high ionic strength (I=5molL(-1)) of the end mobile phase buffer and provides high recovery of humic acids (98%). Accurate and reproducible profiling of studied humic substances, alkaline extracts of various types of soils enables straightforward characterization and differentiation of HSs in arable and forest soils. Selected model aromatic acids were used for separation mechanism elucidation. Copyright © 2015 Elsevier B.V. All rights reserved.
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Nojavan, Saeed; Pourahadi, Ahmad; Hosseiny Davarani, Saied Saeed; Morteza-Najarian, Amin; Beigzadeh Abbassi, Mojtaba
2012-10-01
This study has performed on electromembrane extraction (EME) of some zwitterionic compounds based on their acidic and basic properties. High performance liquid chromatography (HPLC) equipped with UV detection was used for determination of model compounds. Cetirizine (CTZ) and mesalazine (MS) were chosen as model compounds, and each of them was extracted from acidic (as a cation) and basic (as an anion) sample solutions, separately. 1-Octanol and 2-nitrophenyl octylether (NPOE) were used as the common supported liquid membrane (SLM) solvents. EME parameters, such as extraction time, extraction voltage and pH of donor and acceptor solutions were studied in details for cationic and anionic forms of each model compound and obtained results for two ionic forms (cationic and anionic) of each compound were compared together. Results showed that zwitterionic compounds could be extracted in both cationic and anionic forms. Moreover, it was found that the extraction of anionic form of each model compound could be done in low voltages when 1-octanol was used as the SLM solvent. Results showed that charge type was not highly effective on the extraction efficiency of model compounds whereas the position of charge within the molecule was the key parameter. In optimized conditions, enrichment factors (EF) of 27-60 that corresponded to recoveries ranging from 39 to 86% were achieved. Copyright © 2012 Elsevier B.V. All rights reserved.
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Kong, Yanli; Kang, Jing; Shen, Jimin; Chen, Zhonglin; Fan, Leitao
2017-01-01
The influence of humic acid (HA) on the removal of arsenic by FeCl 3 was systematically studied in this paper. Jar tests were performed to investigate the influence on arsenic during FeCl 3 coagulation of the pH adjusting method, the initial As/Fe ratio, the equilibrium As concentration, and co-occurring anions and cations. Compared with results in HA-free systems, the removal trends of arsenic in HA solutions were quite different. It was found that As(V) removal was higher at low equilibrium concentration, yet the opposite was true for As(III) removal. The presence of HA influenced the effective number of active sites for arsenic removal by FeCl 3 flocculation. In addition, in the presence of HA, the impacts of co-existing solutions on arsenic removal were also different from that of an HA-free system. This study examined the influence of co-occurring anions, such as phosphate, sulfate, and silicate on arsenic removal, depending on their ability to compete for sorption sites and to hinder or facilitate the aggregation of ferric hydroxide flocs. The presence of Ca 2+ or Cd 2+ significantly increased arsenic removal at higher pH. Low concentrations of dissolved HA and high concentrations of colloid affected the adsorption of arsenic onto iron oxide. The influence of HA on the adsorption of arsenic onto iron oxide primarily depended on the relative content of the dissolved and mineral combination states of HA and the interface combination forms.
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Arsenate removal from water by a weak-base anion exchange fibrous adsorbent.
Awual, Md Rabiul; Urata, Shinya; Jyo, Akinori; Tamada, Masao; Katakai, Akio
2008-02-01
A weak-base anion exchange fiber named FVA with primary amino groups for selective and rapid removal of arsenate species was prepared by means of electron irradiation induced liquid phase graft polymerization of N-vinylformamide onto polyethylene coated polypropylene fibers and by the subsequent alkaline hydrolysis of amide group on the grafted polymer chains. Two types of FVA were prepared. One was a non-woven cloth type named FVA-c for the batch-mode study, which clarified that uptake of arsenate species decreases with an increase in pH, and chloride and sulfate do not strongly interfere with uptake of arsenate species different from conventional anion exchange resins based on crosslinked polystyrene matrices. The other was a filamentary type one named FVA-f used in the column-mode study, which clarified that arsenate species were successfully removed from neutral pH arsenate solutions containing 1.0-99 mg of As/L at feed flow rates of 100-1050 h(-1) in space velocity (SV). The most important findings are that the 1% breakthrough point in uptake from the arsenate solution containing 1.0mg of As/L at the high feed flow rate of 1050h(-1) in SV was as large as 4670 bed volumes, giving the 1% breakthrough capacity of 0.298 mmol/g of FVA-f. Adsorbed arsenate was able to be quantitatively eluted with 1M hydrochloric acid and FVA-f was simultaneously regenerated. Then, the repeated use of FVA-f was possible.
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Zeng, Zhenping; Yeh, Li-Hsien; Zhang, Mingkan; Qian, Shizhi
2015-10-28
Inspired by nature, functionalized nanopores with biomimetic structures have attracted growing interests in using them as novel platforms for applications of regulating ion and nanoparticle transport. To improve these emerging applications, we study theoretically for the first time the ion transport and selectivity in short nanopores functionalized with pH tunable, zwitterionic polyelectrolyte (PE) brushes. In addition to background salt ions, the study takes into account the presence of H(+) and OH(-) ions along with the chemistry reactions between functional groups on PE chains and protons. Due to ion concentration polarization, the charge density of PE layers is not homogeneously distributed and depends significantly on the background salt concentration, pH, grafting density of PE chains, and applied voltage bias, thereby resulting in many interesting and unexpected ion transport phenomena in the nanopore. For example, the ion selectivity of the biomimetic nanopore can be regulated from anion-selective (cation-selective) to cation-selective (anion-selective) by diminishing (raising) the solution pH when a sufficiently small grafting density of PE chains, large voltage bias, and low background salt concentration are applied.
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Callitriche cophocarpa biomass as a potential low-cost biosorbent for trivalent chromium.
Kyzioł-Komosińska, Joanna; Augustynowicz, Joanna; Lasek, Wojciech; Czupioł, Justyna; Ociński, Daniel
2018-05-15
The present study focused on the use of the dry mass of the macrophyte Callitriche cophocarpa as an effective biosorbent for chromium removal from concentrated solutions, typical for industrial effluents. In order to evaluate the usability of C. cophocarpa as the Cr(III) sorbent, its detailed physicochemical characterization has been performed as well as the preliminary adsorption studies. The biosorbent was characterized by specific surface area (SSA), porosity, total organic carbon (TOC), inorganic content as well as the cation exchange capacity (CEC), dominant exchangeable cations and anion exchange capacity (AEC), point of zero charge (pH pzc ) and buffering capacity. The effect of the initial chromium concentration, solution pH and co-existing anions on the sorption effectiveness have been investigated. Based on theoretical isotherm models, the maximum adsorption capacity of the dry C. cophocarpa has been determined as 77.1 mg Cr(III)/g. Finally, the strength of Cr-binding onto the plant biomass has been evaluated using the BCR extraction method, stating that chromium was strongly and - under environmental conditions - irreversibly bound to the plant biomass. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Yang, Zhen; Yang, Hu; Jiang, Ziwen; Cai, Tao; Li, Haijiang; Li, Haibo; Li, Aimin; Cheng, Rongshi
2013-06-15
In the current work, a series of amphoteric grafting chitosan-based flocculants (carboxymethyl chitosan-graft-polyacrylamide, denoted as CMC-g-PAM) was designed and prepared successfully. The flocculants were applied to eliminate various dyes from aqueous solutions. Among different graft copolymers, CMC-g-PAM11 with a PAM grafting ratio of 74% demonstrated the most efficient performance for removal of both the anionic dye (Methyl Orange, MO) and the cationic dye (Basic Bright Yellow, 7GL) under the corresponding favored conditions (80 mg/L of the flocculant at pH 4.0, and 160 mg/L at pH 11.0). In comparison with its precursors, chitosan and carboxymethyl chitosan, CMC-g-PAM11 showed higher removal efficiencies and wider flocculation windows. More importantly, the graft copolymer produced notably more compacted flocs based on image analysis in combination with fractal theory, which was of great significance in practical water treatment. Furthermore, the flocculation mechanism was discussed in detail. The grafted polyacrylamide chains were found to contribute much to the improved bridging and sweeping flocculation effects, but reduced charge neutralization flocculation for the effect of charge screening. Copyright © 2013 Elsevier B.V. All rights reserved.
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Selective capture of iodide from solutions by microrosette-like δ-Bi₂O₃.
Liu, Long; Liu, Wei; Zhao, Xiaoliang; Chen, Daimei; Cai, Rongsheng; Yang, Weiyou; Komarneni, Sridhar; Yang, Dongjiang
2014-09-24
Radioactive iodine isotopes that are produced in nuclear power plants and used in medical research institutes could be a serious threat to the health of many people if accidentally released to the environment because the thyroid gland can absorb and concentrate them from a liquid. For this reason, uptake of iodide anions was investigated on microrosette-like δ-Bi2O3 (MR-δ-Bi2O3). The MR-δ-Bi2O3 adsorbent showed a very high uptake capacity of 1.44 mmol g(-1) by forming insoluble Bi4I2O5 phase. The MR-δ-Bi2O3 also displayed fast uptake kinetics and could be easily separated from a liquid after use because of its novel morphology. In addition, the adsorbent showed excellent selectivity for I(-) anions in the presence of large concentrations of competitive anions such as Cl(-) and CO3(2-), and could work in a wide pH range of 4-11. This study led to a new and highly efficient Bi-based adsorbent for iodide capture from solutions.
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Ionic liquids for metal extraction from chalcopyrite: solid, liquid and gas phase studies.
Kuzmina, O; Symianakis, E; Godfrey, D; Albrecht, T; Welton, T
2017-08-16
We studied leaching of Cu and Fe from naturally occurring chalcopyrite ore using aqueous solutions of ionic liquids (ILs) based on imidazolium and ethylammonium cations and hydrogensulfate, nitrate, acetate or dicyanamide anions. Liquid, solid and gas phases of the leaching systems were characterised. We have shown that nonoxidative leaching is greatly dependant not only on temperature and pH, but on the anion species of the IL. Solutions of 1-butylimidazolium hydrogen sulfate exhibited the best leaching performance among hydrogen sulphate ILs. We have suggested that the formation of an oxide layer in some ILs may be responsible for a reduced leaching ability. The analysis of the gas phase showed the production of CO 2 and CS 2 in all leached samples. Our results suggested that the CS 2 produced upon leaching could be responsible for decreasing the sulfur, but not oxide, layer on the surface of chalcopyrite samples and therefore more efficient leaching. This is the first study, to our knowledge, to provide a systematic comparison of the leaching performance of ILs composed of different anions and cations and without added oxidants.
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Welch, Ross M.
1973-01-01
The kinetics of vanadium absorption by excised barley (Hordeum vulgare L., cv. Eire) roots were investigated with respect to ionic species of V in solution, time and concentration dependence, Ca sensitivity, and interaction with various anions, cations, and pH levels. The role of metabolism in V absorption was also studied using anaerobic treatment (N2 gas) and chemical inhibitors (NaN3, KCN, or 2,4-dinitrophenol). Approximately one-third of the labeled V initially taken up by excised roots was desorbed to a constant level after 45 min in unlabeled V solutions. The rate of absorption of labeled V from 5 μm NH4VO3 solutions containing 0.5 mm CaSO4 was constant for at least 3 hours. Omission of Ca resulted in a 72% reduction in V uptake when compared to controls with 0.5 mm CaSO4. The rate of uptake of V was highest at pH 4 but dropped to a very low level at pH 10. It was relatively constant between the pH levels of 5 and 8 at which the VO3− ion is the predominant ionic species in solution. The rate of absorption of V was followed as a function of concentrations from 0.5 to 100 μm NH4VO3. It was found to be a linear function of concentration and did not follow saturation kinetics. Absorption experiments carried out with labeled V from either NaVO3 or NH4VO3 sources gave similar results. No anion studied (i.e. HPO42−, HAsO42−, MoO42−, SeO42−, SeO32−, CrO42−, BO33−, No3−, and Cl−) interfered appreciably (i.e. less than 30% inhibition) with the absorption of labeled V. Anaerobic treatment of absorption solution with N2 gas did not inhibit V absorption by excised roots. The results obtained using chemical inhibitors were not consistent. It was concluded that V is not actively absorbed by excised barley roots. PMID:16658421
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Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar.
Lee, Yunsu; Lee, Hanseung; Jung, Dohyun; Chen, Zhengxin; Lim, Seungmin
2018-04-05
This paper presents the effect of anion exchange resin (AER) on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH)₂ saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER.
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Banu, H Thagira; Meenakshi, Sankaran
2017-11-01
The present study deals with the synthesis of chitosan quaternized resin for efficient removal of nitrate and phosphate from aqueous solution. The resin was characterized with FTIR, SEM with EDX and XRD. Batch method was carried out to optimize various parameters such as contact time, initial concentration of nitrate and phosphate, dosage, pH, co-anions and temperature on the adsorption capacity of the adsorbent. The adsorption process illustrated that the Freundlich isotherm and the pseudo-second order are the best fitted models for the sorption of both anions. The respective negative values of ΔH° and ΔG° revealed that the adsorption of both the anions were exothermic and spontaneous. The removal efficiency of nitrate and phosphate on chitosan quaternized resin were 78% and 90% respectively with 0.1g of adsorbent and the initial concentration as 100mg/L. Nitrate and phosphate anions adsorbed effectively on chitosan quaternized resin by replacing Cl - ions from quaternary site through electrostatic attraction as well as ion-exchange mechanism. Hydrogen bonding also played important role in adsorption process. Even after 7th regeneration cycle the adsorbent retained its adsorption capacity as 23.7mg/g and 30.4mg/g for both nitrate and phosphate respectively. Copyright © 2017 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Mulia, Kamarza; Andrie; Krisanti, Elsa A.
2018-03-01
The problem to overcome in oral drug administration is the significant pH changes present in the human digestive system. In this study, ionotropic gelation method employing 2-8% (w/v) tripolyphosphate solutions were used to crosslink chitosan microspheres for a controlled release of paracetamol as a model drug. The release profiles of paracetamol from chitosan microspheres were determined using simulated gastrointestinal fluids having pH values of 1.2, 6.8, and 7.4. The results showed that the paracetamol loading and the encapsulation efficiency values increased with increasing concentration of tripolyphosphate solutions used in the preparation step. Paracetamol released at pH 1.2 and 6.8 buffer solutions was significantly higher than that at pH 7.4; also, more paracetamol was released in the presence of α-amylase and β-glucosidase enzymes. The release profiles showed zero-order release behaviour up to 8 hours where the highest drug release was 39% of the paracetamol loaded in the chitosan microspheres, indicating a strong crosslinking between chitosan and TPP anions. The relatively low accumulated drug release could be compensated by employing suitable enzymes, lower TPP solution concentration, and addition of other biodegradable polymer to reduce the TPP crosslink.
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Tubaon, Ria Marni; Haddad, Paul R; Quirino, Joselito P
2017-03-10
The presence of inorganic anions in a sample interferes with mass spectrometric (MS) analysis. Here, a simple method to remove these ions from a liquid sample in one-step is described. The inorganic anions present in a 50μL sample were extracted into a low pH solution inside a 200μm i.d.×33cm long capillary by the use of an electric field. The selective removal of unwanted anions and retention of target analytes was accomplished by control of the apparent electrophoretic velocities of anions and analytes at a boundary that separated the sample and extraction solution. No physical barrier (e.g., membrane) was required and with the boundary situated at the tip of the capillary, efficient removal of inorganic anions (e.g., >80% removal) and good recovery of target analytes (e.g., >80% recovery) were achieved. The time required for removal of the inorganic anions was found to depend on their initial concentrations. The removal process was investigated using different concentrations of bromide and nitrate (as potassium salts) and negatively chargeable drugs as target analytes. This micro-sample clean-up technique used no organic solvents and little consumables and was studied to the determination of 0.6μg/L arsenic and 8.3μg/L vanadium in 500mg/L sodium chloride using inductively coupled plasma MS and 50μM angiotensin I in 1000mg/L sodium chloride using electrospray ionisation MS. Micro-sample clean-up was performed for 45min at 3kV in both demonstrations. The calculated recoveries for the metals at trace levels were 110-130%, and for the peptide was 103.8%. Copyright © 2017 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
NONE
Many times the start up of granular activated carbon adsorption systems for the control of organic contaminants in wastewater cm exhibit unacceptable increases in the adscurber effluent pH. Experience shows that the duration of the pH increase ranges from several hours to several days, during which time several hundred bed volumes of water can be discharged with a pH in excess of 9. Laboratory studies have identified the cause of the pH rise as an interaction between the naturally occurring anions and protons ar the water and the carbon surface. The interaction can be described as an ion exchange typemore » of phenomenon, in which the carbon surface sorbs the anions and corresponding hydronium ions from the water. Capacities of the carbon for the anions range from 2 to 9 mg/g GAC, depending upon the water characteristics, the carbon type, the nature of the anion and its influent concentration. These studies have shown de the anion sorption and resulting pH increase is independent of the raw material used for die activated carbon production, e.g. bituminous or sub-bituminous coal, peat, wood or coconut. Also, the pH excursions occur with virgin, reactivated, and acid washed granular carbons. Current pH control technologies focus on adjustment of wastewater pH prior to discharge or recycle of the initial effluent water until the pH increase abates. However, improved water pH control options have been realized by altering the carbon surface rather than the water chemistry. The change to the carbon surface is accomplished through a controlled oxidation process. This process provides a more acidic carbon surface with a reduced affinity for the anions in the waste water. As a result, the pH excursions above 9 are eliminated and the initial effluent from the adsorption system can be discharged without further treatment.« less
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Guerrero-Coronilla, Imelda; Morales-Barrera, Liliana; Cristiani-Urbina, Eliseo
2015-04-01
The present study explored the kinetics, equilibrium and thermodynamics of amaranth (acid red 27) anionic dye (AD) biosorption to water hyacinth leaves (LEC). The effect of LEC particle size, contact time, solution pH, initial AD concentration and temperature on AD biosorption was studied in batch experiments. AD biosorption increased with rising contact time and initial AD concentration, and with decreasing LEC particle size and solution pH. Pseudo-second-order chemical reaction kinetics provided the best correlation for the experimental data. Isotherm studies showed that the biosorption of AD onto LEC closely follows the Langmuir isotherm, with a maximum biosorption capacity of about 70 mg g(-1). The thermodynamic parameters confirm that AD biosorption by LEC is non-spontaneous and endothermic in nature. Results indicate that LEC is a strong biosorbent capable of effective detoxification of AD-laden wastewaters. Copyright © 2015 Elsevier Ltd. All rights reserved.
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Effect of Acid-Base Equilibrium on Absorption Spectra of Humic acid in the Presence of Copper Ions
NASA Astrophysics Data System (ADS)
Lavrik, N. L.; Mulloev, N. U.
2014-03-01
The reaction between humic acid (HA, sample IHSS) and a metal ion (Cu2+) that was manifested as absorption bands in the range 210-350 nm was recorded using absorption spectroscopy. The reaction was found to be more effective as the pH increased. These data were interpreted in the framework of generally accepted concepts about the influence of acid-base equilibrium on the dissociation of salts, according to which increasing the solution pH increases the concentration of HA anions. It was suggested that [HA-Cu2+] complexes formed.
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A study of phosphate absorption by magnesium iron hydroxycarbonate.
Du, Yi; Rees, Nicholas; O'Hare, Dermot
2009-10-21
A study of the mechanism of phosphate adsorption by magnesium iron hydroxycarbonate, [Mg(2.25)Fe(0.75)(OH)(6)](CO(3))(0.37).0.65H(2)O over a range of pH has been carried out. The efficiency of the phosphate removal from aqueous solution has been investigated between pH 3-9 and the resulting solid phases have been studied by elemental analysis, XRD, FT-IR, Raman, HRTEM, EDX and solid-state MAS (31)P NMR. The analytical and spectroscopic data suggest that phosphate removal from solution occurs not by anion intercalation of the relevant phosphorous oxyanion (H(2)PO(4)(-) or HPO(4)(2-)) into the LDH but by the precipitation of either an insoluble iron hydrogen phosphate hydrate and/or a magnesium phosphate hydrate.
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Reyman, Dolores; Viñas, Montserrat H; Tardajos, Gloria; Mazario, Eva
2012-01-12
Photoinduced proton transfer reactions of harmane (1-methyl-9H-pyrido[3,4-b]indole) (HAR) in the presence of a proton donor/acceptor such as dihydrogen phosphate anions in aqueous solution have been studied by stationary and time-resolved fluorescence spectroscopy. The presence of high amounts of dihydrogen phosphate ions modifies the acid/base properties of this alkaloid. Thus, by keeping the pH constant at pH 8.8 and by increasing the amount of NaH(2)PO(4) in the solution, it is possible to reproduce the same spectral profiles as those obtained in high alkaline solutions (pH >12) in the absence of NaH(2)PO(4). Under these conditions, a new fluorescence profile appears at around 520 nm. This result could be related to the results of a recent investigation which suggests that a high intake of phosphates may promote skin tumorigenesis. The presence of β-cyclodextrin (β-CD) avoids the proton transfer reactions in this alkaloid by means the formation of an inclusion complex between β-CD and HAR. The formation of this complex originates a remarkable enhancement of the emission intensity from the neutral form in contrast to the cationic and zwitterionic forms. A new lifetime was obtained at 360 nm (2.5 ns), which was associated with the emission of this inclusion complex. At this wavelength, the fluorescence intensity decay of HAR can be described by a linear combination of two exponentials. From the ratio between the pre-exponential factors, we have obtained a value of K = 501 M for the equilibrium of formation of this complex.
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Removal of acid blue 062 on aqueous solution using calcinated colemanite ore waste.
Atar, Necip; Olgun, Asim
2007-07-19
Colemanite ore waste (CW) has been employed as adsorbent for the removal of acid blue 062 anionic dye (AB 062) from aqueous solution. The adsorption of AB 062 onto CW was examined with respect to contact time, calcination temperature, particle size, pH, adsorbent dosage and temperature. The physical and chemical properties of the CW, such as particle sizes and calcinations temperature, play important roles in dye adsorption. The dye adsorption largely depends on the initial pH of the solution with maximum uptake occurring at pH 1. Three simplified kinetics models, namely, pseudo-first order, pseudo-second order, and intraparticle diffusion models were tested to investigate the adsorption mechanisms. The kinetic adsorption of AB 062 on CW follows a pseudo-second order equation. The adsorption data have been analyzed using Langmuir and Freundlich isotherms. The results indicate that the Langmuir model provides the best correlation of the experimental data. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of the adsorption of dye onto CW.
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Ichikawa, Makoto; Ide, Nagatoshi; Shiraishi, Sumihiro; Ono, Kazuhisa
2005-06-01
Combination of cyanocobalamin (VB12) and ascorbic acid (VC) has been widely seen in pharmaceutical products and dietary supplements. However, VB12 has been reported that its behavior in stability in aqueous solution is quite different when VC is mixed. In the present study, we examined the stabilities of these vitamins in acetate buffer (pH 4.8) using high performance liquid chromatography. Degradation of VB12 was not observed in the absence of VC in the buffer. However, when VC was mixed in the VB12 solution, VB12 concentrations decreased in accordance with VC degradation. VB12 and VC degradations were inhibited by adding sodium halides to acetate buffer at pH 4.8. These stabilization effects were also observed in the range from pH 3.5 to 5.3 and by adding potassium, magnesium, and calcium halides. Furthermore, our data demonstrated that increases in the halide anion concentrations and atomic number (Cl-
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NASA Astrophysics Data System (ADS)
Gao, Qianhong; Hua, Jiangtao; Li, Rong; Xing, Zhe; Pang, Lijuan; Zhang, Mingxing; Xu, Lu; Wu, Guozhong
2017-01-01
A novel fibrous adsorbent containing amine and quaternary ammonium groups was prepared by radiation-induced graft of glycidyl methacrylate (GMA) onto ultra-high molecular weight polyethylene (UHMWPE) fiber and further modifying with triethylenetetramine (TETA) and glycidyl trimethylammonium chloride (GTA). The ATR-IR spectra and SEM observation demonstrated that amine and quaternary ammonium groups were immobilized onto the surface of UHMWPE fiber. The principal factors affecting the adsorption of Cr(VI) ions have been investigated including pH of the aqueous solution, contact time, temperature and coexisting anions. This novel fibrous adsorbent could effectively adsorb Cr(VI) in the range of pH 1-9, and the maximum adsorption capacity reached 295 mg/g at pH 3 and 25 °C based on the Langmuir isotherm. It was found that adsorption equilibrium could be achieved within 2 h for initial Cr(VI) of 100 mg/L, following the pseudo-second order model. The effect of coexisting anions (including SO42-, H2PO4-, NO3-and Cl-) on the uptake of Cr(VI) was investigated in detail. Additionally, the adsorption saturated fiber could be regenerated by soaking in 0.5 mol/L NaOH solution, and the adsorption performance of this adsorbent could be maintained at 90% after eight cycles of adsorption-desorption. ATR-IR and XPS analysis revealed that Cr(VI) ions were adsorbed on the fiber adsorbent through ion exchange mechanism.
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Boncina, Matjaz; Rescic, Jurij; Vlachy, Vojko
2008-08-01
The solubility of aqueous solutions of lysozyme in the presence of polyethylene glycol and various alkaline salts was studied experimentally. The protein-electrolyte mixture was titrated with polyethylene glycol, and when precipitation of the protein occurred, a strong increase of the absorbance at 340 nm was observed. The solubility data were obtained as a function of experimental variables such as protein and electrolyte concentrations, electrolyte type, degree of polymerization of polyethylene glycol, and pH of the solution; the last defines the net charge of the lysozyme. The results indicate that the solubility of lysozyme decreases with the addition of polyethylene glycol; the solubility is lower for a polyethylene glycol with a higher degree of polymerization. Further, the logarithm of the protein solubility is a linear function of the polyethylene glycol concentration. The process is reversible and the protein remains in its native form. An increase of the electrolyte (NaCl) concentration decreases the solubility of lysozyme in the presence and absence of polyethylene glycol. The effect can be explained by the screening of the charged amino residues of the protein. The solubility experiments were performed at two different pH values (pH = 4.0 and 6.0), where the lysozyme net charge was +11 and +8, respectively. Ion-specific effects were systematically investigated. Anions such as Br(-), Cl(-), F(-), and H(2)PO(4)(-) (all in combination with Na(+)), when acting as counterions to a protein with positive net charge, exhibit a strong effect on the lysozyme solubility. The differences in protein solubility for chloride solutions with different cations Cs(+), K(+), and Na(+) (coions) were much smaller. The results at pH = 4.0 show that anions decrease the lysozyme solubility in the order F(-) < H(2)PO(4)(-) < Cl(-) < Br(-) (the inverse Hofmeister series), whereas cations follow the direct Hofmeister series (Cs(+) < K(+) < Na(+)) in this situation.
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Eckenrode, Heather M; Jen, Shih-Hui; Han, Jun; Yeh, An-Gong; Dai, Hai-Lung
2005-03-17
Nonlinear optical probe, second harmonic generation (SHG), of the adsorption of the dye molecule malachite green (MG), in cationic form at pH < or = 5, on polystyrene microspheres in aqueous solution is used to study the effect of surface charge and composition on molecular adsorption. Three types of polystyrene microspheres with different surface composition are investigated: (1) a sulfate terminated, anionic surface, (2) a neutral surface without any functional group termination, and (3) an amine terminated, cationic surface. The cationic dye was found to adsorb at all three surfaces, regardless of surface charge. The adsorption free energies, DeltaG's, measured for the three surfaces are -12.67, -12.39, and -10.46 kcal/mol, respectively, with the trend as expected from the charge interactions. The adsorption density on the anionic surface, where attractive charge-charge interaction dominates, is determined by the surface negative charge density. The adsorption densities on the neutral and cationic surfaces are on the other hand higher, perhaps as a result of a balance between minimizing repulsive charge interaction and maximizing attractive molecule-substrate and intermolecular interactions. The relative strength of the SH intensity per molecule, in combination of a model calculation, reveals that the C(2) axis of the MG molecule is nearly perpendicular to the surface on the anionic surface and tilts away from the surface norm when the surface is neutral and further away when cationic. Changing the pH of the solution may alter the surface charge and subsequently affect the adsorption configuration and SH intensity.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Guhlke, S.; Beets, A.L.; Knapp, F.F. Jr.
1997-05-01
Re-188, available from a W-188/Re-188 generator, is an important therapeutic radioisotope for bone pain palliation, cancer therapy and intravascular brachytherapy, etc. Because of the relatively low specific activity of reactor-produced W-188 (ORNL HFIR, 296-370 MBq mCi/mg W-186 for 2 cycles), methods of concentrating the Re-188 bolus (10-12 mL) from clinical scale (18.5-37 BGq W-188) generators (5-6 gm alumina) are thus very important. We demonstrate for the first time a new strategy of generator elution with salts of weak acids and specific perrhenate anion {open_quotes}trapping{close_quotes} with QMA anion columns. Re-188 perrhenate is efficiently eluted (65-75%) from the alumina-based generator with 0.15-0.3more » M ammonium acetate. An acetic acid solution of Re-188 perrhenic acid is obtained by subsequent on-line passage of the generator eluant through a DOWEX AG 50Wx8 (200-400 mesh, H{sup +} form) column. Since acetic acid is not ionized (< 0.001%) at this pH (< pK{sub a} = 4.76) the perrhenate anion is then specifically trapped on a QMA {open_quotes}Light{close_quotes} anion extraction column. QMA elution with 0.9% NaCl, provides Re-188 perrhenate solution in <1 mL. Concentration of 10-20 mL of Re-188 solution (> 15 BGq) in <1 mL has been demonstrated using this simple new approach, which is also effective for concentration of Tc-99m from low specific activity Mo-99 (n,y) generators. The cation/anion tandem system is inexpensive and disposable and use can be easily automated. The availability of this very simple, efficient system is important for broad use of rhenium-188.« less
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Adsorption mechanism of mixed cationic/anionic collectors in feldspar-quartz flotation system.
Vidyadhar, A; Hanumantha Rao, K
2007-02-15
The adsorption mechanism of mixed cationic alkyl diamine and anionic sulfonate/oleate collectors at acidic pH values was investigated on microcline and quartz minerals through Hallimond flotation, electrokinetic and diffuse reflectance FTIR studies. In the presence of anionic collectors, neither of the minerals responded to flotation but the diamine flotation of the minerals was observed to be pH and concentration dependent. The presence of sulfonate enhanced the diamine flotation of the minerals by its co-adsorption. The difference in surface charge between the minerals at pH 2 was found to be the basis for preferential feldspar flotation from quartz in mixed diamine/sulfonate collectors. The infrared spectra revealed no adsorption of sulfonate collector when used alone but displayed its co-adsorption as diamine-sulfonate complex when used with diamine. The presence of sulfonate increased the diamine adsorption due to a decrease in the electrostatic head-head repulsion between the adjacent surface ammonium ions and thereby increasing the lateral tail-tail hydrophobic bonds. The mole ratio of diamine/sulfonate was found to be an important factor in the orientation of alkyl chains and thus the flotation response of minerals. The increase in sulfonate concentration beyond diamine concentration leads to the formation of soluble 1:2 diamine-sulfonate complex or precipitate and the adsorption of these species decreased the flotation since the alkyl chains are in chaotical orientation with a conceivable number of head groups directing towards the solution phase.
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Salama, Ahmed
2018-01-01
A novel superadsorbent anionic hydrogel was synthesized by grafting of poly (3-sulfopropyl methacrylate), P(SPMA), onto carboxymethyl cellulose (CMC). CMC-g-P(SPMA) superadsorbent hydrogel was applied as an efficient and sustainable adsorbent to remove methylene blue (MB) from waste water. Batch adsorption experiments showed that the solution pH had an obvious effect on the adsorption capacity with an optimal sorption pH at 6. The CMC-g-P(SPMA) hydrogel had rapid adsorption kinetics for MB and the adsorption equilibrium reached within 40min. The adsorption kinetics were more accurately described by pseudo second-order model and the Langmuir-fitted adsorption isotherms revealed a maximum capacity of 1675mg/g. The current anionic hydrogel is reusable as the adsorption capacity remained at 89% level after five adsorption-desorption cycles. CMC-g-P(SPMA) hydrogel was presented as a sustainable promising adsorbent with high adsorption capacity and good regenerability for effective cationic dyes removal. Copyright © 2017 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Wang, Fei; Gao, Lei; Zhao, Qing; Zhang, Yang; Dong, Wen-Kui; Ding, Yu-Jie
2018-02-01
The optical properties of a novel chemosensor for cyanide anions based on a symmetric bis(salamo)-type ligand (H3L) were investigated by UV-Vis and fluorescence spectroscopy in MeOH/H2O (1:1 v/v) solution. Sensor H3L can selectively sense CN- based on prominent color changes among other anions. The chemosensor exhibits an apparent fluorescence enhancement at 482 nm to CN- which because cyanide ions interact with Cdbnd N bonds. Combining the corrected Benesi-Hildebrand formula, the binding constant of the formed host-guest complex was calculated as 2.42 × 105 M- 1. Meanwhile, the detection limit of the sensor toward CN- was 8.91 × 10- 7 M. It is worth noting that the designed sensor can be used for rapid detection of cyanide anions in basic pH range, and has great practical value.
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Monteagudo, J M; El-Taliawy, H; Durán, A; Caro, G; Bester, K
2018-06-20
Degradation of a diclofenac aqueous solution was performed using persulfate anions activated by ultrasound. The objective of this study was to analyze different parameters affecting the diclofenac (DCF) removal reaction by the ultrasonic persulfate (US/PS) process and to evaluate the role played by various intermediate oxidative species such as hydroxyl- and sulfate radicals, superoxide radical anion or singlet oxygen in the removal process as well as to determine a possible reaction pathway. The effects of pH, initial persulfate anion concentration, ultrasonic amplitude and temperature on DCF degradation were examined. Sulfate and hydroxyl radicals were involved in the main reaction pathway of diclofenac. Diclofenac amide and three hydroxy-diclofenac isomers (3´-hydroxy diclofenac, 4´-hydroxy diclofenac and 5-hydroxy diclofenac) were identified as reaction intermediates. Copyright © 2018 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Fodor, M.
An ion exchange-complexion separation meihod was developed for the removal of interfering elements in the determination of the uranium content of recovery solutions. By adding (ethylenediamine)tetraacetic acid to the solution, most of the interfering elements can be brought into an anionic complex. Adjusting the soluiion to pH 7 and letting it pass through an Amberlite IRC-50 type cation exchanger of hydrogen form, the uranium remains on the column whereas the interfering elements pass into the effluent. The method was successfully applied in analyzing the recovery solutions of uranium ores. (auth)
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A stochastic cellular automata model of tautomer equilibria
NASA Astrophysics Data System (ADS)
Bowers, Gregory A.; Seybold, Paul G.
2018-03-01
Many chemical substances, including drugs and biomolecules, exist in solution not as a single species, but as a collection of tautomers and related species. Importantly, each of these species is an independent compoundwith its own specific biochemical and physicochemical properties. The species interconvert in a dynamic and often complicated manner, making modelling the overall species composition difficult. Agent-based cellular automata models are uniquely suited to meet this challenge, allowing the equilibria to be simulated using simple rulesand at the same time capturing the inherent stochasticity of the natural phenomenon. In the present example a stochastic cellular automata model is employed to simulate the tautomer equilibria of 9-anthrone and 9-anthrol in the presence of their common anion. The observed KE of the 9-anthrone ⇌ 9-anthrol tautomerisation along with the measured tautomer pKa values were used to model the equilibria at pH values 4, 7 and 10. At pH 4 and 7, the anthrone comprises >99% of the total species population, while at pH 10the anthrone and the anion each represent just under half of the total population. The advantages of the cellular automata approach over the customary coupled differential equation approach are discussed.
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Tsonev, Latchezar I; Hirsh, Allen G
2016-10-14
We have previously described a liquid chromatographic (LC) method for uncoupling controlled, wide range pH gradients and simultaneous controlled gradients of a non-buffering solute on ion exchange resins (Hirsh and Tsonev, 2012) [1]. Here we report the application of this two dimensional LC technique to the problem of resolving Human Transferrin (HT) isoforms. This important iron transporting protein should theoretically occur in several thousand glycoforms, but only about a dozen have been reported. Using dual simultaneous independent gradients (DSIGs) of acetonitrile (ACN) and pH on a mixed bed stationary phase (SP) consisting of a mixture of an anion exchange resin and a reversed phase (RP) resin we partially resolve about 60 isoforms. These are likely to be partially refolded glycoforms generated by interaction of HT with the highly hydrophobic RP SP, as well as distinct folded glycoforms. Thus this study should have interesting implications for both glycoform separation and the study of protein folding. Copyright © 2016 Elsevier B.V. All rights reserved.
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Process for separating and recovering an anionic dye from an aqueous solution
Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.
1998-01-01
A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.
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Mohtashamian, Shahab; Boddohi, Soheil; Hosseinkhani, Saman
2018-02-01
Self-assembled nanogel was prepared by electrostatic complexation of two oppositely charged biological macromolecules, which were cationic nisin and anionic chondroitin sulfate (ChS). The critical factors affected the physical properties of ChS-nisin nanogel was screened and optimized by Plackett-Burman design (PB) and central composite design (CCD). The independent factors selected were: concentration ratio of nisin to ChS, injection rate of nisin solution, buffer solvent type, magnetic stirring rate, pH of initial buffer solution, centrifuge-cooling temperature, and centrifuge rotation speed. Among these factors, concentration ratio changed the entrapment efficiency and loading capacity significantly. In addition, the hydrodynamic diameter and loading capacity were significantly influenced by injection rate and pH of initial buffer solution. The optimized nanogel structure was obtained by concentration ratio of 6.4mg/mL nisin to 1mg/mL ChS, pH of buffer solution at 4.6, and nisin solution injection rate of 0.2mL/min. The observed values of dependent responses were close to predicted values confirmed by model from response surface methodology. The results obviously showed that quality by design concept (QbD) could be effectively applied to optimize the developed ChS-nisin nanogel. Copyright © 2017 Elsevier B.V. All rights reserved.
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Setyono, Daisy; Valiyaveettil, Suresh
2016-01-25
Paper, a readily available renewable resource, comprises of interwoven cellulosic fibers, which can be functionalized to develop interesting low-cost adsorbent material for water purification. In this study, polyethyleneimine (PEI)-functionalized paper was used for the removal of hazardous pollutants such as Au and Ag nanoparticles, Cr(VI) anions, Ni(2+), Cd(2+), and Cu(2+) cations from spiked water samples. Compared to untreated paper, the PEI-coated paper showed significant improvement in adsorption capacities toward the pollutants investigated in this study. Kinetics, isotherm models, pH, and desorption studies were carried out to study the adsorption mechanism of pollutants on the adsorbent surface. Adsorption of pollutants was better described by pseudo-second order kinetics and Langmuir isotherm model. Maximum adsorption of anionic pollutants was achieved at pH 5 while that of cations was at pH>6. Overall, the PEI-functionalized paper showed interesting Langmuir adsorption capacities for heavy metal ions such as Cr(VI) (68 mg/g), Ni(2+) (208 mg/g), Cd(2+) (370 mg/g), and Cu(2+) (435 mg/g) ions at neutral pH. In addition, the modified paper was also used to remove Ag-citrate (79 mg/g), Ag-PVP (46 mg/g), Au-citrate (30 mg/g), Au-PVP (17 mg/g) nanoparticles from water. Desorption of NPs from the adsorbent was done by washing with 2 M HCl or thiourea solution, while heavy metal ions were desorbed using 1 M NaOH or HNO3 solution. The modified paper retained its extraction efficiencies upon desorption of pollutants. Copyright © 2015 Elsevier B.V. All rights reserved.
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Cukrowska, Ewa M; Govender, Koovila; Viljoen, Morris
2004-07-01
New column leaching experiments were designed and used as an alternative rapid screening approach to element mobility assessment. In these experiments, field-moist material was treated with an extracting solution to assess the effects of acidification on element mobility in mine tailings. The main advantage of this version of column leaching experiments with partitioned segments is that they give quick information on current element mobility in conditions closely simulating field conditions to compare with common unrepresentative air-dried, sieved samples used for column leaching experiments. Layers from the tailings dump material were sampled and packed into columns. The design of columns allows extracting leachates from each layer. The extracting solutions used were natural (pH 6.8) and acidified (pH 4.2) rainwater. Metals and anions were determined in the leachates. The concentrations of metals (Ca, Mg, Fe, Mn, Al, Cr, Ni, Co, Zn, and Cu) in sample leachates were determined using ICP OES. The most important anions (NO3-, Cl-, and SO4(2)-) were determined using the closed system izotacophoresis ITP analyser. The chemical analytical data from tailings leaching and physico-chemical data from field measurements (including pH, conductivity, redox potential, temperature) were used for chemometric evaluation of element mobility. Principal factor analysis (PFA) was used to evaluate ions mobility from different layers of tailings dump arising from varied pH and redox conditions. It was found that the results from the partitioned column leaching illustrate much better complex processes of metals mobility from tailings dump than the total column. The chemometric data analysis (PFA) proofed the differences in the various layers leachability that are arising from physico-chemical processes due to chemical composition of tailings dump deposit. Copyright 2004 Elsevier Ltd.
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Liao, Benjamin S; Sram, Jacqueline C; Files, Darin J
2013-01-01
A simple and effective anion ion chromatography (IC) method with anion exchange column and conductivity detector has been developed to determine free sulfites (SO3-2) in dried fruits processed with sulfur dioxide. No oxidation agent, such as hydrogen peroxide, is used to convert sulfites to sulfates for IC analysis. In addition, no stabilizing agent, such as formaldehyde, fructose or EDTA, is required during the sample extraction. This method uses aqueous 0.2 N NaOH as the solvent for standard preparation and sample extraction. The sulfites, either prepared from standard sodium sulfite powder or extracted from food samples, are presumed to be unbound SO3-2 in aqueous 0.2 N NaOH (pH > 13), because the bound sulfites in the sample matrix are released at pH > 10. In this study, sulfites in the standard solutions were stable at room temperature (i.e., 15-25 degrees C) for up to 12 days. The lowest standard of the linear calibration curve is set at 1.59 microg/mL SO3-2 (equivalent to 6.36 microg/g sample with no dilution) for analysis of processed dried fruits that would contain high levels (>1000 microg/g) of sulfites. As a consequence, this method typically requires significant dilution of the sample extract. Samples are prepared with a simple procedure of sample compositing, extraction with aqueous 0.2 N NaOH, centrifugation, dilution as needed, and filtration prior to IC. The sulfites in these sample extracts are stable at room temperature for up to 20 h. Using anion IC, the sulfites are eluted under isocratic conditions with 10 mM aqueous sodium carbonate solution as the mobile phase passing through an anion exchange column. The sulfites are easily separated, with an analysis run time of 18 min, regardless of the dried fruit matrix. Recoveries from samples spiked with sodium sulfites were demonstrated to be between 81 and 105% for five different fruit matrixes (apricot, golden grape, white peach, fig, and mango). Overall, this method is simple to perform and effective for the determination of high levels of sulfites in dried fruits.
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Norgren, Magnus; Gärdlund, Linda; Notley, Shannon M; Htun, Myat; Wågberg, Lars
2007-03-27
For the first time to the knowledge of the authors, well-defined and stable lignin model surfaces have been utilized as substrates in polyelectrolyte adsorption studies. The adsorption of polyallylamine (PAH), poly(acrylic acid) (PAA), and polyelectrolyte complexes (PECs) was monitored using quartz crystal microgravimetry with dissipation (QCM-D). The PECs were prepared by mixing PAH and PAA at different ratios and sequences, creating both cationic and anionic PECs with different charge levels. The adsorption experiments were performed in 1 and 10 mM sodium chloride solutions at pH 5 and 7.5. The highest adsorption of PAH and cationic PECs was found at pH 7.5, where the slightly negatively charged nature of the lignin substrate is more pronounced, governing electrostatic attraction of oppositely charged polymeric substances. An increase in the adsorption was further found when the electrolyte concentration was increased. In comparison, both PAA and the anionic PEC showed remarkably high adsorption to the lignin model film. The adsorption of PAA was further studied on silica and was found to be relatively low even at high electrolyte concentrations. This indicated that the high PAA adsorption on the lignin films was not induced by a decreased solubility of the anionic polyelectrolyte. The high levels of adsorption on lignin model surfaces found both for PAA and the anionic PAA-PAH polyelectrolyte complex points to the presence of strong nonionic interactions in these systems.
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Billing, Beant Kaur; Mayank; Agnihotri, Prabhat K; Singh, Narinder
2018-06-08
Non-covalent bonding via π-π stacking is in demand these days because it does not affect the structure of the carbon nanotube (CNT). Herein, a hybrid material was fabricated via π-π stacking between the aromatic rings of carbon nanotubes and a dihydropyrimidone-based pyrene derivative. The developed CNT@pyrene hybrid material was fully characterized using SEM, EDX, TEM, XRD, and FTIR techniques. The hybrid was developed to improve the heat transport in the hybrid solution by anion addition. The emission profile of the developed hybrid was screened against TBA salts of different anions in EtOH-H2O (10-90% v/v) solvent system to identify the anion that can interact with the hybrid. The hybrid exhibited high sensitivity and selectivity towards NO3- ions with 1.5-fold enhancement in fluorescence intensity, while other anions neither showed significant responses nor interfered in the sensor's response. The limit of NO3- ions detection was found to be 8.1 nM, calculated using the 3-sigma method. It was observed that the proposed hybrid sensor showed stable response at different pH and diverse salt concentrations. The binding mechanism was elucidated by DFT-based theoretical calculations. Real sample analysis was performed for the detection of NO3- concentrations in local water bodies with accuracy as high as 95%. Viscosity and thermal conductivity experiments were performed to measure the effect of concentration, temperature, and pH on the NO3- response.
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Tuning of protein-surfactant interaction to modify the resultant structure.
Mehan, Sumit; Aswal, Vinod K; Kohlbrecher, Joachim
2015-09-01
Small-angle neutron scattering and dynamic light scattering studies have been carried out to examine the interaction of bovine serum albumin (BSA) protein with different surfactants under varying solution conditions. We show that the interaction of anionic BSA protein (pH7) with surfactant and the resultant structure are strongly modified by the charge head group of the surfactant, ionic strength of the solution, and mixed surfactants. The protein-surfactant interaction is maximum when two components are oppositely charged, followed by components being similarly charged through the site-specific binding, and no interaction in the case of a nonionic surfactant. This interaction of protein with ionic surfactants is characterized by the fractal structure representing a bead-necklace structure of micellelike clusters adsorbed along the unfolded protein chain. The interaction is enhanced with ionic strength only in the case of site-specific binding of an anionic surfactant with an anionic protein, whereas it is almost unchanged for other complexes of cationic and nonionic surfactants with anionic proteins. Interestingly, the interaction of BSA protein with ionic surfactants is significantly suppressed in the presence of nonionic surfactant. These results with mixed surfactants thus can be used to fold back the unfolded protein as well as to prevent surfactant-induced protein unfolding. For different solution conditions, the results are interpreted in terms of a change in fractal dimension, the overall size of the protein-surfactant complex, and the number of micelles attached to the protein. The interplay of electrostatic and hydrophobic interactions is found to govern the resultant structure of complexes.
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Process for separating and recovering an anionic dye from an aqueous solution
Rogers, R.; Horwitz, E.P.; Bond, A.H.
1998-01-13
A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.
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NASA Astrophysics Data System (ADS)
Tang, Qingzi; Duan, Tongdan; Li, Peng; Zhang, Ping; Wu, Daishe
2018-04-01
In this work, the potential of a novel carbon nanotube-doped hydroxyapatite composite (CNT-HAP) for fluoride removal was investigated. The synthesized CNT-HAP composite was systematically characterized by X-ray diffraction(XRD), Fourier Transform infrared spectroscopy(FTIR), scanning electron microscope (SEM) and Brunauer–Emmett–Teller(BET). Batch adsorption experiments were conducted to investigate the defluorination capacity of CNT-HAP. The CNT-HAP composite has a maximum adsorption capacity of 11.05 mg·g-1 for fluoride, and the isothermal adsorption data were fitted by the Freundlich model to calculate the thermodynamic parameters. Thermodynamic analysis implies that the adsorption of fluoride on CNT-HAP is a spontaneous process. Furthermore, the adsorption of fluoride follows pseudo-second-order model. The effects of solution pH, co-existing anions and reaction temperature on defluorination efficiency were examined to optimize the operation conditions for fluoride adsorption. It is found that the optimized pH value for fluoride removal by CNT-HAP composite is 6. In addition, among five common anions studied in this work, the presence of HCO3- and PO43- could considerably affect the fluoride removal by CNT-HPA in aqueous media. Finally, the underlying mechanism for the fluoride removal by CNT-HAP is analysed, and an anion exchange process is proposed.
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Triple-Stimuli-Responsive Ferrocene-Containing PEGs in Water and on the Surface.
Alkan, Arda; Steinmetz, Christian; Landfester, Katharina; Wurm, Frederik R
2015-12-02
Triple-stimuli-responsive PEG-based materials are prepared by living anionic ring-opening copolymerization of ethylene oxide and vinyl ferrocenyl glycidyl ether and subsequent thiol-ene postpolymerization modification with cysteamine. The hydrophilicity of these materials can be tuned by three stimuli: (i) temperature (depending on the comonomer ratio), (ii) oxidation state of iron centers in the ferrocene moieties, and (iii) pH-value (through amino groups), both in aqueous solution and at the interface after covalent attachment to a glass surface. In such materials, the cloud point temperatures are adjustable in solution by changing oxidation state and/or pH. On the surface, the contact angle increases with increasing pH and temperature and after oxidation, making these smart surfaces interesting for catalytic applications. Also, their redox response can be switched by temperature and pH, making this material useful for catalysis and electrochemistry applications. Exemplarily, the temperature-dependent catalysis of the chemiluminescence of luminol (a typical blood analysis tool in forensics) was investigated with these polymers.
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Thermal decarboxylation of acetic acid: Implications for origin of natural gas
Kharaka, Y.K.; Carothers, W.W.; Rosenbauer, R.J.
1983-01-01
Laboratory experiments on the thermal decarboxylation of solutions of acetic acid at 200??C and 300??C were carried out in hydrothermal equipment allowing for on-line sampling of both the gas and liquid phases for chemical and stable-carbon-isotope analyses. The solutions had ambient pH values between 2.5 and 7.1; pH values and the concentrations of the various acetate species at the conditions of the experiments were computed using a chemical model. Results show that the concentrations of acetic acid, and not total acetate in solution, control the reaction rates which follow a first order equation based on decreasing concentrations of acetic acid with time. The decarboxylation rates at 200??C (1.81 ?? 10-8 per second) and 300??C (8.17 ?? 10-8 per second) and the extrapolated rates at lower temperatures are relatively high. The activation energy of decarboxylation is only 8.1 kcal/mole. These high decarboxylation rates, together with the distribution of short-chained aliphatic acid anions in formation waters, support the hypothesis that acid anions are precursors for an important portion of natural gas. Results of the ??13C values of CO2, CH4, and total acetate show a reasonably constant fractionation factor of about 20 permil between CO2 and CH4 at 300??C. The ??13C values of CO2 and CH4 are initially low and become higher as decarboxylation increases. ?? 1983.
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Separation of anionic oligosaccharides by high-performance liquid chromatography
DOE Office of Scientific and Technical Information (OSTI.GOV)
Green, E.D.; Baenziger, J.U.
1986-10-01
The authors have developed methods for rapid fractionation of anionic oligosaccharides containing sulfate and/or sialic acid moieties by high-performance liquid chromatography (HPLC). Ion-exchange HPLC on amine-bearing columns (Micropak AX-10 and AX-5) at pH 4.0 is utilized to separate anionic oligosaccharides bearing zero, one, two, three, or four charges, independent of the identity of the anionic moieties (sulfate and/or sialic acid). Ion-exchange HPLC at pH 1.7 allows separation of neutral, mono-, di-, and tetrasialylated, monosulfated, and disulfated oligosaccharides. Oligosaccharides containing three sialic acid residues and those bearing one each of sulfate and sialic acid, however, coelute at pH 1.7. Since themore » latter two oligosaccharide species separate at pH 4.0, analysis at pH 4.0 followed by analysis at pH 1.7 can be utilized to completely fractionate complex mixtures of sulfated and sialylated oligosaccharides. Ion-suppression amine adsorption HPLC has previously been shown to separate anionic oligosaccharides on the basis of net carbohydrate content (size). In this study they demonstrate the utility of ion-suppression amine adsorption HPLC for resolving sialylated oligosaccharide isomers which differ only in the linkages of sialic acid residues (..cap alpha..2,3 vs ..cap alpha..2,6) and/or location of ..cap alpha..2,3- and ..cap alpha..2,6-linked sialic acid moieties on the peripheral branches of oligosaccharides. These two methods can be used in tandem to separate oligosaccharides, both analytically and preparatively, based on their number, types, and linkages of anionic moieties.« less
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Oxidation of bisphenol F (BPF) by manganese dioxide.
Lu, Zhijiang; Lin, Kunde; Gan, Jay
2011-10-01
Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO(2). At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO(2) and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤ pH 5.5) and high pH (≥ pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn(2+) > Ca(2+) > Mg(2+) > Na(+) and HPO(4)(2-) > Cl(-) > NO(3)(-) ≈ SO(4)(2-), respectively. A total of 5 products were identified, from which a tentative pathway was proposed. Copyright © 2011 Elsevier Ltd. All rights reserved.
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Interaction of inorganic anions with iron-mineral adsorbents in aqueous media--a review.
Kumar, Eva; Bhatnagar, Amit; Hogland, William; Marques, Marcia; Sillanpää, Mika
2014-01-01
A number of inorganic anions (e.g., nitrate, fluoride, bromate, phosphate, and perchlorate) have been reported in alarming concentrations in numerous drinking water sources around the world. Their presence even in very low concentrations may cause serious environmental and health related problems. Due to the presence and significance of iron minerals in the natural aquatic environment and increasing application of iron in water treatment, the knowledge of the structure of iron and iron minerals and their interactions with aquatic pollutants, especially inorganic anions in water are of great importance. Iron minerals have been known since long as potential adsorbents for the removal of inorganic anions from aqueous phase. The chemistry of iron and iron minerals reactions in water is complex. The adsorption ability of iron and iron minerals towards inorganic anions is influenced by several factors such as, surface characteristics of the adsorbent (surface area, density, pore volume, porosity, pore size distribution, pHpzc, purity), pH of the solution, and ionic strength. Furthermore, the physico-chemical properties of inorganic anions (pore size, ionic radius, bulk diffusion coefficient) also significantly influence the adsorption process. The aim of this paper is to provide an overview of the properties of iron and iron minerals and their reactivity with some important inorganic anionic contaminants present in water. It also summarizes the usage of iron and iron minerals in water treatment technology. © 2013.
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Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar
Lee, Hanseung; Jung, Dohyun; Chen, Zhengxin
2018-01-01
This paper presents the effect of anion exchange resin (AER) on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH)2 saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER. PMID:29621188
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Cl- channels of the gastric parietal cell that are active at low pH.
Cuppoletti, J; Baker, A M; Malinowska, D H
1993-06-01
HCl secretion across mammalian gastric parietal cell apical membrane may involve Cl- channels. H(+)-K(+)-ATPase-containing membranes isolated from gastric mucosa of histamine-stimulated rabbits were fused to planar lipid bilayers. Channels were recorded with symmetric 800 mM CsCl solutions, pH 7.4. A linear current-voltage (I-V) relationship was obtained, and conductance was 28 +/- 1 pS at 800 mM CsCl. Conductance was 6.9 +/- 2 pS at 150 mM CsCl. Reversal potential was +22 mV with a fivefold cis-trans CsCl concentration gradient, indicating that the channel was anion selective with a discrimination ratio of 6:1 for Cl- over Cs+. Anion selectivity of the channel was I- > Cl- > or = Br- > NO3-, and gluconate was impermeant. Channels obtained at pH 7.4 persisted when pH of medium bathing the trans side of the bilayer (pHtrans) was reduced to pH 3, without a change in conductance, linearity of I-V relationship, or ion selectivity. In contrast, asymmetric reduction of pH of medium bathing the cis side of the bilayer from 7.4 to 3 always resulted in loss of channel activity. At pH 7.4, open probability (Po) of the channel was voltage dependent, i.e., predominantly open at +80 mV but mainly closed at -80 mV. In contrast, with low pHtrans, channel Po at -80 mV was increased 3.5-fold. The Cl- channel was Ca2+ indifferent. In absence of ionophores, ion selectivity for support of H(+)-K(+)-ATPase activity and H+ transport was consistent with that exhibited by the channel and could be limited by substitution with NO3-, whereas maximal H(+)-K(+)-ATPase activity was indifferent to anion present, demonstrating that anion transport can be rate limiting. Cl- channels with similar characteristics (conductance, linear I-V relationship, and ion selectivity) were also present in H(+)-K(+)-ATPase-containing vesicles isolated from resting (cimetidine-treated) gastric mucosa, exhibiting at -80 mV a pH-independent approximately 3.5-fold lower Po than stimulated vesicle channels. At -80 mV, reduction of pHtrans increased Po of both resting and stimulated Cl- channels by five- to sixfold. Changing membrane potential from 0 to -80 mV across stimulated vesicles increased Cl- channel activity an additional 10-fold.(ABSTRACT TRUNCATED AT 400 WORDS)
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Kierdaszuk, Borys
2013-03-01
We examined the emission spectra and steady-state anisotropy of tyrosinate anion fluorescence with one-photon (250-310 nm), two-photon (570-620 nm) and three-photon (750-930 nm) excitation. Similar emission spectra of the neutral (pH 7.2) and anionic (pH 13) forms of N-acetyl-L-tyrosinamide (NATyrA) (pKa 10.6) were observed for all modes of excitation, with the maxima at 302 and 352 nm, respectively. Two-photon excitation (2PE) and three-photon excitation (3PE) spectra of the anionic form were the same as that for one-photon excitation (1PE). In contrast, 2PE spectrum from the neutral form showed ~30-nm shift to shorter wavelengths relative to 1PE spectrum (λmax 275 nm) at two-photon energy (550 nm), the latter being overlapped with 3PE spectrum, both at two-photon energy (550 nm). Two-photon cross-sections for NATyrA anion at 565-580 nm were 10 % of that for N-acetyl-L-tryptophanamide (NATrpA), and increased to 90 % at 610 nm, while for the neutral form of NATyrA decreased from 2 % of that for NATrpA at 570 nm to near zero at 585 nm. Surprisingly, the fundamental anisotropy of NATyrA anion in vitrified solution at -60 °C was ~0.05 for 2PE at 610 nm as compared to near 0.3 for 1PE at 305 nm, and wavelength-dependence appears to be a basic feature of its anisotropy. In contrast, the 3PE anisotropy at 900 nm was about 0.5, and 3PE and 1PE anisotropy values appear to be related by the cos(6) θ to cos(2) θ photoselection factor (approx. 10/6) independently of excitation wavelength. Attention is drawn to the possible effect of tyrosinate anions in proteins on their multi-photon induced fluorescence emission and excitation spectra as well as excitation anisotropy spectra.
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Development of a pH sensing membrane electrode based on a new calix[4]arene derivative.
Kormalı Ertürün, H Elif; Demirel Özel, Ayça; Sayın, Serkan; Yılmaz, Mustafa; Kılıç, Esma
2015-01-01
A new pH sensing poly(vinyl chloride) (PVC) membrane electrode was developed by using recently synthesized 5,17-bis(4-benzylpiperidine-1-yl)methyl-25,26,27,28-tetrahydroxy calix[4]arene as an ionophore. The effects of membrane composition, inner filling solution and conditioning solution on the potential response of the proposed pH sensing membrane electrode were investigated. An optimum membrane composition of 3% ionophore, 67% o-nitrophenyl octyl ether (o-NPOE) as plasticizer, 30% PVC was found. The electrode exhibited a near-Nernstian slope of 58.7±1.1 mV pH(-1) in the pH range 1.9-12.7 at 20±1 °C. It showed good selectivity for H(+) ions in the presence of some cations and anions and a longer lifetime of at least 12 months when compared with the other PVC membrane pH electrodes reported in the literature. Having a wide working pH range, it was not only applied as a potentiometric indicator electrode in various acid-base titrations, but also successfully employed in different real samples. It has good reproducibility and repeatability with a response time of 6-7s. Compared to traditional glass pH electrode, it exhibited excellent potentiometric response after being used in fluoride-containing media. Copyright © 2014 Elsevier B.V. All rights reserved.
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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.
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NASA Astrophysics Data System (ADS)
Hashim, Norhayati; Sharif, Sharifah Norain Mohd; Isa, Illyas Md; Hamid, Shahidah Abdul; Hussein, Mohd Zobir; Bakar, Suriani Abu; Mamat, Mazidah
2017-06-01
The intercalation of L-phenylalanate (LP) into the interlayer gallery of zinc layered hydroxide (ZLH) has been successfully executed using a simple direct reaction method. The synthesised intercalation compound, zinc layered hydroxide-L-phenylalanate (ZLH-LP), was characterised using PXRD, FTIR, CHNS, ICP-OES, TGA/DTG, FESEM and TEM. The PXRD patterns of the intercalation compound demonstrate an intense and symmetrical peak, indicating a well-ordered crystalline layered structure. The appearance of an intercalation peak at a low angle of 2θ with a basal spacing of 16.3 Å, signifies the successful intercalation of the L-phenylalanate anion into the interlayer gallery of the host. The intercalation is also validated by FTIR spectroscopy and CHNS elemental analysis. Thermogravimetric analysis confirms that the ZLH-LP intercalation compound has higher thermal stability than the pristine L-phenylalanine. The observed percentage of L-phenylalanate accumulated release varies in each release media, with 84.5%, 79.8%, 63.8% and 61.8% release in phosphate buffer saline (PBS) solution at pH 4.8, deionised water, PBS solution at pH 7.4 and NaCl solution, respectively. The release behaviour of LP from its intercalation compounds in deionised water and PBS solution at pH 4.8 follows pseudo second order, whereas in NaCl solution and PBS solution at pH 7.4, it follows the parabolic diffusion model. This study shows that the synthesised ZLH-LP intercalation compound can be used for the formation of a new generation of materials for targeted drug release with controlled release properties.
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NASA Astrophysics Data System (ADS)
Klyubin, V. V.; Klyubina, K. A.; Makovetskaya, K. N.
2017-04-01
The electronic absorption spectra of aqueous solutions of iodine monochloride ICl are studied. The spectra of as-prepared solutions display the absorption band associated with hydrated ICl molecules. An additional band indicating that molecular iodine was formed in the solution emerges in the spectrum as dissolution takes place. Only the band belonging to iodine monochloride remains in the absorption spectra, and no additional bands appear after chloride anions Cl- are added to the solution. The absorption spectrum becomes more complex when ICl is dissolved in an alkaline medium. The band belonging to molecular iodine emerges in the spectra at low alkali concentrations, while being transformed to other shorter-wavelength bands at high alkali concentrations (pH ≥ 12).
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Farmer, R.W.; Dussert, B.W.; Kovacic, S.L.
Laboratory studies have identified the cause of the pH rise, which occurs during water treatment with activated carbon, as an interaction between the naturally occurring anions and protons in the water and the carbon surface. The interaction can be described as an ion exchange type of phenomenon, in which the carbon surface sorbs the anions and corresponding hydronium ions from the water. These studies have shown that the anion sorption and resulting pH increase is independent of the raw material used for the activated carbon production, e.g. bituminous or subbituminous coal, peat, wood or coconut. Also, the pH excursions occurmore » with virgin, reactivated, and acid washed granular carbons. Current pH control technologies focus on adjustment of the wastewater pH prior to discharge or recycle of the initial effluent water until the pH increase abates. However, improved water pH control options have been realized by altering the carbon surface through controlled oxidation rather than the water chemistry or extended preprocessing at the treatment site.« less
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Removal of ammonium from aqueous solutions with volcanic tuff.
Marañón, E; Ulmanu, M; Fernández, Y; Anger, I; Castrillón, L
2006-10-11
This paper presents kinetic and equilibrium data concerning ammonium ion uptake from aqueous solutions using Romanian volcanic tuff. The influence of contact time, pH, ammonium concentration, presence of other cations and anion species is discussed. Equilibrium isotherms adequately fit the Langmuir and Freundlich models. The results showed a contact time of 3h to be sufficient to reach equilibrium and pH of 7 to be the optimum value. Adsorption capacities of 19 mg NH(4)(+)/g were obtained in multicomponent solutions (containing NH(4)(+), Zn(2+), Cd(2+), Ca(2+), Na(2+)). The presence of Zn and Cd at low concentrations did not decrease the ammonium adsorption capacity. Comparison of Romanian volcanic tuff with synthetic zeolites used for ammonium removal (5A, 13X and ZSM-5) was carried out. The removal efficiciency of ammonium by volcanic tuff were similar to those of zeolites 5A and 13X at low initial ammonium concentration, and much higher than those of zeolite ZSM-5.
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Carpenter, C E; Broadbent, J R
2009-01-01
Although the mechanisms by which organic acids inhibit growth of bacteria in mildly acidic foods are not fully understood, it is clear that intracellular accumulation of anions is a primary contributor to inhibition of bacterial growth. We hypothesize that intracellular accumulation of anions is driven by 2 factors, external anion concentration and external acidity. This hypothesis follows from basic chemistry principles that heretofore have not been fully applied to studies in the field, and it has led us to develop a novel approach for predicting internal anion concentration by controlling the external concentration of anions and pH. This approach overcomes critical flaws in contemporary experimental design that invariably target concentration of either protonated acid or total acid in the growth media thereby leaving anion concentration to vary depending on the pK(a) of the acids involved. Failure to control external concentration of anions has undoubtedly confounded results, and it has likely led to misleading conclusions regarding the antimicrobial action of organic acids. In summary, we advocate an approach for directing internal anion levels by controlling external concentration of anions and pH because it presents an additional opportunity to study the mechanisms by which organic acids inhibit bacterial growth. Knowledge gained from such studies would have important application in the control of important foodborne pathogens such as Listeria monocytogenes, and may also facilitate efforts to promote the survival in foods or beverages of desirable probiotic bacteria.
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NASA Technical Reports Server (NTRS)
Treiman, Allan H.
1995-01-01
A thermochemical model of the activities of species in carbonate-rich melts would be useful in quantifying chemical equilibria between carbonatite magmas and vapors and in extrapolating liquidus equilibria to unexplored PTX. A regular-solution model of Ca-rich carbonate melts is developed here, using the fact that they are ionic liquids, and can be treated (to a first approximation) as interpenetrating regular solutions of cations and of anions. Thermochemical data on systems of alkali metal cations with carbonate and other anions are drawn from the literature; data on systems with alkaline earth (and other) cations and carbonate (and other) anions are derived here from liquidus phase equilibria. The model is validated in that all available data (at 1 kbar) are consistent with single values for the melting temperature and heat of fusion for calcite, and all liquidi are consistent with the liquids acting as regular solutions. At 1 kbar, the metastable congruent melting temperature of calcite (CaCO3) is inferred to be 1596 K, with (Delta)bar-H(sub fus)(calcite) = 31.5 +/- 1 kJ/mol. Regular solution interaction parameters (W) for Ca(2+) and alkali metal cations are in the range -3 to -12 kJ/sq mol; W for Ca(2+)-Ba(2+) is approximately -11 kJ/sq mol; W for Ca(2+)-Mg(2+) is approximately -40 kJ/sq mol, and W for Ca(2+)-La(3+) is approximately +85 kJ/sq mol. Solutions of carbonate and most anions (including OH(-), F(-), and SO4(2-)) are nearly ideal, with W between 0(ideal) and -2.5 kJ/sq mol. The interaction of carbonate and phosphate ions is strongly nonideal, which is consistent with the suggestion of carbonate-phosphate liquid immiscibility. Interaction of carbonate and sulfide ions is also nonideal and suggestive of carbonate-sulfide liquid immiscibility. Solution of H2O, for all but the most H2O-rich compositions, can be modeled as a disproportionation to hydronium (H3O(+)) and hydroxyl (OH(-)) ions with W for Ca(2+)-H3O(+) (approximately) equals 33 kJ/sq mol. The regular-solution model of carbonate melts can be applied to problems of carbonatite magma + vapor equilibria and of extrapolating liquidus equilibria to unstudied systems. Calculations on one carbonatite (the Husereau dike, Oka complex, Quebec, Canada) show that the anion solution of its magma contained an OH mole fraction of (approximately) 0.07, although the vapor in equilibrium with the magma had P(H2O) = 8.5 x P(CO2). F in carbonatite systems is calculated to be strongly partitioned into the magma (as F(-)) relative to coexisting vapor. In the Husereau carbonatite magma, the anion solution contained an F(-) mole fraction of (approximately) 6 x 10(exp -5).
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A relay identification fluorescence probe for Fe3 + and phosphate anion and its applications
NASA Astrophysics Data System (ADS)
Tang, Xu; Wang, Yun; Han, Juan; Ni, Liang; Wang, Lei; Li, Longhua; Zhang, Huiqin; Li, Cheng; Li, Jing; Li, Haoran
2018-02-01
A simple relay identification fluorescence probe for Fe3 + and phosphate anion with ;on-off-on; switching was designed and synthesized based on the phenylthiazole and biphenylcarbonitrile. Probe 1 displayed highly selective and sensitive recognition to Fe3 + in HEPES aqueous buffer (EtOH/H2O = 2:8, v/v, pH = 7.4) solutions. The optimized structures and HOMO and LUMO of probe 1 and [1-Fe3 +] complex were obtained by the density functional theory (DFT) calculations with B3LYP as the exchange and correlation functional using a suite of Gaussian 09 programs. The [1-Fe3 +] complex solution also showed a high selectivity toward PO43 -. The lower limits of detection of probe 1 to Fe3 + and [1-Fe3 +] complex to PO43 - were estimated to 1.09 × 10- 7 M and 1.86 × 10- 7 M. Besides, the probe 1 also was used to detected the target ions in real water sample and living cells successfully.
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Anions adsorption onto nanoparticles: effects on colloid stability and mobility in the environment
NASA Astrophysics Data System (ADS)
Missana, Tiziana; Benedicto, Ana; Mayordomo, Natalia; Alonso, Ursula
2013-04-01
Nanoparticles and colloids can enhance the contaminant transport in groundwater, if the contaminant is irreversibly adsorbed onto their surface; additionally colloids must be stable and mobile under the chemical conditions of the environment of interest. Colloid stability and mobility are factors directly related to the chemistry of the water, which determines the charge and size of the particles, but these colloidal properties can also be affected by the contaminant adsorption. This last point, which is potentially very relevant on the overall colloid-driven transport, is scarcely investigated. The evaluation of the stability of a colloidal system is generally carried out by measuring the aggregation kinetic after the change of a specific chemical condition, mainly pH or ionic strength of the aqueous solution. The effect of anion adsorption onto the stability of colloidal systems is mostly neglected. Parameters of the nanoparticles,as the point of zero charge (pH PCZ) or the isoelectric point (pH IEP) are determined with "inert" electrolytes and this might not be representative of their real behavior in natural systems. In this work, the effects of the Se(IV) (selenite) adsorption on alumina (Al2O3) nanoparticles have been analyzed. Selenite adsorption was studied in a wide range of pH (2-12) and ionic strengths (0.0005 - 0.1 M in NaClO4) and the effect of the adsorption on the main properties of the colloids (size and charge) were analyzed. Se adsorption on Al2O3 is almost independent of the ionic strength and decreases with increasing pH; sorption data were successfully fit by surface complexation modeling. Selenite adsorption (at medium-high surface occupancies) clearly affected the stability of Al2O3 colloids, with a clear shift of the isoelectric point towards more acid pH and enhancing colloid aggregation when the ionic strength increases. Considering the obtained results, the effect of anions in the chemical composition of natural water, frequently not accounted for in stability studies, will be discussed, as well as their implications on possible colloid-driven selenite transport in the environment.
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Cass, Albert; Finkelstein, Alan; Krespi, Vivian
1970-01-01
Characteristics of nystatin and amphotericin B action on thin (<100 A) lipid membranes are: (a) micromolar amounts increase membrane conductance from 10-8 to over 10-2 Ω-1 cm-2; (b) such membranes are (non-ideally) anion selective and discriminate among anions on the basis of size; (c) membrane sterol is required for action; (d) antibiotic presence on both sides of membrane strongly favors action; (e) conductance is proportional to a large power of antibiotic concentration; (f) conductance decreases ∼104 times for a 10°C temperature rise; (g) kinetics of antibiotic action are also very temperature sensitive; (h) ion selectivity is pH independent between 3 and 10, but (i) activity is reversibly lost at high pH; (j) methyl ester derivatives are fully active; N-acetyl and N-succinyl derivatives are inactive; (k) current-voltage characteristic is nonlinear when membrane separates nonidentical salt solutions. These characteristics are contrasted with those of valinomycin. Observations (a)–(g) suggest that aggregates of polyene and sterol from opposite sides of the membrane interact to create aqueous pores; these pores are not static, but break up (melt) and reform continuously. Mechanism of anion selectivity is obscure. Observations (h)–(j) suggest—NH3 + is important for activity; it is probably not responsible for selectivity, particularly since four polyene antibiotics, each containing two—NH3 + groups, induce ideal cation selectivity. Possibly the many hydroxyl groups in nystatin and amphotericin B are responsible for anion selectivity. The effects of polyene antibiotics on thin lipid membranes are consistent with their action on biological membranes. PMID:5514157
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Mellau, LSB; Jørgensen, RJ; Bartlett, PC; Enemark, JMD; Hansen, AK
2004-01-01
The objective of this experiment was to determine the effect of dietary grain on calcium homeostasis. Six rumen-fistulated dairy cows with 3 or more previous lactations and no history of parturient paresis were randomly assigned to a sequence of diets in a crossover study with 4 periods of 10 days each. Dietary treatments were: A control ration consisting of wrap grass silage alone (1), the control ration supplemented with ammonium chloride and ammonium sulphate salt solution (2), control ration following a period with supplementation (3) and control ration supplemented with increasing amounts of barley from 4 to 10 kg/cow per day, expected to produce subclinical rumen acidosis (4). Daily intake of the diets was adjusted to 14 kg DM/cow per day. On day 11, the calcium-regulating mechanisms in cows were challenged until recumbency by a standardized intravenous EDTA infusion and cows were left to recover spontaneously. Anion supplementation and the feeding of highly fermentable carbohydrate lowered urine pH below 7.0 due to subclinical acidosis. During spontaneous recovery from EDTA induced hypocalcaemia, the cows more quickly regained a whole blood free calcium concentration of 1.00 mmol/L if they had most recently been supplemented with either anionic salts or with increasing amounts of barley, as compared to the basic ration. It is concluded that so-called slug-feeding or 'steaming up' with highly fermentable carbohydrates before parturition in milk fever susceptible cows enhanced calcium homeostasis similar to the effect seen in cows on anionic diets. PMID:15663074
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NASA Astrophysics Data System (ADS)
Taşcioğlu, Sülin; Kaki, E.; Taşcioğlu, Senay
2012-09-01
Ultraviolet and visible spectral properties of aqueous solutions of molybdenum(VI) (Mo), gallic acid (GA), Lalanine (Ala), and L-Phenylalanine (Phe), and of their binary and ternary solutions were investigated in the absence and presence of anionic, cationic, and nonionic surfactant micelles. Evaluation of the spectra in a comparative way revealed that both Ala and Phe form ternary complexes with Mo and GA. The formation of a quaternary complex between Mo, GA, Phe, and cetyltrimethylammonium bromide at pH 4.5 provided a reagent system with a strikingly high sensitivity (1.2•106 l/(mol•cm)) for use in the spectrophotometric determination of Mo. A mechanism of micellar effects was discussed in terms of the substrate molecular charge and hydrophobicity, and rationalized on the basis of the spectral data obtained above and below the isoelectric pH of the amino acids.
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Polyelectrolyte gels as bending actuators: modeling and numerical simulation
NASA Astrophysics Data System (ADS)
Wallmersperger, Thomas; Keller, Karsten; Attaran, Abdolhamid
2013-04-01
Polyelectrolyte gels are ionic electroactivematerials. They have the ability to react as both, sensors and actuators. As actuators they can be used e.g. as artificial muscles or drug delivery control; as sensors they may be used for measuring e.g. pressure, pH or other ion concentrations in the solution. In this research both, anionic and cationic polyelectrolyte gels placed in aqueous solution with mobile anions and cations are investigated. Due to external stimuli the polyelectrolyte gels can swell or shrink enormously by the uptake or delivery of solvent. In the present research a coupled multi-field problem within a continuum mechanics framework is proposed. The modeling approach introduces a set of equations governing multiple fields of the problem, including the chemical field of the ionic species, the electrical field and the mechanical field. The numerical simulation is performed by using the Finite Element Method. Within the study some test cases will be carried out to validate our model. In the works by Gülch et al., the application of combined anionic-cationic gels as grippers was shown. In the present research for an applied electric field, the change of the concentrations and the electric potential in the complete polymer is simulated by the given formulation. These changes lead to variations in the osmotic pressure resulting in a bending of different polyelectrolyte gels. In the present research it is shown that our model is capable of describing the bending behavior of anionic or cationic gels towards the different electrodes (cathode or anode).
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Adsorption behavior of benzenesulfonic acid by novel weakly basic anion exchange resins.
Sun, Yue; Zuo, Peng; Luo, Junfen; Singh, Rajendra Prasad
2017-04-01
Two novel weakly basic anion exchange resins (SZ-1 and SZ-2) were prepared via the reaction of macroporous chloromethylated polystyrene-divinylbenzene (Cl-PS-DVB) beads with dicyclohexylamine and piperidine, respectively. The physicochemical structures of the resulting resins were characterized using Fourier Transform Infrared Spectroscopy and pore size distribution analysis. The adsorption behavior of SZ-1 and SZ-2 for benzenesulfonic acid (BA) was evaluated, and the common commercial weakly basic anion exchanger D301 was also employed for comparison purpose. Adsorption isotherms and influence of solution pH, temperature and coexisting competitive inorganic salts (Na 2 SO 4 and NaCl) on adsorption behavior were investigated and the optimum desorption agent was obtained. Adsorption isotherms of BA were found to be well represented by the Langmuir model. Thermodynamic parameters involving ΔH, ΔG and ΔS were also calculated and the results indicate that adsorption is an exothermic and spontaneous process. Enhanced selectivity of BA sorption over sulfate on the two novel resins was observed by comparison with the commercial anion exchanger D301. The fact that the tested resins loaded with BA can be efficiently regenerated by NaCl solution indicates the reversible sorption process. From a mechanistic viewpoint, this observation clearly suggests that electrostatic interaction is the predominant adsorption mechanism. Furthermore, results of column tests show that SZ-1 possesses a better adsorption property than D301, which reinforces the feasibility of SZ-1 for potential industrial application. Copyright © 2016. Published by Elsevier B.V.
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Lead Removal From Synthetic Leachate Matrices by a Novel Ion-Exchange Material
NASA Technical Reports Server (NTRS)
Street, Kenneth W., Jr.; Hovanitz, Edward S.; Chi, Sulan
2002-01-01
This report discusses the application of a novel polyacrylate-based ion-exchange material (IEM) for the removal of lead (Pb) ions from water. Preliminary testing includes the establishment of the operating pH range, capacity information, and the effect of calcium and anions in the matrix. Batch testing with powder indicates slightly different optimal operational conditions from those used for column testing. The ion exchanger is excellent for removing lead from aqueous solutions.
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1976-03-01
Nonionic polyacryl - aaide was the most effective for the purification and up to 80% removal of pulp fiber was obtained In a wide range of pH tested...Anionic polyolectrolyte. such as 3odium alginate and sodium polyacrylate , however, dispersed the suspension of pulp fiber instead of coagulating it. The...This process is called filter conditioning. They have observed that the continuous application of a polyacryl - amide solution (5-50 ppb) improved the
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Chen, Meijuan; Chu, W
2012-06-15
A visible-light-mediated C-TiO(2) photocatalytic process (Vis/C-TiO(2)) was employed to degrade antibiotic norfloxacin. The influences of catalyst dosage, initial probe compound concentration and solution pH levels on the decay performance and reaction kinetics were investigated and optimized. Based on the experimental results, an equation was established to predict the observed rate constant under neutral pH. In addition, the decay rate was accelerated under weak alkali in the presence of moderate OH(-) anions. Hydroxyl radical was confirmed to play a major role in the Vis/TiO(2) process, where in the presence of OH quencher and electron acceptor, retardation and improvement were found respectively. Furthermore, an original schematic diagram describing the surface property of C-TiO(2) was built and further verified, in which, NH(4)(+) cations normally served as hole scavengers showed a negligible effect because the adsorbed OH(-) formed a barrier for NH(4)(+) ions to approach the holes, and the F(-) anions presented a significant suppression on norfloxacin decay due to the formation of hydrogen bond (OH⋯F) around the C-TiO(2) surface. Besides, the recycling and sedimentation tests justified that the Vis/C-TiO(2) process is a cost-effective and feasible way for wastewater treatment. Copyright © 2012 Elsevier B.V. All rights reserved.
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Ando, Masaki; Imadzu, Sakiyo; Kitagawa, Shinya; Ohtani, Hajime
2010-08-06
A particulate formation-laser scattering detector (PFLSD) was developed and used for evaluating the crystallization efficiency of inorganic polyphosphates (PPs) that reacted with either magnesium or calcium cations. As the solutions for reactive crystallization, 0.5 M ammonium buffer (pH 9.6) containing either 0.15 M MgCl(2) or 0.15 M CaCl(2) (MAP: magnesium ammonium phosphate and HAP: hydroxyapatite solution) were used. In the case of mono- and diphosphate (P1 and P2), the significant dependences of the particulate formation efficiency on various types of both P1/P2 and MAP/HAP reaction solutions were observed with the direct sample injection mode. The PFLSD was hyphenated with the anion-exchange chromatography and the dependence of the particulate formation efficiency on the polymerization degree (n(p)) of PP oligomers, separated chromatographically, was evaluated sequentially. The significant suppression of the particulate formation for PP oligomers was clearly confirmed, i.e., the MAP and HAP reaction solutions did not produce the particulates of the PP oligomers having an n(p) value of more than 3 and 5, respectively. As the overall tendency, the particulate formation efficiency in the case of the HAP solution was superior to that in the case of the MAP solution. Copyright 2010 Elsevier B.V. All rights reserved.
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RECOVERY OF URANIUM AND THORIUM FROM AQUEOUS SOLUTIONS
Calkins, G.D.
1958-06-10
>A process is described for the recovery of uranium and thorium from monazite sand, which is frequently processed by treating it with a hot sodium hydroxide solution whereby a precipitate forms consisting mainly of oxides or hydroxides of the rare earths, thorium and uranium. The precipitate is dissolved in mineral acid, and the acid solution is then neutralized to a pH value of between 5.2 and 6.2 whereby both the uranium and thorium precipitate as the hydroxides, while substantially all the rare earth metal values present remain in the solution. The uranium and thoriunn can then be separated by dissolving the precipitate in a solution containing a mixture of alkali carbonate and alkali bicarbonate: and contacting the carbonate solution with a strong-base anion exchange resin whereby the uranium values are adsorbed on the resin while the thorium remains in solution.
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Nojavan, Saeed; Bidarmanesh, Tina; Memarzadeh, Farkhondeh; Chalavi, Soheila
2014-09-01
A simple electromembrane extraction (EME) procedure combined with ion chromatography (IC) was developed to quantify inorganic anions in different pure water samples and water miscible organic solvents. The parameters affecting extraction performance, such as supported liquid membrane (SLM) solvent, extraction time, pH of donor and acceptor solutions, and extraction voltage were optimized. The optimized EME conditions were as follows: 1-heptanol was used as the SLM solvent, the extraction time was 10 min, pHs of the acceptor and donor solutions were 10 and 7, respectively, and the extraction voltage was 15 V. The mobile phase used for IC was a combination of 1.8 mM sodium carbonate and 1.7 mM sodium bicarbonate. Under these optimized conditions, all anions had enrichment factors ranging from 67 to 117 with RSDs between 7.3 and 13.5% (n = 5). Good linearity values ranging from 2 to 1200 ng/mL with coefficients of determination (R(2) ) between 0.987 and 0.999 were obtained. The LODs of the EME-IC method ranged from 0.6 to 7.5 ng/mL. The developed method was applied to different samples to evaluate the feasibility of the method for real applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Adsorption of anionic and nonionic surfactant mixtures from synthetic detergents on soils.
Rao, Pinhua; He, Ming
2006-05-01
Adsorption of anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) and nonionic surfactant (an alcohol ethoxylates with 12 carbons and 9 oxyethyl groups, A12E9) mixtures, widely used as the major constituents of synthetic detergents in China and become the most common pollutants in the environment, on soils was conducted to investigate the behavior of mixed surfactants in soils. The effects of addition order and mixing ratios of two surfactants, associated with pH and ion strength in solutions, on adsorptions were considered. The results show that saturated adsorption amount of SDBS and A12E9 on soils decreased respectively when A12E9 was added into soils firstly compared with that secondly, possibly resulting from the screening of A12E9 to part adsorption sites on soils and the hydrocarbon chain-chain interactions between SDBS and A12E9. The adsorption of SDBS and A12E9 on soils was enhanced each other at pre-plateau region of isotherms. At plateau region of isotherms, the adsorption of SDBS on soils decreased with the increase of molar fraction of A12E9 in mixed surfactant solutions, while that of A12E9 increased except the molar ratio of SDBS to A12E9 0.0:1.0. With the increase of pH in mixed surfactant solutions, adsorption amount of SDBS and A12E9 on soils decreased, respectively. The reduction of ion strength in soils resulted in the decrease of adsorption amount of SDBS and A12E9 on soils, respectively.
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Fluorescent solute-partitioning characterization of layered soft contact lenses.
Dursch, T J; Liu, D E; Oh, Y; Radke, C J
2015-03-01
Partitioning of aqueous packaging, wetting, and care-solution agents into and out of soft contact lenses (SCLs) is important for improving wear comfort and also for characterizing lens physico-chemical properties. We illustrate both features of partitioning by application of fluorescent-solute partitioning into DAILIES TOTAL1® (delefilcon A) water-gradient SCLs, which exhibit a layered structure of a silicone-hydrogel (SiHy) core sandwiched between thin surface-gel layers. Two-photon fluorescence confocal laser-scanning microscopy and attenuated total-reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) characterize the lens and assess uptake profiles of six prototypical fluorescent solutes. Comparison of solute uptake in a SiHy-core prototype lens (i.e., O2OPTIX(TM)) validates the core SiHy structure of DAILIESTOTAL1®. To establish surface-layer charge, partition coefficients and water contents are obtained for aqueous pH values of 4 and 7.4. Solute fluorescence-intensity profiles clearly confirm a layered structure for the DAILIES TOTAL1® lenses. In all cases, aqueous solute partition coefficients are greater in the surface layers than in the SiHy core, signifying higher water in the surface gels. ATR-FTIR confirms surface-layer mass water contents of 82±3%. Water uptake and hydrophilic-solute uptake at pH 4 compared with that at pH 7.4 reveal that the surface-gel layers are anionic at physiologic pH 7.4, whereas both the SiHy core and O2OPTIX™ (lotrafilcon B) are nonionic. We successfully confirm the layered structure of DAILIES TOTAL1®, consisting of an 80-μm-thick SiHy core surrounded by 10-μm-thick polyelectrolyte surface-gel layers of significantly greater water content and aqueous solute uptake compared with the core. Accordingly, fluorescent-solute partitioning in SCLs provides information on gel structure and composition, in addition to quantifying uptake and release amounts and rates. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
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Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl.
Schnegelsberg, Christoph; Bachmann, Sebastian; Kolter, Marlene; Auth, Thomas; John, Michael; Stalke, Dietmar; Koszinowski, Konrad
2016-06-01
Grignard reagents RMgCl and their so-called turbo variant, the highly reactive RMgCl⋅LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity-enhancing effect. A combination of electrospray-ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion-ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl⋅LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron-rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Dawood, Sara; Sen, Tushar Kanti
2012-04-15
Pine cone a natural, low-cost agricultural by-product in Australia has been studied for its potential application as an adsorbent in its raw and hydrochloric acid modified form. Surface study of pine cone and treated pine cone was investigated using Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The modification process leads to increases in the specific surface area and decreases mean particle sizes of acid-treated pine cone when compared to raw pine cone biomass. Batch adsorption experiments were performed to remove anionic dye Congo red from aqueous solution. It was found that the extent of Congo red adsorption by both raw pine cone biomass and acid-treated biomass increased with initial dye concentration, contact time, temperature but decreased with increasing solution pH and amount of adsorbent of the system. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on pseudo-first-order and intra-particle diffusion models. The different kinetic parameters including rate constant, half-adsorption time, and diffusion coefficient were determined at different physico-chemical conditions. Equilibrium data were best represented by Freundlich isotherm model among Langmuir and Freundlich adsorption isotherm models. It was observed that the adsorption was pH dependent and the maximum adsorption of 32.65 mg/g occurred at pH of 3.55 for an initial dye concentration of 20 ppm by raw pine cone, whereas for acid-treated pine cone the maximum adsorption of 40.19 mg/g for the same experimental conditions. Freundlich constant 'n' also indicated favourable adsorption. Thermodynamic parameters such as ∆G(0), ∆H(0), and ∆S(0) were calculated. A single-stage batch absorber design for the Congo red adsorption onto pine cone biomass also presented based on the Freundlich isotherm model equation. Copyright © 2012 Elsevier Ltd. All rights reserved.
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Effect of Nicotinamide on the Photolysis of Riboflavin in Aqueous Solution
Ahmad, Iqbal; Ahmed, Sofia; Sheraz, Muhammad Ali; Anwar, Zubair; Qadeer, Kiran; Noor, Adnan; Evstigneev, Maxim P.
2016-01-01
The photolysis of riboflavin (RF) in aqueous solution in the presence of nicotinamide (NA) by visible light has been studied in the pH range 1.0–12.0 and the various photoproducts have been identified as known compounds. RF has been determined in degraded solutions by a specific multicomponent spectrometric method in the presence of its photoproducts and NA. The second-order rate constants (k2) for the bimolecular interaction of RF and NA range from 0.54 (pH 1.0) to 9.66 M–1 min–1 (pH 12.0). The log k2–pH profile for the photolysis reaction follows a sigmoid curve showing a gradual increase in the rate of pH due to a change in the ionization behavior of the molecule. The lower rate in the acid region is probably due to protonation of the molecule since the cationic form of RF is less susceptible to photolysis than the neutral form. Similarly, a slowing of the rate in the alkaline region is due to anion formation of the molecule. NA is involved as an electron acceptor during the sequence of reactions and thus enhances the rate of photolysis of RF. Absorption and fluorescence measurements did not provide evidence for the complex formation between the two compounds under the present conditions. PMID:27222605
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Scopelliti, Amanda J.; Ryan, Renae M.; Vandenberg, Robert J.
2013-01-01
The ASCTs (alanine, serine, and cysteine transporters) belong to the solute carrier family 1 (SLC1), which also includes the human glutamate transporters (excitatory amino acid transporters, EAATs) and the prokaryotic aspartate transporter GltPh. Despite the high degree of amino acid sequence identity between family members, ASCTs function quite differently from the EAATs and GltPh. The aim of this study was to mutate ASCT1 to generate a transporter with functional properties of the EAATs and GltPh, to further our understanding of the structural basis for the different transport mechanisms of the SLC1 family. We have identified three key residues involved in determining differences between ASCT1, the EAATs and GltPh. ASCT1 transporters containing the mutations A382T, T459R, and Q386E were expressed in Xenopus laevis oocytes, and their transport and anion channel functions were investigated. A382T and T459R altered the substrate selectivity of ASCT1 to allow the transport of acidic amino acids, particularly l-aspartate. The combination of A382T and T459R within ASCT1 generates a transporter with a similar profile to that of GltPh, with preference for l-aspartate over l-glutamate. Interestingly, the amplitude of the anion conductance activated by the acidic amino acids does not correlate with rates of transport, highlighting the distinction between these two processes. Q386E impaired the ability of ASCT1 to bind acidic amino acids at pH 5.5; however, this was reversed by the additional mutation A382T. We propose that these residues differences in TM7 and TM8 combine to determine differences in substrate selectivity between members of the SLC1 family. PMID:23393130
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Organic hydrogels as potential sorbent materials for water purification
NASA Astrophysics Data System (ADS)
Linardatos, George; Bekiari, Vlasoula; Bokias, George
2014-05-01
Hydrogels are three-dimensional, hydrophilic, polymeric networks capable to adsorb large amounts of water or biological fluids. The networks are composed of homopolymers or copolymers and are insoluble due to the presence of chemical or physical cross-links. Depending on the nature of the structural units, swelling or shrinking of these gels can be activated by several external stimuli, such as solvent, heat, pH, electric stimuli. As a consequence, these materials are attractive for several applications in a variety of fields: drug delivery, muscle mimetic soft linear actuators, hosts of nanoparticles and semiconductors, regenerative medicine etc. Of special interest is the application of hydrogels for water purification, since they can effectively adsorb several water soluble pollutants such as metal ions, inorganic or organic anions, organic dyestaff, etc. In the present work, anionic hydrogels bearing negatively charged -COO- groups were prepared and investigated. These are based on the anionic monomer sodium acrylate (ANa) and the nonionic one N,N-dimethylacrylamide (DMAM). A series of copolymeric hydrogels (P(DMAM-co-ANax) were synthesized. The molar content x of ANa units (expressing the molar charged content of the hydrogel) varies from 0 (nonionic poly(N,N-dimethylacrylamide), PDMAM, hydrogel) up to 1 (fully charged poly(sodium acrylate), PANa, hydrogel). The hydrogels were used to extract organic or inorganic solutes from water. Cationic and anionic model dyes, as well as multivalent inorganic ions, have been studied. It is found that cationic dyes are strongly adsorbed and retained by the hydrogels, while adsorbance of anionic dyes was negligible. Both maximum adsorption and equilibrium binding constant depend on the chemical structure of the dye, the presence of functional chemical groups and the hydrophobic-hydrophilic balance. In the case of metal cations, adsorption depends mostly on the charge of the cation. In addition, crucial factors controlling the adsorption efficiency is the charge content of the hydrogel x, as well as the pH of the aqueous solution, since acrylic acid is a weak acid. ACKNOWLEDGMENTS. This research has been co-financed by the European Union (European Social Fund - ESF) and Greek national funds through the Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF) - Research Funding Program: Archimedes III. Investing in knowledge society through the European Social Fund; research project Archimedes III: "Synthesis and characterization of novel nanostructured materials and study of their use as water purification systems".
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Genz, Anne-Katrin; v Engelhardt, Wolfgang; Busche, Roger
1999-01-01
The fluorescent dye 5-N-hexadecanoyl-aminofluorescein (HAF) was used to study the mechanisms involved in maintaining a relatively constant luminal surface pH (pHs) in the distal colon of the guinea-pig. The fatty acyl chain of the HAF molecule inserts into the apical membrane of epithelial cells. This allows a continuous measurement of the surface pH for several hours. The localization of HAF was confirmed by confocal laser-scanning microscopy and by using monoclonal antibodies against fluorescein. The insertion of HAF into the apical membrane of the colonocytes did not change the transepithelial conductance or the short-circuit current of the epithelium. With the HAF method a pH microclimate was confirmed at the colonic surface. Although the pH of the bulk luminal solution was decreased in bicarbonate-containing solution from 7.4 to 6.4 the pHs changed only in the range 7.54-6.98. In the absence of bicarbonate pHs almost followed changes of bulk luminal pH. In the presence of bicarbonate there was a decrease in pHs after removal of chloride from the luminal side and an increase in pHs after addition of butyrate to the luminal solution. This suggests the involvement of a bicarbonate-anion exchange in bicarbonate secretion: a Cl−-HCO3− as well as a short-chain fatty acid−-HCO3− exchange. The apical K+-H+-ATPase in the distal colon of guinea-pig has little influence on pHs in the presence of physiological buffer concentrations. Our findings indicate that bicarbonate plays a major role in maintaining the pH microclimate at the colonic surface. PMID:10332098
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Preparation of pH-sensitive anionic liposomes designed for drug delivery system (DDS) application.
Aoki, Asami; Akaboshi, Hikaru; Ogura, Taku; Aikawa, Tatsuo; Kondo, Takeshi; Tobori, Norio; Yuasa, Makoto
2015-01-01
We prepared pH-sensitive anionic liposomes composed solely of anionic bilayer membrane components that were designed to promote efficient release of entrapped agents in response to acidic pH. The pH-sensitive anionic liposomes showed high dispersion stability at neutral pH, but the fluidity of the bilayer membrane was enhanced in an acidic environment. These liposomes were rather simple and were composed of dimyristoylphosphatidylcholine (DMPC), an anionic bilayer membrane component, and polyoxyethylene sorbitan monostearate (Tween 80). In particular, the present pH-sensitive anionic liposomes showed higher temporal stability than those of conventional DMPC/DPPC liposomes. We found that pHsensitive properties strongly depended on the molecular structure, pKa value, and amount of an incorporated anionic bilayer membrane component, such as sodium oleate (SO), dimyristoylphosphatidylserine (DMPS), or sodium β-sitosterol sulfate (SS). These results provide an opportunity to manipulate liposomal stability in a pH-dependent manner, which could lead to the formulation of a high performance drug delivery system (DDS).
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Medium effects on fluorescence of ciprofloxacin hydrochloride
NASA Astrophysics Data System (ADS)
Yang, Rui; Fu, Yan; Li, Long-Di; Liu, Jia-Ming
2003-10-01
The medium (pH, organic solvents, cyclodextrin (CD) or surfactants) effects on the fluorescence of ciprofloxacin hydrochloride (CPFX·HCl) were studied in detail. It is found that the three acid constants of ciprofloxacin (CPFX) are near to each other. Therefore the relation curve between pH and fluorescence intensity has no strident change and keeps relative stable in the pH range of 2-7. When pH was in the range of 5.5-6.0, the fluorescence intensity of CPFX reached the max. The kind and amount of organic solvent added to the luminescent system have various effects. Ethanol quenched fluorescence and the fluorescence excitation wavelength is red shift at first and then blue shift. Acetone has complicated effects on the fluorescence properties of CPFX·HCl solution. The experiment result shows that acetone is really a quencher when its volume content in the system is from 0 to 20%, but when its content is 90%, the signal intensity is unexpectedly one and a half times as much as that of no acetone. This means that there is a strong interaction between the acetone and CPFX; CPFX·H + could be included into the γ-CD but the capping effect is not notable. The effect of cationic surfactant cetyltrimethylammonium bromide and non-ionic surfactant TX-100 and TX-80 on CPFX fluorescence was unimpressive, but the anionic surfactant's effect is aberrant. The fluorescence intensity of CPFX·HCl solution experiences three stages of increasing, decreasing and increasing in turn, as sodium dodecyl sulfate is adding gradually. But for sodium lauryl sulfonate, there are only two stages of decreasing and increasing with the concentration increasing. It is problematic to illustrate clearly the effect mechanism of acetone and anionic surfactant at present. Undoubtedly, the experimental results in this paper should be useful in practice works and the research is worth studying still further.
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Unfolding of a model protein on ion exchange and mixed mode chromatography surfaces.
Gospodarek, Adrian M; Hiser, Diana E; O'Connell, John P; Fernandez, Erik J
2014-08-15
Recent studies with proteins indicate that conformational changes and aggregation can occur during ion exchange chromatography (IEC). Such behavior is not usually expected, but could lead to decreased yield and product degradation from both IEC and multi mode chromatography (MMC) that has ligands of both hydrophobic and charged functionalities. In this study, we used hydrogen exchange mass spectrometry to investigate unfolding of the model protein BSA on IEC and MMC surfaces under different solution conditions at 25°C. Increased solvent exposure, indicating greater unfolding relative to that in solution, was found for protein adsorbed on cationic IEC and MMC surfaces in the pH range of 3.0 to 4.5, where BSA has decreased stability in solution. There was no effect of anionic surfaces at pH values in the range from 6.0 to 9.0. Differences of solvent exposure of whole molecules when adsorbed and in solution suggest that adsorbed BSA unfolds at lower pH values and may show aggregation, depending upon pH and the surface type. Measurements on digested peptides showed that classifications of stability can be made for various regions; these are generally retained as pH is changed. When salt was added to MMC systems, where electrostatic interactions would be minimized, less solvent exposure was seen, implying that it is the cationic moieties, rather than the hydrophobic ligands, which cause greater surface unfolding at low salt concentrations. These results suggest that proteins of lower stability may exhibit unfolding and aggregation during IEC and MMC separations, as they can with hydrophobic interaction chromatography. Copyright © 2014 Elsevier B.V. All rights reserved.
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A Measurement and Modeling Study of Hair Partition of Neutral, Cationic, and Anionic Chemicals.
Li, Lingyi; Yang, Senpei; Chen, Tao; Han, Lujia; Lian, Guoping
2018-04-01
Various neutral, cationic, and anionic chemicals contained in hair care products can be absorbed into hair fiber to modulate physicochemical properties such as color, strength, style, and volume. For environmental safety, there is also an interest in understanding hair absorption to wide chemical pollutants. There have been very limited studies on the absorption properties of chemicals into hair. Here, an experimental and modeling study has been carried out for the hair-water partition of a range of neutral, cationic, and anionic chemicals at different pH. The data showed that hair-water partition not only depends on the hydrophobicity of the chemical but also the pH. The partition of cationic chemicals to hair increased with pH, and this is due to their electrostatic interaction with hair increased from repulsion to attraction. For anionic chemicals, their hair-water partition coefficients decreased with increasing pH due to their electrostatic interaction with hair decreased from attraction to repulsion. Increase in pH did not change the partition of neutral chemicals significantly. Based on the new physicochemical insight of the pH effect on hair-water partition, a new quantitative structure property relationship model has been proposed, taking into account of both the hydrophobic interaction and electrostatic interaction of chemical with hair fiber. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Jie
1999-04-01
A novel anion-exchange resin containing three amine groups was prepared by reaction of a chloromethylated polystyrene-divinylbenzene (PS-DVB) resin with diethylenetriamine. After being protonated by contact with an aqueous acid, this resin can be used for ion chromatographic separation of anions. The charge on the resins can be varied from +1 to +3 by changing the mobile phase pH. The selectivity of the new ion exchangers for various inorganic anions was quite different from that of conventional anion exchangers. The performance of this new anion exchanger was studied by changing the pH and the concentration of the eluent, and several differentmore » eluents were used with some common anions as testing analytes. Conductivity detection and UV-visible detection were applied to detect the anions after separation. The new resin can also be used for HPLC separation of neutral organic compounds. Alkylphenols and alkylbenzenes were separated with this new polymeric resin, and excellent separations were obtained under simple conditions. This report contains Chapter 1: General introduction and Chapter 6: General conclusions.« less
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Real-time monitoring of ischemia inside stomach.
Tahirbegi, Islam Bogachan; Mir, Mònica; Samitier, Josep
2013-02-15
The low pH in the gastric juice of the stomach makes it difficult to fabricate stable and functional all-solid-state pH ISE sensors to sense ischemia, mainly because of anion interference and adhesion problem between the ISE membrane and the electrode surface. In this work, the adhesion of ISE membrane on solid surface at low pH was improved by modifying the surface with a conductive substrate containing hydrophilic and hydrophobic groups. This creates a stable and robust candidate for low pH applications. Moreover, anion interference problem at low pH was solved by integration of all-solid-state ISE and internal reference electrodes on an array. So, the same tendencies of anion interferences for all-solid-state ISE and all-solid-state reference electrodes cancel each other in differential potentiometric detection. The developed sensor presents a novel all-solid-state potentiometric, miniaturized and mass producible pH ISE sensor for detecting ischemia on the stomach tissue on an array designed for endoscopic applications. Copyright © 2012 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Wang, Bing; Yang, Zewei; An, Hao; Zhai, Jianping; Li, Qin; Cui, Hao
2015-01-01
TiO2 was coated on the surface of hydroxylated fly ash cenospheres (FACs) by the sol-gel method. Platinum (Pt) was then deposited on these TiO2/FAC particles by a photoreduction method to form PTF photocatalyst. The photocatalytic activity of PTF for the degradation of methylene blue (MB) under visible-light irradiation was determined. The PTF sample that was calcined at 450 °C and had a Pt/TiO2 mass ratio of 1.5% exhibited the optimal photocatalytic activity for degradation of MB with a catalyst concentration of 3 g L-1. MB was photodecomposed by PTF in aqueous solution more effectively at alkali pH than at acidic pH, because more MB molecules were adsorbed on the surface of PTF under alkaline conditions than that under acidic. The effect of various inorganic anions (HCO3-, F-, SO42-, NO3-, and Cl-) on the photodegradation of MB by PTF was also investigated. Addition of anions with a concentration of 5 mM enhanced the photocatalytic efficiency of PTF because of the improved adsorption of MB. This effect weakened as the anion concentration was increased, which was attributed to the ability of the anions to scavenge hydroxyl radicals and holes. Our results indicated that the photodegradation of MB took place mainly on the catalyst surface. The generation of hydroxyl radicals in the photocatalytic reaction was measured by the fluorescence method. KI was used to determine the participation of holes in the photocatalytic reaction. Both hydroxyl radicals and valence-band holes were detected in the PTF system. Recycling tests revealed that calcination of the used PTF helped to regain its photocatalytic activity.
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Zeeb, Benjamin; Saberi, Amir Hossein; Weiss, Jochen; McClements, David Julian
2015-03-21
Delivery systems based on filled hydrogel particles (microgels) can be fabricated from natural food-grade lipids and biopolymers. The potential for controlling release characteristics by modulating the electrostatic interactions between emulsifier-coated lipid droplets and the biopolymer matrix within hydrogel particles was investigated. A multistage procedure was used to fabricate calcium alginate beads filled with lipid droplets stabilized by non-ionic, cationic, anionic, or zwitterionic emulsifiers. Oil-in-water emulsions stabilized by Tween 60, DTAB, SDS, or whey protein were prepared by microfluidization, mixed with various alginate solutions, and then microgels were formed by simple extrusion into calcium solutions. The microgels were placed into a series of buffer solutions with different pH values (2 to 11). Lipid droplets remained encapsulated under acidic and neutral conditions, but were released under highly basic conditions (pH 11) due to hydrogel swelling when the alginate concentration was sufficiently high. Lipid droplet release increased with decreasing alginate concentration, which could be attributed to an increase in the pore size of the hydrogel matrix. These results have important implications for the design of delivery systems to entrap and control the release of lipophilic bioactive components within filled hydrogel particles.
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Zhang, Xiang; Ma, Jun; Lu, Xixin; Huangfu, Xiaoliu; Zou, Jing
2015-12-30
Comparatively investigated the different effects of Fe2(SO4)3 coagulation-filtration and FeCl3 coagulation-filtration on the removal of Mo (VI). And the influence of calcium, sulfate, silicate, phosphate and humic acid (HA) were also studied. The following conclusions can be obtained: (1) compared with the case of FeCl3, Fe2(SO4)3 showed a higher Mo (VI) removal efficiency at pH 4.00-5.00, but an equal removal efficiency at pH 6.00-9.00. (2) The optimum Mo (VI) removal by Fe2(SO4)3 was achieved at pH 5.00-6.00; (3) The presence of calcium can reduce the removal of Mo (VI) over the entire pH range in the present study; (4) The effect of co-existing background anions (including HA) was dominated by three factors: Firstly the influence of co-existing background anions on the content of Fe intercepted from water (intercepted Fe). Secondly the competition of co-existing anions with Mo (VI) for adsorption sites. Thirdly the influence of co-existing background anions on the Zeta potential of the iron flocs. Copyright © 2015 Elsevier B.V. All rights reserved.
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Jiang, Yangwei; Zhang, Dong; Zhang, Yaoyang; Deng, Zhenyu; Zhang, Linxi
2014-05-28
The adsorption-desorption transition of DNA in DNA-dendrimer solutions is observed when high-valence anions, such as hexavalent anions, are added to the DNA-dendrimer solutions. In the DNA-dendrimer solutions with low-valence anions, dendrimers bind tightly with the V-shaped double-stranded DNA. When high-valence anions, such as pentavalent or hexavalent anions, are added to the DNA-dendrimer solutions, the double-stranded DNA chains can be stretched straightly and the dendrimers are released from the double-stranded DNA chains. In fact, adding high-valence anions to the solutions can change the charge spatial distribution in the DNA-dendrimer solutions, and weaken the electrostatic interactions between the positively charged dendrimers and the oppositely charged DNA chains. Adsorption-desorption transition of DNA is induced by the overcharging of dendrimers. This investigation is capable of helping us understand how to control effectively the release of DNA in gene/drug delivery because an effective gene delivery for dendrimers includes non-covalent DNA-dendrimer binding and the effective release of DNA in gene therapy.
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di Synthesis and Characterization of the Platinum-Substituted Keggin Anion alpha-H2SiPtW11O404-
DOE Office of Scientific and Technical Information (OSTI.GOV)
Klonowski, P; Goloboy, JC; Uribe-Romo, FJ
2014-12-15
Acidification of an aqueous solution of K8SiW11O39 and K2Pt(OH)(6) to pH 4 followed by addition of excess tetramethylammonium (TMA) chloride yielded a solid mixture of TMA salts of H2SiPtW11O404- (1) and SiW12O404- (2). The former was separated from the latter by extraction into an aqueous solution and converted into tetra-n-butylammonium (TBA) and potassium salts TBA-1 and K-1. The a-H2SiPtW11O404- was identified as a monosubstituted Keggin anion using elemental analysis, IR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, Pt-195 NMR spectroscopy, (183)W NMR spectroscopy, and W-183-W-183 2D INADEQUATE NMR spectroscopy. Both TBA-1 and K-1 readily cocrystallized with their unsubstituted Keggin anionmore » salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.« less
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NASA Astrophysics Data System (ADS)
Tani, Atsushi; Fukui, Satoshi; Ikawa, Satoshi; Kitano, Katsuhisa
2015-10-01
We investigated fatty acid oxidation by atmospheric-pressure nonthermal helium plasma using linoleic acid, an unsaturated fatty acid, together with evaluating active species induced in liquids. If the ambient gas contains oxygen, direct plasma such as plasma jets coming into contact with the liquid surface supplies various active species, such as singlet oxygen, ozone, and superoxide anion radicals, to the liquid. The direct plasma easily oxidizes linoleic acid, indicating that fatty acid oxidation will occur in the direct plasma. In contrast, afterglow flow, where the plasma is terminated in a glass tube and does not touch the surface of the liquid sample, supplies mainly superoxide anion radicals. The fact that there was no clear observation of linoleic acid oxidation using the afterglow reveals that it may not affect lipids, even in an atmosphere containing oxygen. The afterglow flow can potentially be used for the sterilization of aqueous solutions using the reduced pH method, in medical and dental applications, because it provides bactericidal activity in the aqueous solution despite containing a smaller amount of active species.
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Wen, Guo-Xuan; Han, Min-Le; Wu, Xue-Qian; Wu, Ya-Pan; Dong, Wen-Wen; Zhao, Jun; Li, Dong-Sheng; Ma, Lu-Fang
2016-10-04
A super-stable multifunctional terbium(iii)-organic framework, namely {[Tb(TATAB) (H 2 O) 2 ]·NMP·H 2 O} n (Tb-MOF, H 3 TATAB = 4,4',4''-s-triazine-1,3,5-triyltri-m-aminobenzoic acid, NMP = N-methyl-2-pyrrolidone) was synthesized. Tb-MOF exhibits a 2D sql structure with binuclear [Tb 2 (COO) 4 (H 2 O) 4 ] 2+ units as 4-connected nodes, and free water and NMP molecules are inserted between 2D layers through hydrogen-bonding interactions, forming a sandwich-type architecture. Observably, such a framework remains intact in a remarkable variety of environments such as common solvents and aqueous solutions with metal cations and inorganic anions, as well as with a pH ranging from 1 to 13. In particular, Tb-MOF can not only detect small organic molecules, metal cations and inorganic anions with high sensitivity and high selectivity, but also can accurately detect explosive 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and 2,4,6-trinitrophenol in water. Its luminescence quenching response to Fe 3+ and Cr 2 O 7 2- ions can be explained in terms of the competitive absorption mechanism. In addition, the luminescence intensity of Tb-MOF is strongly correlated with the pH value in a pH range from 1 to 13. Thus, this material can be potentially used as a multi-responsive luminescent sensor.
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Tsonev, Latchezar I; Hirsh, Allen G
2008-07-25
pISep is a major new advance in low ionic strength ion exchange chromatography. It enables the formation of externally controlled pH gradients over the very broad pH range from 2 to 12. The gradients can be generated on either cationic or anionic exchangers over arbitrary pH ranges wherein the stationary phases remain totally charged. Associated pISep software makes possible the calculation of either linear, nonlinear or combined, multi-step, multi-slope pH gradients. These highly reproducible pH gradients, while separating proteins and glycoproteins in the order of their electrophoretic pIs, provide superior chromatographic resolution compared to salt. This paper also presents a statistical mechanical model for protein binding to ion exchange stationary phases enhancing the electrostatic interaction theory for the general dependence of retention factor k, on both salt and pH simultaneously. It is shown that the retention factors computed from short time isocratic salt elution data of a model protein can be used to accurately predict its salt elution concentration in varying slope salt elution gradients formed at varying isocratic pH as well as the pH at which it will be eluted from an anionic exchange column by a pISep pH gradient in the absence of salt.
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Nguyen, Truong X; Kattnig, Daniel; Mansha, Asim; Grampp, Günter; Yurkovskaya, Alexandra V; Lukzen, Nikita
2012-11-08
The kinetics of triplet state quenching of 3,3',4,4'-benzophenone tetracarboxylic acid (BPTC) by DNA bases adenine, adenosine, thymine, and thymidine has been investigated in aqueous solution using time-resolved laser flash photolysis. The observation of the BPTC ketyl radical anion at λ(max) = 630 nm indicates that one electron transfer is involved in the quenching reactions. The pH-dependence of the quenching rate constants is measured in detail. As a result, the chemical reactivity of the reactants is assigned. The bimolecular rate constants of the quenching reactions between triplet BPTC and adenine, adenosine, thymine, and thymidine are k(q) = 2.3 × 10(9) (4.7 < pH < 9.9), k(q) = 4.0 × 10(9) (3.5 < pH < 4.7), k(q) = 1.0 × 10(9) (4.7 < pH < 9.9), and k(q) = 4.0 × 10(8) M(-1) s(-1) (4.7 < pH < 9.8), respectively. Moreover, it reveals that in strong basic medium (pH = 12.0) a keto-enol tautomerism of thymine inhibits its reaction with triplet BPTC. Such a behavior is not possible for thymidine because of its deoxyribose group. In addition, the pH-dependence of the apparent electrochemical standard potential of thymine in aqueous solution was investigated by cyclic voltammetry. The ΔE/ΔpH ≈ -59 mV/pH result is characteristic of proton-coupled electron transfer. This behavior, together with the kinetic analysis, leads to the conclusion that the quenching reactions between triplet BPTC and thymine involve one proton-coupled electron transfer.
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2012-01-01
The kinetics of triplet state quenching of 3,3′,4,4′-benzophenone tetracarboxylic acid (BPTC) by DNA bases adenine, adenosine, thymine, and thymidine has been investigated in aqueous solution using time-resolved laser flash photolysis. The observation of the BPTC ketyl radical anion at λmax = 630 nm indicates that one electron transfer is involved in the quenching reactions. The pH-dependence of the quenching rate constants is measured in detail. As a result, the chemical reactivity of the reactants is assigned. The bimolecular rate constants of the quenching reactions between triplet BPTC and adenine, adenosine, thymine, and thymidine are kq = 2.3 × 109 (4.7 < pH < 9.9), kq = 4.0 × 109 (3.5 < pH < 4.7), kq = 1.0 × 109 (4.7 < pH < 9.9), and kq = 4.0 × 108 M–1 s–1 (4.7 < pH < 9.8), respectively. Moreover, it reveals that in strong basic medium (pH = 12.0) a keto–enol tautomerism of thymine inhibits its reaction with triplet BPTC. Such a behavior is not possible for thymidine because of its deoxyribose group. In addition, the pH-dependence of the apparent electrochemical standard potential of thymine in aqueous solution was investigated by cyclic voltammetry. The ΔE/ΔpH ≈ −59 mV/pH result is characteristic of proton-coupled electron transfer. This behavior, together with the kinetic analysis, leads to the conclusion that the quenching reactions between triplet BPTC and thymine involve one proton-coupled electron transfer. PMID:23038981
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Yue, Xianyang; Liu, Weizhen; Chen, Zuliang; Lin, Zhang
2017-03-01
Mg-Al-Cl layered double hydroxide (Cl-LDH) was prepared to simultaneously remove Cu(II) and Cr(VI) from aqueous solution. The coexisting Cu(II) (20mg/L) and Cr(VI) (40mg/L) were completely removed within 30min by Cl-LDH in a dosage of 2.0g/L; the removal rate of Cu(II) was accelerated in the presence of Cr(VI). Moreover, compared with the adsorption of single Cu(II) or Cr(VI), the adsorption capacities of Cl-LDH for Cu(II) and Cr(VI) can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu(II) (200mg/L) and Cr(VI) (400mg/L). The affecting factors (such as solution initial pH, adsorbent dosage, and contact time) have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg 2+ and Al 3+ in relevant solutions were monitored. To get the underlying mechanism, the Cl-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr(VI) with Cl - in Cl-LDH interlayer, isomorphic substitution of Mg 2+ with Cu 2+ , formation of Cu 2 Cl(OH) 3 precipitation, and the adsorption of Cr(VI) by Cu 2 Cl(OH) 3 . This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by Cl-LDH. Copyright © 2016. Published by Elsevier B.V.
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Chen, Gunng-Shinng; Lee, Shiao-Pieng; Huang, Shu-Fu; Chao, Shih-Chi; Chang, Chung-Yi; Wu, Gwo-Jang; Li, Chung-Hsing; Loh, Shih-Hurng
2018-06-01
Homeostasis of intracellular pH (pH i ) plays vital roles in many cell functions, such as proliferation, apoptosis, differentiation and metastasis. Thus far, Na + -H + exchanger (NHE), Na + -HCO 3 - co-transporter (NBC), Cl - /HCO 3 - exchanger (AE) and Cl - /OH - exchanger (CHE) have been identified to co-regulate pH i homeostasis. However, functional and biological pH i -regulators in human dental pulp stem cells (hDPSCs) have yet to be identified. Microspectrofluorimetry technique with pH-sensitive fluorescent dye, BCECF, was used to detect pH i changes. NH 4 Cl and Na + -acetate pre-pulse were used to induce intracellular acidosis and alkalosis, respectively. Isoforms of pH i -regulators were detected by Western blot technique. The resting pH i was no significant difference between that in HEPES-buffered (nominal HCO 3 - -free) solution or CO 2 /HCO 3 -buffered system (7.42 and 7.46, respectively). The pH i recovery following the induced-intracellular acidosis was blocked completely by removing [Na + ] o , while only slowed (-63%) by adding HOE694 (a NHE1 specific inhibitor) in HEPES-buffered solution. The pH i recovery was inhibited entirely by removing [Na + ] o , while adding HOE 694 pulse DIDS (an anion-transporter inhibitor) only slowed (-55%) the acid extrusion. Both in HEPES-buffered and CO 2 /HCO 3 -buffered system solution, the pH i recovery after induced-intracellular alkalosis was entirely blocked by removing [Cl - ] o . Western blot analysis showed the isoforms of pH i regulators, including NHE1/2, NBCe1/n1, AE1/2/3/4 and CHE in the hDPSCs. We demonstrate for the first time that resting pH i is significantly higher than 7.2 and meditates functionally by two Na + -dependent acid extruders (NHE and NBC), two Cl - -dependent acid loaders (CHE and AE) and one Na + -independent acid extruder(s) in hDPSCs. These findings provide novel insight for basic and clinical treatment of dentistry. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Atmospheric deposition effects on the chemistry of a stream in Northeastern Georgia
Buell, G.R.; Peters, N.E.
1988-01-01
The quantity and quality of precipitation and streamwater were measured from August 1985 through September 1986 in the Brier Creek watershed, a 440-ha drainage in the Southern Blue Ridge Province of northeastern Georgia, to determine stream sensitivity to acidic deposition. Precipitation samples collected at 2 sites had a volume-weighted average pH of 4.40 whereas stream samples collected near the mouth of Brier Creek had a discharge-weighted average pH of 6.70. Computed solute fluxes through the watershed and observed changes in streamwater chemistry during stormflow suggest that cation exchange, mineral weathering, SO42- adsorption by the soil, and groundwater discharge to the stream are probable factors affecting neutralization of precipitation acidity. Net solute fluxes for the watershed indicate that, of the precipitation input, > 99% of the H+, 93% of the NH4+ and NO3-, and 77% of the SO42- were retained. Sources within the watershed yielded base cations, Cl-, and HCO3- and accounted for 84, 47, and 100% of the net transport, respectively. Although streamwater SO42- and NO3- concentrations increased during stormflow, peak concentrations of these anions were much less than average concentrations in the precipitation. This suggests retention of these solutes occurs even when water residence time is short.The quantity and quality of precipitation and streamwater were measured from August 1985 through September 1986 in the Brier Creek watershed, a 440-ha drainage in the Southern Blue Ridge Province of northeastern Georgia, to determine stream sensitivity to acidic deposition. Precipitation samples collected at 2 sites had a volume-weighted average pH of 4.40 whereas stream samples collected near the mouth of Brier Creek had a discharge-weighted average pYH of 6.70. Computed solute fluxes through the watershed and observed changes in streamwater chemistry drying stormflow suggest that cation exchange, mineral weathering, SO42- adsorption by the soil, and groundwater discharge to the stream are probable factors affecting neutralization of precipitation acidity. Although streamwater SO42- and NO3- concentrations increased during stormflow, peak concentrations of these anions were much less than average concentrations in the precipitation. This suggests retention of these solutes occurs even when water residence time is short.
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Safe disposal of radioactive iodide ions from solutions by Ag2O grafted sodium niobate nanofibers.
Mu, Wanjun; Li, Xingliang; Liu, Guoping; Yu, Qianhong; Xie, Xiang; Wei, Hongyuan; Jian, Yuan
2016-01-14
Radioactive iodine isotopes are released into the environment by the nuclear industry and medical research institutions using radioactive materials, and have negative effects on organisms living within the ecosystem. Thus, safe disposal of radioactive iodine is necessary and crucial. For this reason, the uptake of iodide ions was investigated in Ag2O nanocrystal grafted sodium niobate nanofibers, which were prepared by forming a well-matched phase coherent interface between them. The resulting composite was applied as an efficient adsorbent for I(-) anions by forming an AgI precipitate, which also remained firmly attached to the substrates. Due to their one-dimensional morphology, the new adsorbents can be easily dispersed in liquids and readily separated after purification. This significantly enhances the adsorption efficiency and reduces the separation costs. The change in structure from the pristine sodium niobate to Ag2O anchored sodium niobate and to the used adsorbent was examined by using various characterization techniques. The effects of Ag(+) concentration, pH, equilibration time, ionic strength and competing ions on the iodide ion removal ability of the composite were studied. The Ag2O nanocrystal grafted sodium niobate adsorbent showed a high adsorption capacity and excellent selectivity for I(-) anions in basic solutions. Our results are useful for the further development of improved adsorbents for removing I(-) anions from basic wastewater.
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Removal of lead and phosphate ions from aqueous solutions by organo-smectite.
Bajda, Tomasz; Szala, Barbara; Solecka, Urszula
2015-01-01
Smectite has been modified using hexadecyltrimethyl ammonium bromide in an amount of double cationic exchange capacity. This alteration makes it possible to use organo-smectite as a sorbent to remove anionic forms. The experiment consisted of the interchangeable sorption of phosphate(V) and lead(II) by organo-smectite. Research was carried out with varying pH (2-5) and various concentrations (0.1-5 mmol/L). Organo-smectite with previously adsorbed lead ions removed more phosphate than the untreated organo-smectite. Experimental data show that lead is more likely to absorb on the organo-smectite than on the organo-smectite with previously adsorbed phosphate ions. It follows that the most effective use of the organo-smectite is through the sorption of first - Pb cations and then PO4 anions. With an increasing concentration of Pb(II) or P(V), the sorption efficiency increases. The maximum sorption efficiency of lead and phosphate ions is observed at pH 5. This enables the removal of harmful lead and phosphorus compounds from waste water and immobilizes them on the sorbent's surface. The alternating reactions of lead and phosphorus ions result in the crystallization of brompyromorphite Pb5(PO4)3Br.
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NASA Astrophysics Data System (ADS)
Liu, Xing; Liu, Hua-Ji; Cheng, Fa; Chen, Yu
2014-06-01
Oxidized graphene sheets (OGS) were treated with a hyperbranched polyethylenimine (PEI) under hydrothermal conditions to generate nanocomposites of graphene quantum dots (GQDs) functionalized with PEI (GQD-PEIs). The influence of the reaction temperature and the PEI/OGS feed ratio on the photoluminescence properties of the GQD-PEIs was studied. The obtained GQD-PEIs were characterized by TEM, dynamic light scattering, elemental analysis, FTIR, zeta potential measurements and 1H NMR spectroscopy, from which their structural information was inferred. Subsequently, isobutyric amide (IBAm) groups were attached to the GQD-PEIs through the amidation reaction of isobutyric anhydride with the PEI moieties, which resulted in GQD-PEI-IBAm nanocomposites. GQD-PEI-IBAm was not only thermoresponsive, but also responded to other stimuli, including inorganic salts, pH, and loaded organic guests. The cloud point temperature (Tcp) of aqueous solutions of GQD-PEI-IBAm could be modulated through changing the number of IBAm units in GQD-PEI-IBAm, by varying the type and concentration of the inorganic salts and loaded organic guests, or by varying the pH. All the obtained GQD-PEI-IBAm nanocomposites were photoluminescent, and their maximum emission wavelengths were not influenced by outside stimuli. Their emission intensities were influenced a little or negligibly by pH, traditional salting-out anions (Cl- and SO42-), and the relatively polar aspirin guest. However, the traditional salting-in I- anion and the more hydrophobic 1-pyrenebutyric acid (PBA) guest could effectively quench their fluorescence. 2D NOESY 1H NMR spectra verified that GQD-PEI-IBAm accommodated the relatively polar aspirin guest using the PEI-IBAm shell, but adsorbed the relatively hydrophobic PBA guest through the nanographene core. The release rate of the guest encapsulated by the thermoresponsive GQD is different below and above Tcp.Oxidized graphene sheets (OGS) were treated with a hyperbranched polyethylenimine (PEI) under hydrothermal conditions to generate nanocomposites of graphene quantum dots (GQDs) functionalized with PEI (GQD-PEIs). The influence of the reaction temperature and the PEI/OGS feed ratio on the photoluminescence properties of the GQD-PEIs was studied. The obtained GQD-PEIs were characterized by TEM, dynamic light scattering, elemental analysis, FTIR, zeta potential measurements and 1H NMR spectroscopy, from which their structural information was inferred. Subsequently, isobutyric amide (IBAm) groups were attached to the GQD-PEIs through the amidation reaction of isobutyric anhydride with the PEI moieties, which resulted in GQD-PEI-IBAm nanocomposites. GQD-PEI-IBAm was not only thermoresponsive, but also responded to other stimuli, including inorganic salts, pH, and loaded organic guests. The cloud point temperature (Tcp) of aqueous solutions of GQD-PEI-IBAm could be modulated through changing the number of IBAm units in GQD-PEI-IBAm, by varying the type and concentration of the inorganic salts and loaded organic guests, or by varying the pH. All the obtained GQD-PEI-IBAm nanocomposites were photoluminescent, and their maximum emission wavelengths were not influenced by outside stimuli. Their emission intensities were influenced a little or negligibly by pH, traditional salting-out anions (Cl- and SO42-), and the relatively polar aspirin guest. However, the traditional salting-in I- anion and the more hydrophobic 1-pyrenebutyric acid (PBA) guest could effectively quench their fluorescence. 2D NOESY 1H NMR spectra verified that GQD-PEI-IBAm accommodated the relatively polar aspirin guest using the PEI-IBAm shell, but adsorbed the relatively hydrophobic PBA guest through the nanographene core. The release rate of the guest encapsulated by the thermoresponsive GQD is different below and above Tcp. Electronic supplementary information (ESI) available: Elemental analysis data; typical FTIR spectra; typical photographs of the GQD solution before and after phase transition; typical luminescence photographs, and typical photoluminescence spectra. See DOI: 10.1039/c4nr00739e
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Del Caño, Rafael; Mateus, Lucia; Sánchez-Obrero, Guadalupe; Sevilla, José Manuel; Madueño, Rafael; Blázquez, Manuel; Pineda, Teresa
2017-11-01
The identification of the factors that dictate the formation and physicochemical properties of protein-nanomaterial bioconjugates are important to understand their behavior in biological systems. The present work deals with the formation and characterization of bioconjugates made of the protein hemoglobin (Hb) and gold nanoparticles (AuNP) capped with three different molecular layers (citrate anions (c), 6-mercaptopurine (MP) and ω-mercaptoundecanoic acid (MUA)). The main focus is on the behavior of the bioconjugates in aqueous buffered solutions in a wide pH range. The stability of the bioconjugates have been studied by UV-visible spectroscopy by following the changes in the localized surface resonance plasmon band (LSRP), Dynamic light scattering (DLS) and zeta-potential pH titrations. It has been found that they are stable in neutral and alkaline solutions and, at pH lower than the protein isoelectric point, aggregation takes place. Although the surface chemical properties of the AuNPs confer different properties in respect to colloidal stability, once the bioconjugates are formed their properties are dictated by the Hb protein corona. The protein secondary structure, as analyzed by Attenuated total reflectance infrared (ATR-IR) spectroscopy, seems to be maintained under the conditions of colloidal stability but some small changes in protein conformation take place when the bioconjugates aggregate. These findings highlight the importance to keep the protein structure upon interaction with nanomaterials to drive the stability of the bioconjugates. Copyright © 2017 Elsevier Inc. All rights reserved.
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Zhang, Shengxiao; Zhang, Yuanyuan; Bi, Guoming; Liu, Junshen; Wang, Zhigang; Xu, Qiang; Xu, Hui; Li, Xiaoyan
2014-04-15
The polydopamine polymer decorated with magnetic nanoparticles (Fe3O4/PDA) was synthesized and applied for removal of multiple pollutants. The resulted Fe3O4/PDA was characterized with elemental analysis, thermo-gravimetric analyses, vibrating sample magnetometer, high resolution transmission electron microscope, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy. The self-polymerization of dopamine could be completed within 8h, and Fe3O4 nanoparticles were embedded into PDA polymer. Superparamagnetism and large saturation magnetization facilitated collection of sorbents with a magnet. Based on the catechol and amine groups, the PDA polymer provided multiple interactions to combine with pollutants. To investigate the adsorption ability of Fe3O4/PDA, heavy metal ions and dyes were selected as target pollutants. The adsorption of pollutants was pH dependent due to the variation of surface charges at different solution pH. The removal efficiencies of cation pollutants enhanced with solution pH increasing, and that of anion pollutant was just the opposite. Under the optimal solution pH, the maximum adsorption capacity calculated from Langmuir adsorption isotherm for methylene blue, tartrazine, Cu(2+), Ag(+), and Hg(2+) were 204.1, 100.0, 112.9, 259.1, and 467.3 mg g(-1), respectively. The Fe3O4/PDA shows great potential for multiple pollutants removal, and this study is the first application of PDA polymer in environmental remediation. Copyright © 2014 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Avazbaeva, Zaure; Sung, Woongmo; Lee, Jonggwan
In this paper, it has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284–285, 166–174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure–area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as comparedmore » to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl– counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.« less
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Impact of pH on the structure and function of neural cadherin.
Jungles, Jared M; Dukes, Matthew P; Vunnam, Nagamani; Pedigo, Susan
2014-12-02
Neural (N-) cadherin is a transmembrane protein within adherens junctions that mediates cell-cell adhesion. It has 5 modular extracellular domains (EC1-EC5) that bind 3 calcium ions between each of the modules. Calcium binding is required for dimerization. N-Cadherin is involved in diverse processes including tissue morphogenesis, excitatory synapse formation and dynamics, and metastasis of cancer. During neurotransmission and tumorigenesis, fluctuations in extracellular pH occur, causing tissue acidosis with associated physiological consequences. Studies reported here aim to determine the effect of pH on the dimerization properties of a truncated construct of N-cadherin containing EC1-EC2. Since N-cadherin is an anionic protein, we hypothesized that acidification of solution would cause an increase in stability of the apo protein, a decrease in the calcium-binding affinity, and a concomitant decrease in the formation of adhesive dimer. The stability of the apo monomer was increased and the calcium-binding affinity was decreased at reduced pH, consistent with our hypothesis. Surprisingly, analytical SEC studies showed an increase in calcium-induced dimerization as solution pH decreased from 7.4 to 5.0. Salt-dependent dimerization studies indicated that electrostatic repulsion attenuates dimerization affinity. These results point to a possible electrostatic mechanism for moderating dimerization affinity of the Type I cadherin family. Extrapolating these results to cell adhesion in vivo leads to the assertion that decreased pH promotes adhesion by N-cadherin, thereby stabilizing synaptic junctions.
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Process for recovering chaotropic anions from an aqueous solution also containing other ions
Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.
1999-01-01
A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.
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Process for recovering chaotropic anions from an aqueous solution also containing other ions
Rogers, R.; Horwitz, E.P.; Bond, A.H.
1999-03-30
A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.
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Development of low-level liquid-waste-treatment systems, October 1981 - March 1982
NASA Astrophysics Data System (ADS)
Williams, M. K.; Colvin, C. M.
1982-05-01
A plant design for a reverse osmosis (RO) membrane unit was completed. The design includes a conceptual diagram, specifications for a RO unit producing 40 gal/min of permeated product, a list of radioisotopes tested on RO units and the rejections achieved, a discussion of the principle of RO, a discussion of the upper limits of cation and anion concentrations (there are no lower limits), a discussion of membrane configurations and porosities, a discussion of factors affecting membranes, a section on calculating the membrane area needed for a particular application, and capital and operating cost calculations. The three factors found to affect the adsorption of cobalt on ion exchange resins were investigated in an interaction effects design experiment. These factors are solution pH, and sulfite and ammonium concentrations. Greater than 99% of the cobalt can usually be removed from solutions at a pH between 3 and 6. A design for an ion-exchange pilot plant was completed.
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Effects of pH and anions on the sorption of selenium ions onto magnetite.
Kim, Seung Soo; Min, Je Ho; Lee, Jae Kwang; Baik, Min Hoon; Choi, Jong-Won; Shin, Hyung Seon
2012-02-01
This study analyzes the influence of carbonate and silicate, which are generally abundant in granitic groundwater, on the sorption of selenium ions onto magnetite in order to understand the behaviors of selenium in a radioactive waste repository. Selenite was sorbed onto magnetite very well below pH 10, but silicate and carbonate hindered the sorption of selenite onto magnetite. On the other hand, little selenate was sorbed onto magnetite in neutral and weak alkaline solutions of 0.02 M NaNO(3) or NaClO(4), matching the ionic strength in a granitic groundwater, even though silicate or carbonate was not contained in the solutions. The surface complexation constants between selenite and magnetite were obtained by using a geochemical program, FITEQL 4.0, from the experimental data, and the formation of an inner-sphere surface complex such as =FeOSeO(2)(-) was suggested for the sorption of selenite onto magnetite from the diffuse double layer model calculation. Copyright © 2011 Elsevier Ltd. All rights reserved.
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Influence of dispersing agents and solution conditions on the solubility of crude kaolin.
Zaman, Abbas A; Mathur, Sharad
2004-03-01
Experiments measuring the solubility of kaolin particles in terms of the concentration of aluminum and silicon ions in supernatant were carried out as a function of the pH of the slurry over a wide range of dosages of different dispersing agents varying from 0.5 to 12 mg/(g solids). The concentrations of the metal ions in supernatant were found to be strongly affected by the type and the dosage of the dispersants and pH of the solution. In this study, the mechanism of the reaction between the dispersing agents and kaolin particles was studied and the dissolution capacities of metal ions (aluminum and silicon) were identified from kaolin particles in the absence and presence of dispersing agents. The three anionic dispersing agents used were sodium polyacrylate (Na-PAA), sodium hexametaphosphate (Na-HMP), and sodium silicate (Na-silicate), based on the industrial application of these agents and their ability to produce a stable dispersion for this purpose.
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Sheng, Guodong; Hu, Jun; Wang, Xiangke
2008-10-01
Diatomite has a number of unique physicochemical properties and has diversified industrial uses. Natural diatomite has been tested as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that sorption of Th(IV) is strongly dependent on ionic strength at pH<3, and is independent of ionic strength at pH>3. Outer-sphere complexation or ion exchange may be the main sorption mechanism of Th(IV) to diatomite at low pH values, whereas the sorption of Th(IV) at pH>3 is mainly dominated by inner-sphere complexation or precipitation. The competition for Th(IV) between aqueous or surface adsorbed anions (e.g., herein ClO(4)(-), NO(3)(-) and Cl(-)) and surface functional groups of diatomite is important for Th(IV) sorption. The thermodynamic data (DeltaH(0), DeltaS(0), DeltaG(0)) are calculated from the temperature-dependent sorption isotherms. The results suggest that sorption process of Th(IV) on diatomite is spontaneous and endothermic.
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Buekers, Jurgen; Mertens, Jelle; Smolders, Erik
2010-06-01
Previous studies have shown that toxicity of cationic trace metals in soil is partially confounded by effects of the accompanying anions. A similar assessment is reported here for toxicity of an oxyanion, i.e., molybdate (MoO(4) (2-)), the soil toxicity of which is relatively unexplored. Solubility and toxicity were compared between the soluble sodium molybdate (Na(2)MoO(4)) and the sparingly soluble molybdenum trioxide (MoO(3)). Confounding effects of salinity were excluded by referencing the Na(2)MoO(4) effect to that of sodium chloride (NaCl). The pH decrease from the acid MoO(3) amendment was equally referenced to a hydrochloric (HCl) treatment or a lime-controlled MoO(3) treatment. The concentrations of molybdenum (Mo) in soil solution or calcium chloride (CaCl(2)) 0.01 M extracts were only marginally affected by either MoO(3) or Na(2)MoO(4) as an Mo source after 10 to 13 days of equilibration. Effects of Mo on soil nitrification were fully confounded by associated changes in salinity or pH. Effects of Mo on growth of wheat seedlings (Triticum aestivum L) were more pronounced than those on nitrification, and toxicity thresholds were unaffected by the form of added Mo. The Mo thresholds for wheat growth were not confounded by pH or salinity at incipient toxicity. It is concluded that oxyanion toxicity might be confounded in relatively insensitive tests for which reference treatments should be included. Copyright 2010 SETAC.
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Sellés-Marchart, Susana; Casado-Vela, Juan; Bru-Martínez, Roque
2007-08-15
The effects of detergents, trypsin and fatty acids on structural and functional properties of a pure loquat fruit latent polyphenol oxidase have been studied in relation to its regulation. Anionic detergents activated PPO at pH 6.0 below critical micelle concentration (cmc), but inhibited at pH 4.5 well above cmc. This behavior is due to a detergent-induced pH profile alkaline shift, accompanied by changes of intrinsic fluorescence of the protein. Gel filtration experiments demonstrate the formation of PPO-SDS mixed micelles. Partial PPO proteolysis suggest that latent PPO losses an SDS micelle-interacting region but conserves an SDS monomer-interacting site. Unsaturated fatty acids inhibit PPO at pH 4.5, the strongest being linolenic acid while the weakest was gamma-linolenic acid for both, the native and the trypsin-treated PPO. Down-regulation of PPO activity by anionic amphiphiles is discussed based on both, the pH profile shift induced upon anionic amphiphile binding and the PPO interaction with negatively charged membranes.
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Sikora, Adam; Zielonka, Jacek; Adamus, Jan; Debski, Dawid; Dybala-Defratyka, Agnieszka; Michalowski, Bartosz; Joseph, Joy; Hartley, Richard C.; Murphy, Michael P.; Kalyanaraman, Balaraman
2013-01-01
Aromatic boronic acids react rapidly with peroxynitrite (ONOO−) to yield phenols as major products. This reaction was used to monitor ONOO− formation in cellular systems. Previously, we proposed that the reaction between ONOO− and arylboronates (PhB(OH)2) yields a phenolic product (major pathway) and a radical pair PhB(OH)2O•−…•NO2 (minor pathway). [Sikora A. et al., Chem Res Toxicol 24, 687-97, 2011]. In this study, we investigated the influence of a bulky triphenylphosphonium (TPP) group on the reaction between ONOO− and mitochondria-targeted arylboronate isomers (o-, m-, and p-MitoPhB(OH)2). Results from the electron paramagnetic resonance (EPR) spin-trapping experiments unequivocally showed the presence of a phenyl radical intermediate from meta and para isomers, and not from the ortho isomer. The yield of o-MitoPhNO2 formed from the reaction between o-MitoPhB(OH)2 and ONOO− was not diminished by phenyl radical scavengers, suggesting a rapid fragmentation of the o-MitoPhB(OH)2O•− radical anion with subsequent reaction of the resulting phenyl radical with •NO2 in the solvent cage. The DFT quantum mechanical calculations showed that the energy barrier for the dissociation of o-MitoPhB(OH)2O•− radical anion is significantly lower than that of m-MitoPhB(OH)2O•− and p-MitoPhB(OH)2O•− radical anions. The nitrated product, o-MitoPhNO2, is not formed by nitrogen dioxide radical generated by myeloperoxidase in the presence of nitrite anion and hydrogen peroxide, indicating that this specific nitrated product may be used as a diagnostic marker product for ONOO−. Incubation of o-MitoPhB(OH)2 with RAW 264.7 macrophages activated to produce ONOO− yielded the corresponding phenol o-MitoPhOH as well as the diagnostic nitrated product, o-MitoPhNO2. We conclude that the ortho isomer probe reported here is most suitable for specific detection of ONOO− in biological systems. PMID:23611338
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NASA Astrophysics Data System (ADS)
Dutta, Anisha; Boruah, Bornali; Manna, Arun K.; Gohain, Biren; Saikia, Palash M.; Dutta, Robin K.
2013-03-01
A newly observed UV band of aqueous curcumin, a biologically important molecule, in presence of anionic surfactants, viz., sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and sodium dodecylsulfonate (SDSN) in buffered aqueous solutions has been studied experimentally and theoretically. The 425 nm absorption band of curcumin disappears and a new UV-band is observed at 355 nm on addition of the surfactants in the submicellar concentration range which is reversed as the surfactant concentration approaches the critical micelle concentration (CMC). The observed spectral absorption, fluorescence intensity and surface tension behavior, under optimal experimental conditions of submicellar concentration ranges of the surfactants in the pH range of 2.00-7.00, indicate that the new band is due to the β-diketo tautomer of curcumin stabilized by interactions between curcumin and the anionic surfactants. The stabilization of the diketo tautomer by submicellar anionic surfactants described here as well as by submicellar cationic surfactant, reported recently, is unique as this is the only such behavior observed in presence of submicellar surfactants of both charge types. The experimental results are in good agreement with the theoretical calculations using ab initio density functional theory combined with time dependent density functional theory (TD-DFT) calculations.
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Studies of pilocarpine:carbomer intermolecular interactions.
Zoppi, Ariana; Linck, Yamila Garro; Monti, Gustavo A; Genovese, Diego B; Jimenez Kairuz, Alvaro F; Manzo, Rubén H; Longhi, Marcela R
2012-05-10
The interactions between pilocarpine (PIL) and the anionic polyelectrolyte carbomer (CBR) were investigated. The effects of the chemical interactions on the chemical stability of the drug also were evaluated. The binary system was characterized by nuclear magnetic resonance techniques, Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction, scanning electron microscopy (SEM) and thermal analysis. The experiments showed that the complex, prepared by freeze-drying, is a solid amorphous form different from its precursors, thereby offering an interesting alternative for the preparation of extended release matrices. The solution stability of PIL was studied at pH 7 and 8, at 70 °C. The PIL solution stability was evaluated alone and in the presence of CBR. Results indicated that the drug in the presence of the polymer is 3.3 and 3.5 times more stable, at pH 7 and pH 8, respectively, than the drug without CBR. The activation energy and the frequency factor, according to Arrhenius plot, were estimated to be 13.9 ± 0.4 and 14.8 ± 0.5 kcalmol(-1), and 6.1 ± 0.3 and 7.6 ± 0.3, with and without the polymer, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.
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Saikia, Jiban; Saha, Bedabrata; Das, Gopal
2011-02-15
Malachite nanoparticles of 100-150 nm have been efficiently and for the first time used as an adsorbent for the removal of toxic arsenate and chromate. We report a high adsorption capacity for chromate and arsenate on malachite nanoparticle from both individual and mixed solution in pH ∼4-5. However, the adsorption efficiency decreases with the increase of solution pH. Batch studies revealed that initial pH, temperature, malachite nanoparticles dose and initial concentration of chromate and arsenate were important parameters for the adsorption process. Thermodynamic analysis showed that adsorption of chromate and arsenate on malachite nanoparticles is endothermic and spontaneous. The adsorption of these anions has also been investigated quantitatively with the help of adsorption kinetics, isotherm, and selectivity coefficient (K) analysis. The adsorption data for both chromate and arsenate were fitted well in Langmuir isotherm and preferentially followed the second order kinetics. The binding affinity of chromate is found to be slightly higher than arsenate in a competitive adsorption process which leads to the comparatively higher adsorption of chromate on malachite nanoparticles surface. Copyright © 2010 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Wichmann, Kathrin A.; Söhnel, Tilo; Cooper, Garth J. S.
2012-03-01
N1,N10-diacetyltriethylenetetramine (DAT) is a recently-discovered major in vivo metabolite of triethylenetetramine (TETA), a highly-selective CuII chelator currently under clinical development as a novel first-in-class therapeutic for the cardiovascular, renal and retinal complications of diabetes mellitus. Characterisation of DAT is an integral aspect of the pharmacological work-up required to support this clinical development programme and, to our knowledge, no previous synthesis for it has been published. Here we report the synthesis of DAT dihydrochloride (DAT·2 HCl); its crystal structure as determined by X-ray single-crystal (XRD) and powder diffraction (XRPD); and protonation constants and species distribution in aqueous solution, which represents the different protonation states of DAT at different pH values. The crystal structure of DAT·2 HCl reveals 3D-assemblies of alternating 2D-layers comprising di-protonated DAT strands and anionic species, which form an extensive hydrogen-bond network between amine groups, acetyl groups, and chloride anions. Potentiometric titrations show that HDAT+ is the physiologically relevant state of DAT in solution. These findings contribute to the understanding of TETA's pharmacology and to its development for the experimental therapeutics of the diabetic complications.
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Ammonium removal from aqueous solutions by using natural Chinese (Chende) zeolite as adsorbent.
Huang, Haiming; Xiao, Xianming; Yan, Bo; Yang, Liping
2010-03-15
This paper presents a study of the removal of ammonium ion from aqueous solutions using natural Chinese (Chende) zeolite. A series of experiments was conducted to examine the effects of solution pH, particle size, contact time, adsorbent dosage, and the presence of other cation- and anion species on ammonium removal. The findings indicated that these parameters named had a significant effect on the removal of ammonium by the zeolite. The effect of other cations on the removal of ammonium followed the order of preference Na(+)>K(+)>Ca(2+)>Mg(2+) at identical mass concentrations, and the effect of the presence of individual anions followed the order of preference carbonate>chloride>sulfate>phosphate at identical mass concentrations of ammonium ions. Kinetic analysis showed that the adsorption of ammonium on zeolite at different ranges of particle size well followed the pseudo-second-order model and followed the intra-particle diffusion model only during the initial 60 min of the adsorption process. Equilibrium isotherm data was fitted to the linear Langmuir- and Freundlich models with the latter model providing the better description of the process (R(2)=0.991-0.997) compared to the former (R(2)=0.902-0.989). (c) 2009 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Dang, N. T.; Quan, P. T.; Sang, P. H. P.
2017-06-01
This article studies the use of acacia auriculiformis wood sawdust modified with 4,5-dihydroxy-1,3-bis (methoxymethyl) imidazolidin-2-one (m-DMDHEU) and choline chloride for separating CrO4 2- and H2AsO4 - ions in water. NaOH 0.2N/ethanol 70° solution was used to remove lignin from the raw material, the material was then immersed in m-DMDHEU/choline chloride aqueous solution for 24 hours, after that the material was activated at 140oC for one hour. The ability to adsorb and exchange ions of the material was examined using solutions containing CrO4 2- and H2AsO4 - ions in different conditions. The results suggested that the ability to separate CrO4 2- and H2AsO4 - ions of the modified material was better than that of anion resin at pH = 7.0; the chromate adsorption capacity was the highest in acidic condition; the presence of arsenate (V) anions had no effect on the ability to remove chromate. Lastly, the modified material was used to treat water samples containing concentrations of arsenic similar to groundwater in several arsenic-contaminated areas of Vietnam.
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Appelo, C A J; Vinsot, A; Mettler, S; Wechner, S
2008-10-23
A borehole in the Callovo-Oxfordian clay rock in ANDRA's underground research facility was sampled during 1 year and chemically analyzed. Diffusion between porewater and the borehole solution resulted in concentration changes which were modeled with PHREEQC's multicomponent diffusion module. In the model, the clay rock's pore space is divided in free porewater (electrically neutral) and diffuse double layer water (devoid of anions). Diffusion is calculated separately for the two domains, and individually for all the solute species while a zero-charge flux is maintained. We explain how the finite difference formulas for radial diffusion can be translated into mixing factors for solutions. Operator splitting is used to calculate advective flow and chemical reactions such as ion exchange and calcite dissolution and precipitation. The ion exchange reaction is formulated in the form of surface complexation, which allows distributing charge over the fixed sites and the diffuse double layer. The charge distribution affects pH when calcite dissolves, and modeling of the experimental data shows that about 7% of the cation exchange capacity resides in the diffuse double layer. The model calculates the observed concentration changes very well and provides an estimate of the pristine porewater composition in the clay rock.
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Retention and transport of graphene oxide in water-saturated limestone media.
Dong, Shunan; Sun, Yuanyuan; Gao, Bin; Shi, Xiaoqing; Xu, Hongxia; Wu, Jianfeng; Wu, Jichun
2017-08-01
In this work, column experiments were conducted to investigate the transport characteristics of graphene oxide (GO) nanoparticles in limestone media under various electrolytes, solution pH, and humic acid (HA) concentration conditions. In the limestone media, GO exhibited relatively low mobility with the mass recovery rate lower than 65.2%, even when solution ionic strength was low. The presence of HA enhanced its mobility. In addition, the presence of S 2- , a divalent anion, also promoted GO transport in limestone media compared to Cl - under similar ionic strength conditions through neutralizing more positive charge and thus diminishing the cation bridging. Solution pH showed slight effect on the transport of GO in limestone with the mass recovery range from 40.3% to 51.7%. Over all, decreases in solution pH, HA concentration and increases in solution ionic strength reduced the mobility of GO in the limestone media under the tested conditions. These results indicated both environmental conditions and media characteristics played important roles in controlling GO fate and transport in porous media. The one-site kinetic deposition model was applied to describe the interactions between the GO and limestone media and model simulations fitted the observed experimental data very well. As limestone is an important component of aquiferous media in subsurface, findings from this study elucidated the key factors and processes controlling the fate of GO particles in limestone media, which can inform the prediction and assessment of the risks of GO in groundwater environment. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Mécanismes de la non-stœchiométrie dans les nouveaux supraconducteurs à haute Tboldmath_c
NASA Astrophysics Data System (ADS)
Hervieu, M.; Michel, C.; Martin, C.; Huvé, M.; van Tendeloo, G.; Maignan, A.; Pelloquin, D.; Goutenoire, F.; Raveau, B.
1994-11-01
Two new families of high T_c superconductors have been recently discovered : ll the mercury based oxides gg and the ll oxycarbonates gg. The main characteristics of the structural mechanisms were studied by high resolution electron microscopy. This paper deals with the description of the numerous order-disorder phenomena which have been observed on the cation and anion networks. Deux nouvelles familles de supraconducteurs ont récemment vu le jour : ll les oxydes à base de mercure gg et les ll oxycarbonates gg. Les caractéristiques essentielles des mécanismes structuraux ont été étudiées par microscopie électronique haute résolution. Les nombreux phénomènes ordre-désordre observés tant sur le réseau des cations que sur celui des anions sont exposés.
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Hennig, Christoph; Ikeda-Ohno, Atsushi; Emmerling, Fanziska; Kraus, Werner; Bernhard, Gert
2010-04-21
The limiting U(IV) carbonate species in aqueous solution was investigated by comparing its structure parameters with those of the complex preserved in a crystal structure. The solution species prevails in aqueous solution of 0.05 M U(IV) and 1 M NaHCO(3) at pH 8.3. Single crystals of Na(6)[U(CO(3))(5)].12H(2)O were obtained directly from this mother solution. The U(IV) carbonate complex in the crystal structure was identified as a monomeric [U(CO(3))(5)](6-) anionic complex. The interatomic distances around the U(IV) coordination polyhedron show average distances of U-O = 2.461(8) A, U-C = 2.912(4) A and U-O(dist) = 4.164(6) A. U L(3)-edge EXAFS spectra were collected from the solid Na(6)[U(CO(3))(5)].12H(2)O and the corresponding solution. The first shell of the Fourier transforms (FTs) revealed, in both samples, a coordination of ten oxygen atoms at an average U-O distance of 2.45 +/- 0.02 A, the second shell originates from five carbon atoms with a U-C distance of 2.91 +/- 0.02 A, and the third shell was fit with single and multiple scattering paths of the distal oxygen at 4.17 +/- 0.02 A. These data indicate the identity of the [U(CO(3))(5)](6-) complex in solid and solution state. The high negative charge of the [U(CO(3))(5)](6-) anion is compensated by Na(+) cations. In solid state the Na(+) cations form a bridging network between the [U(CO(3))(5)](6-) units, while in liquid state the Na(+) cations seem to be located close to the anionic complex. The average metal-oxygen distances of the coordination polyhedron show a linear correlation to the radius contraction of the neighbouring actinide(IV) ions and indicate the equivalence of the [An(CO(3))(5)](6-) coordination within the series of thorium, uranium, neptunium and plutonium.
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Lu, Qinghong; Ku, Mannching Sherry
2012-03-01
The stability in solution of HKI-272 (Neratinib) was studied as a function of pH. The drug is most stable from pH 3 to 4, and degradation rate increases rapidly around pH 6 and appears to approach a maximum asymptotic limit in the range of pH 812. Pseudo first-order reaction kinetics was observed at all pH values. The structure of the major degradation product indicates that it is formed by a cascade of reactions within the dimethylamino crotonamide group of HKI-272. It is assumed that the rate-determining step is the initial isomerization from allyl amine to enamine functionality, followed by hydrolysis and subsequent cyclization to a stable lactam. The maximum change in degradation rate as a function of pH occurs at about pH 6, which corresponds closely to the theoretical pKa value of the dimethylamino group of HKI-272 when accounting for solvent/temperature effects. The observed relationship between pH and degradation rate is discussed, and a self-catalyzed mechanism for the allylamine-enamine isomerization reaction is proposed. The relevance of these findings to other allylamine drugs is discussed in terms of the relative stability of the allylic anion intermediate through which, the isomerization occurs.
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Origin of the instability of octadecylamine Langmuir monolayer at low pH
Avazbaeva, Zaure; Sung, Woongmo; Lee, Jonggwan; ...
2015-11-30
In this paper, it has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284–285, 166–174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure–area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as comparedmore » to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl– counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.« less
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Pérez-Isidoro, Rosendo; Ruiz-Suárez, J C
2016-09-01
We study how zwitterionic and anionic biomembrane models interact with neurotransmitters (NTs) and anesthetics (ATs) in the presence of Ca(2+) and different pH conditions. As NTs we used acetylcholine (ACh), γ-aminobutyric acid (GABA), and l-glutamic acid (LGlu). As ATs, tetracaine (TC), and pentobarbital (PB) were employed. By using differential scanning calorimetry (DSC), we analyzed the changes such molecules produce in the thermal properties of the membranes. We found that calcium and pH play important roles in the interactions of NTs and ATs with the anionic lipid membranes. Changes in pH promote deprotonation of the phosphate groups in anionic phospholipids inducing electrostatic interactions between them and NTs; but if Ca(2+) ions are in the system, these act as bridges. Such interactions impact the physical properties of the membranes in a similar manner that anesthetics do. Beyond the usual biochemical approach, we claim that these effects should be taken into account to understand the excitatory-inhibitory orchestrated balance in the nervous system. Copyright © 2016 Elsevier B.V. All rights reserved.
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Nie, Mengyan; Wharton, Julian A.; Cranny, Andy; Harris, Nick R.; Wood, Robert J.K.; Stokes, Keith R.
2013-01-01
The ability to predict structural degradation in-service is often limited by a lack of understanding of the evolving chemical species occurring within a range of different microenvironments associated with corrosion sites. Capillary electrophoresis (CE) is capable of analysing nanolitre solution volumes with widely disparate concentrations of ionic species, thereby producing accurate and reliable results for the analysis of the chemical compositions found within microenvironment corrosion solutions, such as those found at crevice and pit corrosion sites. In this study, CE with contactless conductivity detection (CCD) has been used to characterize pitting and crevice corrosion solution chemistries for the first time. By using the capillary electrophoresis with contactless conductivity detection (CE-CCD) system, direct and simultaneous detection of seven metal cations (Cu2+, Ni2+, Fe3+, Fe2+, Cr3+, Mn2+, and Al3+) and chloride anions was achieved with a buffer solution of 10 mM 2,6-pyridinedicarboxylic acid and 0.5 mM cetyltrimethylammonium hydroxide at pH 4 using a pre-column complexation method. The detection limits obtained for the metal cations and chloride anions were 100 and 10 ppb, respectively. The CE-CCD methodology has been demonstrated to be a versatile technique capable of speciation and quantifying the ionic species generated within artificial pit (a pencil electrode) and crevice corrosion geometries for carbon steels and nickel-aluminium bronze, thus allowing the evolution of the solution chemistry to be assessed with time and the identification of the key corrosion analyte targets for structural health monitoring. PMID:28788335
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Sirichai, S; de Mello, A J
2001-01-01
The separation and detection of both print and film developing agents (CD-3 and CD-4) in photographic processing solutions using chip-based capillary electrophoresis is presented. For simultaneous detection of both analytes under identical experimental conditions a buffer pH of 11.9 is used to partially ionise the analytes. Detection is made possible by indirect fluorescence, where the ions of the analytes displace the anionic fluorescing buffer ion to create negative peaks. Under optimal conditions, both analytes can be analyzed within 30 s. The limits of detection for CD-3 and CD-4 are 0.17 mM and 0.39 mM, respectively. The applicability of the method for the analysis of seasoned photographic processing developer solutions is also examined.
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METHOD OF PROCESSING MONAZITE SAND
Welt, M.A.; Smutz, M.
1958-08-26
A process is described for recovering thorium, uranium, and rare earth values from monazite sand. The monazite sand is first digested with sulfuric acid and the resulting "monazite sulfate" solution is adjusted to a pH of between 0.4 and 3.0, and oxalate anions are added causing precipitation of the thorium and the rare earths as the oxalates. The oxalate precipitate is separated from the uranium containing supernatant solution, and is dried and calcined to the oxides. The thorium and rare earth oxides are then dissolved in nitric acid and the solution is contacted with tribntyl phosphate whereby an organic extract phase containing the cerium and thorium values is obtained, together with an aqueous raffinate containing the other rare earth values. The organic phase is then separated from the aqueous raffinate and the cerium and thorium are back extracted with an aqueous medium.
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Griffiths, Peter C; Paul, Alison; Fallis, Ian A; Wellappili, Champa; Murphy, Damien M; Jenkins, Robert; Waters, Sarah J; Nilmini, Renuka; Heenan, Richard K; King, Stephen M
2007-10-15
The physical properties of weak polyelectrolytes may be tailored via hydrophobic modification to exhibit useful properties under appropriate pH and ionic strength conditions as a consequence of the often inherently competing effects of electrostatics and hydrophobicity. Pulsed-gradient spin-echo NMR (PGSE-NMR), electron paramagnetic resonance (EPR), small-angle neutron scattering (SANS) surface tension, fluorescence, and pH titration have been used to examine the solution conformation and aggregation behavior of a series of hydrophobically modified hyperbranched poly(ethylene imine) (PEI) polymers in aqueous solution, and their interaction with sodium dodecylsulfate (SDS). PGSE-NMR gave a particularly insightful picture of the apparent molecular weight distribution. The presence of the hydrophobes led to a lower effective charge on the polymer at any given pH, compared to the (parent) nonmodified samples. Analysis of the SANS data showed that the propensity to form highly elliptical or rod-like aggregates at higher pHs, reflecting both the changes in protonation behavior induced by the hydrophobic modification and an hydrophobic interaction, but that these structures were disrupted with decreasing pH (increasing charge). The parent samples were not surface active yet the hydrophobically modified samples show pronounced surface activity and the presence of small hydrophobic domains. The surface activity increased with an increase in the degree of modification. On addition of SDS, the onset of the formation of polymer/surfactant complexes was insensitive to the degree of modification with the resultant PEI/SDS complexes resembling the size and shape of simple SDS micelles. Indeed, the presence of the SDS effectively nullifies the effects of the hydrophobe. Hydrophobic modification is therefore a viable option to tailor pH dependent properties, whose effects may be removed by the presence of surfactant.
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Lee, Seung-Chan; Kang, Jin-Kyu; Sim, Eun-Hye; Choi, Nag-Choul; Kim, Song-Bae
2017-11-10
The aim of this study was to investigate Cr(VI) removal from chromium-plating rinse water using modacrylic anion-exchange fibers (KaracaronTM KC31). Batch experiments were performed with synthetic Cr(VI) solutions to characterize the KC31 fibers in Cr(VI) removal. Cr(VI) removal by the fibers was affected by solution pH; the Cr(VI) removal capacity was the highest at pH 2 and decreased gradually with a pH increase from 2 to 12. In regeneration and reuse experiments, the Cr(VI) removal capacity remained above 37.0 mg g -1 over five adsorption-desorption cycles, demonstrating that the fibers could be successfully regenerated with NaCl solution and reused. The maximum Cr(VI) removal capacity was determined to be 250.3 mg g -1 from the Langmuir model. In Fourier-transform infrared spectra, a Cr = O peak newly appeared at 897 cm -1 after Cr(VI) removal, whereas a Cr-O peak was detected at 772 cm -1 due to the association of Cr(VI) ions with ion-exchange sites. X-ray photoelectron spectroscopy analyses demonstrated that Cr(VI) was partially reduced to Cr(III) after the ion exchange on the surfaces of the fibers. Batch experiments with chromium-plating rinse water (Cr(VI) concentration = 1178.8 mg L -1 ) showed that the fibers had a Cr(VI) removal capacity of 28.1-186.4 mg g -1 under the given conditions (fiber dose = 1-10 g L -1 ). Column experiments (column length = 10 cm, inner diameter = 2.5 cm) were conducted to examine Cr(VI) removal from chromium-plating rinse water by the fibers under flow-through column conditions. The Cr(VI) removal capacities for the fibers at flow rates of 0.5 and 1.0 mL min -1 were 214.8 and 171.5 mg g -1 , respectively. This study demonstrates that KC31 fibers are effective in the removal of Cr(VI) ions from chromium-plating rinse water.
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NASA Astrophysics Data System (ADS)
Cheng, Ling-Li; Wang, Mei; Zhu, Hui; Li, Kun; Zhu, Rong-Rong; Sun, Xiao-Yu; Yao, Si-De; Wu, Qing-Sheng; Wang, Shi-Long
2009-09-01
Using 266 nm laser flash photolysis it has been demonstrated that Berberine (BBR) in aqueous solution is ionized via a mono-photonic process giving a hydrated electron, anion radical that formed by hydrated electron react with steady state of BBR, and neutral radical that formed from rapid deprotonation of the radical cation of BBR. The quantum yield of photoionization is determined to be 0.03 at room temperature with KI solution used as a reference. Furthermore utilizing pH changing method and the SO 4rad - radical oxidation method, the assignment of radical cation of BBR was further confirmed, the p Ka value of it was calculated, and the related set up rate constant was also determined.
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NASA Astrophysics Data System (ADS)
Edwards, David C.; Nielsen, Steen B.; Jarzęcki, Andrzej A.; Spiro, Thomas G.; Myneni, Satish C. B.
2005-07-01
The deprotonation and iron complexation of the hydroxamate siderophore, desferrioxamine B (desB), and a model hydroxamate ligand, acetohydroxamic acid (aHa), were studied using infrared, resonance Raman and UV-vis spectroscopy. The experimental spectra were interpreted by a comparison with DFT calculated spectra of aHa (partly hydrated) and desB (reactive groups of unhydrated molecule) at the B3LYP/6-31G* level of theory. The ab initio models include three water molecules surrounding the deprotonation site of aHa to account for partial hydration. Experiments and calculations were also conducted in D 2O to verify spectral assignments. These studies of aHa suggest that the cis-keto-aHa is the dominant form, and its deprotonation occurs at the oxime oxygen atom in aqueous solutions. The stable form of iron-complexed aHa is identified as Fe(aHa) 3 for a wide range of pH conditions. The spectral information of aHa and an ab initio model of desB were used to interpret the chemical state of different functional groups in desB. Vibrational spectra of desB indicate that the oxime and amide carbonyl groups can be identified unambiguously. Vibrational spectral analysis of the oxime carbonyl after deprotonation and iron complexation of desB indicates that the conformational changes between anion and the iron-complexed anion are small. Enhanced electron delocalization in the oxime group of Fe-desB when compared to that of Fe(aHa) 3 may be responsible for higher stability constant of the former.
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Metals removal from aqueous solution by iron-based bonding agents.
Deliyanni, Eleni A; Lazaridis, Nikolaos K; Peleka, Efrosini N; Matis, Konstantinos A
2004-01-01
GOAL AND SCOPE AND BACKGROUND: The application of a promising method, termed sorptive flotation, for the removal of chromium(VI) and zinc ions was the aim of the present paper. A special case of sorptive flotation is adsorbing colloid flotation. Suitable sorbent preparation techniques have been developed in the laboratory. Sorptive flotation, consisting of the sorption and flotation processes combined in series, has proved to give fast and satisfactory treatment of the industrial streams and effluents bearing dilute aqueous solutions of zinc and chromium(VI). Goethite has proved to be effective for the removal of chromium(VI) and zinc ions. Also, adsorbing colloid flotation with ferric hydroxide (as the co-precipitant) could be an alternative method to the above-mentioned separation of metal ions. In both cases, chromium(VI) (pH=4) and zinc (pH=7) removal was about 100%. The reasons for selecting the iron-based bonding materials, like goethite and/or in-situ produced ferric hydroxide, are that they are cheap, easily synthesized, suitable both for cation and anion sorption, and, furthermore, that they present low risks for adding a further pollutant to the system. Promising results were obtained. The application of goethite and in-situ produced ferric hydroxide has demonstrated their effectiveness in the removal of heavy metal ions, such as chromium anions and zinc cations. A proposed continuation of current work is the utilization of similar iron oxides, for instance synthesized akaganeite. The comparison between the results reported in this paper with the results reported in the literature, also deserves attention.
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Kumar, Raja; Sinha, Alok
2017-02-01
Influence of common dye-bath additives, namely sodium chloride, ammonium sulphate, urea, acetic acid and citric acid, on the reductive decolouration of Direct Green 1 dye in the presence of Fe 0 was investigated. Organic acids improved dye reduction by augmenting Fe 0 corrosion, with acetic acid performing better than citric acid. NaCl enhanced the reduction rate by its 'salting out' effect on the bulk solution and by Cl - anion-mediated pitting corrosion of iron surface. (NH 4 ) 2 SO 4 induced 'salting out' effect accompanied by enhanced iron corrosion by SO 4 2- anion and buffering effect of NH 4 + improved the reduction rates. However, at 2g/L (NH 4 ) 2 SO 4 concentration, complexating of SO 4 2- with iron oxides decreased Fe 0 reactivity. Urea severely compromised the reduction reaction, onus to its chaotropic and 'salting in' effect in solution, and due to it masking the Fe 0 surface. Decolouration obeyed biphasic reduction kinetics (R 2 >0.993 in all the cases) exhibiting an initial rapid phase, when more than 95% dye reduction was observed, preceding a tedious phase. Maximum rapid phase reduction rate of 0.955/min was observed at pH2 in the co-presence of all dye-bath constituents. The developed biphasic model reckoned the influence of each dye-bath additive on decolouration and simulated well with the experimental data obtained at pH2. Copyright © 2016. Published by Elsevier B.V.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Maldonado, R.; Kevan, L.; Szajdzinska-Pietek, E.
1984-11-01
The electron spin echo modulation (ESEM) and electron spin resonance (ESR) spectra of the cation radical of N,N,N',N'-tetramethylbenzidine (TMB) in frozen sodium dodecyl sulfate (SDS)= and dodecyltrimethylammonium chloride (DTAC) micelles were studied as a function of sodium chloride concentration. TMB/sup +center-dot/ was produced by photoionization at 350 nm of the parent compound in the micelles at 77 K. From the ESEM analysis it is found that the cation--water interactions increase with salt addition in both anionic and cationic micelles to a maximum near 0.2 M NaCl and then decrease somewhat. The increase is interpreted in terms of an increase inmore » the water density at the micellar surface due to an increased surface concentration of hydrated counterions. The decrease may be due to TMB moving further from the polar micellar surface with added salt. From ESR spectra the photoionization yields of TMB at 77 K were determined. For DTAC micelles the yields are found to decrease with salt addition as expected from electrostatic considerations. For SDS micelles the photoionization yields increase for salt concentrations up to about 0.15 M and decrease for greater salt concentrations up to 0.5 M. The initial increase in cation yield correlates with electrostatic expectations. The decrease may be due to TMB moving further from the polar micellar surface with added salt. The possible effect of differing TMB protonation equilibria between anionic and cationic micelles on the photoionization yields was found to be unimportant by adjusting the bulk solution pH. An important conclusion is that salt addition can be used to optimize charge separation for photoionized solutes in anionic micelles.« less
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Mitigation of corrosion attack on carbon steel coated cermet alloy in different anion contents
NASA Astrophysics Data System (ADS)
Khalid, Muhamad Azrin Mohd; Ismail, Azzura
2017-12-01
This research study evaluated the corrosion mechanism attack on carbon steel coated with cermet alloys (WC-9% Ni) in seawater at different sulphate-to-chloride ratios. The four different sulphate-to-chloride ratios were synthesised with the same seawater salinity of 3.5 % and same pH of real seawater. The corrosion tests involved immersion and electrochemical tests. The immersion test is used to determine the cermet coating ability to withstand the corrosion attack based on different ratios of anions present in the seawater at different periods of immersion. The corrosion attack was characterized by optical and Scanning Electron Microscopy (SEM). The aggressive anions present in the seawater influenced the corrosion attack on the cermet coating. For immersion test, results revealed that increasing sulphate more than chloride, increased the weight loss of cermets. The electrochemistry analysis showed that the passive layer forms on cermet coating prevented the material from further corrosion attack. However, due to its porosity, the passive layer collapsed and exposed the material for other corrosion reaction. For electrochemical test, the result shows that the solution with sulphate-to-chloride ratio of 0.14 (real seawater) has the highest corrosion current and Open Circuit Potential (OCP) compared to other solutions (different sulphate-to-chloride ratio). In conclusion, sulfate and chloride show their competition to attack the cermet coating on carbon steel and the higher the amount of chloride present in seawater, the higher the corrosion rate and pits formed on the cermet coating.
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Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf
2013-11-07
The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.
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Willoughby, T.C.; See, R.B.; Schroder, L.J.
1989-01-01
Three experiments were conducted to determine the stability of nitrate-ion concentrations in simulated deposition samples. In the four experiment-A solutions, nitric acid provided nitrate-ion concentrations ranging from 0.6 to 10.0 mg/L and that had pH values ranging from 3.8 to 5.0. In the five experiment-B solutions, sodium nitrate provided nitrate-ion concentrations ranging from 0.5 to 3.0 mg/L. The pH was adjusted to about 4.5 for each of the solutions by addition of sulfuric acid. In the four experiment-C solutions, nitric acid provided nitrate-ion concentrations ranging from 0.5 to 3.0 mg/L. Major cation and anion concentrations were added to each solution to simulate natural deposition. Aliquots were removed from the 13 original solutions and analyzed by ion chromatography about once a week for 100 days to determine if any changes occurred in nitrate-ion concentrations throughout the study period. No substantial changes were observed in the nitrate-ion concentrations in solutions that had initial concentrations below 4.0 mg/L in experiments A and B, although most of the measured nitrate-ion concentrations for the 100-day study were below the initial concentrations. In experiment C, changes in nitrate-ion concentrations were much more pronounced; the measured nitrate-ion concentrations for the study period were less than the initial concentrations for 62 of the 67 analyses. (USGS)
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Bronckers, Antonius L J J; Guo, Jing; Zandieh-Doulabi, Behrouz; Bervoets, Theodore J; Lyaruu, Donacian M; Li, Xiangming; Wangemann, Philine; DenBesten, Pamela
2011-12-01
Ameloblasts need to regulate pH during the formation of enamel crystals, a process that generates protons. Solute carrier family 26A member 4 (SLC26A4, or pendrin) is an anion exchanger for chloride, bicarbonate, iodine, and formate. It is expressed in apical membranes of ion-transporting epithelia in kidney, inner ear, and thyroid where it regulates luminal pH and fluid transport. We hypothesized that maturation ameloblasts express SLC26A4 to neutralize acidification of enamel fluid in forming enamel. In rodents, secretory and maturation ameloblasts were immunopositive for SLC26A4. Staining was particularly strong in apical membranes of maturation ameloblasts facing forming enamel. RT-PCR confirmed the presence of mRNA transcripts for Slc26a4 in enamel organs. SLC26A4 immunostaining was also found in mineralizing connective tissues, including odontoblasts, osteoblasts, osteocytes, osteoclasts, bone lining cells, cellular cementoblasts, and cementocytes. However, Slc26a4-null mutant mice had no overt dental phenotype. The presence of SLC26A4 in apical plasma membranes of maturation ameloblasts is consistent with a potential function as a pH regulator. SLC26A4 does not appear to be critical for ameloblast function and is probably compensated by other pH regulators. © 2011 Eur J Oral Sci.
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Polymeric micellar pH-sensitive drug delivery system for doxorubicin.
Hrubý, Martin; Konák, Cestmír; Ulbrich, Karel
2005-03-02
A novel polymeric micellar pH-sensitive system for delivery of doxorubicin (DOX) is described. Polymeric micelles were prepared by self-assembly of amphiphilic diblock copolymers in aqueous solutions. The copolymers consist of a biocompatible hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic block containing covalently bound anthracycline antibiotic DOX. The starting block copolymers poly(ethylene oxide)-block-poly(allyl glycidyl ether) (PEO-PAGE) with a very narrow molecular weight distribution (Mw/Mn ca. 1.05) were prepared by anionic ring opening polymerization using sodium salt of poly(ethylene oxide) monomethyl ether as macroinitiator and allyl glycidyl ether as functional monomer. The copolymers were covalently modified via reactive double bonds by the addition of methyl sulfanylacetate. The resulting ester subsequently reacted with hydrazine hydrate yielding polymer hydrazide. The hydrazide was coupled with DOX yielding pH-sensitive hydrazone bonds between the drug and carrier. The resulting conjugate containing ca. 3 wt.% DOX forms micelles with Rh(a)=104 nm in phosphate-buffered saline. After incubation in buffers at 37 degrees C DOX was released faster at pH 5.0 (close to pH in endosomes; 43% DOX released within 24 h) than at pH 7.4 (pH of blood plasma; 16% DOX released within 24 h). Cleavage of hydrazone bonds between DOX and carrier continues even after plateau in the DOX release from micelles incubated in aqueous solutions is reached.
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[What is the contribution of Stewart's concept in acid-base disorders analysis?].
Quintard, H; Hubert, S; Ichai, C
2007-05-01
To explain the different approaches for interpreting acid-base disorders; to develop the Stewart model which offers some advantages for the pathophysiological understanding and the clinical interpretation of acid-base imbalances. Record of french and english references from Medline data base. The keywords were: acid-base balance, hyperchloremic acidosis, metabolic acidosis, strong ion difference, strong ion gap. Data were selected including prospective and retrospective studies, reviews, and case reports. Acid-base disorders are commonly analysed by using the traditional Henderson-Hasselbalch approach which attributes the variations in plasma pH to the modifications in plasma bicarbonates or PaCO2. However, this approach seems to be inadequate because bicarbonates and PaCO2 are completely dependent. Moreover, it does not consider the role of weak acids such as albuminate, in the determination of plasma pH value. According to the Stewart concept, plasma pH results from the degree of plasma water dissociation which is determined by 3 independent variables: 1) strong ion difference (SID) which is the difference between all the strong plasma cations and anions; 2) quantity of plasma weak acids; 3) PaCO2. Thus, metabolic acid-base disorders are always induced by a variation in SID (decreased in acidosis) or in weak acids (increased in acidosis), whereas respiratory disorders remains the consequence of a change in PaCO2. These pathophysiological considerations are important to analyse complex acid-base imbalances in critically ill patients. For example, due to a decrease in weak acids, hypoalbuminemia increases SID which may counter-balance a decrease in pH and an elevated anion gap. Thus if using only traditional tools, hypoalbuminemia may mask a metabolic acidosis, because of a normal pH and a normal anion gap. In this case, the association of metabolic acidosis and alkalosis is only expressed by respectively a decreased SID and a decreased weak acids concentration. This concept allows to establish the relationship between hyperchloremic acidosis and infusion of solutes which contain large concentration of chloride such as NaCl 0.9%. Finally, the Stewart concept permits to understand that sodium bicarbonate as well as sodium lactate induces plasma alkalinization. In fact, sodium remains in plasma, whereas anion (lactate or bicarbonate) are metabolized leading to an increase in plasma SID. Due to its simplicity, the traditional Henderson-Hasselbalch approach of acid-base disorders, remains commonly used. However, it gives an inadequate pathophysiological analysis which may conduct to a false diagnosis, especially with complex acid-base imbalances. Despite its apparent complexity, the Stewart concept permits to understand precisely the mechanisms of acid-base disorders. It has to become the most appropriate approach to analyse complex acid-base abnormalities.
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Removal of metal(oid)s from contaminated water using iron-coated peat sorbent.
Kasiuliene, Alfreda; Carabante, Ivan; Bhattacharya, Prosun; Caporale, Antonio Giandonato; Adamo, Paola; Kumpiene, Jurate
2018-05-01
This study aimed at combining iron and peat to produce a sorbent suitable for a simultaneous removal of cations and anions from a solution. Peat powder, an industrial residue, was coated with iron by immersing peat into iron salt solutions. The adsorption efficiency of the newly produced sorbent towards As, Cr, Cu and Zn was tested by means of batch adsorption experiments at a constant pH value of 5. Coating of Fe on peat significantly increased the adsorption of As (from <5% to 80%) and Cr (from <3% to 25%) in comparison to uncoated peat. Removal of cations on coated peat slightly decreased (by 10-15%), yet remained within acceptable range. Electron Microscopy combined with X-Ray Energy Dispersive Spectroscopy revealed that iron coating on the peat was rather homogenous and As and Cr were abundantly adsorbed on the surface. By contrast, Cu and Zn displayed a sparing distribution on the surface of the iron coated peat. These results indicate that iron-peat simultaneously target sufficient amounts of both cations and anions and can be used for a one-step treatment of contaminated groundwater. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.
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Organoboron compounds as Lewis acid receptors of fluoride ions in polymeric membranes.
Jańczyk, Martyna; Adamczyk-Woźniak, Agnieszka; Sporzyński, Andrzej; Wróblewski, Wojciech
2012-07-06
Newly synthesized organoboron compounds - 4-octyloxyphenylboronic acid (OPBA) and pinacol ester of 2,4,6-trifluorophenylboronic acid (PE-PBA) - were applied as Lewis acid receptors of fluoride anions. Despite enhanced selectivity, the polymer membrane electrodes containing the lipophilic receptor OPBA exhibited non-Nernstian slopes of the responses toward fluoride ions in acidic conditions. Such behavior was explained by the lability of the B-O bond in the boronic acids, and the OH(-)/F(-) exchange at higher fluoride content in the sample solution. In consequence, the stoichiometry of the OPBA-fluoride complexes in the membrane could vary during the calibration, changing the equilibrium concentration of the primary anion in membrane and providing super-Nernstian responses. The proposed mechanism was supported by (19)F NMR studies, which indicated that the fluoride complexation proceeds more effectively in acidic solution leading mainly to PhBF(3)(-) species. Finally, the performances of the membranes based on the phenylboronic acid pinacol ester, with a more stable B-O bond, were tested. As it was expected, Nernstian fluoride responses were recorded for such membranes with worsened fluoride selectivity. Copyright © 2012 Elsevier B.V. All rights reserved.
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Mercury removal from aqueous solutions by zinc cementation.
Ku, Young; Wu, Ming-Huan; Shen, Yung-Shen
2002-01-01
The main purpose of this research is to study the addition effect of the surfactant and other operating factors on the treatment of wastewater containing mercury ions in aqueous solution by cementation with sacrificing metal, zinc. The removal of mercury ions from aqueous solutions by cementation of zinc powder was found to be a function of solution pH and temperature, amount of zinc, concentration of mercury ion, contact time and the addition of several organic surfactants. Cementation of mercury was shown to be a feasible process to achieve a very high degree of mercury removal over a broad operational range within a fairly reasonable contact time. The reaction rate is approximately first order with respect to the concentration of mercury ion in aqueous solution. Among the surfactants used in this study, only the presence of SDS, an anionic surfactant, slightly enhanced the cementation rate of mercury. The presence of CTAB and Triton-X100 retarded the cementation of mercury by zinc.
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Method of separating thorium from plutonium
Clifton, David G.; Blum, Thomas W.
1984-01-01
A method of chemically separating plutonium from thorium. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.
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Method of separating thorium from plutonium
Clifton, D.G.; Blum, T.W.
A method of chemically separating plutonium from thorium is claimed. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.
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Method of separating thorium from plutonium
Clifton, D.G.; Blum, T.W.
1984-07-10
A method is described for chemically separating plutonium from thorium. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.
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Possart, Josephine; Martens, Arthur; Schleep, Mario; Ripp, Alexander; Scherer, Harald; Kratzert, Daniel; Krossing, Ingo
2017-09-07
By reaction of two equivalents of Me 3 Si-F-Al(OR F ) 3 1 with an equimolar amount of PPh 2 Cl, the salt [Ph 2 P-PPh 2 Cl] + [(R F O) 3 Al-F-Al(OR F ) 3 ] - 2 is prepared smoothly in 91 % yield (NMR, XRD). The synthesis of [Ph 2 P-PPh 3 ] + [(R F O) 3 Al-F-Al(OR F ) 3 ] - 3 is best achieved by a two-step reaction: first, two equivalents of 1 react with one PPh 3 to give [Me 3 Si-PPh 3 ] + [(R F O) 3 Al-F-Al(OR F ) 3 ] - 4 (NMR, XRD), which, upon reaction with PPh 2 Cl, yields pure 3 and Me 3 SiCl (NMR, XRD). Typically, a stoichiometry of two equivalents of 1 with respect to one equivalent of the chloride donor should be used. Otherwise, the residual strong Lewis acidity of the [(R F O) 3 Al-F-Al(OR F ) 3 ] - anion in the presence of the [F-Al(OR F ) 3 ] - anion-that forms with less than two equivalents of 1-leads to further chloride exchange reactions that complicate work-up. This route presents the easiest way to introduce the least-coordinating [(R F O) 3 Al-F-Al(OR F ) 3 ] - anion into a system. We expect a wide use of this route in all areas, in which chloride-bond heterolysis in combination with very weakly coordinating anions is desirable. Additionally, we performed calculations on the bond dissociation mechanisms of [R 2 P-PMe 3 ] + and the isoelectronic Me 2 P-SiMe 3 and Me 2 Si-PMe 3 in dependence of the solvent permittivity. These calculations show, especially for the neutral reference compounds, a heavy influence of the solvent on the dissociation mechanism, which is why we suggest investigating these properties in solution instead of gas phase. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Ueno, Kaori; Hirono, Chikara; Kitagawa, Michinori; Shiba, Yoshiki; Sugita, Makoto
2016-11-01
Intracellular pH (pH i ) regulation fundamentally participates in maintaining HCO 3 - release from HCO 3 - -secreting epithelia. We used parotid intralobular ducts loaded with BCECF to investigate the contributions of a carbonic anhydrase (CA), anion channels and a Na + -H + exchanger (NHE) to pH i regulation for HCO 3 - secretion by cAMP and Ca 2+ signals. Resting pH i was dispersed between 7.4 and 7.9. Forskolin consistently decreased pH i showing the dominance of pH i -lowering activities, but carbachol gathered pH i around 7.6. CA inhibition suppressed the forskolin-induced decrease in pH i , while it allowed carbachol to consistently increase pH i by revealing that carbachol prominently activated NHE via Ca 2+ -calmodulin. Under NHE inhibition, forskolin and carbachol induced the remarkable decreases in pH i , which were slowed predominantly by CA inhibition and by CA or anion channel inhibition, respectively. Our results suggest that forskolin and carbachol primarily activate the pH i -lowering CA and pH i -raising NHE, respectively, to regulate pH i for HCO 3 - secretion.
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McLEan, D.C.
1959-03-10
A method is described for eluting uranium from anion exchange resins so as to decrease vanadium and iron contamination and permit recycle of the major portion of the eluats after recovery of the uranium. Diminution of vanadium and iron contamination of the major portion of the uranium is accomplished by treating the anion exchange resin, which is saturated with uranium complex by adsorption from a sulfuric acid leach liquor from an ore bearing uranium, vanadium and iron, with one column volume of eluant prepared by passing chlorine into ammonium hydroxide until the chloride content is about 1 N and the pH is about 1. The resin is then eluted with 8 to 9 column volumes of 0.9 N ammonium chloride--0.1 N hydrochloric acid solution. The eluants are collected separately and treated with ammonia to precipitate ammonium diuranate which is filtered therefrom. The uranium salt from the first eluant is contaminated with the major portion of ths vanadium and iron and is reworked, while the uranium recovered from the second eluant is relatively free of the undesirable vanadium and irons. The filtrate from the first eluant portion is discarded. The filtrate from the second eluant portion may be recycled after adding hydrochloric acid to increase the chloride ion concentration and adjust the pH to about 1.
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Mg-Al and Zn-Fe layered double hydroxides used for organic species storage and controlled release.
Seftel, E M; Cool, P; Lutic, D
2013-12-01
Layered double hydroxides (LDH) containing (Mg and Al) or (Zn and Fe) were prepared by coprecipitation at constant pH, using NaOH and urea as precipitation agents. The most pure LDH phase in the Zn/Fe system was obtained with urea and in Mg/Al system when using NaOH. The incorporation of phenyl-alanine (Phe) anions in the interlayer of the LDH was performed by direct coprecipitation, ionic exchange and structure reconstruction of the mixed oxide obtained by the calcination of the coprecipitated product at 400°C. The reconstruction method and the direct coprecipitation in a medium containing Phe in the initial mixture were less successful in terms of high yields of organic-mineral composite than the ionic exchange method. A spectacular change in sample morphology and yield in exchanged solid was noticed for the Zn3Fe sample obtained by ionic exchange for 6h with Phe solution. A delivery test in PBS of pH=7.4 showed the release of the Phe in several steps up to 25 h indicating different host-guest interactions between the Phe and the LDH matrix. This behavior makes the preparation useful to obtain late delivery drugs, by the incorporation of the anion inside the LDH layer. © 2013.
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Analysis of the improvement of selenite retention in smectite by adding alumina nanoparticles.
Mayordomo, Natalia; Alonso, Ursula; Missana, Tiziana
2016-12-01
Smectite clay is used as barrier for hazardous waste retention and confinement. It is a powerful material to retain cations, but less effective for retaining anionic species like selenite. This study shows that the addition of a small percentage of γ-Al 2 O 3 nanoparticles to smectite significantly improves selenite sorption. γ-Al 2 O 3 nanoparticles provide high surface area and positively charged surface sites within a wide range of pH, since their point of zero charge is at pH8-9. An addition of 20wt% of γ-Al 2 O 3 to smectite is sufficient to approach the sorption capacity of pure alumina. To analyze the sorption behavior of the smectite/oxide mixtures, a nonelectrostatic surface complexation model was considered, accounting for the surface complexation of HSeO 3 - and SeO 3 2- , the anion competition, and the formation of surface ternary complexes with major cations present in the solution. Selenite sorption in mixtures was satisfactorily described with the surface parameters and complexation constants defined for the pure systems, accounting only for the mixture weight fractions. Sorption in mixtures was additive despite the particle heteroaggregation observed in previous stability studies carried out on smectite/γ-Al 2 O 3 mixtures. Copyright © 2016 Elsevier B.V. All rights reserved.
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Sladkov, Vladimir; Fourest, Blandine
2009-03-20
Separation and simultaneous determination of a number of organic acid anions (oxalate, mellitate, trimellitate and benzoate) and U(VI) with direct UV detection is developed for analysis of uranium carbide (UC) dissolution products by capillary zone electrophoresis (CZE). Reverse polarity mode is used. It is found that complex formation of U(VI) with carbonate, used as a carrier electrolyte, allows U(VI) to be determined, as negatively charged species, in a single run with organic acid anions. Some parameters such as pH value, composition of electrolyte and detection wavelength are optimized. Under the chosen conditions (carbonate buffer (ionic strength of 100 mM), pH 9.8, 0.15 mM tetradecyltrimethylammonium bromide (TTAB)) a complete separation is achieved. Calibration plots are linear in two ranges of concentration for U(VI) ( approximately 1 x 10(-5) to 1 x 10(-3)), mellitate and trimellitate ( approximately 5 x 10(-6) to 5 x 10(-4)), and about one range ( approximately 1 x 10(-4) to 5 x 10(-3)) for oxalate and benzoate. Accuracy of the procedure is checked by the "added-found" method in standard mixture solutions. Relative standard deviation is within the range of 2-10% and the recovery is in the range of 90-110%. This method is applied for the analysis of real UC dissolution samples.
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Zhao, Pin; Gao, Baoyu; Yue, Qinyan; Liu, Pan; Shon, Ho Kyong
2016-08-01
Octanoic acid (OA) was selected to represent fatty acids in effluent organic matter (EOM). The effects of feed solution (FS) properties, membrane orientation and initial permeate flux on OA fouling in forward osmosis (FO) were investigated. The undissociated OA formed a cake layer quickly and caused the water flux to decline significantly in the initial 0.5hr at unadjusted pH3.56; while the fully dissociated OA behaved as an anionic surfactant and promoted the water permeation at an elevated pH of 9.00. Moreover, except at the initial stage, the sudden decline of water flux (meaning the occurrence of severe membrane fouling) occurred in two conditions: 1. 0.5mmol/L Ca(2+), active layer facing draw solution (AL-DS) and 1.5mol/L NaCl (DS); 2. No Ca(2+), active layer-facing FS (AL-FS) and 4mol/L NaCl (DS). This demonstrated that cake layer compaction or pore blocking occurred only when enough foulants were absorbed into the membrane surface, and the water permeation was high enough to compact the deposit inside the porous substrate. Furthermore, bovine serum albumin (BSA) was selected as a co-foulant. The water flux of both co-foulants was between the fluxes obtained separately for the two foulants at pH3.56, and larger than the two values at pH9.00. This manifested that, at pH3.56, BSA alleviated the effect of the cake layer caused by OA, and OA enhanced BSA fouling simultaneously; while at pH9.00, the mutual effects of OA and BSA eased the membrane fouling. Copyright © 2016. Published by Elsevier B.V.
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Chen, Liang; Zhao, Xin; Pan, Bingcai; Zhang, Weixian; Hua, Ming; Lv, Lu; Zhang, Weiming
2015-03-02
In this study, we employed a new nanocomposite adsorbent HZO-201, which featured high stability under varying solution chemistry, for preferable removal of phosphate from synthetic solution and a real effluent. An anion exchange resin (D-201) was employed as the host of HZO-201, where nano-hydrous zirconium oxide (HZO) was encapsulated as the active species. D-201 binds phosphate through nonspecific electrostatic affinity, whereas the loaded HZO nanoparticles capture phosphate through formation of the inner-sphere complexes. Quantitative contribution of both species to phosphate adsorption was predicted based on the double-Langmuir model. Preferable removal of phosphate by HZO-201 was observed in the presence of the competing anions at higher levels (Cl(-), NO3(-), SO4(2-), HCO3(-)). Fixed-bed adsorption indicated that the effective volume capacity of a synthetic water (2.0 mg P-PO4(3-)/L) by using HZO-201 was ∼1600 BV in the first run (<0.5mg P-PO4(3-)/L), comparable to Fe(III)-based nanocomposite HFO-201 (∼1500 BV) and much larger than D-201 (<250 BV). The exhausted HZO-201 can be in situ regenerated by using a binary NaOH-NaCl solution for cyclic runs, whether fed with the synthetic solution or real effluent. In general, HZO-201 is a promising alternative to Fe(III)-based adsorbents for trace phosphate removal from effluent particularly at acidic pH. Copyright © 2014 Elsevier B.V. All rights reserved.
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Mote, Nilesh R; Patel, Ketan; Shinde, Dinesh R; Gaikwad, Shahaji R; Koshti, Vijay S; Gonnade, Rajesh G; Chikkali, Samir H
2017-10-16
Self-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC 6 H 4 NH(CO)NH 2 }{Ph 2 PC 6 H 4 NH(CO)NH 2 }PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC 6 H 4 NH(CO)NHPh}{Ph 2 PC 6 H 4 NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 °C.
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Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation.
Ding, Shi-Ling; Wang, Xi-Kui; Jiang, Wen-Qiang; Meng, Xia; Zhao, Ru-Song; Wang, Chen; Wang, Xia
2013-05-01
This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO₂ loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO₂ photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.
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Harnisch, Falk; Schröder, Uwe; Scholz, Fritz
2008-03-01
A proton exchange (Nafion-117), a cation exchange (Ultrex CMI7000), an anion exchange (Fumasep FAD), and a bipolar (FumasepFBM) membrane have been studied to evaluate the principle suitability of ion exchange membranes as separators between the anode and the cathode compartment of biological fuel cells. The applicability of these membranes is severely affected by the neutral pH, and the usually low ionic strength of the electrolyte solutions. Thus, the ohmic resistance of the monopolar membranes was found to greatly increase at neutral pH and at decreasing electrolyte concentrations. None of the studied membranes can prevent the acidification of the anode and the alkalization of the cathode compartment, which occurs in the course of the fuel cell operation. Bipolar membranes are shown to be least suitable for biofuel cell application since they show the highest polarization without being able to prevent pH splitting between the anode and cathode compartments.
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Switchable nanoassembly from an azobenzene-containing dye.
Wang, Jing; Ha, Chang-Sik
2011-07-01
In this work, we investigated optical properties and the morphology of the amphiphilic azobenzene dye 1 containing hydroxyl azobenzene and C10 alkyl chains. Since the hydroxyl group on 1 has a pKa of 9.38, the deprotonation of the hydroxyl group occurs at pH > pKa (9.38) and thus the 1 nanoparticles are negatively charged. The deprotonated hydroxyl group is hydrophilic relative to the long alkyl chain that is hydrophobic, while the hydrophobic and hydrophilic parts are connected by covalent bonds. When such an azobenzene molecule 1 with both hydrophobic and hydrophilic groups exists in solution, "self-aggregation" may occur due to the hydrophobic interaction between the long alkyl chains. The scattered morphology at pH 7.0 (neutral state) and the aggregated morphology at pH 10.5 (anionic state) of 1 were demostrated by transmission electron microscopy (TEM) and atomic force microscopy (AFM) images. Formation of supramolecular aggregation-induced vesicular-like structures are highly interesting due to the ability to respond to external triggers, pH. The pH value can be reversed by adding acid or base to the system, that is, switching the aggregation "on" and "off" can be repeated.
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Viudez, Alfonso J; Madueño, Rafael; Pineda, Teresa; Blázquez, Manuel
2006-09-14
6-Mercaptopurine-coated gold nanoparticles (6MP-AuNPs) have been prepared by modification of the nanoparticle surface with 6MP upon displacement of the protective layer of citrate anions. The modification has been studied by UV-vis and FTIR spectroscopies. A study of the stability of these 6MP-AuNPs in aqueous solutions as a function of ionic strength and pH has shown the importance of the charges on the stabilization. The protonation of N9 of the 6MP molecules brings about a sudden flocculation phenomenon. However, the flocculation is reversible upon changing the pH to values where the molecules become newly charged. Evidence of the competence between the interaction of capping solvent molecules and the attractive forces between particles is also shown in this paper.
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Method and apparatus for chromatographic quantitative analysis
Fritz, James S.; Gjerde, Douglas T.; Schmuckler, Gabriella
1981-06-09
An improved apparatus and method for the quantitative analysis of a solution containing a plurality of anion species by ion exchange chromatography which utilizes a single eluent and a single ion exchange bed which does not require periodic regeneration. The solution containing the anions is added to an anion exchange resin bed which is a low capacity macroreticular polystyrene-divinylbenzene resin containing quarternary ammonium functional groups, and is eluted therefrom with a dilute solution of a low electrical conductance organic acid salt. As each anion species is eluted from the bed, it is quantitatively sensed by conventional detection means such as a conductivity cell.
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Chang, Shih-Hsien; Wang, Kai-Sung; Hu, Pei-I; Lui, I-Chun
2009-04-30
Copper-surfactant wastewaters are often encountered in electroplating, printed circuit boards manufacturing, and metal finishing industries, as well as in retentates from micellar-enhanced ultrafiltration process. A low-cost three-dimensional steel wool cathode reactor was evaluated for electrolytic recovery of Cu ion from dilute copper solution (0.2mM) in the presence of sodium dodecyl sulfate (SDS), octylphenol poly (ethyleneglycol) 9.5 ether (TX), nonylphenol poly (oxyethylene) 9 ether (NP9) and polyoxyethylene (20) sorbitan monooleate (TW) and also mixed surfactants (anionic/nonionic). The reactor showed excellent copper recovery ability in comparison to a parallel-plate reactor. The reactor rapidly recovered copper with a reasonable current efficiency. 93% of copper was recovered at current density of 1 A m(-2) and pH 4 in the presence of 8.5mM SDS. Initial solution pH, cathodic current density, solution mixing condition, SDS concentration, and initial copper concentrations significantly influenced copper recovery. The copper recovery rate increased with an increase in aqueous SDS concentrations between 5 and 8.5mM. The influences of nonionic surfactants on Cu recovery from SDS-Cu solution depended not only on the type of surfactants used, but also on applied concentrations. From the copper recovery perspective, TX at 0.1mM or NP should be selected rather than TW, because they did not inhibit copper recovery from SDS-Cu solution.
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pH profile of the adsorption of nucleotides onto montmorillonite. I - Selected homoionic clays
NASA Technical Reports Server (NTRS)
Lawless, J. G.; Church, F. M.; Mazzurco, J.; Banin, A.; Huff, R.; Kao, J.; Cook, A.; Lowe, T.; Orenberg, J. B.; Edelson, E.
1985-01-01
The effect of pH and adsorbed ions on the adsorption of purine and pyrimidine nucleotides on montmorillonite clay was studied experimentally. The specific nucleotides examined were: 5 prime-AMP; 3-prime AMP; and 5 prime-CMP. The pH of the clay samples was adjusted to various levels in the 2-12 pH range using microliter volumes of concentrated acid (1N HCl) and base (1NHNaOH). It was found that preferential adsorption among nulceotides was dependent on the pH level and on the characteristics of the substituted metal cation and anion exchange mechanisms. Below pH 4, adsorption was attributed to cation and anion exchange mechanisms. Above pH 4, however, adsorption was attributed to the complexation mechanisms occurring between the metal cations in the clay exchange site and in the biomolecule. The possible role of homoionic clays in the concentration mechanisms of biomonomers in the prebiotic environment is discussed.
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Effect of humic acid on ciprofloxacin removal by magnetic multifunctional resins
Wang, Wei; Cheng, Jiade; Jin, Jing; Zhou, Qing; Ma, Yan; Zhao, Qingqing; Li, Aimin
2016-01-01
Background organic matter significantly influences the removal of emerging contaminants in natural water. In this work, the adsorption of ciprofloxacin (CPX) onto a series of magnetic multifunctional resins (GMA10-GMA90) in the presence and absence of humic acid (HA) was conducted to demonstrate the effect of HA. Both hydrophobic and ion exchange interactions contributed to CPX adsorption. Negative charge-assisted hydrogen bonds also participated in the adsorption process, resulting in the high adsorption amount of anionic CPX onto the negatively charged GMA30 under basic solutions. HA could impact CPX adsorption not only as a competitive adsorbate but also as an additional adsorbent. At pH 5.6, the additional adsorption sites provided by adsorbed HA molecules on the resins dominated and thus facilitated the adsorption process. While at pH 10, HA inhibited the adsorption of CPX by directly competing for ion exchange sites and coexisting with CPX in the solution. The ratio of the amount of CPX adsorbed by dissolved HA to that by the resin reached as high as 1.61 for GMA90. The adsorbed HA molecules onto the resins could provide additional adsorption sites for CPX as proven by the enhanced CPX adsorption in HA-preloading systems at pH 5.6. PMID:27464502
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Effect of humic acid on ciprofloxacin removal by magnetic multifunctional resins
NASA Astrophysics Data System (ADS)
Wang, Wei; Cheng, Jiade; Jin, Jing; Zhou, Qing; Ma, Yan; Zhao, Qingqing; Li, Aimin
2016-07-01
Background organic matter significantly influences the removal of emerging contaminants in natural water. In this work, the adsorption of ciprofloxacin (CPX) onto a series of magnetic multifunctional resins (GMA10-GMA90) in the presence and absence of humic acid (HA) was conducted to demonstrate the effect of HA. Both hydrophobic and ion exchange interactions contributed to CPX adsorption. Negative charge-assisted hydrogen bonds also participated in the adsorption process, resulting in the high adsorption amount of anionic CPX onto the negatively charged GMA30 under basic solutions. HA could impact CPX adsorption not only as a competitive adsorbate but also as an additional adsorbent. At pH 5.6, the additional adsorption sites provided by adsorbed HA molecules on the resins dominated and thus facilitated the adsorption process. While at pH 10, HA inhibited the adsorption of CPX by directly competing for ion exchange sites and coexisting with CPX in the solution. The ratio of the amount of CPX adsorbed by dissolved HA to that by the resin reached as high as 1.61 for GMA90. The adsorbed HA molecules onto the resins could provide additional adsorption sites for CPX as proven by the enhanced CPX adsorption in HA-preloading systems at pH 5.6.
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NASA Astrophysics Data System (ADS)
Zamiri, M.; Giahi, M.
2016-12-01
Novel C,N-doped TiO2 nanoparticles were prepared by a solid phase reaction. The catalyst was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). The results showed that crystallite size of synthesized C,N-doped TiO2 particles were in nanoscale. UV light photocatalytic studies were carried out using sodium naphthalenesulfonate formaldehyde condensate (SNF) as a model pollutant. The effects of initial concentration of surfactant, catalyst amount, pH, addition of oxidant on the reaction rate were ascertained and optimum conditions for maximum degradation was determined. The results indicated that for a solution of 20 mg/L of SNF, almost 98.7% of the substance were removed at pH 4.0 and 0.44 g/L photocatalyst load, with addition of 1 mM K2S2O8 and irradiation time of 90 min. The kinetics of the process was studied, and the photodegradation rate of SNF was found to obey pseudo-first-order kinetics equation represented by the Langmuir-Hinshelwood model.
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The Management of Silica in Los Alamos National Laboratory Tap Water - A Study of Silica Solubility
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wohlberg, C.; Worland, V.P.; Kozubal, M.A.
1999-07-01
Well water at Los Alamos National Laboratory (LANL) has a silica (SiO{sub 2}) content of 60 to 100 mg/L, with 4 mg/L of magnesium, 13 mg/L calcium and lesser concentrations of other ions. On evaporation in cooling towers, when the silica concentration reaches 150 to 220 mg/L, silica deposits on heat transfer surfaces. When the high silica well water is used in the reprocessing of plutonium, silica remains in solution at the end of the process and creates a problem of removal from the effluent prior to discharge or evaporation. The work described in this Report is divided into twomore » major parts. The first part describes the behavior of silica when the water is evaporated at various conditions of pH and in the presence of different classes of anions: inorganic and organic. In the second part of this work it was found that precipitation (floccing) of silica was a function of solution pH and mole ratio of metal to silica.« less
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Kesraoui, Aida; Moussa, Asma; Ali, Ghada Ben; Seffen, Mongi
2016-08-01
The aim of the present work is to develop an effective and inexpensive pollutant-removal technology using lignocellulosic fibers: Luffa cylindrica, for the biosorption of an anionic dye: alpacide blue. The influence of some experimental parameters such as pH, temperature, initial concentration of the polluted solution, and mass of the sorbent L. cylindrica on the biosorption of alpacide blue by L. cylindrica fibers has been investigated. Optimal parameters for maximum quantity of biosorption dye were achieved after 2 h of treatment in a batch system using an initial dye concentration of 20 mg/L, a mass of 1 g of L. cylindrica fibers, and pH 2. In these conditions, the quantity of dye retained is 2 mg/g and the retention rate is 78 %. Finally, a mathematical modeling of kinetics and isotherms has been used for mathematical modeling; the model of pseudo-second order is more appropriate to describe this phenomenon of biosorption. Concerning biosorption isotherms, the Freundlich model is the most appropriate for a biosorption of alpacide blue dye by L. cylindrica fibers.
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Stoner, L C; Kregenow, F M
1980-10-01
We describe a single-cell technique for measuring membrane potential, membrane resistance, and the efflux of rapidly penetrating solutes such as Cl and H2O. Erythrocytes from Amphiuma means were aspirated into a Sylgard (Dow Corning Corp.)-coated capillary. The aspirated cell separated a solution within the capillary from a solution in the bath. Each of these two solutions was contiguous with approximately 5% of the total membrane surface. Microelectrodes placed concentrically within the capillary permit the measurement of intracellular voltage, specific membrane resistance, and the electrical seal between the two solutions. The intracellular voltage averaged -17.7 mV (pH 7.6) and changed as either intra- or extracellular chloride was varied. The average specific membrane resistance measured by passing current across the exposed membrane surface was 110 ohm-cm2. 36Cl and tritiated H2O fluxes (0.84 +/- 0.05 x 10(-6) M . cm-2 . min-1 and 6.4 +/- 1.5 x 10(-3) M . cm-2 . min-1, respectively) were determined by noting the rate at which isotope leaves the cell and crosses the membrane exposed to the bath. Our measured values for the flux of 36Cl and tritiated H2O approximate reported values for free-floating cells. 36Cl efflux, in addition, is inhibited by 4-acetamido-4'-isothiocyano-stilbene 2,2'-disulfonic acid (SITS) and furosemide, known inhibitors of the anion exchange mechanism responsible for the rapid anion fluxes of red blood cells. One can also demonstrate directly that > 89% of 36Cl efflux is "electrically silent" by analyzing the flux in the presence of an imposed transcellular voltage.
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Svane, Simon; Kjeldsen, Frank; McKee, Vickie; McKenzie, Christine J
2015-07-14
The three dimetallic compounds [Ga2(bpbp)(OH)2(H2O)2](ClO4)3, [In2(bpbp)(CH3CO2)2](ClO4)3 and [Zn2(bpbp)(HCO2)2](ClO4) (bpbp(-) = 2,6-bis((N,N'-bis(2-picolyl)amino)methyl)-4-tertbutylphenolate) were evaluated as stable solid state precursors for reactive solution state receptors to use for the recognition of the biologically important anion pyrophosphate in water at neutral pH. Indicator displacement assays using in situ generated complex-pyrocatechol violet adducts, {M2(bpbp)(HxPV)}(n+) M = Ga(3+), In(3+), Zn(2+), were tested for selectivity in their reactions with a series of common anions: pyrophosphate, phosphate, ATP, arsenate, nitrate, perchlorate, chloride, sulfate, formate, carbonate and acetate. The receptor employing Ga(3+) showed a slow but visually detectable response (blue to yellow) in the presence of one equivalent of pyrophosphate but no response to any other anion, even when they were present in much higher concentrations. The systems based on In(3+) or Zn(2+) show less selectivity in accord with visibly discernible responses to several of the anions. These results demonstrate a facile method for increasing anion selectivity without modification of an organic dinucleating ligand scaffold. The comfortable supramolecular recognition of pyrophosphate by the dimetallic complexes is demonstrated by the single crystal X-ray structure of [Ga2(bpbp)(HP2O7)](ClO4)2 in which the pyrophosphate is coordinated to the two gallium ions via four of its oxygen atoms.
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Munagapati, Venkata Subbaiah; Yarramuthi, Vijaya; Kim, Yeji; Lee, Kwon Min; Kim, Dong-Su
2018-02-01
The adsorption characteristics of Reactive Black 5 (RB5) and Cong Red (CR) onto Banana Peel Powder (BPP) from aqueous solution were investigated as a function of pH, contact time, initial dye concentration and temperature. The BPP was characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) analysis. FTIR results revealed that hydroxyl (-OH), amine (-NH) and carboxyl (-C˭O) functional groups present on the surface of BPP. The SEM results show that BPP has an irregular and porous surface morphology which is adequate for dye adsorption. The equilibrium data were analyzed using Langmuir and Freundlich isotherm models. Experimental results were best represented by the Langmuir isotherm model. The adjustments of models were confirmed by the Chi-square (χ 2 ) test and the correlation coefficients (R 2 ). The maximum monolayer adsorption capacities of RB5 and CR on BPP calculated from Langmuir isotherm model were 49.2 and 164.6mg/g at pH 3.0 and 298K. Experimental data were also tested in terms of adsorption kinetics using pseudo-first-order and pseudo-second-order kinetic models. The results showed that the adsorption processes of both RB5 and CR followed well pseudo-second-order kinetic models. The calculated thermodynamic parameters ΔG°, ΔH° and ΔS° showed that the adsorption of RB5 and CR onto BPP was feasible, spontaneous and endothermic in the temperature range 298-318K. The RB5 and CR were desorbed from BPP using 0.1M NaOH. The recovery for both anionic dyes was found to be higher than 90%. Based on these it can be concluded that BPP can be used as an effective, low cost, and eco-friendly adsorbent for CR removal than RB5 from aqueous solution. Copyright © 2017 Elsevier Inc. All rights reserved.
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Effect of hydrotalcite-like compounds on the aqueous solubility of some poorly water-soluble drugs.
Ambrogi, Valeria; Fardella, Giuseppe; Grandolini, Giuliano; Nocchetti, Morena; Perioli, Luana
2003-07-01
A new approach of improving drug dissolution properties is described. This method exploits the property of a carrier owing to the hydrotalcite-type anionic clays (HTlc). HTlc is an inorganic layered solid that lodges anionic compounds among its layers. As HTlc dissolves at acidic pH values (pH < 4), the anions intercalated among the layers are promptly released in the medium. In this article some nonsteroidal antiinflammatory drugs were chosen as models of poorly water-soluble drugs. They were intercalated in HTlc and solubility measurements in acidic medium were performed. A remarkable improvement of drug solubility was observed especially in the case of indomethacin. Copyright 2003 Wiley-Liss, Inc. and the American Pharmacists Association
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NASA Astrophysics Data System (ADS)
Marini, Vanderléia Gava; Zimmermann, Lizandra Maria; Machado, Vanderlei Gageiro
2010-02-01
Solutions of 2,4-dinitrodiphenylamine ( 1) in dimethylsulfoxide (DMSO) are colorless but upon deprotonation they become red. Addition of various anionic species (HSO 4-, H 2PO 4-, NO 3-, CN -, CH 3COO -, F -, Cl -, Br -, and I -) to solutions of 1 revealed that only CN -, F -, CH 3COO -, and H 2PO 4- led to the appearance of the red color in solution. The presence of increasing amounts of water in solutions containing 1 made it progressively selective toward CN - and the system with the addition of 4.3% (v/v) of water was highly selective for CN - among all anions studied. The experimental data collected indicated that proton transfer from 1 to the anion occurs, and a model was used to explain the experimental results, which considers two 1:anion stoichiometries, 1:1 and 1:2. For the latter, the data suggest that the anion forms firstly a hydrogen-bonded complex with a second anion equivalent necessary for the abstraction of the proton, with the formation of a [HA 2] - complex. The study performed here demonstrates the important role of the environment of the anion and 1 for the efficiency of the chromogenic chemosensor. Besides the different affinities of each anion for water, the solvation of both the anion and 1 is responsible for reducing the interaction between these species. In small amounts, water or hydrogen-bonded DMSO-water complexes are able to stabilize the conjugated base of 1 through hydrogen bonding, making 1 more acidic, which explains the change from 1:1 and 1:2 toward 1:1 1:anion stoichiometry upon addition of water. In addition, water is able to solvate the anion and also 1, which hinders the formation of 1:1 hydrogen-bonded 1:anion complexes prior to the abstraction of the proton.
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Marini, Vanderléia Gava; Zimmermann, Lizandra Maria; Machado, Vanderlei Gageiro
2010-02-01
Solutions of 2,4-dinitrodiphenylamine (1) in dimethylsulfoxide (DMSO) are colorless but upon deprotonation they become red. Addition of various anionic species (HSO(4)(-), H(2)PO(4)(-), NO(3)(-), CN(-), CH(3)COO(-), F(-), Cl(-), Br(-), and I(-)) to solutions of 1 revealed that only CN(-), F(-), CH(3)COO(-), and H(2)PO(4)(-) led to the appearance of the red color in solution. The presence of increasing amounts of water in solutions containing 1 made it progressively selective toward CN(-) and the system with the addition of 4.3% (v/v) of water was highly selective for CN(-) among all anions studied. The experimental data collected indicated that proton transfer from 1 to the anion occurs, and a model was used to explain the experimental results, which considers two 1:anion stoichiometries, 1:1 and 1:2. For the latter, the data suggest that the anion forms firstly a hydrogen-bonded complex with a second anion equivalent necessary for the abstraction of the proton, with the formation of a [HA(2)](-) complex. The study performed here demonstrates the important role of the environment of the anion and 1 for the efficiency of the chromogenic chemosensor. Besides the different affinities of each anion for water, the solvation of both the anion and 1 is responsible for reducing the interaction between these species. In small amounts, water or hydrogen-bonded DMSO-water complexes are able to stabilize the conjugated base of 1 through hydrogen bonding, making 1 more acidic, which explains the change from 1:1 and 1:2 toward 1:1 1:anion stoichiometry upon addition of water. In addition, water is able to solvate the anion and also 1, which hinders the formation of 1:1 hydrogen-bonded 1:anion complexes prior to the abstraction of the proton. Copyright (c) 2009 Elsevier B.V. All rights reserved.
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Xu, Zhengming; Han, Dexia; Li, Yuan; Zhang, Pingling; You, Lijun; Zhao, Zhengang
2018-04-23
In this study, the FPA90-Cl resin was magnetized with supported Fe 3 O 4 particles using a chemical co-precipitation method and its removal performance of bromate and coexisting precursors was explored. The magnetized FPA90-Cl resin was structurally characterized by SEM, FT-IR, and XRD. The effects of the initial concentrations, temperature, and resin dosage on bromate and bromide ion removal in drinking water were investigated using batch experiments. The magnetized FPA90-Cl resin exhibited a high removal efficiency for bromate and bromide ions at three initial concentrations, and the residual bromate concentrations were under the maximum contaminant level (MCL) of 10 μg L -1 after 80 min. The adsorption data of bromate and bromide ion could be well described by a pseudo-first-order kinetic model (R 2 ˃ 0.98). The bromate removal alone was further studied by varying the initial solution pH, temperature, and competitive anions. The results showed that the magnetized FPA90-Cl resin could be used over a wide pH range (4.0-9.0). The maximum sorption capacity of the magnetized FPA90-Cl resin for bromate reached 132.83 mg g -1 at 298 K. The Freundlich and Redlich-Peterson isotherm models fit the bromate adsorption equilibrium better (R 2 ˃ 0.99) than the Langmuir isotherm model (R 2 ˃ 0.98). The thermodynamic analysis showed that the bromate adsorption process was endothermic. The negative ΔG and positive ΔS indicated that the process was spontaneous and that randomness increased after adsorption, respectively. The competition of coexisting anions with bromate was in the order of SO 4 2- > CO 3 2- > Cl - > NO 3 - > HCO 3 - > PO 4 3- . Additionally, the magnetized FPA90-Cl resin could maintain a high bromate and bromide ion adsorption capacity after five cycles of regeneration by a 0.1 M NaCl solution. Graphical abstract ᅟ.
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Erhayem, Mohamed; Sohn, Mary
2014-01-15
In many studies humic acid, fulvic acid, or natural organic matter is used interchangeably to model the effect of naturally derived organic matter on geochemical processes in the environment. In this study, the term NOOM (naturally occurring organic matter) is used to include both humic and fulvic acids as well as natural organic matter and compares the effect of NOOM type on NOOM removal onto nano-TiO2. In general, regardless of variations in solution chemistry, the order of the percentage of removal of NOOM onto nano-TiO2 was humic acid>natural organic matter>fulvic acid. The order of adsorption constant values of NOOM onto nano-TiO2 was also found to be humic acid>natural organic matter>fulvic acid under all conditions studied. The extent of NOOM removal by nano-TiO2 was enhanced in the presence of the divalent ions, magnesium and calcium, at pH7.8 when compared to the presence of the monovalent ions, sodium and potassium. Also, lower NOOM removal by nano-TiO2 in the presence of sodium salts of dihydrogen phosphate, bicarbonate and nitrate relative to chloride was observed and was likely due to the competition between polyatomic anions and NOOM adsorption onto the surface of nano-TiO2 indicating an anionic effect. Low concentrations of NOOM (10-20 mg L(-1)) destabilized nano-TiO2 in solution, however, the stability of nano-TiO2 increased as the amount of NOOM adsorbed onto nano-TiO2 increased at higher dissolved NOOM concentrations and significant stabilization was seen at 25 mg L(-1) NOOM. Thus, the three fractions of NOOM, humic and fulvic acids and natural organic matter and their concentrations were found to affect nano-TiO2 stability to different degrees although pH dependent trends in cation and anion effects had similar patterns. While the effects of adsorption of these three commonly used types of NOOM onto nanoparticles are similar, there are important differences that can be related to structural differences. © 2013.
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Improved method and apparatus for chromatographic quantitative analysis
Fritz, J.S.; Gjerde, D.T.; Schmuckler, G.
An improved apparatus and method are described for the quantitative analysis of a solution containing a plurality of anion species by ion exchange chromatography which utilizes a single element and a single ion exchange bed which does not require periodic regeneration. The solution containing the anions is added to an anion exchange resin bed which is a low capacity macroreticular polystyrene-divinylbenzene resin containing quarternary ammonium functional groups, and is eluted therefrom with a dilute solution of a low electrical conductance organic acid salt. As each anion species is eluted from the bed, it is quantitatively sensed by conventional detection means such as a conductivity cell.
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Mechanism of Scrapie Prion Precipitation with Phosphotungstate Anions
2015-01-01
The phosphotungstate anion (PTA) is widely used to facilitate the precipitation of disease-causing prion protein (PrPSc) from infected tissue for applications in structural studies and diagnostic approaches. However, the mechanism of this precipitation is not understood. In order to elucidate the nature of the PTA interaction with PrPSc under physiological conditions, solutions of PTA were characterized by NMR spectroscopy at varying pH. At neutral pH, the parent [PW12O40]3– ion decomposes to give a lacunary [PW11O39]7– (PW11) complex and a single orthotungstate anion [WO4]2– (WO4). To measure the efficacy of each component of PTA, increasing concentrations of PW11, WO4, and mixtures thereof were used to precipitate PrPSc from brain homogenates of scrapie prion-infected mice. The amount of PrPSc isolated, quantified by ELISA and immunoblotting, revealed that both PW11 and WO4 contribute to PrPSc precipitation. Incubation with sarkosyl, PTA, or individual components of PTA resulted in separation of higher-density PrP aggregates from the neuronal lipid monosialotetrahexosylganglioside (GM1), as observed by sucrose gradient centrifugation. These experiments revealed that yield and purity of PrPSc were greater with polyoxometalates (POMs), which substantially supported the separation of lipids from PrPSc in the samples. Interaction of POMs and sarkosyl with brain homogenates promoted the formation of fibrillar PrPSc aggregates prior to centrifugation, likely through the separation of lipids like GM1 from PrPSc. We propose that this separation of lipids from PrP is a major factor governing the facile precipitation of PrPSc by PTA from tissue and might be optimized further for the detection of prions. PMID:25695325
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Chattopadhyaya, M; Murugan, N Arul; Rinkevicius, Zilvinas
2016-09-15
We study the linear and nonlinear optical properties of a well-known acid-base indicator, bromophenol blue (BPB), in aqueous solution by employing static and integrated approaches. In the static approach, optical properties have been calculated using time-dependent density functional theory (TD-DFT) on the fully relaxed geometries of the neutral and different unprotonated forms of BPB. Moreover, both closed and open forms of BPB were considered. In the integrated approach, the optical properties have been computed over many snapshots extracted from molecular dynamics simulation using a hybrid time-dependent density functional theory/molecular mechanics approach. The static approach suggests closed neutral ⇒ anionic interconversion as the dominant mechanism for the red shift in the absorption spectra of BPB due to a change from acidic to basic pH. It is found by employing an integrated approach that the two interconversions, namely open neutral ⇒ anionic and open neutral ⇒ dianionic, can contribute to the pH-dependent shift in the absorption spectra of BPB. Even though both static and integrated approaches reproduce the pH-dependent red shift in the absorption spectra of BPB, the latter one is suitable to determine both the spectra and spectral broadening. Finally, the computed static first hyperpolarizability for various protonated and deprotonated forms of BPB reveals that this molecule can be used as a nonlinear optical probe for pH sensing in addition to its highly exploited use as an optical probe.
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Humic substance charge determination by titration with a flexible cationic polyelectrolyte
NASA Astrophysics Data System (ADS)
Tan, Wen-Feng; Norde, Willem; Koopal, Luuk K.
2011-10-01
The anionic charge of humic substances (HS) plays a major role in the interaction of HS with other components. Therefore, the potential of the polyelectrolyte titration technique to obtain the charge density of HS in simple 1-1 electrolyte solutions has been investigated. Titrations are carried out with an automatic titrator combined with the "Mütek particle charge detector" which allows determination of the Mütek potential and the pH as a function of the added amount of titrant which is a solution of poly-diallyldimethylammonium chloride (polyDADMAC), a cationic strong polyelectrolyte. When the Mütek potential reverses its sign the iso-electric point (IEP) of the polyDADMAC-HS complex is reached. The polyDADMAC/HS mass ratio at the IEP gives information on the HS charge density and from the pH changes in solution an estimate of the charge regulation in the HS-polyDADMAC complex can be obtained. In general, for polyDADMAC-HS complexes an increase in the dissociation of the acid groups of HS is found (charge regulation). The charge regulation decreases with increasing concentration of 1-1 background electrolyte. Cation incorporation can be neglected at 1-1 electrolyte concentrations ⩽ 1 mmol L -1 and a 1-1 stoichiometry exists between the polyDADMAC and HS charge. However, at these low salt concentrations the charge regulation is substantial. A detailed analysis of purified Aldrich humic acid (PAHA) at pH 5 and a range of KCl concentrations reveals that the anionic charge of PAHA in the complex increases at 5 mmol L -1 KCl by 30% and at 150 mmol L -1 KCl by 12%. On the other hand, increasing amounts of K + become incorporated in the complex: at 5 mmol L -1 KCl 5% and at 150 mmol L -1 KCl 24% of the PAHA charge is balanced by K +. By comparing at pH 5 the mass ratios polyDADMAC/PAHA in the complex at the IEP with the theoretical mass ratios of polyDADMAC/PAHA required to neutralize PAHA in the absence of charge regulation and K + incorporation, it is found that at 50 mmol L -1 KCl the extra negative charge due to the interaction between polyDADMAC and PAHA is just compensated by K + incorporation in the complex. Therefore, a pseudo 1-1 stoichiometry exists at about 50 mmol L -1 1-1 electrolyte concentration and only at this salt concentration polyDADMAC titrations and conventional proton titrations give identical results. Most likely this is also true for other HA samples and other pH values. For FA further study is required to reveal the conditions for which polyDADMAC and proton titrations give identical results.
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NASA Astrophysics Data System (ADS)
Wigger, Cornelia; Van Loon, Luc R.
2018-06-01
The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described.
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Wigger, Cornelia; Van Loon, Luc R
2018-06-01
The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl 2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl 2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl 2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described. Copyright © 2018 Elsevier B.V. All rights reserved.
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Inhibition of nuclear waste solutions containing multiple aggressive anions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Congdon, J.W.
1988-01-01
The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans, supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions, however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion.
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Inhibition of nuclear waste solutions containing multiple aggressive anions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Congdon, J.W.
1988-05-01
The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions; however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion.
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Zhou, Shi-ping; Duan, Chang-qun; Liu, Hong-cheng; Hu, Qiu-fen
2005-10-01
A highly sensitive, selective and rapid method for the determination of zinc based on the rapid reaction of zinc(II) with 2-(2-quinolylazo)-5-dimthylaminophenol (QADMAP) and the solid phase extraction of zinc ion with anion exchange resin cartridge was developed. In the presence of pH 8.5 buffer solution and Triton X-100 medium, QADMAP can react with zinc(II) to form a stable 2 :1 complex (QADMAP:Zn(II)). The molar absorptivity is 1.22 x 10(5)L x moL(-1) x cm(-1) at 590 nm. Beer's law is obeyed in the range of 0-1.0 microg x mL(-1). The zinc ions in the samples can be enriched and separated by solid phase extraction with anion exchange resincartridge. Testing results show that recovery for zinc(II) was from 95% to 104%, and RSD was below 3%. This method was applied to the determination of zinc in water and food with good results.
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Purification and labeling strategies for (68)Ga from (68)Ge/ (68)Ga generator eluate.
Mueller, Dirk; Klette, Ingo; Baum, Richard P
2013-01-01
For successful labeling, (68)Ge/(68)Ga generator eluate has to be concentrated (from 10 mL or more to less than 1 mL) and to be purified of metallic impurities, especially Fe(III), and (68)Ge breakthrough. Anionic, cationic and fractional elution methods are well known. We describe two new methods: (1) a combined cationic-anionic purification and (2) an easy-to-use and reliable cationic purification with NaCl solution. Using the first method, (68)Ga from 10 mL generator eluate was collected on a SCX cartridge, then eluted with 1.0 mL 5.5 M HCl directly on an anion exchanger (30 mg AG1X8). After drying with a stream of helium, (68)Ga was eluted with 0.4 mL water into the reaction vial. We provide as an example labeling of BPAMD. Using the second method, (68)Ga from 10 mL generator eluate was collected on a SCX cartridge, then eluted with a hydrochloric solution of sodium chloride (0.5 mL 5 M NaCl, 12.5 μL 5.5 M HCl) into the reaction vial, containing 40 μg DOTATOC and 0.5 mL 1 M ammonium acetate buffer pH 4.5. After heating for 7 min at 90°C, the reaction was finished. Radiochemical purity was higher than 95% without further purification. No (68)Ge breakthrough was found in the final product.
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Ionic Liquid-Solute Interactions Studied by 2D NOE NMR Spectroscopy.
Khatun, Sufia; Castner, Edward W
2015-07-23
Intermolecular interactions between a Ru(2+)(bpy)3 solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {(1)H-(19)F} HOESY and {(1)H-(1)H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru(2+)(bpy)3 solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru(2+)(bpy)3 solute interacts with both the polar head and the nonpolar tail groups of the 1-butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.
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VALIDATION FOR THE PERMANGANATE DIGESTION OF REILLEX HPQ ANION RESIN
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kyser, E.
2009-09-23
The flowsheet for the digestion of Reillex{trademark} HPQ was validated both under the traditional alkaline conditions and under strongly acidic conditions. Due to difficulty in performing a pH adjustment in the large tank where this flowsheet must be performed, the recommended digestion conditions were changed from pH 8-10 to 8 M HNO{sub 3}. Thus, no pH adjustment of the solution is required prior to performing the permanganate addition and digestion and the need to sample the digestion tank to confirm appropriate pH range for digestion may be avoided. Neutralization of the acidic digestion solution will be performed after completion ofmore » the resin digestion cycle. The amount of permanganate required for this type of resin (Reillex{trademark} HPQ) was increased from 1 kg/L resin to 4 kg/L resin to reduce the amount of residual resin solids to a minimal amount (<5%). The length of digestion time at 70 C remains unchanged at 15 hours. These parameters are not optimized but are expected to be adequate for the conditions. The flowsheet generates a significant amount of fine manganese dioxide (MnO{sub 2}) solids (1.71 kg/L resin) and involves the generation of a significant liquid volume due to the low solubility of permanganate. However, since only two batches of resin (40 L each) are expected to be digested, the total waste generated is limited.« less
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Improvement of drug loading onto ion exchange resin by cyclodextrin inclusion complex.
Samprasit, Wipada; Rojanarata, Theerasak; Akkaramongkolporn, Prasert; Ngawhirunpat, Tanasait; Sila-on, Warisada; Opanasopit, Praneet
2013-11-01
Ion exchange resins have ability to exchange their counter ions for ionized drug in the surrounding medium, yielding "drug resin complex." Cyclodextrin can be applied for enhancement of drug solubility and stability. Cyclodextrin inclusion complex of poorly water-soluble NSAIDs, i.e. meloxicam and piroxicam, was characterized and its novel application for improving drug loading onto an anionic exchange resin, i.e. Dowex® 1×2, was investigated. β-Cyclodextrin (β-CD) and hydroxypropyl β-cyclodextrin (HP-β-CD) were used for the preparation of inclusion complex with drugs in solution state at various pH. The inclusion complex was characterized by phase solubility, continuous variation, spectroscopic and electrochemistry methods. Then, the drug with and without cyclodextrin were equilibrated with resin at 1:1 and 1:2 weight ratio of drug and resin. Solubility of the drugs was found to increase with increasing cyclodextrin concentration and pH. The increased solubility was explained predominantly due to the formation of inclusion complex at low pH and the increased ionization of drug at high pH. According to characterization studies, the inclusion complex was successfully formed with a 1:1 stoichiometry. The presence of cyclodextrin in the loading solution resulted in the improvement of drug loading onto resin. Enhancing drug loading onto ion-exchange resin via the formation of cyclodextrin inclusion complex is usable in the development of ion-exchange based drug delivery systems, which will beneficially reduce the use of harmful acidic or basic and organic chemicals.
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Comparative study of selenite adsorption on carbon based adsorbents and activated alumina.
Jegadeesan, G; Mondal, K; Lalvani, S B
2003-08-01
The sorption characteristics of carbon-based adsorbents such as activated carbon and chitin for the removal of selenite, Se (IV), an anionic, hazardous contaminant, are compared with those of alpha and gamma alumina. Batch experiments were conducted to determine the influence of pH, concentration of adsorbate, adsorbent loading and temperature on the sorption characteristics of the adsorbents. Generally, low pH of the solution resulted in favorable selenium removal. With the exception of activated carbon, uptakes decreased with increase in temperature. In comparison, chitin was found to be far less effective for the removal of Se (IV) from aqueous solutions. The data also showed that gamma alumina provided higher selenium removal percentages (99%) compared to alpha alumina (94%), activated carbon (87%) and chitin (49%). The selenite removal was found to decrease with increasing initial Se (IV) concentration in the solution. Adsorption capacities of the adsorbents are reported in terms of their Langmuir adsorption isotherms. The adsorption capacity (on unit mass basis) of the adsorbents for selenite is in the order: chitin (specific area (sa) = 9.58 m2 g(-1)) < activated carbon (sa = 96.37 m2 g(-1)) < alpha alumina (sa = 6 m2 g(-1)) < gamma alumina (sa = 150 m2 g(-1)).
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A newly high alkaline lipase: an ideal choice for application in detergent formulations
2011-01-01
Background Bacterial lipases received much attention for their substrate specificity and their ability to function in extreme environments (pH, temperature...). Many staphylococci produced lipases which were released into the culture medium. Reports of thermostable lipases from Staphylococcus sp. and active in alkaline conditions are not previously described. Results A newly soil-isolated Staphylococcus sp. strain ESW secretes an induced lipase in the culture medium. The effects of temperature, pH and various components in a detergent on the activity and stability of Staphylococcus sp. lipase (SL1) were studied in a preliminary evaluation for use in detergent formulation solutions. The enzyme was highly active over a wide range of pH from 9.0 to 13.0, with an optimum at pH 12.0. The relative activity at pH 13.0 was about 60% of that obtained at pH 12.0. It exhibited maximal activity at 60°C. This novel lipase, showed extreme stability towards non-ionic and anionic surfactants after pre-incubation for 1 h at 40°C, and relative stability towards oxidizing agents. Additionally, the crude enzyme showed excellent stability and compatibility with various commercial solid and liquid detergents. Conclusions These properties added to the high activity in high alkaline pH make this novel lipase an ideal choice for application in detergent formulations. PMID:22123072
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CATALYTIC PROMOTION OF THE ADSORPTION OF VANADIUM ON AN ANIONIC EXCHANGE RESIN
Bailes, R.H.; Ellis, D.A.
1958-08-26
An improvement in the process for the recovery of vanadium from acidic phosphatic solutions is presented. In this process the vanadium is first oxidized to the pentavaleat state, and is then separated by contacting such solutions with an anion exchange resin whereby adsorption of the complexed pentavalent vanadium is effected. The improvement lies in the fact that adsorp tion of the vanadium complex by the anion exchange resin is promoted and improved by providing fiuoride ions in solution to be contacted.
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Stratton-Phelps, Meri; House, John K
2004-10-01
To determine whether feeding a commercial anionic dietary supplement as a urinary acidifier to male goats may be useful for management of urolithiasis. 8 adult sexually intact male Toggenburg, Saanen, and Nubian goats. Goats were randomly assigned by age-, breed-, and weight-matched pairs to an oat or grass hay diet that was fed for 12 days. On days 13 to 14 (early sample collection time before supplementation), measurements were made of blood and urine sodium, potassium, calcium, magnesium, chloride, phosphorus, and sulfur concentrations; blood and urine pH; urine production; and water consumption. During the next 28 days, the anionic dietary supplement was added to the oat and grass hay diets to achieve a dietary cation-anion difference of 0 mEq/100g of dry matter. Blood and urine samples were analyzed during dietary supplementation on days 12 to 13 (middle sample collection time) and 27 to 28 (late sample collection time). Blood bicarbonate, pH, and urine pH of goats fed grass hay and goats fed oat hay were significantly decreased during the middle and late sample collection times, compared with the early sample collection time. Water consumption and urine production in all goats increased significantly during the late sample collection time, compared with the early sample collection time. The anionic dietary supplement used in our study increases urine volume, alters urine ion concentrations, and is an efficacious urinary acidifier in goats. Goats treated with prolonged anionic dietary supplementation should be monitored for secondary osteoporosis from chronic urinary calcium loss.
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Photodegradation of Acid Violet 7 with AgBr-ZnO under highly alkaline conditions.
Krishnakumar, B; Swaminathan, M
2012-12-01
The photocatalytic activity of AgBr-ZnO was investigated for the degradation of Acid Violet 7 (AV 7) in aqueous solution using UV-A light. AgBr-ZnO is found to be more efficient than commercial ZnO and prepared ZnO at pH 12 for the mineralization of AV 7. The effects of operational parameters such as the amount of photocatalyst, dye concentration, initial pH on photo mineralization have been analyzed. Expect oxone, other oxidants decrease the degradation efficiency. Addition of metal ions and anions decrease the degradation efficiency of AgBr-ZnO significantly. The mineralization of AV 7 has also been confirmed by COD measurements. The mechanism of degradation by AgBr-ZnO is proposed to explain its higher activity under UV light. The catalyst is found to be reusable. Copyright © 2012 Elsevier B.V. All rights reserved.
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Bioremediation of uranium contamination with enzymatic uranium reduction
Lovley, D.R.; Phillips, E.J.P.
1992-01-01
Enzymatic uranium reduction by Desulfovibrio desulfuricans readily removed uranium from solution in a batch system or when D. desulfuricans was separated from the bulk of the uranium-containing water by a semipermeable membrane. Uranium reduction continued at concentrations as high as 24 mM. Of a variety of potentially inhibiting anions and metals evaluated, only high concentrations of copper inhibited uranium reduction. Freeze-dried cells, stored aerobically, reduced uranium as fast as fresh cells. D. desulfuricans reduced uranium in pH 4 and pH 7.4 mine drainage waters and in uraniumcontaining groundwaters from a contaminated Department of Energy site. Enzymatic uranium reduction has several potential advantages over other bioprocessing techniques for uranium removal, the most important of which are as follows: the ability to precipitate uranium that is in the form of a uranyl carbonate complex; high capacity for uranium removal per cell; the formation of a compact, relatively pure, uranium precipitate.
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Han, Sungyub; Hong, Seongmin; Li, Xiao
2013-11-15
The sensitivity of surface-enhanced Raman spectroscopy (SERS) highly depends on experimental factors including aggregating agents and pH. Using silver nanoparticles as the substrate, the effect of five cationic (K(+), Na(+), Mg(2+), Li(+), Ca(2+)) and three anionic (Cl(-), Br(-), I(-)) aggregating agents was examined on the SERS detection of tobacco-related biomarkers, namely cotinine (COT) and trans-3'-hydroxycotinine (3HC). The optimal concentrations of the aggregating agents with respect to highest SERS intensity varied widely (from 1.5 mM for MgCl2 to 150 mM for LiCl). Both cations and anions strongly influenced the SERS enhancement. When Cl(-) was used as the anion, Mg(2+) and Na(+) exhibited the highest SERS intensities for COT and 3HC, respectively. When Mg(2+) was used as the cation, Cl(-) and Br(-) generated the highest SERS enhancement for COT and 3HC, respectively. Clearly, SERS enhancement also depended on the target molecule. Among the 11 aggregating agent combinations tested, the highest SERS enhancement is obtained using 1.5 mM MgCl2 for COT at pH 7.0 and 50 mM NaBr for 3HC at pH 3.0. Copyright © 2013 Elsevier Inc. All rights reserved.
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Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi
2017-09-05
The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.
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Pu, Kan-Yi; Liu, Bin
2010-03-11
Cationic and anionic poly(fluorenyleneethynylene-alt-benzothiadiazole)s (PFEBTs) are designed and synthesized via Sonagashira coupling reaction to show light-up signatures toward proteins. Due to the charge transfer character of the excited states, the fluorescence of PFEBTs is very weak in aqueous solution, while their yellow fluorescence can be enhanced by polymer aggregation. PFEBTs show fluorescence turn-on rather than fluorescence quenching upon complexation with proteins. Both electrostatic and hydrophobic interactions between PFEBTs and proteins are found to improve the polymer fluorescence, the extent of which is dependent on the nature of the polymer and the protein. Changes in solution pH adjust the net charges of proteins, providing an effective way to manipulate electrostatic interactions and in turn the increment in the polymer fluorescence. In addition, the effect of protein digestion on the fluorescence of polymer/protein complexes is probed. The results indicate that electrostatic interaction induced polymer fluorescence increase cannot be substantially reduced through cleaving protein into peptide fragments. In contrast, hydrophobic interactions, mainly determined by the hydrophobicity of proteins, can be minimized by digestion, imparting a light-off signature for the polymer/protein complexes. This study thus not only highlights the opportunities of exerting nonspecific interactions for protein sensing but also reveals significant implications for biosensor design.
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Boric acid and boronic acids inhibition of pigeonpea urease.
Reddy, K Ravi Charan; Kayastha, Arvind M
2006-08-01
Urease from the seeds of pigeonpea was competitively inhibited by boric acid, butylboronic acid, phenylboronic acid, and 4-bromophenylboronic acid; 4-bromophenylboronic acid being the strongest inhibitor, followed by boric acid > butylboronic acid > phenylboronic acid, respectively. Urease inhibition by boric acid is maximal at acidic pH (5.0) and minimal at alkaline pH (10.0), i.e., the trigonal planar B(OH)3 form is a more effective inhibitor than the tetrahedral B(OH)4 -anionic form. Similarly, the anionic form of phenylboronic acid was least inhibiting in nature.
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The association of uranium with organic matter in Holocene peat: An experimental leaching study
Zielinski, R.A.; Meier, A.L.
1988-01-01
Uraniferous peat was sampled from surface layers of a Holocene U deposit in northeastern Washington State. Dried, sized, and homogenized peat that contained 5980 ??307 ppm U was subjected to a variety of leaching conditions to determine the nature and strength of U-organic bonding in recently accumulated organic matter. The results complement previous experimental studies of U uptake on peat and suggest some natural or anthropogenic disturbances that are favorable for remobilizing U. The fraction of U leached in 24 h experiments at 25??C ranged from 0 to 95%. The most effective leach solutions contained anions capable of forming stable dissolved complexes with uranyl (UO2+2) cation. These included H2SO4 (pH = 1.5) and concentrated (>0.01 M) solutions of sodium bicarbonate-carbonate (pH = 7.0-10.0), or sodium pyrophosphate (pH = 10). Effective leaching by carbonate and pyrophosphate in the absence of added oxidant, and the insignificant effect of added oxidant (as pressurized O2) strongly suggest that U is initially fixed on organic matter as an oxidized U(VI) species. Uranium is more strongly bound than some other polyvalent cations, based on its resistance to exchange in the presence of large excesses of dissolved Ca2+ and Cu2+. Measurements of the rate of U leaching indicate faster rates in acid solution compared to carbonate solution, and are consisten with simultaneous attack of sites with different affinities for U. Sulfuric acid appears a good choice for commercial extraction of U from mined peat. In situ disturbances such as overliming of peat soils, addition of fertilizers containing pyrophosphate, or incursions of natural carbonate-rich waters could produce significant remobilization of U, and possibly compromise the quality of local domestic water supplies. ?? 1988.
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Scandium complexes with the tetraphenylethylene and anthracene dianions.
Ellis, John E; Minyaev, Mikhail E; Nifant'ev, Ilya E; Churakov, Andrei V
2018-06-01
The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare-earth metal-carbon bonding. The crystal structures of (18-crown-6)bis(tetrahydrofuran-κO)sodium bis(η 6 -1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C 4 H 8 O) 2 (C 12 H 24 O 6 )][Sc(C 26 H 20 ) 2 ]·2C 4 H 8 O or [Na(18-crown-6)(THF) 2 ][Sc(η 6 -C 2 Ph 4 ) 2 ]·2(THF), (1b), (η 5 -1,3-diphenylcyclopentadienyl)(tetrahydrofuran-κO)(η 6 -1,1,2,2-tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C 17 H 13 )(C 26 H 20 )(C 4 H 8 O)]·0.5C 7 H 8 or [(η 5 -1,3-Ph 2 C 5 H 3 )Sc(η 6 -C 2 Ph 4 )(THF)]·0.5(toluene), (5b), poly[[(μ 2 -η 3 :η 3 -anthracenediyl)bis(η 6 -anthracenediyl)bis(η 5 -1,3-diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K 2 Sc 2 (C 14 H 10 ) 3 (C 17 H 13 ) 2 (C 4 H 8 O) 4 ]·C 4 H 8 O} n or [K(THF) 2 ] 2 [(1,3-Ph 2 C 5 H 3 ) 2 Sc 2 (C 14 H 10 ) 3 ]·THF, (6), and 1,4-diphenylcyclopenta-1,3-diene, C 17 H 14 , (3a), have been established. The [Sc(η 6 -C 2 Ph 4 ) 2 ] - complex anion in (1b) contains the tetraphenylethylene dianion in a symmetrical bis-η 3 -allyl coordination mode. The complex homoleptic [Sc(η 6 -C 2 Ph 4 ) 2 ] - anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The 1D 1 H and 13 C{ 1 H}, and 2D COSY 1 H- 1 H and 13 C- 1 H NMR data are presented for M[Sc(Ph 4 C 2 ) 2 ]·xTHF [M = Na and x = 4 for (1a); M = K and x = 3.5 for (2a)] in THF-d 8 media. Complex (5b) exhibits an unsymmetrical bis-η 3 -allyl coordination mode of the dianion, but this changes to a η 4 coordination mode for (1,3-Ph 2 C 5 H 3 )Sc(Ph 4 C 2 )(THF) 2 , (5a), in THF-d 8 solution. A 45 Sc NMR study of (2a) and UV-Vis studies of (1a), (2a) and (5a) indicate a significant covalent contribution to the Sc-Ph 4 C 2 bond character. The unique Sc ate complex, (6), contains three anthracenide dianions demonstrating both a η 6 -coordination mode for two bent ligands and a μ 2 -η 3 :η 3 -bridging mode of a flat ligand. Each [(1,3-Ph 2 C 5 H 3 ) 2 Sc 2 (C 14 H 10 ) 3 ] 2- dianionic unit is connected to four neighbouring units via short contacts with [K(THF) 2 ] + cations, forming a two-dimensional coordination polymer framework parallel to (001).
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Maitlo, Hubdar Ali; Kim, Jung Hwan; Park, Joo Yang
2017-04-01
Dual-chambered fuel cells with an iron anode and an air-carbon cathode separated by an ion exchange membranes have been used to treat arsenate during power production. To select an effective catholyte, the dual-chambered fuel cell consisted 90 mL of 0.1 M HCl or 0.5 M NaCl as the catholyte and 1 L of 0.1 M NaHCO 3 as the anolyte at an initial pH 5. The 0.1 M HCl was an effective catholyte, with which 1 ppm arsenate in 1 L of anolyte was reduced to 5 ppb in 1 h, and the maximum power density was about 6.3 w/m 2 with an anion exchange membrane fuel cell (AEM_FC) and 4.4 w/m 2 with a cation exchange membrane fuel cell (CEM_FC). Therefore, 90 mL of 0.1 M HCl was used as a catholyte to treat 20 L of 0.1 M NaHCO 3 anolyte containing 1 ppm arsenate at an initial pH of 5 or 7. The arsenate level at pH 5 decreased to less than 5 ppb in 4 h, and the maximum power density was 5.9 W/m 2 and 4.7 W/m 2 with AEM_FC and CEM_FC, respectively. When using 0.01 M NaHCO 3 as the anolyte at pH 5, arsenate was reduced to less than 5 ppb in 8 and 24 h for AEC_FC and CEM_FC, respectively. However, when using an anolyte at pH 7, arsenate could not be effectively removed in 24 h. Therefore, when using carbonate as an anolyte, the solution should be adjusted to a weakly acidic pH in order to remove arsenate. Copyright © 2017 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Mehan, Sumit; Kumar, S.; Aswal, V. K.; Schweins, R.
2016-05-01
SANS experiments of three-component system of anionic silica nanoparticles, anionic BSA protein and anionic SDS surfactants have been carried out without and with electrolyte in aqueous solution. In both the cases, the interaction of surfactant with protein results in formation of bead-necklace structure of protein-surfactant complexes in solution. These protein-surfactant complexes interact very differently with nanoparticles in absence and presence of electrolyte. In absence of electrolyte, nanoparticles remain in dispersed phase in solution, whereas with the addition of electrolyte the nanoparticles fractal aggregates are formed. SANS describes the phase behavior to be governed by competition of electrostatic and depletion interactions among the components solution.
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NASA Astrophysics Data System (ADS)
Rueck, Angelika C.; Strauss, Wolfgang S. L.; Schneckenburger, Herbert; Steiner, Rudolf W.
1992-06-01
Light-induced reactions of different hydrophilic meso-tetraphenyl porphyrins (TPPS4, TPPC4, T4MPyP) were investigated during PDT treatment. These measurements were carried out in vitro using micro-spectrofluorometry and were correlated with measurements in buffer solutions. In the case of the anionic TPPS4, before light exposure, a neutral free base and a protonated species could be detected simultaneously in the cells. During irradiation, the protonated species first disappeared. Due to the fact that a coexistence of a protonated and unprotonated species requires a pH value around 5, TPPS4 was at first located in the lysosomes (pH 5) and was released into the cytoplasm during irradiation as a result of lysosomal rupture. Further light exposure led to a drastic fluorescence formation in the nuclei, in particular the nucleoli of the cells, which was concomitant with a renewed observation of a fluorescence emission spectrum similar to that of the protonated species. In the case of the anionic TPPC4, a similar fluorescence increase was observed during irradiation. However, the formation of a protonated species played a less important role. The cationic T4MPyP again showed fluorescence increase during irradiation. Two Soret-bands separated by about 20 nm could be detected. The red-shifted band may be due to a special intercalation of T4MPyP in nucleic acids.
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Alonso, María; Alvarez, M Angeles; García, M Esther; Ruiz, Miguel A; Hamidov, Hayrullo; Jeffery, John C
2010-12-20
The anionic oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) displayed multisite reactivity when faced with different electrophilic reagents. The reactions with the group 14 organochloride compounds ER(4-x)Cl(x) (E = Si, Ge, Sn, Pb) led to either phosphide-like, oxophosphinidene-bridged derivatives [MCp{P(OE')R*}(CO)(2)] (E' = SiMe(3), SiPh(3), GePh(3), GeMe(2)Cl) or to terminal oxophosphinidene complexes [MCp{P(O)R*}(CO)(2)(E')] (E' = SnPh(3), SnPh(2)Cl, PbPh(3); Mo-Pb = 2.8845(4) Å for the MoPb compound). A particular situation was found in the reaction with SnMe(3)Cl, this giving a product existing in both tautomeric forms, with the phosphide-like complex [MCp{P(OSnMe(3))R*}(CO)(2)] prevailing at room temperature and the tautomer [MCp{P(O)R*}(CO)(2)(SnMe(3))] being the unique species present below 203 K in dichloromethane solution. The title anions also showed a multisite behavior when reacting with transition-metal based electrophiles. Thus, the reactions with the complexes [M'Cp(2)Cl(2)] (M' = Ti, Zr) gave phosphide-like derivatives [MCp{P(OM')R*}(CO)(2)] (M = Mo, M' = TiCp(2)Cl, ZrCp(2)Cl; M = W, M' = ZrCp(2)Cl), displaying a bridging κ(1),κ(1)-P,O- oxophosphinidene ligand connecting MCp(CO)(2) and M'Cp(2)Cl metal fragments (W-P = 2.233(1) Å, O-Zr = 2.016(4) Å for the WZr compound]. In contrast, the reactions with the complex [AuCl{P(p-tol)(3)}] gave the metal-metal bonded derivatives trans-[MCp{P(O)R*}(CO)(2){AuP(p-tol)(3)}] (M = Mo, W; Mo-Au = 2.7071(7) Å). From all the above results it was concluded that the terminal oxophosphinidene complexes are preferentially formed under conditions of orbital control, while charge-controlled reactions tend to give derivatives with the electrophilic fragment bound to the oxygen atom of the oxophosphinidene ligand (phosphide-like, oxophosphinidene-bridged derivatives).
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Massue, Julien; Quinn, Susan J; Gunnlaugsson, Thorfinnur
2008-06-04
1.Eu, a cyclen based Eu(III)-thiol conjugate, was incorporated onto the surface of water-soluble gold nanoparticles to give AuNP-1.Eu. The self-assembly between AuNP-1.Eu and the antenna 2 resulted in the formation of the highly luminescent lanthanide system, AuNP-1.Eu-2, at pH 7.4. The sensing of flavin monophosphate 3 is demonstrated, whereby 3 displaced the antenna 2 in AuNP-1.Eu-2, resulting in the formation of AuNP-1.Eu-3 and quenching of the Eu(III) emission.
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Tang, Qingzi; Duan, Tongdan; Li, Peng; Zhang, Ping; Wu, Daishe
2018-01-01
In this work, the potential of a novel hydroxyapatite decorated with carbon nanotube composite (CNT-HAP) for fluoride removal was investigated. The synthesized CNT-HAP composite was systematically characterized by X-ray diffraction(XRD), Fourier Transform infrared spectroscopy(FTIR), scanning electron microscope (SEM) and Brunauer-Emmett-Teller(BET). Batch adsorption experiments were conducted to investigate the defluorination capacity of CNT-HAP. The CNT-HAP composite has a maximum adsorption capacity of 11.05 mg·g -1 for fluoride, and the isothermal adsorption data were fitted by the Freundlich model to calculate the thermodynamic parameters. Thermodynamic analysis implies that the adsorption of fluoride on CNT-HAP is a spontaneous process. Furthermore, the adsorption of fluoride follows pseudo-second-order model. The effects of solution pH, co-existing anions and reaction temperature on defluorination efficiency were examined to optimize the operation conditions for fluoride adsorption. It is found that the optimized pH-value for fluoride removal by CNT-HAP composite is 6. In addition, among five common anions studied in this work, the presence of [Formula: see text] and [Formula: see text] could considerably affect the fluoride removal by CNT-HPA in aqueous media. Finally, the underlying mechanism for the fluoride removal by CNT-HAP is analyzed, and an anion exchange process is proposed.
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Tang, Qingzi; Duan, Tongdan; Li, Peng; Zhang, Ping; Wu, Daishe
2018-01-01
In this work, the potential of a novel hydroxyapatite decorated with carbon nanotube composite (CNT-HAP) for fluoride removal was investigated. The synthesized CNT-HAP composite was systematically characterized by X-ray diffraction(XRD), Fourier Transform infrared spectroscopy(FTIR), scanning electron microscope (SEM) and Brunauer–Emmett–Teller(BET). Batch adsorption experiments were conducted to investigate the defluorination capacity of CNT-HAP. The CNT-HAP composite has a maximum adsorption capacity of 11.05 mg·g−1 for fluoride, and the isothermal adsorption data were fitted by the Freundlich model to calculate the thermodynamic parameters. Thermodynamic analysis implies that the adsorption of fluoride on CNT-HAP is a spontaneous process. Furthermore, the adsorption of fluoride follows pseudo-second-order model. The effects of solution pH, co-existing anions and reaction temperature on defluorination efficiency were examined to optimize the operation conditions for fluoride adsorption. It is found that the optimized pH-value for fluoride removal by CNT-HAP composite is 6. In addition, among five common anions studied in this work, the presence of HCO3- and PO43- could considerably affect the fluoride removal by CNT-HPA in aqueous media. Finally, the underlying mechanism for the fluoride removal by CNT-HAP is analyzed, and an anion exchange process is proposed. PMID:29696138
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The Influence of Salt Anions on Heavy Metal Ion Adsorption on the Example of Nickel
Mende, Mandy; Schwarz, Dana; Steinbach, Christine; Schwarz, Simona
2018-01-01
The biodegradable polysaccharide chitosan possesses protonated and natural amino groups at medium pH values and has therefore been used as an adsorbing material for nickel salts in water treatment. Nickel is a problematic heavy metal ion which can cause various diseases and disorders in living organisms. Here, we show the influence of oxyanions (e.g., nitrate and sulfate) to the adsorption of nickel ions. Hence, simultaneously we are addressing the increasing global problem of nitrate and sulfate ion pollution in groundwater and surface water. A series of adsorption experiments was carried out in order to determine (i) the adsorption equilibrium, (ii) the adsorption capacity in dependence on the initial nickel ion concentration, and (iii) the influence of the anion presented in solution for the adsorption capacity. Surface morphology of chitosan flakes before and after the adsorption process has been studied with SEM-EDX analysis. The chitosan flakes exhibited promising adsorption capacities of 81.9 mg·g−1 and 21.2 mg·g−1 for nickel (sulfate) and nickel (nitrate), respectively. The calculated values of Gibbs free energy change ΔG0 confirm the higher adsorption of nickel ions in presence of sulfate ions. Hence, higher anion valence leads to a higher adsorption capacity. PMID:29510485
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Sorption and retention of diclofenac on zeolite in the presence of cationic surfactant.
Sun, Ken; Shi, Yan; Wang, Xiaoyu; Li, Zhaohui
2017-02-05
Diclofenac (DC) is one of the most widely prescribed non-steroidal anti-inflammatory drugs and one of the commonly found pharmaceuticals in aquatic environments and wastewater treatment plants. It possesses negative charges when solution pH is greater than its pKa value, while most of the soil components and sediment minerals bear negative charges, too, resulting in a net repulsion between the soil minerals and DC. Surfactant-modified zeolite (SMZ) has been studied extensively over the last 20 years for its effective removal of anionic contaminants tested under different experimental scales. However, its application for the removal of anionic drugs, such as DC, was less reported. This study focused on the sorption of DC by SMZ under different physic-chemical conditions, supplemented with instrumental analyses, in order to elucidate the mechanism of DC sorption by SMZ and to expand the SMZ application further. The results showed that the retention of DC was on the external surfaces of SMZ with extremely fast removal rate. Both anion exchange and partitioning of DC into the adsorbed surfactant micelles (admicelles) were responsible for the extended DC sorption. Interactions of DC with SMZ were facilitated with the benzene ring, the CO, and the CH 2 CH 3 functional groups. Copyright © 2016 Elsevier B.V. All rights reserved.
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Alagha, Lana; Wang, Shengqun; Yan, Lujie; Xu, Zhenghe; Masliyah, Jacob
2013-03-26
Quartz crystal microbalance with dissipation (QCM-D) was applied to investigate the adsorption characteristics of polyacrylamide-based polymers (PAMs) on anisotropic basal planes of kaolinite. Kaolinite basal planes were differentiated by depositing kaolinite nanoparticles (KNPs) on silica and alumina sensors in solutions of controlled pH values. Adsorption of an in-house synthesized organic-inorganic Al(OH)3-PAM (Al-PAM) as an example of cationic hybrid PAM and a commercially available partially hydrolyzed polyacrylamide (MF1011) as an example of anionic PAM was studied. Cationic Al-PAM was found to adsorb irreversibly and preferentially on tetrahedral silica basal planes of kaolinite. In contrast, anionic MF1011 adsorbed strongly on aluminum-hydroxy basal planes, while its adsorption on tetrahedral silica basal planes was weak and reversible. Adsorption study revealed that both electrostatic attraction and hydrogen-bonding mechanisms contribute to adsorption of PAMs on kaolinite. The adsorbed Al-PAM layer was able to release trapped water overtime and became more compact, while MF1011 film became more dissipative as backbones stretched out from kaolinite surface with minimal overlapping. Experimental results obtained from this study provide clear insights into the phenomenon that governs flocculation-based solid-liquid separation processes using multicomponent flocculants of anionic and cationic nature.
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Vijayaraghavan, K; Teo, Ting Ting; Balasubramanian, R; Joshi, Umid Man
2009-05-30
The ability of Sargassum sp. to biosorb four metal ions, namely lead, copper, zinc, and manganese from a synthetic multi-solute system and real storm water runoff has been investigated for the first time. Experiments on synthetic multi-solute systems revealed that Sargassum performed well in the biosorption of all four metal ions, with preference towards Pb, followed by Cu, Zn, and Mn. The solution pH strongly affected the metal biosorption, with pH 6 being identified as the optimal condition for achieving maximum biosorption. Experiments at different biosorbent dosages revealed that good biosorption capacity as well as high metal removal efficiency was observed at 3g/L. The biosorption kinetics was found to be fast with equilibrium being attained within 50 min. According to the Langmuir isotherm model, Sargassum exhibited maximum uptakes of 214, 67.5, 24.2 and 20.2mg/g for lead, copper, zinc, and manganese, respectively in single-solute systems. In multi-metal systems, strong competition between four metal ions in terms of occupancy binding sites was observed, and Sargassum showed preference in the order of Pb>Cu>Zn>Mn. The application of Sargassum to remove four heavy metal ions in real storm water runoff revealed that the biomass was capable of removing the heavy metal ions. However, the biosorption performance was slightly lower compared to that of synthetic metal solutions. Several factors were responsible for this difference, and the most important factor is the presence of other contaminants such as anions, organics, and other trace metals in the runoff.
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Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy
Khatun, Sufia; Castner, Edward W.
2014-11-26
Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulkmore » IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.« less
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de Almeida, Francine Tatiane Rezende; Ferreira, Bruno Christiano Silva; Moreira, Ana Luísa da Silva Lage; de Freitas, Rossimiriam Pereira; Gil, Laurent Frédéric; Gurgel, Leandro Vinícius Alves
2016-03-15
This study describes the synthesis of a new chitosan derivative (C2) with zwitterionic characteristics and its use for the removal of cationic species Cu(2+), Co(2+), and Ni(2+) and anionic species of Cr(6+) in a single aqueous solution. The new adsorbent was synthesized by quaternization of the amine group of chitosan and esterification of hydroxyl groups with EDTA dianhydride. These combined reactions gave both cationic and anionic characteristics to C2 with the release of quaternary ammonium groups and carboxylic groups. The capacity of C2 to adsorb Cu(2+), Co(2+), Ni(2+), and oxyanions of Cr(6+) was evaluated in a batch process with different contact times, pH values, and initial concentrations. Adsorption isotherms were best fitted to the Langmuir and Sips models. The maximum adsorption capacities (Q(max)) of C2 for adsorption of Cu(2+), Co(2+), Ni(2+), and Cr(6+) were 0.698, 1.125, 0.725, and 1.910 mmol/g, respectively. The Δ(ads)G° values were in the range from -20 to -28 kJ/mol. These values suggest a mixed mechanism controlling adsorption. Desorption studies using an aqueous solution consisting of 0.1 mol/L HNO3 were carried out. The reusability of the recovered C2 adsorbent after desorption was also evaluated. Copyright © 2015 Elsevier Inc. All rights reserved.
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Fabrication of N, P-codoped reduced graphene oxide and its application for organic dye removal
NASA Astrophysics Data System (ADS)
Wu, Yu; Yang, Feng; Liu, Xiaoxia; Tan, Guangqun; Xiao, Dan
2018-03-01
N, P-codoped reduced graphene oxide (PA-RGO) was synthesized from graphene oxide (GO) and phytic acid (PA) mixture with the reductant of hydrazine hydrate (N2H4) via one-pot solution method. PA can modify the surface of RGO to enhance the hydrophilicity of RGO, and supply anionic functional groups, which can complex with cationic dye via anion-cation interaction. PA-RGO with different amount doped PA were used to remove multiple organic dyes from aqueous solution. The adsorption properties of the PA-RGO-2.0 towards Rhodamine B (RhB) were investigated under various parameters such as different pH of initial solution, different dosage of the PA-RGO-2.0, shaking speed and temperature. To study structural and chemical characterization of PA-RGO-2.0, Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscope (AFM), X-ray photoelectron and spectroscopy (XPS) were used, and UV-vis spectrum was used to monitor the absorbance of adsorbate. The batch adsorption experiments of RhB on PA-RGO-2.0 showed that the RhB equilibrium capacity was about 149 mg/g. In addition, the adsorption process was well-matched with the pseudo-second-order rate model. The as-prepared composites were found to be highly selective for cationic organic dyes. The good reusability of PA-RGO indicated that the adsorbent possessed potential practical application.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Shen, Zhizhang; Ilton, Eugene S.; Prange, Micah P.
Classical molecular dynamics (MD) simulations were used to study the interactions of up to 2 M NaCl and NaNO3 aqueous solutions with the presumed inert boehmite (010) and gibbsite (001) surfaces. The force field parameters used in these simulations were validated against density functional theory calculations of Na+ and Cl- hydrated complexes adsorbed at the boehmite (010) surface. In all the classical MD simulations and regardless of the ionic strength or the nature of the anion, Na+ ions were found to preferably form inner-sphere complexes over outer-sphere complexes at the aluminum (oxy)hydroxide surfaces, adsorbing closer to the surface than bothmore » water molecules and anions. In contrast, Cl- ions were distributed almost equally between inner- and outer-sphere positions. The resulting asymmetry in adsorption strengths offers molecular-scale evidence for the observed isoelectric point (IEP) shift to higher pH at high ionic strength for aluminum (oxy)hydroxides. As such, the MD simulations also provided clear evidence against the assumption that the basal surfaces of boehmite and gibbsite are inert to background electrolytes. Finally, the MD simulations indicated that, although the adsorption behavior of Na+ in NaNO3 and NaCl solutions was similar, the different affinities of NO3- and Cl- for the aluminum (oxy)hydroxide surfaces might have macroscopic consequences, such as difference in the sensitivity of the IEP to the electrolyte concentration.« less
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Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bowman-James, Kristen
2004-12-01
This project have focuses on the basic chemical aspects of anion receptor design of functional pH independent systems, with the ultimate goal of targeting the selective binding of sulfate, as well as design of separations strategies for selective and efficient removal of targeted anions. Key findings include: (1) the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate anion from acidic, nitrate-containing aqueous media. Areas probed during the last funding period include: the design, synthesis, and physical andmore » structural characterization of receptors and investigation of anion and dual ion pair extraction using lipophilic amide receptors for anion binding. A new collaboration has been added to the project in addition to the one with Dr. Bruce Moyer at Oak Ridge National Laboratory, with Professor Jonathan Sessler at the University of Texas at Austin.« less
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Thompson; Parks; Brown
2000-02-15
The uptake and release behavior of cobalt(II) was studied over thousands of hours in CO(2)-free aqueous suspensions of kaolinite under three pairs of total cobalt concentration (Co(T)) and near-neutral pH (7.5-7.8) conditions. Dissolved cobalt, aluminum, and silicon concentrations were monitored by ICPMS, and cobalt-containing products were identified by EXAFS spectroscopy. In each uptake experiment, cobalt sorbed to kaolinite as a mixture of surface-adsorbed monomers or polymers and hydrotalcite-like precipitates of the approximate composition Co(x)Al(OH)(2x+2)(A(n-))(1/n), where 2
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NASA Astrophysics Data System (ADS)
Silva, Sônia M. L.; Coelho, Letícia N.; Malachias, Ângelo; Perez, Carlos A.; Pesquero, Jorge L.; Magalhães-Paniago, Rogério; de Oliveira, Mônica C.
2011-04-01
The present study investigated the effect of the 6-monodeoxy-6-monoamine-β-cyclodextrin(Am-β-CD)/DNA (Am-β-CD/DNA) complex, as well as of culture medium components and proteins, at pH 7.4 and 5.0, on membranes of anionic and pH-sensitive liposomes comprised of DOPE-CHEMS, using energy dispersive X-ray diffraction (EDXD). At pH 7.4, the Am-β-CD/DNA complex induced the appearance of lamellar and hexagonal phases of DOPE. However, at pH 5.0, only non-lamellar phases could be observed. The presence of biological components led to a disruption of lipid order, but the pH-sensitivity of liposomes was maintained.
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NASA Astrophysics Data System (ADS)
Ghosh, Sumit
2010-11-01
Interaction between anionic surfactant, sodium dodecyl benzene sulphonate, (SDBS) and an anionic dye Eriochrome Black-T, (EBT) has been investigated by visible spectroscopy, conductometry, dynamic light scattering and zeta potential measurements. Spectral changes of EBT observed on addition of SDBS indicate formation of quinone-hydrazone tautomer at pH 7.0, whereas in absence of SDBS this change appears at pH ˜ 9.45. However, at pH 7.0 this change in tautomerism is not observed in presence of sodium dodecyl sulphate (SDS). Experimental results indicate presence of charge transfer interaction between less stable quinone-hydrazone tautomer of EBT and SDBS molecules, which is confirmed using Benesi-Hildebrand and Scott equations.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Petrosyants, S.P.; Buslaeva, E.R.
1986-04-01
The interaction of aluminum and gallium solvates with ..pi..-acid ligand in 1,2-propanediol solutions has been investigated. The formation of associates of hexacoordinate aluminum solvates depends on the solvation of the anions in the bulk of the solution or on the faces of the solvento complexes. In the case of gallium the association of the solvates with the anions is determined by two factors: the existence of a configurational equilibrium for the solvento complexes and the preferential solvation of the competitive ..pi..-acid ligands.
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NASA Astrophysics Data System (ADS)
Barsbay, Murat; Kavaklı, Pınar Akkaş; Güven, Olgun
2010-03-01
A novel polymeric ligand exchanger (PLE) was prepared for the removal of phosphate ions from water. 2,2'-dipyridylamine (DPA), a bidentate ligand forming compound with high coordination capacity with a variety of metal ions was bound to glycidyl methacrylate (GMA) grafted polypropylene/polyethylene (PP/PE) nonwoven fabric synthesized by radiation-induced grafting technique. DPA attachment on epoxy ring of GMA units was tested in different solvents, i.e. methanol, ethanol, dioxane and dimethylsulfoxide (DMSO). The highest amount of modification was achieved in dioxane. In order to prepare the corresponding PLE for the removal of phosphate, DPA-immobilized fabric was loaded with Cu(II) ions. Phosphate adsorption experiments were performed in batch mode at different pH (5-9) and phosphate concentrations. The fabric was found to be effective for the removal of phosphate ions. At every stage of preparation and use, the nonwoven fabric was characterized by thermal (i.e. DSC and TGA) and spectroscopic (FTIR) methods. Competitive adsorption experiments were also carried out using two solutions with different concentration levels at pH 7 to see the effect of competing ions. Phosphate adsorption was found to be effective and selective from solutions having trace amounts of competitive anions. It is expected that the novel PLE synthesized can be used for the removal of phosphate ions in low concentrations over a large range of pH.
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Cavallaro, Gennara; Giammona, Gaetano; Pasotti, Luca; Pallavicini, Piersandro
2011-09-12
A new approach is presented to obtain fluorescent sensors for pH windows that work in water and under biomimetic conditions. A single molecule that features all-covalently linked components is used, thus making it capable of working as a fluorescent sensor with an OFF/ON/OFF response to pH value. The components are a tertiary amine, a pyridine, and a fluorophore (pyrene). The forms with both protonated bases or both neutral bases quench the pyrene fluorescence, whereas the form with the neutral pyridine and protonated amine groups is fluorescent. The molecular sensor is also equipped with a long alkyl chain to make it highly hydrophobic in all its protonated and unprotonated forms, that is, either when neutral or charged. Accordingly, it can be confined at any pH value either in traditional (i.e., low-molecular-weight) nonionic surfactant micelles or inside polymeric, biocompatible micellar containers. Relevant for future applications in vivo, thanks to its strong hydrophobicity, no leakage of the molecular sensor is observed from the polymeric biocompatible micelles. Due to the proximity of the pyridine and amine functions in the molecular structure and the poor hydration inside the micelles, the observed pK(a) values are low so that the ON window is positioned at very low pH values. However, the window can be shifted to biologically relevant values by comicellization of anionic species. In particular, in the micelles of the nonionic surfactant TritonX-100, a shift of the ON window to pH 4-6 is obtained by addition of the anionic sodium dodecyl sulphate surfactant, whose negative charge promotes the stability of the protonated forms of the pyridine and amine fragments. In the case of the polymeric micelles, we introduce the use of the amphiphilic polystyrene sulfonate anionic polyelectrolyte, the comicellization of which induces a shift and sharpening of the ON window that is centered at pH 4. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Lu, Connie C.; Peters, Jonas C.
2008-01-01
This paper presents aspects of the coordination chemistry of mono- and divalent manganese complexes supported by the anionic tris(phosphino)borate ligand, [PhBPiPr3] (where [PhBPiPr3] = [PhB(CH2PiPr2)3]−). The Mn(II) halide complexes, [PhBPiPr3]MnCl (1 and [PhBPiPr3]MnI (2), have been characterized by X-ray diffraction, SQUID magnetometry, and EPR spectroscopy. Compound 2 serves as a precursor to a series of Mn azide, alkyl, and amide species: [PhBPiPr3]Mn(N3) (3), [PhBPiPr3]Mn(CH2Ph) (4), [PhBPiPr3]Mn(Me) (5), [PhBPiPr3]Mn(NH(2,6-iPr2-C6H3)) (6), [PhBPiPr3]Mn(dbabh) (7), and [PhBPiPr3]Mn(1-Ph(isoindolate)) (8). The complexes 2 – 8 feature a divalent-metal center and are pseudotetrahedral. They collectively represent an uncommon structural motif for low-coordinate, polyphosphine-supported Mn complexes. Two Mn(I) species have also been prepared. These include the Tl-Mn adduct, [PhBPiPr3]Tl-MnBr(CO)4 (9), and the octahedral complex [PhBPiPr3]Mn(CNtBu)3 (10). Some of our initial synthetic efforts to generate [PhBPiPr3]Mn≡Nx species are briefly described, as are DFT studies that probe the electronic viability of these types of multiply bonded target structures. PMID:17029370
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Sorption of the herbicide aminocyclopyrachlor by cation modified clay minerals
USDA-ARS?s Scientific Manuscript database
Aminocyclopyrachlor is a newly registered herbicide for the control of broadleaf weeds, grasses, vines and woody species in non-crops, turf, sod farms, and residential areas. At typical soil pH levels, aminocyclopyrachlor is in the anionic form. Anionic pesticides are generally weakly retained by mo...
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NASA Astrophysics Data System (ADS)
Penta, Naresh K.; Amanapu, H. P.; Peethala, B. C.; Babu, S. V.
2013-10-01
Four different anionic surfactants, sodium dodecyl sulfate, dodecyl benzene sulfonic acid (DBSA), dodecyl phosphate and Sodium lauroyl sarcosine, selected from the sulfate, phosphate, and carboxylic family, were investigated as additives in silica dispersions for selective polishing of silicon dioxide over silicon nitride films. We found that all these anionic surfactants suppress the nitride removal rates (RR) for pH ≤4 while more or less maintaining the oxide RRs, resulting in high oxide-to-nitride RR selectivity. The RR data obtained as a function of pH were explained based on pH dependent distributions of surfactant species, change in the zeta potentials of oxide and nitride surfaces, and thermogravimetric data. It appears that the negatively charged surfactant species preferentially adsorb on the positively charged nitride surface below IEP through its electrostatic interactions and form a bilayer adsorption, resulting in the suppression of nitride RRs. In contrast to the surfactants, K2SO4 interacts only weakly with the nitride surface and hence cannot suppress its RR.
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Inhibition of nuclear waste solutions containing multiple aggressive anions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Congdon, J.W.
1987-01-01
The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans, supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions, however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion. 10more » refs., 5 figs., 2 tabs.« less
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Adsorption of a reactive dye on chemically modified activated carbons--influence of pH.
Orfão, J J M; Silva, A I M; Pereira, J C V; Barata, S A; Fonseca, I M; Faria, P C C; Pereira, M F R
2006-04-15
The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and basic properties, without changing its textural parameters significantly. Different techniques (N2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H2 flow at 700 degrees C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH(pzc) of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.
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Afsar, Baris; Elsurer, Rengin
2015-07-01
Metabolic acidosis is a common feature in chronic renal failure patients, worsening progressively as renal function declines. There are conflicting data in hemodialysis (HD) patients with regard to acidosis, alkalosis and mortality. In HD patients, cognitive impairment, depression, sleep disorders and impaired quality of life are very common. Besides, these conditions are related with increased morbidity and mortality. However, no previous study investigated the relationship between pH, venous bicarbonate and anion gap with depression, sleep problems and cognitive function in HD patients. In this study we investigated these relationships. In total, 65 HD patients were included. The demographic parameters and laboratory parameters including bicarbonate, pH and anion gap was measured for all patients. Depressive symptoms, sleep quality and cognitive function, were measured by Beck depression inventory, The Pittsburgh Sleep Quality Index and by Mini Mental State Examination, respectively. We found that, sleep quality but not cognitive function or depression was independently related with venous pH and bicarbonate. Anion gap has no independent relationship with sleep quality, cognitive function and depression. In conclusion, metabolic acidosis and bicarbonate levels were independently related with sleep quality in HD patients. However, there was no association between metabolic acidosis and bicarbonate levels with cognitive function and depression.
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Adsorption of Dyes in Studying the Surface Chemistry of Ultradispersed Diamond
NASA Astrophysics Data System (ADS)
Khokhlova, T. D.; Yunusova, G. R.; Lanin, S. N.
2018-05-01
The effect the surface chemistry of ultradispersed diamond (UDD) has on the adsorption of watersoluble dyes is considered. A comparison is made to adsorption on graphitized thermal carbon black (GTCB), which has a homogeneous and nonporous surface. The adsorption isotherms of dyes and the dependence of the adsorption on the pH of solutions are measured. It is found that UDD adsorbs acid (anionic) dyes—acid orange (AO) and acid anthraquinone blue (AAB)—but barely adsorbs a basic (cationic) dye, methylene blue (MB), because of the predominance of positively charged basic groups on the surface of UDD. The maximum adsorption of AO is much lower on UDD than on GTCB, while the maximum adsorption of AAB is similar for both surfaces. The adsorption of AO on UDD depends strongly on the pH of the solution, while the adsorption of AAB is independent of this parameter. It is suggested that the adsorption of AAB is determined not only by ionic and hydrophobic interactions but also by coordination interactions with impurity metal ions on a UDD surface. It is concluded that the adsorption of dyes characterizes the chemistry of a UDD surface with high sensitivity.
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NASA Astrophysics Data System (ADS)
Mahmoud, Mohamed E.; Khalifa, Mohamed A.; El Wakeel, Yasser M.; Header, Mennatllah S.; Abdel-Fattah, Tarek M.
2017-04-01
A novel magnetic nanosorbent was designed using chemical grafting of nano-magnetite (Nano-Fe3O4) with nanolayer of activated carbon (AC) via urea intermediate for the formation of Nano-Fe3O4-Urea-AC. Characterizing was carried out using FT-IR, SEM, HR-TEM, TGA, point of zero charge (Pzc) and surface area analysis. The designed sorbent maintained its magnetic properties and nanosized structure in the range of 8.7-14.1 nm. The surface area was identified as 389 m2/g based on the BET method. Sorption of uranyl ions from aqueous solutions was studied and evaluated in different experimental conditions. Removal of uranyl ions increased with increasing in pH value and the maximum percentage removal was established at pH 5.0. The removal and sorption processes of uranyl ions by Nano-Fe3O4-Urea-AC sorbent were studied and optimized using the batch technique. The key variables affecting removal of uranyl ions were studied including the effect of the contact time, dosage of Nano-Fe3O4-Urea-AC sorbent, reaction temperature, initial uranyl ions concentration and interfering anions and cations.
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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).
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[Bromate reduction by granular activated carbon].
Huang, Xin; Gao, Nai-yun; Lu, Pin-pin
2007-10-01
Batch experiments were conducted to evaluate the kinetics of reducing bromate to bromide by granular activated carbon. Solution conditions were studied in details, such as pH, ionic strength, temperature and initial bromate concentration. The results showed the removal capacity of GAC was positively relevant to surface basic functional groups. The whole process was inhibited by other anions in solution and the inhibition sequence was NO3(-) > SO4(2-) > Cl(-). Pseudo-second order rate equation and intraparticle diffusion model were applied to fit the process of bromate reduction and the process of bromide formation, respectively, with regression coefficients higher than 0.97 at most cases. Bromate removal was found to be favored under conditions with low pH value and low ionic strength. Both sorption rate of bromate and formation rate of bromide were decreased, and then increased along with the increase of temperature during 15-42 degree C. In this experiment, the maximum adsorption capacity of GAC is 769.23 micromol/g (98.4 mg/g), whereas the sorption process is slow and easily influenced. It is concluded that the sorption of bromate by the micropore portion of GAC was influenced by the release of bromide.
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Isolation and characterization of coagulant extracted from Moringa oleifera seed by salt solution.
Okuda, T; Baes, A U; Nishijima, W; Okada, M
2001-02-01
It is known that M. oleifera contains a natural coagulant in the seeds. In our previous research, the method using salt water to extract the active coagulation component from M. oleifera seeds was developed and compared with the conventional method using water. In this research, the active coagulation component was purified from a NaCl solution crude extract of Moringa oleifera seeds. The active component was isolated and purified from the crude extract through a sequence of steps that included salting-out by dialysis, removal of lipids and carbohydrates by homogenization with acetone, and anion exchange. Specific coagulation activity of the active material increased up to 34 times more than the crude extract after the ion exchange. The active component was not the same as that of water extract. The molecular weight was about 3000 Da. The Lowry method and the phenol-sulfuric acid method indicated that the active component was neither protein nor polysaccharide. The optimum pH of the purified active component for coagulation of turbidity was pH 8 and above. Different from the conventional water extracts, the active component can be used for waters with low turbidity without increase in the dissolved organic carbon concentration.
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pH titration monitored by quantum cascade laser-based vibrational circular dichroism.
Rüther, Anja; Pfeifer, Marcel; Lórenz-Fonfría, Víctor A; Lüdeke, Steffen
2014-04-10
Vibrational circular dichroism (VCD) spectra of aqueous solutions of proline were recorded in the course of titrations from basic to acidic pH using a spectrometer equipped with a quantum cascade laser (QCL) as an infrared light source in the spectral range from 1320 to 1220 cm(-1). The pH-dependent spectra were analyzed by singular value decomposition and global fitting of a two-pK Henderson-Hasselbalch model. The analysis delivered relative fractions of the three different protonation species. Their agreement with the relative fractions obtained from performing the same analysis on pH-dependent Fourier transform infrared (FT-IR) and QCL-IR spectra validates the quantitative results from QCL-VCD. Global fitting of the pH-dependent VCD spectra of L-proline allowed for extraction of pure spectra corresponding to anionic, zwitterionic, and cationic L-proline. From a static experiment, only pure spectra of the zwitterion would be accessible in a straightforward way. A comparison to VCD spectra calculated for all three species led to assignment of vibrational modes that are characteristic for the respective protonation states. The study demonstrates the applicability of QCL-VCD both for quantitative evaluation and for qualitative interpretation of dynamic processes in aqueous solutions.
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Gordon, A. M.; Godt, R. E.; Donaldson, S. K. B.; Harris, C. E.
1973-01-01
The maximal calcium-activated isometric tension produced by a skinned frog single muscle fiber falls off as the ionic strength of the solution bathing this fiber is elevated declining to zero near 0.5 M as the ionic strength is varied using KCl. When other neutral salts are used, the tension always declines at high ionic strength, but there is some difference between the various neutral salts used. The anions and cations can be ordered in terms of their ability to inhibit the maximal calcium-activated tension. The order of increasing inhibition of tension (decreasing tension) at high ionic strength for anions is propionate- ≃ SO4 -- < Cl- < Br-. The order of increasing inhibition of calcium-activated tension for cations is K+ ≃ Na+ ≃ TMA+ < TEA+ < TPrA+ < TBuA+. The decline of maximal calcium-activated isometric tension with elevated salt concentration (ionic strength) can quantitatively explain the decline of isometric tetanic tension of a frog muscle fiber bathed in a hypertonic solution if one assumes that the internal ionic strength of a muscle fiber in normal Ringer's solution is 0.14–0.17 M. There is an increase in the base-line tension of a skinned muscle fiber bathed in a relaxing solution (no added calcium and 3 mM EGTA) of low ionic strength. This tension, which has no correlate in the intact fiber in hypotonic solutions, appears to be a noncalcium-activated tension and correlates more with a declining ionic strength than with small changes in [MgATP], [Mg], pH buffer, or [EGTA]. It is dependent upon the specific neutral salts used with cations being ordered in increasing inhibition of this noncalcium-activated tension (decreasing tension) as TPrA+ < TMA+ < K+ ≃ Na+. Measurements of potentials inside these skinned muscle fibers bathed in relaxing solutions produced occasional small positive values (<6 mV) which were not significantly different from zero. PMID:4543066
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Goff, Jesse P; Koszewski, Nicholas J
2018-06-01
Most studies demonstrating that diets with low dietary cation-anion difference (DCAD) reduce hypocalcemia in cows add enough anions to the diet to reduce urine pH below 7.0. One objective of these experiments was to determine whether there is any benefit to periparturient plasma Ca concentration if diet anion addition results in a lesser degree of acidification of the cow and urine pH does not go below 7.0. Another method for reducing hypocalcemia involves feeding a prepartal diet that is Ca deficient. This places the cow in negative Ca balance before calving, stimulating parathyroid hormone (PTH) and 1,25-dihydroxyvitamin D secretion before calving and thus promoting Ca homeostasis at calving. As practiced in the field, low-Ca diets are often about 0.5% Ca. Our second objective was to determine whether a 0.46% Ca diet would be sufficiently low in Ca to stimulate PTH secretion before calving. A meta-analysis of the literature suggests that a 0.5% Ca, low-DCAD diet will reduce hypocalcemia better than a 0.7% Ca diet. A third objective was to compare periparturient plasma Ca in cows fed 0.46 or 0.72% Ca diets with similar DCAD. In experiment 1, anions (primarily chloride) or anions plus Ca were added to a 1.4% K basal diet to create the following diets: 0.46% Ca and +167 mEq/kg of DCAD, 0.46% Ca and -13 mEq/kg of DCAD, and 0.72% Ca and -17 mEq/kg of DCAD. In experiment 2, the same amounts of anion were added to a 2.05% K basal diet to create the following diets: 0.46% Ca and +327 mEq/kg of DCAD, 0.46% Ca and +146 mEq/kg of DCAD, and 0.72% Ca and +140 mEq/kg of DCAD. In experiment 1, cows fed the diet with 0.46% Ca and +167 mEq/kg of DCAD had significantly lower plasma Ca concentration after calving than cows fed the 0.46 or 0.72% Ca diets with anions. Periparturient plasma Ca concentrations did not differ in cows fed the low-DCAD diets with 0.46 or 0.72% Ca. Urine pH was reduced from 8.27 in the diet with 0.46% Ca and +167 mEq/kg of DCAD to 7.07 and 7.41 in the 0.46 and 0.72% Ca anion diets, respectively. Precalving plasma PTH and 1,25-dihydroxyvitamin D concentrations were similar in cows fed the 0.46% Ca diets and the 0.72% Ca diets, suggesting that the 0.46% Ca diets were not low enough in Ca to place the cow in negative Ca balance before calving. In experiment 2, adding the anion supplements to a 2.05% K diet did not reduce urine pH below 8.0. Periparturient plasma Ca concentrations did not differ in cows in any group in experiment 2. Precalving diets that are 0.46% Ca fed ad libitum are too high in Ca to stimulate Ca homeostasis before calving. Adding anions to a diet can benefit periparturient cow plasma Ca concentration, but only if it alters acid-base status enough to reduce urine pH below 7.5. The Authors. Published by FASS Inc. and Elsevier Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
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Hafez, M A; Khalifa, M E
1997-05-01
A rapid and simple general complexometric method was presented for the determination of lead, cadmium and thallium or mercury or arsenic(V) in laboratory synthesized mixtures similar to those of some ores, minerals and alloys of such metals. The precision and accuracy attainable in successive titrations of Pb(2+), Cd(2+) and Tl(3+) or Hg(2+) or AsO(3-)(4) (As(5+)) with 0.05 and/or 0.01 mol 1(-1) solutions of disodium ethylenediaminetetraacetate (Na(2)EDTA) and standard Pb(NO(3))(2) of the same concentration using Bromo-Cresol Orange (BCO) as a new metallochromic indicator with visual endpoint indication were studied. For the analysis of a three component mixtures of the aforementioned ions, Tl(3+) was at first directly titrated with Na(2)EDTA at pH 0.5-1 (HNO(3)) using BCO as indicator. At the thallium endpoint an excess of Na(2)EDTA was added and the pH was adjusted at pH approximately 4.8 using hexamine-HNO(3) buffer (solution A). The excess EDTA was back-titrated with standard solution of Pb(NO(3))(2). 1,10-Phenanthroline (1,10-phen) was added to release the EDTA combined with Cd(2+), while thiosemicarbazide (TSC) was used to liberate the EDTA from the mercury-EDTA chelate. To determine AsO(3-)(4) ion in such type of mixtures the pH of (solution A) was raised to a value of 10 using ammonia buffer. Excess standard Mg(2+) solution was added and the formed precipitate of MgNH(4)AsO(4) was separated, dissolved and its magnesium content equivalent to AsO(3-)(4) was determined complexometrically using Eriochrome Black-T (EBT) indicator. The interference caused by different anions, cations and organic acids was investigated. A comparison of the indicators BCO and Xylenol Orange (XO) for successive titration of the studied metal ions was carried out. The proposed successive titration method was applied successfully to some real samples of ores, minerals and alloys of the studied metal ions and the results were satisfactory and agreed with those obtained by AAS.
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Valinsky, William C; Touyz, Rhian M; Shrier, Alvin
2017-08-01
Thiazides block Na + reabsorption while enhancing Ca 2+ reabsorption in the kidney. As previously demonstrated in immortalized mouse distal convoluted tubule (MDCT) cells, chlorothiazide application induced a robust plasma membrane hyperpolarization, which increased Ca 2+ uptake. This essential thiazide-induced hyperpolarization was prevented by the Cl - channel inhibitor 5-Nitro-2-(3-phenylpropylamino) benzoic acid (NPPB), implicating NPPB-sensitive Cl - channels, however the nature of these Cl - channels has been rarely described in the literature. Here we show that MDCT cells express a dominant, outwardly rectifying Cl - current at extracellular pH7.4. This constitutive Cl - current was more permeable to larger anions (Eisenman sequence I; I - >Br - ≥Cl - ) and was substantially inhibited by >100mM [Ca 2+ ] o , which distinguished it from ClC-K2/barttin. Moreover, the constitutive Cl - current was blocked by NPPB, along with other Cl - channel inhibitors (4,4'-diisothiocyanatostilbene-2,2'-disulfonate, DIDS; flufenamic acid, FFA). Subjecting the MDCT cells to an acidic extracellular solution (pH<5.5) induced a substantially larger outwardly rectifying NPPB-sensitive Cl - current. This acid-induced Cl - current was also anion permeable (I - >Br - >Cl - ), but was distinguished from the constitutive Cl - current by its rectification characteristics, ion sensitivities, and response to FFA. In addition, we have identified similar outwardly rectifying and acid-sensitive currents in immortalized cells from the inner medullary collecting duct (mIMCD-3 cells). Expression of an acid-induced Cl - current would be particularly relevant in the acidic IMCD (pH<5.5). To our knowledge, the properties of these Cl - currents are unique and provide the mechanisms to account for the Cl - efflux previously speculated to be present in MDCT cells. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.
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Electrochemical oxidation of iron and alkalinity generation for efficient sulfide control in sewers.
Lin, Hui-Wen; Kustermans, Caroline; Vaiopoulou, Eleni; Prévoteau, Antonin; Rabaey, Korneel; Yuan, Zhiguo; Pikaar, Ilje
2017-07-01
The addition of iron salts is one of the most commonly used dosing strategies for sulfide control in sewers. However, iron salts decrease the sewage pH which not only reduces the effectiveness of sulfide precipitation but also enhances the release of residual sulfide to the sewer atmosphere. Equally important, concentrated iron salt solutions are corrosive and their frequent transport, handling, and on-site storage often come with Occupational Health and Safety (OH&S) concerns. Here, we experimentally demonstrated a novel sulfide control approach using electrochemical systems with parallel placed iron electrodes. This enabled combining anodic dissolved iron species release with cathodic hydroxyl anion production, which alleviates all the aforementioned concerns. A long-term experiment was successfully carried out achieving an average sulfide removal efficiency of 95.4 ± 4.4% at low voltage input of 2.90 ± 0.54 V over the course of 8 weeks. This electrochemical method was demonstrated to successfully achieve efficient sulfide control. In addition, it increases the sewage pH, thereby overcoming the drawbacks associated with the pH decrease in the case of conventional iron salt dosing. Ferrous ions were produced at an overall coulombic efficiency (CE) of 98.2 ± 1.2%, whereas oxygen evolution and direct sulfide oxidation were not observed. Short-term experiments showed that increasing either inter-electrode gap or current density increased the cell voltage associated with the increase in the ohmic drop of the system. Overall, this study highlights the practical potential of in-situ generation of dissolved iron species and simultaneous hydroxyl anion generation for efficient sulfide control in sewers. Copyright © 2017 Elsevier Ltd. All rights reserved.
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Selective removal of uranium ions from contaminated waters using modified-X nanozeolite.
Shakur, H R; Rezaee Ebrahim Saraee, Kh; Abdi, M R; Azimi, G
2016-12-01
In order to efficiently remove of uranium anionic species (which are the most dominant species of uranium in natural water at neutral pH) from contaminated waters, nano-NaX zeolite was synthesized and then modified using various divalent cations (Mg 2+ , Ca 2+ , Mn 2+ ) and ZnO nanoparticles (from 1.7 to 10.3wt%). Different characterization techniques of XRF, XRD, FE-SEM, TEM, FT-IR, and AAS were used to characterize the final synthesized absorbents. Sorption experiments by batch technique were done to study the effect of solid-liquid ratio, initial uranium concentration, contact time and temperature under neutral condition of pH and presence of all anions and cations which are available in the waters. Results showed that although nano-NaX zeolite due to its negative framework charge had a low sorption capacity for adsorption of uranium anionic species, but modification of parent nano-NaX zeolite with ZnO nanoparticles and various cations effectively improved its uranium adsorption capacity. Also, results showed that under optimum condition of pH=7.56, contact time of 60min at 27°C with solid-liquid ratio of 20g/L a maximum uranium removal efficiency of 99.7% can be obtained in the presence of all anions and cations which are available in the drinking waters by NaX/ZnO nanocomposite. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Functional characterization of a ClC transporter by solid-supported membrane electrophysiology
Garcia-Celma, Juan; Szydelko, Adrian
2013-01-01
EcClC, a prokaryotic member of the ClC family of chloride channels and transporters, works as coupled H+/Cl− exchanger. With a known structure and the possibility of investigating its behavior with different biochemical and biophysical techniques, the protein has become an important model system for the family. Although many aspects of its function have been previously characterized, it was difficult to measure transport on the same sample under different environmental conditions. To overcome this experimental limitation, we have studied EcClC by solid-supported membrane electrophysiology. The large transport-related transient currents and a simple way of relating transport rates to the measured signal have allowed a thorough investigation of ion selectivity, inhibition, and the dependence of transport on changes in ion concentration and pH. Our results confirm that the protein transports larger anions with about similar rates, whereas the smaller fluoride is not a substrate. We also show that 4,4′-diisothiocyano-2,2’-stilbenedisulfonic acid (DIDS), a known inhibitor of other anion transport protein, irreversibly inhibits EcClC from the intracellular side. The chloride dependence shows an apparent saturation at millimolar concentrations that resembles a similar behavior in eukaryotic ClC channels. Our experiments have also allowed us to quantify the pH dependence of transport. EcClC shows a strong activation at low pH with an apparent pKa of 4.6. The pronounced pH dependence is lost by the mutation of a conserved glutamate facing the extracellular solution that was previously shown to be an acceptor for transported protons, whereas it is largely retained by the mutation of an equivalent residue at the intracellular side. Our results have provided a quantitative basis for the transport behavior of EcClC, and they will serve as a reference for future investigations of novel electrogenic transporters with still-uncharacterized properties. PMID:23478993
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Quenching of triplet-excited flavins by flavonoids. Structural assessment of antioxidative activity.
Huvaere, Kevin; Olsen, Karsten; Skibsted, Leif H
2009-10-02
The mechanism of flavin-mediated photooxidation of flavonoids was investigated for aqueous solutions. Interaction of triplet-excited flavin mononucleotide with phenols, as determined by laser flash photolysis, occurred at nearly diffusion-controlled rates (k approximately 1.6 x 10(9) L mol(-1) s(-1) for phenol at pH 7, 293 K), but protection of the phenolic function by methylation inhibited reaction. Still, electron transfer was proposed as the dominating mechanism due to the lack of primary kinetic hydrogen/deuterium isotope effect and the low activation enthalpy (<20 kJ mol(-1)) for photooxidation. Activation entropy worked compensating in a series of phenolic derivatives, supporting a common oxidation mechanism. An ortho-hydroxymethoxy pattern was equally reactive (k approximately 2.3 x 10(9) L mol(-1) s(-1) for guaiacol at pH 7) as compounds with ortho-dihydroxy substitution (k approximately 2.4 x 10(9) L mol(-1) s(-1) for catechol at pH 7), which are generally referred to as good antioxidants. This refutes the common belief that stabilization of incipient phenoxyl radicals through intramolecular hydrogen bonding is the driving force behind the reducing activity of catechol-like compounds. Instead, such bonding improves ionization characteristics of the substrates, hence the differences in reactivity with (photo)oxidation of isolated phenols. Despite the similar reactivity, radicals from ortho-dihydroxy compounds are detected in high steady-state concentrations by electron paramagnetic resonance (EPR) spectroscopy, while those resulting from oxidation of ortho-hydroxymethoxy (or isolated phenolic) patterns were too reactive to be observed. The ability to deprotonate and form the corresponding radical anions at neutral pH was proposed as the decisive factor for stabilization and, consequently, for antioxidative action. Thus, substituting other ionizable functions for the ortho- or para-hydroxyl in phenolic compounds resulted in stable radical anion formation, as demonstrated for para-hydroxybenzoic acid, in contrast to its methyl ester.
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NASA Astrophysics Data System (ADS)
Erdawati, E.; Darsef, D.
2018-04-01
A sol gel method with citric acid as an anionic surfactant was used to fabricate nano magnesium ferrites (MgFe2O4) under different calcination temperatures for 2h, respectively. The microstructure and surface morphology of magnesium ferrite powder were characterized by FTIR, XRD, SEM, and BET. The results of this study are useful for adsorption Congo red. The results showed that increasing solution pH and extending contact time are favorable for improving adsorption efficiency. with initial Congo red concentration of 50 mg/L and 100 mg/L. Adsorption data fits well with the Langmuir isotherm models with a maximum adsorption capacity (qm) and a Langmuir adsorption equilibrium constant (K) of 65.1 mg/g and 0.090 L/mg, respectively. The adsorption kinetic agrees well with pseudo second order model with the pseudo second rate constants (K2) of 0.0468 and0.00189 g/mg/min for solutions with initial congo red of 50 and 100 mg/L, respectively
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Modifying protein adsorption by layers of glutathione pre-adsorbed on Au(111)
NASA Astrophysics Data System (ADS)
Vallée, Anne; Humblot, Vincent; Méthivier, Christophe; Dumas, Paul; Pradier, Claire-Marie
2011-12-01
Molecular interaction with metal surfaces raises fundamental questions regarding their binding tendency, their dispersion on the surface, as well as their conformation which may change their biological properties; addressing these questions, and being able to tune protein interactions, is of primary importance for the control of biointerfaces. In this study, one tripeptide, GSH (glu-cys-gly), was used to condition gold surfaces and thus influence the adsorption of bovine serum albumin (BSA). Depending on the pH value of the GSH solution, cationic, zwitterionic or anionic forms of the tripeptide could be stabilised on the surface, before interacting with BSA solutions. The amount of proteins was observed to depend both on the chemical state of the adsorbed underlying peptide and on the solvent of the protein solution, indicating an important role of electrostatic interactions upon protein adsorption. Moreover, atomic force microscopy (AFM), and synchrotron IR microscopy revealed a heterogeneous distribution of proteins on the GSH layer.
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Synthesis and biological activity of organothiophosphoryl polyoxotungstates.
Sun, Zhengang; Liu, Jutao; Ma, Jianfang; Liu, Jingfu
2002-01-01
Organothiophosphoryl polyoxotungstates R(contains)XW(infinityinfinity)O(contains exists) (/-) , R(contains) P(contains)W(infinity),O(infinity) (/-), R(contains)PW( exists)O(contains) (Delta) (-)(X = P, Si, Ge, B or Ga; R = PhP(S), C(6)H(11)P(S)) have been prepared from lacunary polyoxoanions and PhP(S). The products were characterized by elemental analysis, IR, and NMR spectroscopy. According to spectroscopic observations, the hybrid anions consist of a lacunary anion framework on which are grafted two equivalent or groups through P-O-W bridges. Some of the title compounds showed the antigerm activity.
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Shamsayei, Maryam; Yamini, Yadollah; Asiabi, Hamid; Safari, Meysam
2018-02-22
The authors describe a 3-component nanoparticle system composed of a silica-coated magnetite (Fe 3 O 4 ) core and a layered double (Cu-Cr) hydroxide nanoplatelet shell. The sorbent has a high anion exchange capacity for extraction anionic species. A simple online system, referred to as "on-line packed magnetic-in-tube solid phase microextraction" was designed. The nanoparticles were placed in a stainless steel cartridge via dry packing. The cartridge was then applied to the preconcentration acidic drugs including naproxen and indomethacin from urine and plasma. Extraction and desorption times, pH values of the sample solution and flow rates of sample solution and eluent were optimized. Analytes were then quantified by HPLC with UV detection. Under optimal conditions, the limits of detection range from 70 to 800 ng L -1 , with linear responses from 0.1-500 μg L -1 (water samples), 0.6-500 μg L -1 (spiked urine), and 0.9-500 μg L -1 (spiked plasma). The inter- and intra-assay precisions (RSDs, for n = 5) are in the range of 2.2-5.4%, 2.8-4.9%, and 2.0-5.2% at concentration levels of 5, 25 and 50 μg L -1 , respectively. The method was applied to the analysis of the drugs in spiked human urine and plasma, and good results were achieved. Graphical abstract Fe 3 O 4 @SiO 2 @CuCr-LDH magnetic nanoparticles were synthesized and packed in to a stainless steel column. The column was applied to solid phase microextraction of acidic drugs from biological samples.
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Sulyok, Michael; Miró, Manuel; Stingeder, Gerhard; Koellensperger, Gunda
2005-08-01
In this paper, flow-through microdialysis is presented as a novel analytical tool for automatic sampling of low molecular weight organic anions (LMWOA), such as oxalate and citrate, in solid samples of environmental concern. The microsampling methodology involves the implantation of dedicated capillary-type probes offering unrivalled spatial resolution (ca. 200μm) in definite soil sites. These passive samplers are aimed at monitoring local processes, such as the release of organic acids occurring in the rhizosphere environment, in nearly real-time. The influence of chemical and physical variables (composition and flow rate of the perfusion liquid, ionic strength and pH of the outer medium and presence of metal ions therein) was assessed in vitro using liquid-phase assays. On the other hand, the resistance of the external solid medium to mass transfer, and the actual applicability of in vivo calibration methods were investigated using quartz sand as an inert model soil. Microdialysers furnished with 3cm long semipermeable tubular membranes were perfused with 0.01M NaNO 3 at a flow rate of 2.0μl/min, yielding dialysis recoveries ≥45% for both assayed LMWOAs in simulated background soil electrolyte solutions, and ≥24% in the interstitial liquid of complex solid samples. Full knowledge of the fate of LMWOAs in soils was obtained through the application of stimulus-response approaches that mimic the discrete exudation pulses of roots. Highly time-resolved microdialysates were used to discern readily available species such as free carboxylic anions and LMW metal-organic acid complexes from adsorbed, precipitated or mineralised analyte species in a variety of soil samples containing variable amounts of organic matter, exchangeable cations and different levels of metal pollution.
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Möller, Kristina; Crescenzi, Carlo; Nilsson, Ulrika
2004-01-01
Diphenyl phosphate is a hydrolysis product and possible metabolite of the flame retardant and plasticiser additive triphenyl phosphate. A molecularly imprinted polymer solid-phase extraction (MISPE) method for extracting diphenyl phosphate from aqueous solutions has been developed and compared with SPE using a commercially available mixed-mode anion exchanger. The imprinted polymer was prepared using 2-vinylpyridine (2-Vpy) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, and a structural analogue of the analyte as the template molecule. The imprinted polymer was evaluated for use as a SPE sorbent, in tests with both aqueous standards and spiked urine samples, by comparing recovery and breakthrough data obtained using the imprinted form of the polymer and a non-imprinted form (NIP). Extraction from aqueous solutions resulted in more than 80% recovery. Adsorption by the molecularly imprinted polymer (MIP) was non-selective, but selectivity was achieved by selective desorption in the wash steps. Diphenyl phosphate could also be selectively extracted from urine samples, although the urine matrix reduced the capacity of the MISPE cartridges. Recoveries from urine extraction were higher than 70%. It was important to control pH during sample loading. The MISPE method was found to yield a less complex LC-ESI-MS chromatogram of the urine extracts compared with the mixed-mode anion-exchanger method. An LC-ESI-MS method using a Hypercarb LC column with a graphitised carbon stationary phase was also evaluated for organophosphate diesters. LC-ESI-MS using negative-ion detection in selected ion monitoring (SIM) mode was shown to be linear for diphenyl phosphate in the range 0.08-20 ng microL(-1).
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Identifying the causes of oil sands coke leachate toxicity to aquatic invertebrates.
Puttaswamy, Naveen; Liber, Karsten
2011-11-01
A previous study found that coke leachates (CL) collected from oil sands field sites were acutely toxic to Ceriodaphnia dubia; however, the cause of toxicity was not known. Therefore, the purpose of this study was to generate CL in the laboratory to evaluate the toxicity response of C. dubia and perform chronic toxicity identification evaluation (TIE) tests to identify the causes of CL toxicity. Coke was subjected to a 15-d batch leaching process at pH 5.5 and 9.5. Leachates were filtered on day 15 and used for chemical and toxicological characterization. The 7-d median lethal concentration (LC50) was 6.3 and 28.7% (v/v) for pH 5.5 and 9.5 CLs, respectively. Trace element characterization of the CLs showed Ni and V levels to be well above their respective 7-d LC50s for C. dubia. Addition of ethylenediaminetetraacetic acid significantly (p ≤ 0.05) improved survival and reproduction in pH 5.5 CL, but not in pH 9.5 CL. Cationic and anionic resins removed toxicity of pH 5.5 CL only. Conversely, the toxicity of pH 9.5 CL was completely removed with an anion resin alone, suggesting that the pH 9.5 CL contained metals that formed oxyanions. Toxicity reappeared when Ni and V were added back to anion resin-treated CLs. The TIE results combined with the trace element chemistry suggest that both Ni and V are the cause of toxicity in pH 5.5 CL, whereas V appears to be the primary cause of toxicity in pH 9.5 CL. Environmental monitoring and risk assessments should therefore focus on the fate and toxicity of metals, especially Ni and V, in coke-amended oil sands reclamation landscapes. Copyright © 2011 SETAC.
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Ikeda-Ohno, Atsushi; Tsushima, Satoru; Takao, Koichiro; Rossberg, André; Funke, Harald; Scheinost, Andreas C; Bernhard, Gert; Yaita, Tsuyoshi; Hennig, Christoph
2009-12-21
The electrochemical behavior and complex structure of Np carbonato complexes, which are of major concern for the geological disposal of radioactive wastes, have been investigated in aqueous Na(2)CO(3) and Na(2)CO(3)/NaOH solutions at different oxidation states by using cyclic voltammetry, X-ray absorption spectroscopy, and density functional theory calculations. The end-member complexes of penta- and hexavalent Np in 1.5 M Na(2)CO(3) with pH = 11.7 have been determined as a transdioxo neptunyl tricarbonato complex, [NpO(2)(CO(3))(3)](n-) (n = 5 for Np(V), and 4 for Np(VI)). Hence, the electrochemical reaction of the Np(V/VI) redox couple merely results in the shortening/lengthening of bond distances mainly because of the change of the cationic charge of Np, without any structural rearrangement. This explains the observed reversible-like feature on their cyclic voltammograms. In contrast, the electrochemical oxidation of Np(V) in a highly basic carbonate solution of 2.0 M Na(2)CO(3)/1.0 M NaOH (pH > 13) yielded a stable heptavalent Np complex of [Np(VII)O(4)(OH)(2)](3-), indicating that the oxidation reaction from Np(V) to Np(VII) in the carbonate solution involves a drastic structural rearrangement from the transdioxo configuration to a square-planar-tetraoxo configuration, as well as exchanging the coordinating anions from carbonate ions (CO(3)(2-)) to hydroxide ions (OH(-)).
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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).
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Ion exchange polymers for anion separations
Jarvinen, Gordon D.; Marsh, S. Fredric; Bartsch, Richard A.
1997-01-01
Anion exchange resins including at least two positively charged sites and a ell-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.
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Ion exchange polymers for anion separations
Jarvinen, G.D.; Marsh, S.F.; Bartsch, R.A.
1997-09-23
Anion exchange resins including at least two positively charged sites and a well-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.
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The Polar and Electrical Nature of Dye Binding Sites on Human Red Blood Cell Membranes.
positive charges at the binding sites. By increasing the concentration of the anionic BPB (or by the addition of the anionic detergent sodium lauryl ... sulfate ) these positive charges appear to be successively titrated, rendering the membrane binding sites electrically neutral at this pH. The average
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OXIDATIVE STRESS ACTIVATES ANION EXCHANGE PROTEIN 2 AND AP-1 IN AIRWAY EPITHELIAL CELLS
Anion exchange protein 2 (AE2) is a membrane-bound protein that mediates chloride-bicarbonate exchange. In addition to regulating intracellular pH and cell volume, AE2 exports superoxide (O.) to the extracellular matrix in an HCO-dependent process. Given this ability to export O....
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The tautomerization between keto- to phenol-hydrazone induced by anions in the solution
NASA Astrophysics Data System (ADS)
Shang, Xuefang; Yuan, Jianmei; Wang, Yingling; Zhang, Jinlian; Xu, Xiufang
2012-02-01
Two simple anion receptors, 2-[(2-hydroxy-5-nitrophenyl)methylene]hydrazone (1) and 2-[(3,5-dibromo-2-hydroxyphenyl)methylene]hydrazone (2) with -OH binding sites, were synthesized and characterized. The anion binding ability of receptors 1 and 2 with halide anions (F-, Cl-, Br- and I-), AcO- and HPO4- was investigated using visual (naked-eye), UV-vis titration experiments in dry DMSO together with DFT theoretical calculation. The addition of F-, AcO- and HPO4- to the host solution resulted in a red shift of the charge-transfer absorbance band accompanied by a color change from yellow to orange in the naked-eye experiments. Receptor 1 containing a nitro group at the para position and receptor 2 containing two bromine groups at the ortho and para positions both showed strong binding ability for HPO4- ion in the form of phenol-hydrazone. Moreover, receptor 1, induced by anion species in the solution, converted to the form of phenol-hydrazone from keto-hydrazone.
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Mnisi, Robert Londi; Ndibewu, Peter Papoh
2017-11-04
The bark of Moringa oleifera, a cheap and readily available natural biopolymeric resource material, found to significantly reduce coliform load and turbidity in contaminated water is investigated in this paper. Its surface and adsorptive properties are investigated to explore its adsorptive potential in removing V(V) from aqueous solutions. Surface properties were investigated using FTIR, HRSEM/EDS, IC, and BET-N 2 adsorption techniques. Adsorptive properties were investigated by optimizing adsorption parameters such as pH, temperature, initial metal concentration, and adsorbent dosage, using V(V) as an adsorbate. The adsorption-desorption isotherms are typical of type II with a H3 hysteresis loop and is characteristic of a largely macroporous material. Bottle ink pores are observed, which can provide good accessibility of the active sites, even though the internal BET surface area is typically low (1.79 g/m 2 ). Solution pH significantly influences the adsorptive potential of the material. The low surface area negatively impacts on the adsorption capacity, but is compensated for by the exchangeable anions (Cl - , F - , PO 4 3- , NO 3 - , and SO 4 2- ) and cations (Ca 2+ , K + , Mg 2+ , and Al 3+ ) at the surface and the accessibility of the active sites. Adsorption isotherm modeling show that the surface is largely heterogeneous with complex multiple sites and adsorption is not limited to monolayer.
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Wang, J; Ashley, K; Kennedy, E R; Neumeister, C
1997-11-01
A simple, fast, and sensitive method was developed for the determination of hexavalent chromium (CrVI) in workplace samples. Ultrasonic extraction in alkaline solutions with 0.05 M (NH4)2SO4-0.05 M NH3 provided good extraction efficiency of CrVI from the sample and allowed the retention of CrVI on an ion-exchange resin (95%). The CrVI in the sample solution was then separated as an anion from trivalent chromium [CrIII] and other cations by elution from the anion-exchange resin with 0.5 M (NH4)2SO4 in 0.1 M NH3 (pH 8) buffer solution. The eluate was then acidified with hydrochloric acid and complexed with 1,5-diphenylcarbazide reagent prior to flow injection analysis. By analyzing samples with and without oxidation of CrIII to CrVI using CeIV, the method can measure CrVI and total Cr. For optimizing the separation and determination procedure, preliminary trials conducted with two certified reference materials (CRMs 013-050 and NIST 1633a) and three spiked samples (ammonia buffer solution, cellulose ester filters and acid washed sand) indicated that the recovery of CrVI was quantitative (> 90%) with this method. The limit of detection for FIA-UV/VIS determination of the Cr-diphenylcarbazone complex was in the sub-nanogram range (0.11 ng). The technique was also applied successfully to a workplace coal fly ash sample that was collected from a power plant and paint chips that were collected from a heating gas pipe and a university building. The principal advantages of this method are its simplicity, sensitivity, speed and potential portability for field analysis.
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Yan, Yingjie; Liao, Qi-Nan; Ji, Feng; Wang, Wei; Yuan, Shoujun; Hu, Zhen-Hu
2017-02-01
3,5-Dinitrobenzamide has been widely used as a feed additive to control coccidiosis in poultry, and part of the added 3,5-dinitrobenzamide is excreted into wastewater and surface water. The removal of 3,5-dinitrobenzamide from wastewater and surface water has not been reported in previous studies. Highly reactive hydroxyl radicals from UV/hydrogen peroxide (H 2 O 2 ) and UV/titanium dioxide (TiO 2 ) advanced oxidation processes (AOPs) can decompose organic contaminants efficiently. In this study, the decomposition of 3,5-dinitrobenzamide in aqueous solution during UV/H 2 O 2 and UV/TiO 2 oxidation processes was investigated. The decomposition of 3,5-dinitrobenzamide fits well with a fluence-based pseudo-first-order kinetics model. The decomposition in both two oxidation processes was affected by solution pH, and was inhibited under alkaline conditions. Inorganic anions such as NO 3 - , Cl - , SO 4 2- , HCO 3 - , and CO 3 2- inhibited the degradation of 3,5-dinitrobenzamide during the UV/H 2 O 2 and UV/TiO 2 oxidation processes. After complete decomposition in both oxidation processes, approximately 50% of 3,5-dinitrobenzamide was decomposed into organic intermediates, and the rest was mineralized to CO 2 , H 2 O, and other inorganic anions. Ions such as NH 4 + , NO 3 - , and NO 2 - were released into aqueous solution during the degradation. The primary decomposition products of 3,5-dinitrobenzamide were identified using time-of-flight mass spectrometry (LCMS-IT-TOF). Based on these products and ions release, a possible decomposition pathway of 3,5-dinitrobenzamide in both UV/H 2 O 2 and UV/TiO 2 processes was proposed.
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Adsorption properties of congo red from aqueous solution onto N,O-carboxymethyl-chitosan.
Wang, Li; Wang, Aiqin
2008-03-01
N,O-carboxymethyl-chitosans (N,O-CMC) with different degree of substitution (DS) were synthesized under heterogeneous conditions by controlling the reaction temperature. The factors influencing adsorption capacity of N,O-CMC such as the DS of N,O-CMC, initial pH value of the dye solution and adsorption temperature for anionic dye congo red (CR) were investigated. Compared with chitosan (78.90 mg/g), N,O-CMC with the DS of 0.35 exhibited much higher adsorption capacity (330.62 mg/g) for CR at the same adsorption conditions. The adsorption kinetics and isotherms showed that the sorption processes were better fitted by pseudo-second-order equation and the Langmuir equation, respectively. The adsorption mechanism of N,O-CMC was also discussed by means of IR and XPS spectra. The results in this study indicated that N,O-CMC was an attractive candidate for removing CR from the dye wastewater.
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Allantoin as a solid phase adsorbent for removing endotoxins.
Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Gagnon, Pete
2013-10-04
In this study we present a simple and robust method for removing endotoxins from protein solutions by using crystals of the small-molecule compound 2,5-dioxo-4-imidazolidinyl urea (allantoin) as a solid phase adsorbent. Allantoin crystalline powder is added to a protein solution at supersaturated concentrations, endotoxins bind and undissolved allantoin crystals with bound endotoxins are removed by filtration or centrifugation. This method removes an average of 99.98% endotoxin for 20 test proteins. The average protein recovery is ∼80%. Endotoxin binding is largely independent of pH, conductivity, reducing agent and various organic solvents. This is consistent with a hydrogen-bond based binding mechanism. Allantoin does not affect protein activity and stability, and the use of allantoin as a solid phase adsorbent provides better endotoxin removal than anion exchange, polymixin affinity and biological affinity methods for endotoxin clearance. Copyright © 2013 Elsevier B.V. All rights reserved.
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High-performance cation-exchange chromatofocusing of proteins.
Kang, Xuezhen; Frey, Douglas D
2003-03-28
Chromatofocusing using high-performance cation-exchange column packings, as opposed to the more commonly used anion-exchange column packings, is investigated with regard to the performance achieved and the range of applications possible. Linear or convex gradients in the range from pH 2.6 to 9 were formed using a variety of commercially available column packings that provide a buffering capacity in different pH ranges, and either polyampholytes or simple mixtures having a small number (three or fewer) of buffering species as the elution buffer. The resolutions achieved using cation-exchange or anion-exchange chromatofocusing were in general comparable, although for certain pairs of proteins better resolution could be achieved using one type of packing as compared to the other, evidently due to the way electrostatic charges are distributed on the protein surface. Several chromatofocusing methods were investigated that take advantage of the acid-base properties of commercially available cation-exchange column packings. These include the use of gradients with a composite shape, the use of very low pH ranges, and the use of elution buffers containing a single buffering species. The advantages of chromatofocusing over ion-exchange chromatography using a salt gradient at constant pH were illustrated by employing the former method and a cation-exchange column packing to separate beta-lactoglobulins A and B, which is a separation reported to be impossible using the latter method and a cation-exchange column packing. Trends in the apparent isoelectric points determined using cation- and anion-exchange chromatofocusing were interpreted using applicable theories. Results of this study indicate that cation-exchange chromatofocusing is a useful technique which is complementary to anion-exchange chromatofocusing and isoelectric focusing for separating proteins at both the analytical and preparative scales.
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Badr, Ibrahim H A; Meyerhoff, Mark E
2005-10-15
More detailed analytical studies of a new fluoride-selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4',5'-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-visible spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band lambda(max) of the porphyrin and a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 microM-1.6 mM. Optical selectivity coefficients of <10(-6) for common anions (e.g., sulfate, chloride, nitrate, etc.) and <10(-4) for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF3-based fluoride ion-selective electrode method.
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Badr, Ibrahim H. A.; Meyerhoff, Mark E.
2008-01-01
More detailed analytical studies of a new fluoride selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4′,5′-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-VIS spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band λmax of the porphyrin as well as a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 μM to 1.6 mM. Optical selectivity coefficients of < 10−6 for common anions (e.g., sulfate, chloride, nitrate etc.) and < 10−4 for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF3 based fluoride ion-selective electrode method. PMID:16223262
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The formation and stability of saline minerals at the Martian surface
NASA Astrophysics Data System (ADS)
Tosca, Nicholas James, III
Evaporite minerals have been identified throughout the martian sedimentary record. Because evaporites can record detailed paleo-environmental information and often host fossil biosignatures on Earth, they are priority targets for future exploration. However, understanding processes that control the formation of these minerals on Mars requires an understanding of the behavior of Fe in highly concentrated evaporating fluids. In this study, a model is developed using the Pitzer ion interaction approach that accurately describes thermodynamic properties of the Fe2(SO4)3-H2SO4-H 2O system. Incorporating this model into a multicomponent thermodynamic database enables detailed study of evaporite mineral formation and stability on Mars. From geochemical modeling, the variation in evaporite mineralogy on Mars may be traced to volatile-anion input -- a variable intimately tied to pH. Using the "chemical divide" concept, evaporites at the martian surface can be used as sensitive probes of pH, atmospheric composition, and cation proportion in solution. Applying this approach to saline assemblages in Nakhlite meteorites and in Meridiani Planum sediments reveals two geochemical systems; each characterized by different pH and anion proportion. A complicating factor however is the concomitant oxidation of soluble Fe-bearing minerals. Such a process may have contributed to complex Fe mineralogy observed at Meridiani Planum through diagenesis. Fe-oxidation experiments at high ionic strength show a progression of mineral phases that begins with the formation of schwertmannite and subsequent ageing to jarosite and nano-crystalline goethite; a process strongly controlled by pH. Low water activity and small particle size drive the ageing of goethite to hematite which provides the final step of a mechanism that is consistent with the distribution of Fe-minerals at Meridiani Planum. These results show that the instability of Fe2+-sulfate minerals at the martian surface may lead to the association of Fe-oxide and Fe-hydroxysulfate minerals with evaporite salts. Indeed, such a geologic association has been observed through remote sensing techniques. Thus, as the Fe-sulfates are sensitive to pH, Fe-oxidation and relative humidity, understanding these phase relationships in greater detail will ultimately exploit the presence of these minerals as a unique set of geochemical probes.
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NASA Astrophysics Data System (ADS)
Dippon, Urs; Pabst, Silke; Klitzke, Sondra
2016-04-01
The worldwide marked for engineered nanoparticles (ENPs) is growing and concerns on the environmental fate- and toxicity of ENPs are rising. Understanding the transport of ENPs within and between environmental compartments such as surface water and groundwater is crucial for exposition modeling, risk assessment and ultimately the protection of drinking water resources. The transport of ENPs is strongly influenced by the surface properties and aggregation behavior of the particles, which is strongly controlled by synthetic and natural organic coatings. Both, surface properties and aggregation characteristics are also key properties for the industrial application of ENPs, which leads to the development and commercialization of an increasing number of surface-functionalized ENPs. These include metals and oxides such as Cerium dioxide (CeO2) with various organic coatings. Therefore, we investigate CeO2 ENPs with different surface coatings such as weakly anionic polyvinyl alcohol (PVA) or strongly anionic poly acrylic acid (PAA) with respect to their colloidal stability in aqueous matrix under various hydrochemical conditions (pH, ionic strength) and their transport behavior in sand filter columns. Furthermore, we investigate the interaction of naturally occurring organic matter (NOM) with CeO2 ENPs and its effect on surface charge (zeta potential), colloidal stability and transport. While uncoated CeO2 ENPs aggregate at pH > 4 in aqueous matrix, our results show that PAA and PVA surface coatings as well as NOM sorbed to CeO2-NP surfaces can stabilize CeO2 ENPs under neutral and alkaline pH conditions in 1 mM KCl solution. Under slightly acidic conditions, differences between the three particle types were observed. PVA can stabilize particle suspensions in presence of 1 mM KCl at pH > 4.3, PAA at pH >4.0 and NOM at >3.2. While the presence of KCl did not influence particle size of NOM-CeO2 ENPs, CaCl2 at >2 mM lead to aggregation. Further results on the influence of KCl and CaCl2 on aggregation of coated CeO2 ENPs and transport in sand filter columns will be presented.
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NASA Astrophysics Data System (ADS)
Samanta, Anuva; Paul, Bijan Kumar; Guchhait, N.
2011-05-01
In this report we have studied micellization process of anionic, cationic and non-ionic surfactants using N,N-dimethylaminonapthyl-(acrylo)-nitrile (DMANAN) as an external fluorescence probe. Micropolarity, microviscosity, critical micellar concentration of these micelles based on steady state absorption and fluorescence and time resolved emission spectroscopy of the probe DMANAN show that the molecule resides in the micelle-water interface for ionic micelles and in the core for the non-ionic micelle. The effect of variation of pH of the micellar solution as well as fluorescence quenching measurements of DMANAN provide further support for the location of the probe in the micelles.
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Yang, Xiao; Zhang, Shaohua; Yu, Wei; Liu, Zhongling; Lei, Lei; Li, Na; Zhang, Hanqi; Yu, Yong
2014-06-01
An ionic liquid-anionic surfactant based aqueous two-phase extraction was developed and applied for the extraction of tetracycline, oxytetracycline and chloramphenicol in honey. The honey sample was mixed with Na2EDTA aqueous solution. The sodium dodecyl sulfate, ionic liquid 1-octyl-3-methylimidazolium bromide and sodium chloride were added in the mixture. After the resulting mixture was ultrasonically shaken and centrifuged, the aqueous two phase system was formed and analytes were extracted into the upper phase. The parameters affecting the extraction efficiency, such as the volume of ionic liquid, the category and amount of salts, sample pH value, extraction time and temperature were investigated. The limits of detection of tetracycline, oxytetracycline and chloramphenicol were 5.8, 8.2 and 4.2 μg kg(-1), respectively. When the present method was applied to the analysis of real honey samples, the recoveries of analytes ranged from 85.5 to 110.9% and relative standard deviations were lower than 6.9%. Copyright © 2014 Elsevier B.V. All rights reserved.
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Mocanu, Georgeta; Nichifor, Marieta; Stanciu, Magdalena C
2015-03-30
Micelles formed in aqueous solution by dextran with hydrophobic (alkyl) end-groups were stabilized through divinyl sulfone crosslinking of the dextran shell. The efficacy of the crosslinking reaction was influenced by the divinyl sulfone amount, the pH and micelle concentration. Crosslinked micelles with a moderate crosslinking degree were further functionalized by attachment of 10 and 17 moles% N-(2-hydroxypropyl)-N,N-dimethyl-N-benzylammonium chloride groups along the dextran chain. The size and shape of both crosslinked micelles and their cationic derivatives were analyzed by DLS and TEM. The prepared micelles were able to bind anionic diclofenac (60-370 mg/g), hydrophobic anionic indometacin (70-120 mg/g), and hydrophobic alpha-tocopherol (170-220 mg/g) or ergocalciferol (90-110 mg/g) by hydrophobic or/and electrostatic forces. The release experiments and the antioxidant activity of bound alpha-tocopherol highlighted the potential of the new nano-sized micelles mainly as carriers for prolonged and controlled delivery of hydrophobic drugs. Copyright © 2014 Elsevier Ltd. All rights reserved.
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Terenteva, E A; Apyari, V V; Dmitrienko, S G; Garshev, A V; Volkov, P A; Zolotov, Yu A
2018-04-01
Positively charged polyhexamethylene guanidine hydrochloride-stabilized silver nanoparticles (PHMG-AgNPs) were prepared and applied as a colorimetric probe for single-step determination of pyrophosphate and sulfate. The approach is based on the nanoparticles aggregation leading to change in their absorption spectra and color of the solution. Due to both electrostatic and steric stabilization these nanoparticles show decreased sensitivity relatively to many common anions, which allows for simple and rapid direct single-step determination of pyrophosphate and sulfate. Effects of different factors (time of interaction, pH, concentrations of anions and the nanoparticles) on aggregation of PHMG-AgNPs and analytical performance of the procedure were investigated. The method allows for the determination of pyrophosphate and sulfate in the range of 0.16-2μgmL -1 and 20-80μgmL -1 with RSD of 2-5%, respectively. The analysis can be performed using either spectrophotometry or naked-eye detection. Practical application of the method was shown by the example of pyrophosphate determination in baking powder sample. Copyright © 2017 Elsevier B.V. All rights reserved.
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Evaluation of the factors governing metal biosorption and metal toxicity in acidic soil isolates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pradhan, A.A.
1992-06-09
This research project was designed to determine the feasibility of microbial biosorption processes for removing metal ions from aqueous systems. A culture of acidic soil actinomycetes, grown in an aerobic environment in a completely mixed, semibatch culture reactor, was used for the study. The experiments were based on removal of copper and lead from test solutions. The anionic systems tested were nitrate, sulfate, and chloride. To determine the factors influencing biosorption and to characterize metal uptake by cellular and extracellular components of the microbial system, a dialysis testing procedure was developed. The effectiveness of biosorption was influenced by pH, initialmore » concentration of metals, type of anionic system, and organic content of the system. respirometric runs were carried out to identify potential inhibitory effects of metal accumulation on microbial activities. In general, metal accumulation resulted in a decrease in the microbial oxygen uptake rate. Also, a lag phase was observed before the onset of the respiratory activity particularly at concentrations of copper and lead greater than 100 ppM.« less
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Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide
Balistrieri, L.S.; Chao, T.T.
1990-01-01
This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.
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Takayanagi, Toshio; Motomizu, Shoji
2006-09-01
Cationic polyelectrolyte of chitosan was used for the reversal of electroosmotic flow in capillary zone electrophoresis. The chitosan was dissolved in acetic acid solution, and stable electroosmotic flow was obtained at the chitosan concentrations between 50 and 300 microg/mL. Separation of inorganic anions was carried out using the dynamically coated capillary by capillary zone electrophoresis. Nine kinds of anions were separated and detected with the capillary. The electrophoretic mobility of the analyte anions decreased with increasing concentrations of chitosan in the migrating solution through ion-ion interaction, but the migration order of the analyte anions was not changed in the concentration range of the chitosan examined. The signal shape for the analyte anions was developed by using field-enhanced sample stacking with 10 mM sodium sulfate.
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Anion binding by bambus[6]uril probed in the gas phase and in solution.
Révész, Agnes; Schröder, Detlef; Svec, Jan; Wimmerová, Michaela; Sindelar, Vladimir
2011-10-20
Electrospray ionization mass spectrometry (ESI-MS) is used to probe the binding of small anions to the macrocycle of bambus[6]uril. For the halide ions, the experimental patterns suggest F(-) < Cl(-) < Br(-) < I(-), which is consistent with the order of anion binding found in the condensed phase. Parallel equilibrium studies in the condensed phase establish the association constants of halide anions and bambus[6]uril in mixed solvents. A detailed analysis of the mass spectrometric data is used to shed light on the correlations between the binding constants in the condensed phase and the ion abundances observed using ESI-MS. From the analysis it becomes apparent that ESI-MS can indeed represent the situation in solution to some extent, but the sampling in the gas-phase experiment is not 1:1 compared to that in solution.
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Photo-degradation of clofibric acid by ultraviolet light irradiation at 185 nm.
Li, Wenzhen; Lu, Shuguang; Chen, Nuo; Gu, Xiaogang; Qiu, Zhaofu; Fan, Ji; Lin, Kuangfei
2009-01-01
As a metabolite of lipid regulators, clofibric acid (CA) was investigated in this study for its ultraviolet (UV) degradation at monochromatic wavelength of 185 nm using Milli-Q water and sewage treatment plant (STP) effluent. The effects of CA initial concentration, solution pH, humic acid (HA), nitrate and bicarbonate anions on CA degradation performances were evaluated. All CA degradation patterns well fitted the pseudo-first-order kinetic model. The results showed that OH generated from water photolysis by UV185 irradiation was involved, resulting in indirect CA photolysis but contributed less to the whole CA removal when compared to the main direct photolysis process. Acid condition favored slightly to CA degradation and other constituents in solution, such as HA (5.0-100.0 mg L(-1)), nitrate and bicarbonate anions (1.0x10(-3) mol L(-1) and 0.1 mol L(-1)), had negative effects on CA degradation. When using real STP effluent CA degradation could reach 97.4% (without filtration) and 99.3% (with filtration) after 1 hr irradiation, showing its potential mean in pharmaceuticals removal in UV disinfection unit. Mineralization tests showed that rapid chloride ion release happened, resulting in no chlorinated intermediates accumulation, and those non-chlorinated intermediate products could further be nearly completely degraded to CO2 and H2O after 6 hrs.
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Arteta, Marianna Yanez; Campbell, Richard A; Nylander, Tommy
2014-05-27
We relate the adsorption from mixtures of well-defined poly(amidoamine) (PAMAM) dendrimers of generations 4 and 8 with sodium dodecyl sulfate (SDS) at the air-water interface to the bulk solution properties. The anionic surfactant shows strong attractive interactions with the cationic dendrimers at pH 7, and electrophoretic mobility measurements indicate that the association is primarily driven by electrostatic interactions. Optical density measurements highlight the lack of colloidal stability of the formed bulk aggregates at compositions close to charge neutrality, the time scale of which is dependent on the dendrimer generation. Adsorption at the air-water interface was followed from samples immediately after mixing using a combination of surface tension, neutron reflectometry, and ellipsometry measurements. In the phase separation region for dendrimers of generation 4, we observed high surface tension corresponding to a depleted surfactant solution but only when the aggregates carried an excess of surfactant. Interestingly, these depleted adsorption layers contained spontaneously adsorbed macroscopic aggregates, and these embedded particles do not rearrange to spread monomeric material at the interface. These findings are discussed in relation to the interfacial properties of mixtures involving dendrimers of generation 8 as well as polydisperse linear and hyperbranched polyelectrolytes where there is polyelectrolyte bound to a surfactant monolayer. The results presented here demonstrate the capability of dendrimers to sequester anionic surfactants in a controllable manner, with potential applications as demulsification and antifoaming agents.
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Su, Jing; Sun, Yuan-Qiang; Huo, Fang-Jun; Yang, Yu-Tao; Yin, Cai-Xia
2010-11-01
A novel strategy for the determination of oxalate anions was successfully established using a copper ion and pyrocatechol violet (PV) ensemble. The sensor ensemble can discriminate oxalate over other common anions including F(-), Cl(-), I(-), Br(-), HPO(4)(2-), PO(4)(3-), AcO(-), CO(3)(2-), SO(4)(2-), ClO(4)(-), P(2)O(7)(4-), S(2-) (deposited by Ag(+)), CN(-) (shielded by Fe(3+)) and can detect oxalate at low microgram levels in quasi-physiological aqueous solutions. The detection of the oxalate anion gives rise to a rapid observable visual color change from blue to yellow.
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Trier, Xenia; Granby, Kit; Christensen, Jan H
2011-10-07
A tiered approach is proposed for the discovery of unknown anionic and nonionic polyfluorinated alkyl surfactants (PFASs) by reversed phase ultra high performance liquid chromatography (UHPLC)--negative electrospray ionisation--quadrupole time of flight mass spectrometry (UHPLC-ESI(-)-QTOF-MS). The chromatographic separation, ionisation and detection of PFASs mixtures, was achieved at high pH (pH=9.7) with NH(4)OH as additive. To distinguish PFASs from other chemicals we used the characteristic negative mass defects of PFASs, their specific losses of 20 Da (HF) and the presence of series of chromatographic peaks, belonging to homologues series with m/z of n×50 Da (CF(2)) or n×100 Da (CF(2)CF(2)). The elemental composition of the precursor ions were deducted from the accurate m/z values of the deprotonated molecules [M-H](-). In case of in-source fragmentation, the presence of dimers, e.g. [M(2)-H](-) and adduct ions such as [M-H+solvent](-) and [(M-H)(M-H+Na)(n)](-) were used to confirm the identity of the precursor ions. In relation to quantification of PFASs, we discuss how their surfactancy influence the ESI processes, challenge their handling in solution and choices of precursor-to-product ions for MSMS of e.g., structural PFAS isomers. The method has been used to discover PFASs in industrial blends and in extracts from food contact materials. Copyright © 2011 Elsevier B.V. All rights reserved.
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Fluoride removal in water by a hybrid adsorbent lanthanum-carbon.
Vences-Alvarez, Esmeralda; Velazquez-Jimenez, Litza Halla; Chazaro-Ruiz, Luis Felipe; Diaz-Flores, Paola E; Rangel-Mendez, Jose Rene
2015-10-01
Various health problems associated with drinking water containing high fluoride levels, have motivated researchers to develop more efficient adsorbents to remove fluoride from water for beneficial concentrations to human health. The objective of this research was to anchor lanthanum oxyhydroxides on a commercial granular activated carbon (GAC) to remove fluoride from water considering the effect of the solution pH, and the presence of co-existing anions and organic matter. The activated carbon was modified with lanthanum oxyhydroxides by impregnation. SEM and XRD were performed in order to determine the crystal structure and morphology of the La(III) particles anchored on the GAC surface. FT-IR and pK(a)'s distribution were determined in order to elucidate both the possible mechanism of the lanthanum anchorage on the activated carbon surface and the fluoride adsorption mechanism on the modified material. The results showed that lanthanum ions prefer binding to carboxyl and phenolic groups on the activated carbon surface. Potentiometric titrations revealed that the modified carbon (GAC-La) possesses positive charge at a pH lower than 9. The adsorption capacity of the modified GAC increased five times in contrast to an unmodified GAC adsorption capacity at an initial F(-) concentration of 20 mg L(-1). Moreover, the presence of co-existing anions had no effect on the fluoride adsorption capacity at concentrations below 30 mg L(-1), that indicated high F(-) affinity by the modified adsorbent material (GAG-La). Copyright © 2015 Elsevier Inc. All rights reserved.
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Srivastava, Varsha; Sillanpää, Mika
2017-01-01
Synthesis of malachite@clay nanocomposite was successfully carried out for the removal of cationic (Methylene Blue, MB) and anionic dyes (Congo Red, CR) from synthetic wastewater. Nanocomposite was characterized by TEM, SEM, FT-IR, EDS analysis and zeta potential. TEM analysis indicated that the particle diameter of nanocomposite was in the range of 14 to 23nm. Various important parameters viz. contact time, concentration of dyes, nanocomposite dosage, temperature and solution pH were optimized to achieve maximum adsorption capacity. In the case of MB, removal decreased from 99.82% to 93.67% while for CR, removal decreased from 88.55% to 75.69% on increasing dye concentration from 100 to 450mg/L. pH study confirmed the higher removal of CR in acidic range while MB removal was higher in alkaline range. Kinetic study revealed the applicability of pseudo-second-order model for the adsorption of both dyes. Negative values of ΔG 0 for both systems suggested the feasibility of dye removal and support for spontaneous adsorption of CR and MB on nanocomposite. Nanocomposite showed 277.77 and 238.09mg/g Langmuir adsorption capacity for MB and CR respectively. Desorption of dyes from the dye loaded nanocomposite was easily carried out with acetone. The results indicate that the prepared malachite@clay nanocomposite is an efficient adsorbent with high adsorption capacity for the aforementioned dyes. Copyright © 2016. Published by Elsevier B.V.
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Cation–Anion Interactions within the Nucleic Acid Ion Atmosphere Revealed by Ion Counting
Gebala, Magdalena; Giambasu, George M.; Lipfert, Jan; Bisaria, Namita; Bonilla, Steve; Li, Guangchao; York, Darrin M.; Herschlag, Daniel
2016-01-01
The ion atmosphere is a critical structural, dynamic, and energetic component of nucleic acids that profoundly affects their interactions with proteins and ligands. Experimental methods that “count” the number of ions thermodynamically associated with the ion atmosphere allow dissection of energetic properties of the ion atmosphere, and thus provide direct comparison to theoretical results. Previous experiments have focused primarily on the cations that are attracted to nucleic acid polyanions, but have also showed that anions are excluded from the ion atmosphere. Herein, we have systematically explored the properties of anion exclusion, testing the zeroth-order model that anions of different identity are equally excluded due to electrostatic repulsion. Using a series of monovalent salts, we find, surprisingly, that the extent of anion exclusion and cation inclusion significantly depends on salt identity. The differences are prominent at higher concentrations and mirror trends in mean activity coefficients of the electrolyte solutions. Salts with lower activity coefficients exhibit greater accumulation of both cations and anions within the ion atmosphere, strongly suggesting that cation–anion correlation effects are present in the ion atmosphere and need to be accounted for to understand electrostatic interactions of nucleic acids. To test whether the effects of cation–anion correlations extend to nucleic acid kinetics and thermodynamics, we followed the folding of P4–P6, a domain of the Tetrahymena group I ribozyme, via single-molecule fluorescence resonance energy transfer in solutions with different salts. Solutions of identical concentration but lower activity gave slower and less favorable folding. Our results reveal hitherto unknown properties of the ion atmosphere and suggest possible roles of oriented ion pairs or anion-bridged cations in the ion atmosphere for electrolyte solutions of salts with reduced activity. Consideration of these new results leads to a reevaluation of the strengths and limitations of Poisson–Boltzmann theory and highlights the need for next-generation atomic-level models of the ion atmosphere. PMID:26517731
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Hirshberg, Daniel; Sharon, Daniel; Afri, Michal; Lavi, Ronit; Frimer, Aryeh A; Metoki, Noa; Eliaz, Noam; Kwak, Won-Jin; Sun, Yang-Kook; Aurbach, Doron
2018-04-04
Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.
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Sorption of imazaquin in soils with positive balance of charges.
Rocha, Wadson S D; Regitano, Jussara B; Alleoni, Luis R F; Tornisielo, Valdemar L
2002-10-01
The herbicide imazaquin has both an acid and a basic ionizable groups, and its sorption depends upon the pH, the electric potential (psi0), and the oxide and the organic carbon (OC) contents of the soil. Sorption and extraction experiments using 14C-imazaquin were performed in surface and subsurface samples of two acric oxisols (an anionic "rhodic" acrudox and an anionic "xanthic" acrudox) and one non-acric alfisol (a rhodic kandiudalf), treated at four different pH values. Imazaquin showed low to moderate sorption to the soils. Sorption decreased and aqueous extraction increased as pH increased. Up to pH 5.8, sorption was higher in subsurface than in surface layers of the acric soils, due to the positive balance of charges resulted from the high Fe and Al oxide and the low OC contents. It favored electrostatic interactions with anionic molecules of imazaquin. For the subsurface samples of these highly weathered soils, where psi0 was positive and OC was low, it was not possible to predict sorption just by considering imazaquin speciation and its hydrophobic partition to the organic domains of the soil. Moreover, if Koc measured for thesurface samples were assumed to represent the whole profile in predictive models for leaching potential, then it would result in underestimation of sorption potential in subsurface, and consequently result in overestimation of the leaching potential.
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Manna, Anamika; Sahoo, Dibakar; Chakravorti, Sankar
2012-03-01
We report an interesting pH-tunable energy transfer between an acceptor ionic styryl dye 2-(4-(dimethylamino)styryl)-1-methylpyridinium iodide and a donor charge-transfer dye 1,8-naphthalimide in a vesicular medium. The polyethylene-b-polyethylene glycol block copolymer intercalates with the sodium dodecyl sulfate anionic surfactant to form self-aggregated nanocomposites. These nanocomposites interact with the donor molecules in aqueous solution to form "vesicles", and the donor molecules become attached on the outer wall by hydrogen bonding. The acceptor molecules are observed to be loaded in the vesicular interior. By controlling the spectral overlap of the donor and acceptor molecules by changing the pH of the medium, the energy-transfer efficiency in vesicles has been studied. The efficiency of energy transfer in vesicular media (55%) is found to be less compared to that in aqueous media (80%) at pH 7. The fall in efficiency has been attributed to the perturbation imparted by the vesicular wall due to the good matching of the donor-acceptor distance with the wall thickness. At low pH, the efficiency shows an abrupt increase (95%) due to the release of the acceptor molecules from the vesicular medium causing subsequent reduction of donor-acceptor separation and an increase of the spectral overlap at that pH.
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Xu, Jiawen; Wu, Cuiyu; Deng, Jianbin; Liao, Wenwei; Ling, Yuxiang; Yang, Yuanxiu; Zhao, Yina; Zhao, Yunlin; Hu, Xi; Wang, Hui; Liu, Yunguo
2017-01-01
A method for grafting ethylenediamine to a magnetic graphene oxide composite (EDA-GO@Fe3O4) was developed for Cr(VI) decontamination. The physicochemical properties of EDA-GO@Fe3O4 were characterized using HRTEM, EDS, FT-IR, TG-DSC, and XPS. The effects of pH, sorbent dose, foreign anions, time, Cr(VI) concentration, and temperature on decontamination process were studied. The solution pH can largely affect the decontamination process. The pseudo-second-order model is suitable for being applied to fit the adsorption processes of Cr(VI) with GO@Fe3O4 and EDA-GO@Fe3O4. The intra-particle diffusion is not the rate-controlling step. Isotherm experimental data can be described using the Freundlich model. The effects of multiple factors on the Cr(VI) decontamination was investigated by a 25−1 fractional factorial design (FFD). The adsorption process can significantly be affected by the main effects of A (pH), B (Cr(VI) concentration), and E (Adsorbent dose). The combined factors of AB (pH × Cr(VI) concentration), AE (pH × Adsorbent dose), and BC (Cr(VI) concentration × Temperature) had larger effects than other factors on Cr(VI) removal. These results indicated that EDA-GO@Fe3O4 is a potential and suitable candidate for treatment of heavy metal wastewater. PMID:29084287
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Developmental expression of SLC26A4 (Pendrin) during amelogenesis in developing rodent teeth
Bronckers, Antonius LJJ; Guo, Jing; Zandieh-Doulabi, Behrouz; Bervoets, Theodore J; Lyaruu, Donacian M.; Li, Xiangming; Wangemann, Philine; DenBesten, Pamela
2012-01-01
Ameloblasts need to regulate pH during formation of enamel crystals, a process that generates protons. Solute carrier family 26A member 4 (SLC26A4, or pendrin) is an anion exchanger for chloride, bicarbonate, iodine and formate. It is expressed in apical membranes of ion-transporting epithelia in kidney, inner ear and thyroid where it regulates luminal pH and fluid transport. We hypothesized that maturation ameloblasts express SLC26A4 to neutralize acidification of enamel fluid in forming enamel. In rodents, secretory and maturation ameloblasts were immunopositive for SLC26A4. Staining was particularly strong in apical membranes of maturation ameloblasts facing forming enamel. RT-PCR confirmed the presence of mRNA transcripts for Slc26a4 in enamel organs. SLC26A4 immunostaining was also found in mineralizing connective tissues including odontoblasts, osteoblasts, osteocytes, osteoclasts, bone lining cells, cellular cementoblasts and cementocytes. However, Slc26a4-null mutant mice had no overt dental phenotype. The presence of SLC26A4 in apical plasma membranes of maturation ameloblasts is consistent with a potential function as pH regulator. SLC26A4 does not appear critical for ameloblast functioning and is likely compensated by other pH regulators. PMID:22243245
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1-anilino-8-naphthalene sulfonate as a protein conformational tightening agent.
Matulis, D; Baumann, C G; Bloomfield, V A; Lovrien, R E
1999-05-01
1-Anilino-8-naphthalene sulfonate (ANS) anion is conventionally considered to bind to preexisting hydrophobic (nonpolar) surfaces of proteins, primarily through its nonpolar anilino-naphthalene group. Such binding is followed by an increase in ANS fluorescence intensity, similar to that occurring when ANS is dissolved in organic solvents. It is generally assumed that neither the negative sulfonate charge on the ANS, nor charges on the protein, participate significantly in ANS-protein interaction. However, titration calorimetry has demonstrated that most ANS binding to a number of proteins occurs through electrostatic forces, in which ion pairs are formed between ANS sulfonate groups and cationic groups on the proteins (D. Matulis and R. E. Lovrien, Biophys. J., 1998, Vol. 74, pp. 1-8). Here we show by viscometry and diffusion coefficient measurements that bovine serum albumin and gamma-globulin, starting from their acid-expanded, most hydrated conformations, undergo extensive molecular compaction upon ANS binding. As the cationic protein binds negatively charged ANS anion it also takes up positively charged protons from water to compensate the effect of the negative charge, and leaves the free hydroxide anions in solution thus shifting pH upward (the Scatchard-Black effect). These results indicate that ANS is not always a definitive reporter of protein molecular conformation that existed before ANS binding. Instead, ANS reports on a conformationally tightened state produced by the interplay of ionic and hydrophobic characters of both protein and ligand.
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Dynamic basis for dG•dT misincorporation via tautomerization and ionization
NASA Astrophysics Data System (ADS)
Kimsey, Isaac J.; Szymanski, Eric S.; Zahurancik, Walter J.; Shakya, Anisha; Xue, Yi; Chu, Chia-Chieh; Sathyamoorthy, Bharathwaj; Suo, Zucai; Al-Hashimi, Hashim M.
2018-02-01
Tautomeric and anionic Watson-Crick-like mismatches have important roles in replication and translation errors through mechanisms that are not fully understood. Here, using NMR relaxation dispersion, we resolve a sequence-dependent kinetic network connecting G•T/U wobbles with three distinct Watson-Crick mismatches: two rapidly exchanging tautomeric species (Genol•T/UG•Tenol/Uenol population less than 0.4%) and one anionic species (G•T-/U- population around 0.001% at neutral pH). The sequence-dependent tautomerization or ionization step was inserted into a minimal kinetic mechanism for correct incorporation during replication after the initial binding of the nucleotide, leading to accurate predictions of the probability of dG•dT misincorporation across different polymerases and pH conditions and for a chemically modified nucleotide, and providing mechanisms for sequence-dependent misincorporation. Our results indicate that the energetic penalty for tautomerization and/or ionization accounts for an approximately 10-2 to 10-3-fold discrimination against misincorporation, which proceeds primarily via tautomeric dGenol•dT and dG•dTenol, with contributions from anionic dG•dT- dominant at pH 8.4 and above or for some mutagenic nucleotides.
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NASA Astrophysics Data System (ADS)
Zhang, Zhuanfang; Pang, Haijun; Ma, Huiyuan; Li, Shaobin; Zhao, Chunyan
2018-01-01
Four new inorganic-organic supramolecular compounds, namely, (H2tib)2[GeW12O40] (1), [Mn(Htib)4][HGeW12O40]2·4H2O (2), [Mn(tib)]2(H2O)6[GeW12O40]·4H2O (3) and [Mn(tib)]2(H2O)6[GeW12O40]·2H2O (4) (tib = 1, 3, 5-tris-(1-imidazolyl)-benzene), have been synthesized through the hydrothermal reaction of [GeW12O40]4- anions, MnII cations and tib ligands under different pH conditions. Compounds 1 and 2 were prepared at lower pH (pH ≈ 2.0 for 1 and 3.2 for 2). Compound 1 exhibits a simple monomer structure. In 2, the Mn cation is coordinated with four tib ligands and two [GeW12 O40]4- anions to form a dimer, in which each of [GeW12 O40]4- anion connects with one Mn cation. Compounds 3 and 4 were pr
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NASA Astrophysics Data System (ADS)
Su, Jun-Xia; Wang, Xiao-Ting; Chang, Jing; Wu, Gui-Yuan; Wang, Hai-Ming; Yao, Hong; Lin, Qi; Zhang, You-Ming; Wei, Tai-Bao
2017-07-01
In this manuscript, a new colorimetric and fluorescent chemosensor (T) was designed and synthesized, it could successively detect Cu2 + and H2PO4- in DMSO/H2O (v/v = 9:1, pH = 7.2) buffer solution with high selectivity and sensitivity. When added Cu2 + ions into the solution of T, it showed a color changes from yellow to colorless, meanwhile, the green fluorescence of sensor T quenched. This recognition behavior was not affected in the presence of other cations, including Hg2 +, Ag+, Ca2 +, Co2 +, Ni2 +, Cd2 +, Pb2 +, Zn2 +, Cr3 +, and Mg2 + ions. More interestingly, the Cu2 + ions contain sensor T solution could recover the color and fluorescence upon the addition of H2PO4- anions in the same medium. And other surveyed anions (including F-, Cl-, Br-, I-, AcO-, HSO4-, ClO4-, CN- and SCN-) had nearly no influence on the recognition behavior. The detection limits of T to Cu2 + and T-Cu2 + to H2PO4- were evaluated to be 1.609 × 10- 8 M and 0.994 × 10- 7 M, respectively. In addition, the sensor T also could be served as a recyclable component and the logic gate output was also defined in sensing materials. The test strips based on sensor T were fabricated, which acted as a convenient and efficient Cu2 + and H2PO4- test kits.
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Åsberg, Dennis; Leśko, Marek; Samuelsson, Jörgen; Kaczmarski, Krzysztof; Fornstedt, Torgny
2014-10-03
This is the first investigation in a series that aims to enhance the scientific knowledge needed for reliable analytical method transfer between HPLC and UHPLC using the quality by design (QbD) framework. Here, we investigated the differences and similarities from a thermodynamic point of view between RP-LC separations conducted with 3.5μm (HPLC) and 1.7μm (UHPLC) C18 particles. Three different model solutes and one pharmaceutical compound were used: the uncharged cycloheptanone, the cationic benzyltriethylammonium chloride, the anionic sodium 2-naphatlene sulfonate and the pharmaceutical compound omeprazole, which was anionic at the studied pH. Adsorption data were determined for the four solutes at varying fractions of organic modifier and in gradient elution in both the HPLC and UHPLC system, respectively. From the adsorption data, the adsorption energy distribution of each compound was calculated and the adsorption isotherm model was estimated. We found that the adsorption energy distribution was similar, with only minor differences in degree of homogeneity, for HPLC and UHPLC stationary phases. The adsorption isotherm model did not change between HPLC and UHPLC, but the parameter values changed considerably especially for the ionic compounds. The dependence of the organic modifier followed the same trend in HPLC as in UHPLC. These results indicates that the adsorption mechanism of a solute is the same on HPLC and UHPLC stationary phases which simplifies design of a single analytical method applicable to both HPLC and UHPLC conditions within the QbD framework. Copyright © 2014. Published by Elsevier B.V.
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Studies of anions sorption on natural zeolites.
Barczyk, K; Mozgawa, W; Król, M
2014-12-10
This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method. Copyright © 2014 Elsevier B.V. All rights reserved.
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Aoyagi, Wataru; Omiya, Masaki
2016-01-01
An ionic polymer-metal composite (IPMC) actuator composed of a thin perfluorinated ionomer membrane with electrodes plated on both surfaces undergoes a large bending motion when a low electric field is applied across its thickness. Such actuators are soft, lightweight, and able to operate in solutions and thus show promise with regard to a wide range of applications, including MEMS sensors, artificial muscles, biomimetic systems, and medical devices. However, the variations induced by changing the type of anion on the device deformation properties are not well understood; therefore, the present study investigated the effects of different anions on the ion exchange process and the deformation behavior of IPMC actuators with palladium electrodes. Ion exchange was carried out in solutions incorporating various anions and the actuator tip displacement in deionized water was subsequently measured while applying a step voltage. In the step voltage response measurements, larger anions such as nitrate or sulfate led to a more pronounced tip displacement compared to that obtained with smaller anions such as hydroxide or chloride. In AC impedance measurements, larger anions generated greater ion conductivity and a larger double-layer capacitance at the cathode. Based on these mechanical and electrochemical measurements, it is concluded that the presence of larger anions in the ion exchange solution induces a greater degree of double-layer capacitance at the cathode and results in enhanced tip deformation of the IPMC actuators. PMID:28773599
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Photophysics and Photochemistry of 2-Aminobenzoic Acid Anion in Aqueous Solution
NASA Astrophysics Data System (ADS)
Pozdnyakov, Ivan P.; Plyusnin, Victor F.; Grivin, Vjacheslav P.
2009-11-01
Nanosecond laser flash photolysis and absorption and fluorescence spectroscopy were used to study photochemical processes of 2-aminobenzoic acid anion (ABA-) in aqueous solutions. Excitation of this species gives rise to the ABA- triplet state to the ABA• radical and to the hydrated electron (eaq-). The last two species result from two-photon processes. In a neutral medium, the main decay channels of ABA- triplet state, the ABA• radical, and eaq- are T-T annihilation, recombination, and capture by the ABA- anion, respectively.
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Salih, Bekir; Celikbiçak, Omür; Döker, Serhat; Doğan, Mehmet
2007-03-28
Poly(N-(hydroxymethyl)methacrylamide)-1-allyl-2-thiourea) hydrogels, poly(NHMMA-ATU), were synthesized by gamma radiation using (60)Co gamma source in the ternary mixture of NHMMA-ATU-H(2)O. These hydrogels were used for the specific gold, silver, platinum and palladium recovery, pre-concentration and matrix elimination from the solutions containing trace amounts of precious metal ions. Elimination of inorganic matrices such as different transition and heavy metal ions, and anions was performed by adjusting the solution pH to 0.5 that was the selective adsorption pH of the precious metal ions. Desorption of the precious metal ions was performed by using 0.8 M thiourea in 3M HCl as the most efficient desorbing agent with recovery values more than 95%. In the desorption medium, thiourea effect on the atomic signal was eliminated by selecting proper pyrolysis and atomization temperatures for all precious metal ions. Precision and the accuracy of the results were improved in the graphite furnace-atomic absorption spectrometer (GFAAS) measurements by applying the developed matrix elimination method performing the adsorption at pH 0.5. Pre-concentration factors of the studied precious metal ions were found to be at least 1000-fold. Detection limits of the precious metal ions were found to be less than 10 ng L(-1) of the all studied precious metal ions by using the proposed pre-concentration method. Determination of trace levels of the precious metals in the sea-water, anode slime, geological samples and photographic fixer solutions were performed using GFAAS clearly after applying the adsorption-desorption cycle onto the poly(NHMMA-UTU) hydrogels.
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NASA Astrophysics Data System (ADS)
Jamett, Nathalie E.; Hernández, Pía C.; Casas, Jesús M.; Taboada, María E.
2018-02-01
This article presents the results on speciation of ferric iron generated by the dissolution of chemical reagent hydromolysite (ferric chloride hexahydrate, FeCl3:6H2O) in water at 298.15 K, 313.15 K, and 333.15 K (25 °C, 40 °C, and 60 °C). Experiments were performed with a thermoregulated system up to the equilibrium point, as manifested by solution pH. Solution samples were analyzed in terms of concentration, pH, and electrical conductivity. Measurements of density and refractive index were obtained at different temperatures and iron concentrations. A decrease of pH was observed with the increase in the amount of dissolved iron, indicating that ferric chloride is a strong electrolyte that reacts readily with water. Experimental results were modeled using the hydrogeochemical code PHREEQC in order to obtain solution speciation. Cations and neutral and anion complexes were simultaneously present in the system at the studied conditions according to model simulations, where dominant species included Cl-, FeCl2+, FeCl2 +, FeOHCl 2 0 , and H+. A decrease in the concentration of Cl- and Fe3+ ions took place with increasing temperature due to the association of Fe-Cl species. Standard equilibrium constants for the formation of FeOHCl 2 0 obtained in this study were log Kf0 = -0.8 ± 0.01 at 298.15 K (25 °C), -0.94 ± 0.02 at 313.15 K (40 °C), and -1.03 ± 0.01 at 333.15 K (60 °C).
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Effects of sorbate speciation on sorption of selected sulfonamides in three loamy soils
Kurwadkar , Sudarshan T.; Adams, Craig D.; Meyer, Michael T.; Kolpin, Dana W.
2007-01-01
Sorption of sulfamethazine (SMN) and sulfathiazole (STZ) was investigated in three soils, a North Carolina loamy sand, an Iowa sandy loam, and a Missouri loam, under various pH conditions. A significant increase in the sorption coefficient (KD) was observed in all three soils, as the sulfonamides converted from an anionic form at higher pH to a neutral/cationic form at lower pH. Above pH 7.5, sulfonamides exist primarily in anionic form and have higher aqueous solubility and no cationic character, thereby consequently leading to lower sorption to soils. The effect of speciation on sorption is not the same for all sulfonamides; it is a function of the pH of the soil and the pKa of the sulfonamides. The results indicate that, for the soils under investigation, SMN has comparatively lower KD values than STZ. The pH-dependent sorption of sulfonamides was observed to be consistent in all three soils investigated. The KD values for each speciated formcationic, neutral, and anionicwere calculated using an empirical model in which the species-specific sorption coefficients (KD0, KD1, and KD2) were weighted with their respective fractions present at any given pH.
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Zhang, Weihua; Zheng, Juan; Zheng, Pingping; Tsang, Daniel C W; Qiu, Rongliang
2015-07-01
Recycling sewage sludge by pyrolysis has attracted increasing attention for pollutant removal from wastewater and soils. This study scrutinized As(III) sorption behavior on sludge-derived biochar (SDBC) under different pyrolysis conditions and solution chemistry. The SDBC pyrolyzed at a higher temperature showed a lower As(III) sorption capacity and increasingly nonlinear isotherm due to loss of surface sites and deoxygenation-dehydrogenation. The Langmuir sorption capacity on SDBC (3.08-6.04 mg g) was comparable to other waste-derived sorbents, with the highest As(III) sorption on SDBC pyrolyzed at 400°C for 2 h. The As(III) sorption kinetics best fit with the pseudo-second-order equation, thus suggesting the significance of the availability of surface sites and initial concentration. Sorption of As(III) was faster than that of Cr(VI) but slower than that of Pb(II), which was attributed to their differences in molar volume (correlated to diffusion coefficients) and sorption mechanisms. The X-ray photoelectron spectra revealed an increase of oxide oxygen (O) with a decrease of sorbed water, indicative of ligand exchange with hydroxyl groups on SDBC surfaces. The As(III) sorption was not pH dependent in acidic-neutral range (pH < 8) due to the buffering capacity and surface characteristics of the SDBC; however, sorption was promoted by increasing pH in the alkaline range (pH > 8) because of As(III) speciation in solution. An increasing ionic strength (0.001-0.1 mol L) facilitated As(III) sorption, indicating the predominance of ligand exchange over electrostatic interactions, while high concentrations (0.1 mol L) of competing anions (fluoride, sulfate, carbonate, and phosphate) inhibited As(III) sorption. These results suggest that SDBC is applicable for As(III) immobilization in most environmentally relevant conditions. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.
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Measurements and theoretical interpretation of points of zero charge/potential of BSA protein.
Salis, Andrea; Boström, Mathias; Medda, Luca; Cugia, Francesca; Barse, Brajesh; Parsons, Drew F; Ninham, Barry W; Monduzzi, Maura
2011-09-20
The points of zero charge/potential of proteins depend not only on pH but also on how they are measured. They depend also on background salt solution type and concentration. The protein isoelectric point (IEP) is determined by electrokinetical measurements, whereas the isoionic point (IIP) is determined by potentiometric titrations. Here we use potentiometric titration and zeta potential (ζ) measurements at different NaCl concentrations to study systematically the effect of ionic strength on the IEP and IIP of bovine serum albumin (BSA) aqueous solutions. It is found that high ionic strengths produce a shift of both points toward lower (IEP) and higher (IIP) pH values. This result was already reported more than 60 years ago. At that time, the only available theory was the purely electrostatic Debye-Hückel theory. It was not able to predict the opposite trends of IIP and IEP with ionic strength increase. Here, we extend that theory to admit both electrostatic and nonelectrostatic (NES) dispersion interactions. The use of a modified Poisson-Boltzmann equation for a simple model system (a charge regulated spherical colloidal particle in NaCl salt solutions), that includes these ion specific interactions, allows us to explain the opposite trends observed for isoelectric point (zero zeta potential) and isoionic point (zero protein charge) of BSA. At higher concentrations, an excess of the anion (with stronger NES interactions than the cation) is adsorbed at the surface due to an attractive ionic NES potential. This makes the potential relatively more negative. Consequently, the IEP is pushed toward lower pH. But the charge regulation condition means that the surface charge becomes relatively more positive as the surface potential becomes more negative. Consequently, the IIP (measuring charge) shifts toward higher pH as concentration increases, in the opposite direction from the IEP (measuring potential). © 2011 American Chemical Society
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NO3 −-induced pH Changes in Mammalian Cells
Chow, Chung-Wai; Kapus, Andras; Romanek, Robert; Grinstein, Sergio
1997-01-01
The effect of NO3 − on intracellular pH (pHi) was assessed microfluorimetrically in mammalian cells in culture. In cells of human, hamster, and murine origin addition of extracellular NO3 − induced an intracellular acidification. This acidification was eliminated when the cytosolic pH was clamped using ionophores or by perfusing the cytosol with highly buffered solutions using patch-pipettes, ruling out spectroscopic artifacts. The NO3 −- induced pH change was not due to modulation of Na+/H+ exchange, since it was also observed in Na+/H+ antiport-deficient mutants. Though NO3 − is known to inhibit vacuolar-type (V) H+-ATPases, this effect was not responsible for the acidification since it persisted in the presence of the potent V-ATPase inhibitor bafilomycin A1. NO3 −/HCO3 − exchange as the underlying mechanism was ruled out because acidification occurred despite nominal removal of HCO3 −, despite inhibition of the anion exchanger with disulfonic stilbenes and in HEK 293 cells, which seemingly lack anion exchangers (Lee, B.S., R.B. Gunn, and R.R. Kopito. 1991. J. Biol. Chem. 266:11448– 11454). Accumulation of intracellular NO3 −, measured by the Greiss method after reduction to NO2 −, indicated that the anion is translocated into the cells along with the movement of acid equivalents. The simplest model to explain these observations is the cotransport of NO3 − with H+ (or the equivalent counter-transport of NO3 − for OH−). The transporter appears to be bi-directional, operating in the forward as well as reverse directions. A rough estimate of the fluxes of NO3 − and acid equivalents suggests a one-to-one stoichiometry. Accordingly, the rate of transport was unaffected by sizable changes in transmembrane potential. The cytosolic acidification was a saturable function of the extracellular concentration of NO3 − and was accentuated by acidification of the extracellular space. The putative NO3 −-H+ cotransport was inhibited markedly by ethacrynic acid and by α-cyano-4-hydroxycinnamate, but only marginally by 4,4′-diisothiocyanostilbene-2,2′ disulfonate or by p-chloromercuribenzene sulfonate. The transporter responsible for NO3 −-induced pH changes in mammalian cells may be related, though not identical, to the NO3 −-H+ cotransporter described in Arabidopsis and Aspergillus. The mammalian cotransporter may be important in eliminating the products of NO metabolism, particularly in cells that generate vast amounts of this messenger. By cotransporting NO3 − with H+ the cells would additionally eliminate acid equivalents from activated cells that are metabolizing actively, without added energetic investment and with minimal disruption of the transmembrane potential, inasmuch as the cotransporter is likely electroneutral. PMID:9236211
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Cai, Jianguo; Zhang, Yanyang; Pan, Bingcai; Zhang, Weiming; Lv, Lu; Zhang, Quanxing
2016-10-01
Water decontamination from fluoride is still a challenging task of global concern. Recently, Al-based layered double hydroxides (LDHs) have been extensively studied for specific fluoride adsorption from water. Unfortunately, they cannot be readily applied in scaled-up application due to their ultrafine particles as well as the regeneration issues caused by their poor stability at alkaline pHs. Here, we developed a novel (LDH)-based hybrid adsorbent, i.e., LALDH-201, by impregnating nanocrystalline Li/Al LDHs (LADLH) inside a commercial polystyrene anion exchanger D201. TEM image and XRD spectra of the resultant nanocomposite confirmed that the LDHs particles were nanosized inside the pores of D201 of highly crystalline nature and well-ordered layer structure. After impregnation, the chemical and mechanical stability of LALDH were significantly improved against pH variation, facilitating its application at a wide pH range (3.5-12). Fluoride adsorption onto LALDH-201 was compared to D201 and activated alumina, evidencing the preferable removal fluoride of LALDH-201. Fluoride adsorption onto LALDH-201 followed pseudo-second-order model, with the maximum capacity (62.5 mg/g from the Sips model) much higher than the other two adsorbents. Fixed-bed adsorption run indicated the qualified treatable volume of the fluoride contaminated groundwater (4.1 mg/L initially) with LALDH-201 was about 11 times as much as with the anion exchanger D201 when the breakthrough point was set as 1.5 mg/L. The capacity of LALDH-201 could be effectively refreshed for continuous column operation without observable loss by using the mixed solution of 0.01 M NaOH + 1 M NaCl. The above results suggested that the hybrid adsorbent LALDH-201 is very promising for water defluoridation in scaled-up application. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Pei, Lei; Lucy, Charles A
2014-10-24
Polycationic polymers are widely used in capillary electrophoresis (CE) as surface coatings to prevent protein adsorption and control electroosmotic flow (EOF). Such semi-permanent coatings are formed by flushing the capillary with a quaternary amine-based polymer such as poly(diallydimethylammonium chloride) (PDADMAC) or polybrene. Compared to covalent capillary coatings, the claimed advantages of adsorptive polycation coatings are their simple preparation and that they are not limited to the pH 2-8 range as are covalent coatings. However, while the latter is commonly claimed, few studies have demonstrated the stability of polycationic coatings at extreme pH. Herein PDADMAC and polybrene are studied as model cationic coatings. PDADMAC with higher molecular weight (M.W.) demonstrated higher EOF stability at pH 9.5, with PDADMAC of M.W. less than 200,000 being unstable at pH 9.5. X-ray photoelectron spectroscopy (XPS) shows that the quaternary amines of PDADMAC and polybrene were slowly converted to tertiary amines in alkaline solution and more rapidly when adsorbed on a silica surface. The degraded polycation deprotonated at pH >7, resulting in loss of polymer from the surface and diminishing EOF. Successive multiple ionic layer (SMIL) coatings show greater alkaline stability by distancing the polycation from the surface. Separations of inorganic anions at pH 9.5 illustrate the degradation behavior and enhanced stability of higher M.W. polycationic coatings. Copyright © 2014 Elsevier B.V. All rights reserved.
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A manganese catalase from Thermomicrobium roseum with peroxidase and catecholase activity.
Baginski, Robin; Sommerhalter, Monika
2017-01-01
An enzyme with catechol oxidase activity was identified in Thermomicrobium roseum extracts via solution assays and activity-stained SDS-PAGE. Yet, the genome of T. roseum does not harbor a catecholase gene. The enzyme was purified with two anion exchange chromatography steps and ultimately identified to be a manganese catalase with additional peroxidase and catecholase activity. Catalase activity (6280 ± 430 IU/mg) clearly dominated over pyrogallol peroxidase (231 ± 53 IU/mg) and catecholase (3.07 ± 0.56 IU/mg) activity as determined at 70 °C. Most enzyme kinetic properties were comparable to previously characterized manganese catalase enzymes. Catalase activity was highest at alkaline pH values and showed inhibition by excess substrate and chloride. The apparent K m and k cat values were 20 mM and 2.02 × 10 4 s -1 subunit -1 at 25 °C and pH 7.0.
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Al Hasan, Naila M; Johnson, Grant E; Laskin, Julia
2013-09-01
Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy(n-) and VxOyCl(n-) ions (x = 1-14, y = 2-36, n = 1-3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N(+), tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCl(n-) and VxOyCl(L)((n-1)-) clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl((1-2)-) and VxOy ((1-2)-) anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.
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NASA Astrophysics Data System (ADS)
Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia
2013-09-01
Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including VxOy n- and VxOyCln- ions (x = 1-14, y = 2-36, n = 1-3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V14O36Cl(L)5 (L = Et4N+, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged VxOyCln- and VxOyCl(L)(n-1)- clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller VxOyCl(1-2)- and VxOy (1-2)- anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged VxOyCl and VxOy species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of VxOyCl and VxOy anions through low-energy CID. Furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Deng, Shihu; Kong, Xiangyu; Wang, Xue B.
2015-01-14
Due to fast solvent evaporation in electrospray ionization (ESI), the concentration of initially dilute electrolyte solutions rapidly increases to afford formation of supersaturated droplets and generating various pristine anhydrous salt clusters in the gas phase. The size, composition, and charge distributions of these clusters, in principle witness the nucleation evolution in solutions. Herein, we report a microscopic study on the initial stage of nucleation and crystallization of sodium/potassium thiocyanate salt solutions simulated in the ESI process. Singly charged M x(SCN)⁻ x+1, doubly charged M y(SCN)²⁻ y+2 (M = Na, K), and triply charged K z(SCN)³⁻ z+3 anion clusters were producedmore » via electrospray of the corresponding salt solutions, and were characterized by negative ion photoelectron spectroscopy (NIPES). The vertical detachment energies (VDEs) of these sodium/potassium thiocyanate cluster anions were obtained, and theoretical calculations were carried out for sodium thiocyanate clusters in assisting spectral identification. The measured VDEs of singly charged anions M x(SCN)⁻ x+1 (M = Na and K) demonstrate they are superhalogen anions. The existence of doubly charged anions M y (SCN)²⁻ y+2 (y = 2x, x ≥ 4 and 3 for M = Na and K, respectively) and triply charged anions K z(SCN)³⁻ z+3 (z = 3x, x ≥ 6) were initially discovered from the photoelectron spectra for those singly charged anions of Msub>x(SCN)⁻ x+1 with the same mass-to-charge ratio (m/z), and later independently confirmed by observation of their distinct mass spectral distributions and by taking their NIPE spectra for those pure multiply charged anions with their m/z different from the singly charged species. For large clusters, multiply charged clusters are found to become preferred, but at higher temperatures those multiply charged clusters are suppressed. The series of anion clusters investigated here range from molecular-like M₁(SCN)⁻ 2 to nano-sized K₂₂(SCN)³⁻ 25, providing a vivid molecular-level growth pattern reflecting the initial salt nucleation process.« less
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Hydrogen bond breaking in aqueous solutions near the critical point
Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming
2001-01-01
The nature of water-anion bonding is examined using X-ray absorption fine structure spectroscopy on a 1mZnBr2/6m NaBr aqueous solution, to near critical conditions. Analyses show that upon heating the solution from 25??C to 500??C, a 63% reduction of waters occurs in the solvation shell of ZnBr42-, which is the predominant complex at all pressure-temperature conditions investigated. A similar reduction in the hydration shell of waters in the Br- aqua ion was found. Our results indicate that the water-anion and water-water bond breaking mechanisms occurring at high temperatures are essentially the same. This is consistent with the hydration waters being weakly hydrogen bonded to halide anions in electrolyte solutions. ?? 2001 Elsevier Science B.V.
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Silica micro- and nanoparticles reduce the toxicity of surfactant solutions.
Ríos, Francisco; Fernández-Arteaga, Alejandro; Fernández-Serrano, Mercedes; Jurado, Encarnación; Lechuga, Manuela
2018-04-20
In this work, the toxicity of hydrophilic fumed silica micro- and nanoparticles of various sizes (7 nm, 12 nm, and 50 μm) was evaluated using the luminescent bacteria Vibrio fischeri. In addition, the toxicity of an anionic surfactant solution (ether carboxylic acid), a nonionic surfactant solution (alkyl polyglucoside), and a binary (1:1) mixture of these solutions all containing these silica particles was evaluated. Furthermore, this work discusses the adsorption of surfactants onto particle surfaces and evaluates the effects of silica particles on the surface tension and critical micellar concentration (CMC) of these anionic and nonionic surfactants. It was determined that silica particles can be considered as non-toxic and that silica particles reduce the toxicity of surfactant solutions. Nevertheless, the toxicity reduction depends on the ionic character of the surfactants. Differences can be explained by the different adsorption behavior of surfactants onto the particle surface, which is weaker for nonionic surfactants than for anionic surfactants. Regarding the effects on surface tension, it was found that silica particles increased the surface activity of anionic surfactants and considerably reduced their CMC, whereas in the case of nonionic surfactants, the effects were reversed. Copyright © 2018 Elsevier B.V. All rights reserved.
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Sorption of hydrophilic dyes on anodic aluminium oxide films and application to pH sensing.
Silina, Yuliya E; Kuchmenko, Tatyana A; Volmer, Dietrich A
2015-02-07
The sorption of selected hydrophilic pH-sensitive dyes (bromophenol blue, bromothymol blue, bromocresol purple, alizarin red, methyl orange, congo red, rhodamine 6G) on films of anodized aluminium oxide (AAO) was investigated in this study. Depth and pore structure of the AAO channels were adjusted by changing electrolysis time and current density during treatment of aluminium foil in oxalic acid, sulfosalycilic acid and sulfuric acid at concentration levels between 0.2 and 0.6 M. The dyes were immobilized on the AAO surface by direct saturation of the films in dye solutions. It was shown by scanning electron microscopy and X-ray spectral analysis that the dyes penetrated into the AAO channels by more than 1.5 μm, even at static saturation conditions. The anionic dyes linked to the porous AAO surface exhibited differential shifts of the UV absorption bands in their acidic/basic forms. By combining several dyes, the films have an application range between pH = 0.5-9 in aqueous media. The dye-modified AAO film was a simple, portable, inexpensive and reusable pH sensor with very fast response time and clear colour transitions.
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A laboratory scale study on arsenic(V) removal from aqueous medium using calcined bauxite ore.
Mohapatra, Debasish; Mishra, Debaraj; Park, Kyung Ho
2008-01-01
The present work deals with the As(V) removal from an aqueous medium by calcined refractory grade bauxite (CRB) as a function of solution pH, time, As(V) concentration and temperature. The residual As(V) was lowered from 2 mg/L to below 0.01 mg/L in the optimum pH range 4.0-7.0 using a 5 g/L CRB within 3 h contact time. The adsorption data fits well with Langmuir isotherm and yielded Langmuir monolayer capacity of 1.78 mg As(V)/g of CRB at pH 7.0. Presence of anions such as silicate and phosphate decreased As(V) adsorption efficiency. An increase temperature resulted a decrease in the amount of As(V) adsorbed by 6%. The continuous fixed bed column study showed that at the adsorbent bed depth of 30 cm and residence time of 168 min, the CRB was capable of treating 340 bed volumes of As(V) spiked water (C0 = 2 mg/L) before breakthrough (Ce = 0.01 mg/L). This solid adsorbent, although not reusable, can be considered for design of adsorption columns as an efficiency arsenic adsorption media.
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Manenti, Diego R; Módenes, Aparecido N; Soares, Petrick A; Boaventura, Rui A R; Palácio, Soraya M; Borba, Fernando H; Espinoza-Quiñones, Fernando R; Bergamasco, Rosângela; Vilar, Vítor J P
2015-01-01
In this work, the application of an iron electrode-based electrocoagulation (EC) process on the treatment of a real textile wastewater (RTW) was investigated. In order to perform an efficient integration of the EC process with a biological oxidation one, an enhancement in the biodegradability and low toxicity of final compounds was sought. Optimal values of EC reactor operation parameters (pH, current density and electrolysis time) were achieved by applying a full factorial 3(3) experimental design. Biodegradability and toxicity assays were performed on treated RTW samples obtained at the optimal values of: pH of the solution (7.0), current density (142.9 A m(-2)) and different electrolysis times. As response variables for the biodegradability and toxicity assessment, the Zahn-Wellens test (Dt), the ratio values of dissolved organic carbon (DOC) relative to low-molecular-weight carboxylates anions (LMCA) and lethal concentration 50 (LC50) were used. According to the Dt, the DOC/LMCA ratio and LC50, an electrolysis time of 15 min along with the optimal values of pH and current density were suggested as suitable for a next stage of treatment based on a biological oxidation process.
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Guan, Qian; Noblitt, Scott D.; Henry, Charles S.
2012-01-01
The use of mixtures of ionic and zwitterionic surfactants in poly(dimethylsiloxane) (PDMS) microchips is reported. The effect of surfactant concentration on EOF was studied for a single anionic surfactant (sodium dodecyl sulfate, SDS), a single zwitterionic surfactant (N-tetradecylammonium-N,N-dimethyl-3-ammonio-1-propanesulfonate, TDAPS), and a mixed SDS/TDAPS surfactant system. SDS increased the EOF as reported previously while TDAPS showed an initial increase in EOF followed by a reduction at higher concentrations. When TDAPS was added to a solution containing SDS, the EOF decreased in a concentration dependent manner. The EOF for all three surfactant systems followed expected pH trends, with increasing EOF at higher pH. The mixed surfactant system allowed tuning of the EOF across a range of pH and concentration conditions. After establishing the EOF behavior, the adsorption/desorption kinetics were measured and showed a slower adsorption/desorption rate for TDAPS than SDS. Finally, the separation and electrochemical detection of model catecholamines in buffer and reduced glutathione (GSH) in red blood cell lysate using the mixed surfactant system were explored. The mixed surfactant system provided shorter analysis times and/or improved resolution when compared to the single surfactant systems. PMID:22222982
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Electroactive Self-Assembled Monolayers Detect Micelle Formation.
Dionne, Eric R; Badia, Antonella
2017-02-15
The interfacial electrochemistry of self-assembled monolayers (SAMs) of ferrocenyldodecanethiolate on gold (FcC 12 SAu) electrodes is applied to detect the micellization of some common anionic surfactants, sodium n-alkyl sulfates, sodium n-alkyl sulfonates, sodium diamyl sulfosuccinate, and sodium dodecanoate, in aqueous solution by cyclic voltammetry. The apparent formal redox potential (E°' SAM ) of the FcC 12 SAu SAM is used to track changes in the concentration of the unaggregated surfactant anions and determine the critical micelle concentration (cmc). The effect of added salt (NaF) on the sodium alkyl sulfate concentration dependence of E°' SAM is also investigated. Weakly hydrated anions, such as ClO 4 - , pair with the electrogenerated SAM-bound ferroceniums to neutralize the excess positive charge created at the SAM/electrolyte solution interface and stabilize the oxidized cations. E°' SAM exhibits a Nernstian-type dependence on the anion activity in solution. Aggregation of the surfactant anions into micelles above the cmc causes the free surfactant anion activity to deviate from the molar concentration of added surfactant, resulting in a break in the plot of E°' SAM versus the logarithm of the concentration of anionic surfactant. The concentration at which this deviation occurs is in good agreement with literature or experimentally determined values of the cmc. The effects of Ohmic potential drop, liquid junction potential, and surfactant adsorption behavior on E°' SAM are addressed. Ultimately, the E°' SAM response as a function of the anionic surfactant concentration exhibits the same features reported using potentiometry and surfactant ion-selective electrodes, which provide a direct measure of the free surfactant anion activity, thus making FcC 12 SAu SAM electrodes useful for the detection of surfactant aggregation and micelle formation.
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Gan, Weibing; Liu, Qi
2008-08-01
Heterocoagulation experiments of kaolinite with solvent-diluted-bitumen were carried out to investigate the effect of hydrolyzable metal cations and citric acid on the liberation of bitumen from kaolinite. The adsorption of Ca(2+) and Mg(2+) on kaolinite, and zeta potentials of kaolinite and bitumen droplets in solutions containing 10(-3)mol/L of Ca(2+), Mg(2+) and Fe(3+) with or without citric acid were also measured. It was found that the heterocoagulation of bitumen with kaolinite was enhanced in the presence of the metal cations from pH 7 to pH 10.5, accompanied by a decrease in the magnitude of the zeta potentials and an increase in the adsorption of the metal cations on kaolinite and possibly on bitumen droplets. The addition of 5 x 10(-4)mol/L citric acid reduced the degree of coagulation from 90% to less than 40% in the presence of 10(-3)mol/L Ca(2+) and Mg(2+) cations at pH approximately 10, and at pH approximately 8 for Fe(3+). It was found that hydrolyzable metal cations enhanced bitumen-kaolinite interactions through electrical double layer compression and specific adsorption of the metal hydrolysis species on the surface of kaolinite. The effect of metal cations was removed by citric acid through formation of metal-citrate complexes and/or the adsorption of citrate anions, which restored the zeta potentials of both kaolinite and bitumen. Therefore, electrostatic attraction or repulsion was responsible for the coagulation or dispersion of kaolinite particles from bitumen droplets in the tested system.
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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.
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METHOD FOR THE RECOVERY OF CESIUM VALUES
Rimshaw, S.J.
1960-02-16
A method is given for recovering Cs/sup 137/ from radioactive waste solutions together with extraneous impurities. Ammonium alum is precipitated in the waste solution. The alum, which carries the cesium, is separated from the supernatant liquid and then dissolved in water. The resulting aqueous solution is then provided with a source of hydroxyl ions, which precipitates aluminum as the hydroxide, and the aluminum hydroxide is separated from the resulting liquid. This liquid, which contains anionic impurities together with ammonium and cesium, is passed through an anion exchange resin bed which removes the anionic impurities. The ammonium in the effluent is removed by destructive distiilation, leaving a substantiaily pure cesium salt in the effluent.
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Abney, Kent D.; Kinkead, Scott A.; Mason, Caroline F. V.; Rais, Jiri
1997-01-01
Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.
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Abney, K.D.; Kinkead, S.A.; Mason, C.F.V.; Rais, J.
1997-09-09
Preparation and use is described for polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.
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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.
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The role of charge in the surfactant-assisted stabilization of the natural product curcumin.
Wang, Zifan; Leung, Mandy H M; Kee, Tak W; English, Douglas S
2010-04-20
Colloidal solutions of surfactants that form micelles or vesicles are useful for solubilizing and stabilizing hydrophobic molecules that are otherwise sparingly soluble in aqueous solutions. In this paper we investigate the use of micelles and vesicles prepared from ionic surfactants for solubilizing and stabilizing curcumin, a medicinal natural product that undergoes alkaline hydrolysis in water. We identify spectroscopic signatures to evaluate curcumin partitioning and deprotonation in surfactant mixtures containing micelles or vesicles. These spectroscopic signatures allow us to monitor the interaction of curcumin with charged surfactants over a wide range of pH values. Titration data are presented to show the pH dependence of curcumin interactions with negatively and positively charged micelles and vesicles. In solutions of cationic micelles or positively charged vesicles, strong interaction between the Cur(-1) phenoxide ion and the positively charged surfactants results in a change in the acidity of the phenolic hydrogen and a lowering of the apparent lowest pK(a) value for curcumin. In the microenvironments formed by anionic micelles or negatively charged bilayers, our data indicates that curcumin partitions as the Cur(0) species, which is stabilized by interactions with the respective surfactant aggregates, and this leads to an increase in the apparent pK(a) values. Our results may explain some of the discrepancies within the literature with respect to reported pK(a) values and the acidity of the enolic versus phenolic protons. Hydrolysis rates, quantum yields, and molar absorption coefficients are reported for curcumin in a variety of solutions.
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Woehler, Andrew; Lin, Kun-Han; Neher, Erwin
2014-11-15
Significantly more Ca(2+) influx is required for eliciting release of neurotransmitter during whole cell patch clamp recording in the Calyx of Held, when gluconate with 3 mm free ATP is used as pipette filling solution, as compared to a methanesulfonate-based solution with excess Mg(2+). This reduction in efficiency of Ca(2+) in eliciting release is due to low-affinity Ca(2+) binding of both gluconate and ATP(2-) anions. To study these effects we developed a simple fluorimeteric titration procedure, which reports the dissociation constant, KD, of a given Ca(2+) indicator dye, multiplied by 1 plus the sum of Ca(2+) binding ratios of any anions, which act as low-affinity Ca(2+) ligands. For solutions without Ca(2+) binding anions we find KD values for Fura2FF ranging from 11.5 ± 1.7 to 15.6 ± 7.47 μm depending on the dominant anion used. For Fura6F and KCl-based solutions we find KD = 17.8 ± 1.3 μm. For solutions with gluconate as the main anion and for solutions that contain nucleotides, such as ATP and GTP, we find much higher values for the product. Assuming that the KD of the indicator dye is equal to that of KCl-based solutions we calculate the summed Ca(2+) binding ratios and find a value of 3.55 for a solution containing 100 mm potassium gluconate and 4 mm ATP. Gluconate contributes a value of 1.75 to this number, while the contribution of ATP depends strongly on the presence of Mg(2+) and varies from 0.8 (with excess Mg(2+)) to 13.8 (in the presence of 3 mm free ATP). Methanesulfonate has negligible Ca(2+) binding capacity. These results explain the reduced efficiency of Ca(2+) influx in the presence of gluconate or nucleotides, as these anions are expected to intercept Ca(2+) ions at short distance. © 2014 The Authors. The Journal of Physiology © 2014 The Physiological Society.
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Alarfaj, Nawal A; El-Tohamy, Maha F
2016-01-01
A highly selective, sensitive, accurate, and reproducible luminescence procedure for determination of antifungal drug tolnaftate was developed. The introduced method was based on the formation of Europa Universalis III (Eu(III))-tolnaftate complex using sodium sulfite as a deoxygenated agent in the presence of acetate buffer (pH = 6) and micellar solution of anionic surfactant sodium dodecyl sulfate. The optimum conditions (effect of pH, buffer, surfactant, Eu(III), and sodium sulfite concentrations) for the luminescence signal were investigated and optimized. The luminescence signals were recorded at λex = 270 nm and λem = 460 nm. The method has a good linear response (0.2-130 μg/mL(-1)) between the luminescence intensity and the concentrations of the drug (r = 0.999), with a LOD 0.07 μg/mL(-1) and LOQ 0.2 μg/mL(-1). The luminescence signals of Eu (III)-tolnaftate-sodium dodecyl sulfate were found to be 200-fold more sensitive without the presence of micelle solution. The interferences of some additives, metals, amino acids, sugars, and other related pharmacological action drugs were examined and no interference was recorded. The proposed method was used for quick and simple determination of tolnaftate in its pharmaceuticals and biological fluids.
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Apak, Reşat; Güçlü, Kubilay; Ozyürek, Mustafa; Bektas Oğlu, Burcu; Bener, Mustafa
2008-01-01
Antioxidants are health beneficial compounds through their combat with reactive oxygen and nitrogen species and free radicals that may cause tissue damage leading to various diseases. This work reports the development of a simple and widely applicable antioxidant capacity index for dietary polyphenols, vitamins C and E, and plasma antioxidants utilizing the copper(II)-neocuproine (Cu(II)-Nc) reagent as the chromogenic oxidizing agent. This novel method based on an electron-transfer mechanism was named by our research group as 'cupric reducing antioxidant capacity', abbreviated as the CUPRAC method. The method is comprised of mixing the antioxidant solution with aqueous copper(II) chloride, alcoholic neocuproine, and ammonium acetate aqueous buffer at pH 7, and subsequently measuring the developed absorbance at 450 nm after 30 min. Since the color development is fast for compounds like ascorbic acid, gallic acid, and quercetin but slow for naringin and naringenin, the latter compounds are assayed after incubation at 50 degrees C on a water bath for 20 min. The flavonoid glycosides are hydrolyzed to their corresponding aglycones by refluxing in 1.2 M: HCl-containing 50% MeOH so as to exert maximal reducing power towards Cu(II)-Nc. The CUPRAC antioxidant capacities of synthetic mixtures are equal to the sum of individual capacities of antioxidant constituents, indicating lack of chemical deviations from Beer's law. Tests on antioxidant polyphenols demonstrate that the highest CUPRAC capacities are observed for epicatechin gallate, epigallocatechin gallate, quercetin, fisetin, epigallocatechin, catechin, and caffeic acid in this order, in accord with the number and position of the -OH groups as well the conjugation level of the molecule. The parallelism of the linear calibration curves of pure antioxidants in water and in a given complex matrix (plant extract) demonstrates that there are no chemical interactions of interferent nature among the solution constituents, and that the antioxidant capacities of the tested antioxidants are additive, in conformity to the Beer's law. For individual determination of ascorbic acid in fruit juices with a modified CUPRAC procedure, flavonoids are pre-extracted as their La(III) complexes prior to assay. For apricot extracts, a modified version of the CUPRAC assay based on anion exchange separation at pH 3 is applied, since sulfited-dried sample extracts contain the hydrosulfite anion interfering with the determination. For herbal tea infusions, the standard CUPRAC protocol is applied. The CUPRAC reagent is stable, easily accessible, low-cost, and is sensitive toward thiol-type antioxidants unlike FRAP. The reaction is carried out at nearly physiological pH as opposed to the acidic pH of FRAP or to the alkaline pH of Folin methods, constituting a basic advantage for the realistic assay of biological fluids.
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NASA Astrophysics Data System (ADS)
Biswas, Sohag; Dasgupta, Teesta; Mallik, Bhabani S.
2016-09-01
We present the reactivity of an organic intermediate by studying the proton transfer process from water to ketyl radical anion using gas phase electronic structure calculations and the metadynamics method based first principles molecular dynamics (FPMD) simulations. Our results indicate that during the micro solvation of anion by water molecules systematically, the presence of minimum three water molecules in the gas phase cluster is sufficient to observe the proton transfer event. The analysis of trajectories obtained from initial FPMD simulation of an aqueous solution of the anion does not show any evident of complete transfer of the proton from water. The cooperativity of water molecules and the relatively weak anion-water interaction in liquid state prohibit the full release of the proton. Using biasing potential through first principles metadynamics simulations, we report the observation of proton transfer reaction from water to ketyl radical anion with a barrier height of 16.0 kJ/mol.
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ANION EXCHANGE METHOD FOR SEPARATION OF METAL VALUES
Hyde, E.K.; Raby, B.A.
1959-02-10
A method is described for selectively separating radium, bismuth, poloniums and lead values from a metallic mixture of thc same. The mixture is dissolved in aqueous hydrochloric acid and the acidity is adjusted to between 1 to 2M in hydrochloric acid to form the anionic polychloro complexes of polonium and bismuth. The solution is contacted with a first anion exchange resin such as strong base quaternary ammonia type to selectively absorb the polonium and bismuth leaving the radium and lead in the effluent. The effluent, after treatment in hydrochloric acid to increase the hydrochloric acid concentration to 6M is contacted with a second anion exchange iesin of the same type as the above to selectively adsorb the lead leaving the radium in the effluent. Radium is separately recovered from the effluent from the second exchange column. Lead is stripped from the loaded resin of the second column by treatment with 3M hydrochloric acid solution. The loaded resin of the first column is washed with 8M hydrochloric acid solution to recover bismuth and then treated with strong nitric acid solution to recover polonium.
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ERYTHROPOIETIC FACTOR PURIFICATION
White, W.F.; Schlueter, R.J.
1962-05-01
A method is given for purifying and concentrating the blood plasma erythropoietic factor. Anemic sheep plasma is contacted three times successively with ion exchange resins: an anion exchange resin, a cation exchange resin at a pH of about 5, and a cation exchange resin at a pH of about 6. (AEC)
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A theoretical study of the decomposition of gold (I) complexes
NASA Astrophysics Data System (ADS)
Tossell, J. A.
1998-04-01
Structures, energetics and excitation energies are calculated for the gold (I) complexes CH 3Au, (CH 3) 2Au -, CH 3AuOH 2, CH 3AuPH 3 and PH 3AuCl at the Hartree-Fock and MP2 levels of theory, and for CH 3AuP(CH 3) 3, CH 3AuP(OH) 3 and Au 3Cl 3 at the HF level. The lowest-energy neutral triplet state of each 2-coordinate compound dissociates into either two or three radical species (always including the CH 3 radical), with the exception of (CH 3) 2Au - which shows only slight Au-C bond elongation. In contrast, the doublet anion states dissociate neutral ligands, like PH 3, but do not dissociate CH 3. These results indicate that gold (I) chemical vapor deposition processes must involve excited states of the neutrals rather than their anions.
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The relative hydrolytic reactivities of pyrophosphites and pyrophosphates.
Mistry, Dharmit; Powles, Nicholas
2013-09-14
The pH-rate profiles for the hydrolysis of pyrophosphate (PP(V)) and pyrophosphite (PP(III), pyro-di-H-phosphonate) are a complex function of pH, reflecting the different ionic species and their relative reactivities. PP(III) is more reactive than PP(V) at all pHs and only PP(III) shows a hydroxide-ion reaction at high pH, so it is 10(10)-fold more reactive than PP(V) in 0.1 M NaOH. The pK(a2) of PP(III) ~0.44, so the dominant species at pH's > 1 is the di-anion PP(III)(2-). Although there is no observable (NMR or ITC) binding of Mg(2+) to the PP(III) di-anion there is a modest increase in the rate of hydrolysis of PP(III) by Mg(2+). PP(III) is neither a substrate nor an inhibitor of pyrophosphatase, the enzyme that efficiently catalyses the hydrolysis of PP(V).
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Photophysics and photochemistry of 2-aminobenzoic acid anion in aqueous solution.
Pozdnyakov, Ivan P; Plyusnin, Victor F; Grivin, Vjacheslav P
2009-12-24
Nanosecond laser flash photolysis and absorption and fluorescence spectroscopy were used to study photochemical processes of 2-aminobenzoic acid anion (ABA(-)) in aqueous solutions. Excitation of this species gives rise to the ABA(-) triplet state to the ABA* radical and to the hydrated electron (e(aq)(-)). The last two species result from two-photon processes. In a neutral medium, the main decay channels of ABA(-) triplet state, the ABA* radical, and e(aq)(-) are T-T annihilation, recombination, and capture by the ABA(-) anion, respectively.
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NASA Astrophysics Data System (ADS)
Patra, Digambara; Barakat, Christelle
2011-09-01
Hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroburate, modified the properties of aqueous surfactant solutions associated with curcumin. Because of potential pharmaceutical applications as an antioxidant, anti-inflammatory and anti-carcinogenic agent, curcumin has received ample attention as potential drug. The interaction of curcumin with various charged aqueous surfactant solutions showed it exists in deprotonated enol form in surfactant solutions. The nitro and hydroxyl groups of o-nitrophenol interact with the carbonyl and hydroxyl groups of the enol form of curcumin by forming ground state complex through hydrogen bonds and offered interesting information about the nature of the interactions between the aqueous surfactant solutions and curcumin depending on charge of head group of the surfactant. IL[bmin][BF 4] encouraged early formation of micelle in case of cationic and anionic aqueous surfactant solutions, but slightly prolonged micelle formation in the case of neutral aqueous surfactant solution. However, for curcumin IL [bmin][BF 4] favored strong association (7-fold increase) with neutral surfactant solution, marginally supported association with anionic surfactant solution and discouraged (˜2-fold decrease) association with cationic surfactant solution.
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Bush, M S; Reid, A R; Allt, G
1991-09-01
Previous investigations of the blood-nerve barrier have correlated the greater permeability of ganglionic endoneurial vessels, compared to those of nerve trunks, with the presence of fenestrations and open intercellular junctions. Recent studies have demonstrated reduced endothelial cell surface charge in blood vessels showing greater permeability. To determine the distribution of anionic sites on the plasma membranes and basal laminae of endothelial cells in dorsal root ganglia, cationic colloidal gold and cationic ferritin were used. Electron microscopy revealed the existence of endothelial microdomains with differing labelling densities. Labelling indicated that caveolar and fenestral diaphragms and basal laminae are highly anionic at physiological pH, luminal plasma membranes and endothelial processes are moderately charged and abluminal plasma membranes are weakly anionic. Tracers did not occur in caveolae or cytoplasmic vesicles. In vitro tracer experiments at pH values of 7.3, 5.0, 3.5 and 2.0 indicated that the anionic charge on the various endothelial domains was contributed by chemical groups with differing pKa values. In summary, the labelling of ganglionic and sciatic nerve vessels was similar except for the heavy labelling of diaphragms in a minority of endoneurial vessels in ganglia. This difference is likely to account in part for the greater permeability of ganglionic endoneurial vessels. The results are discussed with regard to the blood-nerve and -brain barriers and vascular permeability in other tissues and a comparison made between the ultrastructure and anionic microdomains of epi-, peri- and endoneurial vessels of dorsal root ganglia and sciatic nerves.
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X-Ray Crystallographic Studies of Electrostatic Effects in Cubic Insulin
NASA Astrophysics Data System (ADS)
Gursky, Olga
1992-09-01
Cubic crystals of bovine insulin were obtained at pH 9 from sodium phosphate buffer. Pathway dependence of crystallization was analysed and crystallization using controlled nucleation was developed. Crystal stability and solubility were surveyed by dialysing the crystals against salt solutions varying in salt composition and ionic strength. Crystals dialysed in 0.1-0.2M Li, Na, K, Rb, NH(4) or Tl salt solutions at pH 9 diffracted to beyond 2.8A, while crystals dialysed in Cs, Mg, Ca or La rapidly lost lattice order. Change in the solvent anion did not affect crystal stability. Electron density maps calculated from X-ray data to 2.8A resolution showed two specific cation binding sites which may be occupied by monovalent cations with ionic radii <1.5A. One site lies between insulin dimers near crystallographic two-fold axis without the close involvement of protein charged groups. Cation binding at this site is important for crystal stability. The other site is alternatively occupied by B10 His in one of its two conformations. At pH 7, the Tl occupancy at both sites was decreased, at pH 9.5 the Tl occupancy of the site near B10 His was increased. The structure was refined using the refined model of cubic porcine insulin and the X-ray data collected to 2A resolution from a bovine insulin crystal at pH 9, to R = 16.1% for the data extending from 10A to 2A. High -resolution data from crystals at pH 7 and pH 10 were collected and analysed. The weights of the two B10 His conformers and the cation occupancy near B10 vary in the pH range from 7 to 10, indicating histidine titration. Shifts in the positions of B1-B4 at pH 7 suggest titration of the B-chain terminal amino groups. Co-operative conformational changes in the surface charged residues A1, A4, B21, B29, B30 at pH 10.2 suggest titration of the A-chain terminal amino groups. In several crystals treated with dichloroethane, the syn-dichloroethane was bound in the niche across the two-fold axis connecting insulin monomers. Dichloroethane binding does not perturb the site geometry and probably leads to cubic insulin preparations of increased stability.
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Esteves, Catarina V; Esteban-Gómez, David; Platas-Iglesias, Carlos; Tripier, Raphaël; Delgado, Rita
2018-05-11
The triethylbenzene-bis-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) compound (tbmce) was designed with an imposed structural rigidity at the m-xylyl spacer to be compared to a less restrained and known parent compound (bmce). The framework of both compounds differs only in the substituents of the m-xylyl spacer. The study was centered in the differences observed in the acid-base reactions of both compounds, their copper(II) and zinc(II) complexation behaviors, as well as in the uptake of phosphate and polyphosphate anions (HPPi 3- , ATP 4- , ADP 3- , AMP 2- , PhPO 4 2- , and HPO 4 2- ). On the one hand, the acid-base reactions showed lower values for the third and fourth protonation constants of tbmce than for bmce, suggesting that the ethyl groups of the spacer in tbmce force the two cyclen units to more conformational restricted positions. On the other hand, the stability constant values for copper(II) and zinc(II) complexes revealed that bmce is a better chelator than tbmce pointing out to additional conformational restraints imposed by the triethylbenzene spacer. The binding studies of phosphates by the dinuclear copper(II) and zinc(II) complexes showed much smaller effective association constants for the dicopper complexes. Single-crystal X-ray and computational (density functional theory) studies suggest that anion binding promotes the formation of tetranuclear entities in which anions are bridging the metal centers. Our studies also revealed the dinuclear zinc(II) complex of bmce as a promising receptor for phosphate anions, with the largest effective association constant of 5.94 log units being observed for the formation of [Zn 2 bmce(HPPi)] + . Accordingly, a colorimetric study via an indicator displacement assay to detect phosphates in aqueous solution found that the [Zn 2 bmce] 4+ complex acts as the best receptor for pyrophosphate displaying a detection limit of 2.5 nM by changes visible to naked eye.
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Ščančar, Janez; Berlinger, Balázs; Thomassen, Yngvar; Milačič, Radmila
2015-09-01
A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Linear gradient elution from 100% water to 100% 0.7 M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO4(2-) species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO4(2-), MoO4(2-) and WO4(2-) are present and were eluted in sharp chromatographic peaks, while VO4(3-) species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420 s, 320 to 370 s, 300 to 350 s and 240 to 360 s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02 ng Cr mL(-1)), molybdate (0.1 ng Mo mL(-1)), tungstate (0.1 ng W mL(-1)) and vanadate (0.2 ng V mL(-1)). The accuracy of analytical procedure for the determination of chromate was checked by analysis of CRM 545, Cr(VI) in welding dust loaded on a filter. Good agreement between determined and reported certified values was obtained. For molybdate, tungstate and vanadate the assessment of accuracy was performed by spiking welding fume filters. Good recoveries for all investigated species (98-101%) confirmed the accuracy of the analytical procedure. Copyright © 2015 Elsevier B.V. All rights reserved.
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Ramesh, Sunita A; Tyerman, Stephen D; Xu, Bo; Bose, Jayakumar; Kaur, Satwinder; Conn, Vanessa; Domingos, Patricia; Ullah, Sana; Wege, Stefanie; Shabala, Sergey; Feijó, José A; Ryan, Peter R; Gilliham, Matthew; Gillham, Matthew
2015-07-29
The non-protein amino acid, gamma-aminobutyric acid (GABA) rapidly accumulates in plant tissues in response to biotic and abiotic stress, and regulates plant growth. Until now it was not known whether GABA exerts its effects in plants through the regulation of carbon metabolism or via an unidentified signalling pathway. Here, we demonstrate that anion flux through plant aluminium-activated malate transporter (ALMT) proteins is activated by anions and negatively regulated by GABA. Site-directed mutagenesis of selected amino acids within ALMT proteins abolishes GABA efficacy but does not alter other transport properties. GABA modulation of ALMT activity results in altered root growth and altered root tolerance to alkaline pH, acid pH and aluminium ions. We propose that GABA exerts its multiple physiological effects in plants via ALMT, including the regulation of pollen tube and root growth, and that GABA can finally be considered a legitimate signalling molecule in both the plant and animal kingdoms.
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Ramesh, Sunita A.; Tyerman, Stephen D.; Xu, Bo; Bose, Jayakumar; Kaur, Satwinder; Conn, Vanessa; Domingos, Patricia; Ullah, Sana; Wege, Stefanie; Shabala, Sergey; Feijó, José A.; Ryan, Peter R.; Gillham, Matthew
2015-01-01
The non-protein amino acid, gamma-aminobutyric acid (GABA) rapidly accumulates in plant tissues in response to biotic and abiotic stress, and regulates plant growth. Until now it was not known whether GABA exerts its effects in plants through the regulation of carbon metabolism or via an unidentified signalling pathway. Here, we demonstrate that anion flux through plant aluminium-activated malate transporter (ALMT) proteins is activated by anions and negatively regulated by GABA. Site-directed mutagenesis of selected amino acids within ALMT proteins abolishes GABA efficacy but does not alter other transport properties. GABA modulation of ALMT activity results in altered root growth and altered root tolerance to alkaline pH, acid pH and aluminium ions. We propose that GABA exerts its multiple physiological effects in plants via ALMT, including the regulation of pollen tube and root growth, and that GABA can finally be considered a legitimate signalling molecule in both the plant and animal kingdoms. PMID:26219411
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[Determination of inorganic ions in explosive residues by capillary zone electrophoresis].
Feng, Junhe; Guo, Baoyuan; Lin, Jin-Ming; Xu, Jianzhong; Zhou, Hong; Sun, Yuyou; Liu, Yao; Quan, Yangke; Lu, Xiaoming
2008-11-01
Five anions (chlorate, perchlorate, nitrate, nitrite, and sulfate) and two cations (ammonium and potassium) in explosive residues have been separated and determined by capillary zone electrophoresis (CZE) with indirect ultraviolet detection. The electrolyte buffer for the cation separation was 10 mmol/L pyridine (pH 4.5) -3 mmol/L 18-crown-6-ether. Ammonium and potassium ions were baseline separated in less than 2.6 min with the detection limits of 0.10 mg/L and 0.25 mg/L (S/N = 3), respectively. The electrolyte buffer for the anion separation consisted of 40 mmol/L boric acid-1.8 mmol/L potassium dichromate-2 mmol/L sodium tetraborate (pH 8.6), and tetramethyl ammonium hydroxide (TMAOH) was used as electroosmotic flow modifier. All five anions were well separated in less than 4.6 min with the detection limit range of 0.10 - 1.85 mg/L (S/N = 3). The method was successfully used in real sample investigations to confirm the type of explosives.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Khalifa, M.E.
An alizarin red S (ARS)-modified anion exchange resin was prepared by a simple reaction of ARS with the anion exchange Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2.8--5) with a maximum sorption capacity of 0.68 mmol/g at pH 3.2 to 4.0. Iron(III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II),more » Cd(II), Al(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0.2 mol/L HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH {approx} 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Ioannou, A.; Dimirkou, A.
1997-08-01
The constant capacitance model was used to describe phosphate adsorption on hematite, kaolinite, and a kaolinite-hematite system (k-h). The model assumes a ligand exchange mechanism and considers the charge on both adsorbate and adsorbent. The model is shown to provide a quantitative description of phosphate adsorption on these, including the effect of varying pH values. The computer program Ma-Za 2, a program that fits equilibrium constants to experimental data using an optimization technique, was used to obtain optimal values for the anion surface complexation constants on hematite, kaolinite, and a kaolinite-hematite system, while the PC program Ma-Za 1 in Q-Basicmore » language was used for the application of the constant capacitance model. The model represented adsorption of phosphate anions well over the entire pH range studied (3.8--9.0). The main advantage of the model is its ability to represent changes in anion adsorption occurring with changes in pH. Extension of the model to describe phosphate adsorption in a mixed system, such as the kaolinite-hematite system, using the surface protonation-dissociation constant of hematite was qualitatively successful. In mixed system the model reproduced the shape of the adsorption isotherms well over the pH range 3.8--9.0. However, phosphate adsorption was overestimated. The hematite and the kaolinite-hematite system were synthesized and identified by X-ray, NMR, and FT-IR spectroscopy.« less
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Adsorption of natural dissolved organic matter at the oxide/water interface
Davis, James A.
1982-01-01
Natural organic matter is readily adsorbed by alumina and kaolinite in the pH range of natural waters. Adsorption occurs by complex formation between surface hydroxyls and the acidic functional groups of the organic matter. Oxides with relatively acidic surface hydroxyls, e.g. silica, do not react strongly with the organic matter. Under conditions typical for natural waters, almost complete surface coverage by adsorbed organic matter may be expected for alumina, hydrous iron oxides and the edge sites of aluminosilicates. Potentiometric titration and electrophoresis indicate that most of the acidic functional groups of the adsorbed organic matter are neutralized by protons from solution. The organic coating is expected to have a great influence on subsequent adsorption of inorganic cations and anions.
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Briand, Glen G; Chivers, Tristram; Krahn, Mark; Parvez, Masood
2002-12-16
The dilithium salts of the phosphonate dianions [PhP(E)(N(t)Bu)(2)](2-) (E = O, S, Se) are generated by the lithiation of [PhP(E)(NH(t)Bu)(2)] with n-butyllithium. The formation of the corresponding telluride (E = Te) is achieved by oxidation of [Li(2)[PhP(N(t)Bu)(2)
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Cho, Dong-Gyu; Kim, Jong Hoon; Sessler, Jonathan L
2008-09-10
The benzil-cyanide reaction is a cyanide-specific reaction that has been exploited to produce a colorimetric indicator for this toxic anion. This was done by producing a pi-extended analogue of benzil, 7, which is soluble in a 70:30 (v/v) mixture of methanol-water. In this medium, dilute solutions of 7 are yellow but produce colorless products when exposed to low concentrations of cyanide anion (> or = 1.7 microM; added as an aqueous NaCN solution), but no other common anions (e.g., OH(-), F(-), N3(-), benzoate(-), and H2PO4(-)). On the basis of these observations and supporting mechanistic analyses, it is concluded that the modified benzil system 7 is a promising cyanide anion indicator that is attractive in terms of its selectivity, ease-of-use, water compatibility, and the low, naked-eye discernible cyanide detection limit it provides.
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Predictions of diagenetic reactions in the presence of organic acids
NASA Astrophysics Data System (ADS)
Harrison, Wendy J.; Thyne, Geoffrey D.
1992-02-01
Stability constants have been estimated for cation complexes with anions of monofunctional and difunctional acids (combinations of Ca, Mg, Fe, Al, Sr, Mn, U, Th, Pb, Cu, Zn with formate, acetate, propionate, oxalate, malonate, succinate, and salicylate) between 0 and 200°C. Difunctional acid anions form much more stable complexes than monofunctional acid anions with aluminum; the importance of the aluminum-acetate complex is relatively minor in comparison to aluminum oxalate and malonate complexes. Divalent metal cations such as Mg, Ca, and Fe form more stable complexes with acetate than with difunctional acid anions. Aluminum-oxalate can dominate the species distribution of aluminum under acidic pH conditions, whereas the divalent cation-acetate and oxalate complexes rarely account for more than 60% of the total dissolved cation, and then only in more alkaline waters. Mineral thermodynamic affinities were calculated using the reaction path model EQ3/6 for waters having variable organic acid anion (OAA) contents under conditions representative of those found during normal burial diagenesis. The following scenarios are possible: 1) K-feldspar and albite are stable, anorthite dissolves 2) All feldpars are stable 3) Carbonates can be very unstable to slightly unstable, but never increase in stability. Organic acid anions are ineffective at neutral to alkaline pH in modifying stabilities of aluminosilicate minerals whereas the anions are variably effective under a wide range of pH in modifying carbonate mineral stabilities. Reaction path calculations demonstrate that the sequence of mineral reactions occurring in an arkosic sandstone-fluid system is only slightly modified by the presence of OAA. A spectrum of possible sandstone alteration mineralogies can be obtained depending on the selected boundary conditions: EQ3/6 predictions include quartz overgrowth, calcite replacement of plagioclase, albitization of plagioclase, and the formation of porosity-occluding calcite cement, smectite, and illite, all of which are commonly documented in rocks. Under some circumstances, OAA-bearing waters are less effective at producing porosity in an arkosic sandstone than are OAA-free waters. In the scenarios modeled in this study the role of OAA in fluid-rock interactions is to contribute to the total alteration assemblage but not necessarily to dominate it, except under exceptional circumstances that might include, for example, hydrocarbon contaminant plumes in aquifers, wetland environments, and within hydrocarbon source-rocks.
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Simple guanidinium motif for the selective binding and extraction of sulfate
Seipp, Charles A.; Williams, Neil J.; Bryantsev, Vyacheslav S.; ...
2017-06-30
A simple bidentate anion receptor, shown previously to adopt a rigid pseudobicyclic conformation while binding anions in the solid state, selectively binds sulfate in aqueous solutions with logK1 and logK2 values of 3.78 ± 0.12 M-1 and 2.10 ± 0.23 M-1, respectively. This anion receptor has little to no affinity for nitrate and chloride in the same solutions. A lipophilic derivative was synthesized in four steps to yield an extractant that is capable of partitioning sulfate into 1,2 dichloroethane from water in the presence of large excesses of chloride. This extractant demonstrated D values as high as 2.5 with onlymore » 30 mM of anion receptor.« less
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Simple guanidinium motif for the selective binding and extraction of sulfate
DOE Office of Scientific and Technical Information (OSTI.GOV)
Seipp, Charles A.; Williams, Neil J.; Bryantsev, Vyacheslav S.
A simple bidentate anion receptor, shown previously to adopt a rigid pseudobicyclic conformation while binding anions in the solid state, selectively binds sulfate in aqueous solutions with logK1 and logK2 values of 3.78 ± 0.12 M-1 and 2.10 ± 0.23 M-1, respectively. This anion receptor has little to no affinity for nitrate and chloride in the same solutions. A lipophilic derivative was synthesized in four steps to yield an extractant that is capable of partitioning sulfate into 1,2 dichloroethane from water in the presence of large excesses of chloride. This extractant demonstrated D values as high as 2.5 with onlymore » 30 mM of anion receptor.« less
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Zampella, Mariavittoria; Adamo, Paola
2010-01-01
A study on variable charge soils (volcanic Italian and podzolic Scottish soils) was performed to investigate the influence of soil properties on the chemical composition of soil solution. Zinc speciation, bioavailability and toxicity in the soil solution were examined. The soils were spiked with increasing amounts of Zn (0, 100, 200, 400 and 1000 mg/kg) and the soil solutions were extracted using rhizon soil moisture samplers. The pH, total organic carbon (TOC), base cations, anions, total Zn and free Zn2+ in soil solution were analysed. A rapid bioassay with the luminescent bacterium Escherichia coli HB101 pUCD607 was performed to assess Zn toxicity. The influence of soil type and Zn treatments on the chemical composition of soil solution and on Zn toxicity was considered and discussed. Different trends of total and free Zn concentrations, base cations desorption and luminescence of E. coli HB101 pUCD607 were observed. The soil solution extracted from the volcanic soils had very low total and free Zn concentrations and showed specific Zn2+/Ca2+ exchange. The soil solution from the podzolic soil had much higher total and free Zn concentrations and showed no evidence of specific Zn2+/Ca2+ exchange. In comparison with the subalkaline volcanic soils, the acidic podzol showed enhanced levels of toxic free Zn2+ and consequently stronger effects on E. coli viability.
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Homoleptic organolanthanide compounds supported by the bis(dimethylsilyl)benzyl ligand
Boteju, Kasuni C.; Ellern, Arkady; Sadow, Aaron D.
2016-12-19
Here, a β-SiH functionalized benzyl anion [C(SiHMe 2) 2Ph]$-$s obtained by deprotonation of HC(SiHMe 2) 2Ph with KCH 2Ph or by reaction of KOtBu and (Me 2HSi) 3CPh; LnI 3(THF)n and three equivalents of this carbanion combine to provide homoleptic tris(alkyl)lanthanide compounds Ln{C(SiHMe 2) 2Ph} 3 (Ln = La, Ce, Pr, Nd) containing secondary metal–ligand interactions.
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Liu, Chuen-Ying; Chen, Tse-Hsien; Misra, Tarun Kumar
2007-06-22
An analytical approach of the 32-membered macrocyclic polyamine, 1,5,9,13,17,21,25,29-octaazacyclodotriacontane ([32]ane-N8) was described for the capillary electrochromatographic (CEC) separation of derivatized mono- and disaccharides. The column displayed reversal electroosmotic flow (EOF) at pH below 7.0, while a cathodic EOF was shown at pH above 7.0. The reductive amination of saccharides was carried out with p-aminobenzoic acid. Some parameters that affect the CEC separations were investigated. Several competitive ligands, such as Tris, EDTA and phosphate were also examined for the effect on the performance. We achieved a complete separation of all compounds as well as the excess derivatizing agent by using borate buffer (pH 9.0) in a mode of concentration gradient (60 mM inlet side and 70 mM outlet side). The relative standard deviation of the retention time measured for each sample was less than 4% in six continuous runs, suggesting that the bonded phase along with the gradient formed inside the column was quite stable. With the mixing modes of anion coordination, anion exchange, and shape discrimination, the interaction adequately accomplishes the separation of carbohydrates which are epimers or have different glycosidic linkage, although the electrophoretic migration is also involved in the separation mechanism.
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Gohain, Biren; Dutta, Robin K
2008-07-15
The premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions monitored by surface tension and spectroscopic measurements has been described. The measurements have been made for three anionic sulfonephthalein dyes and cationic surfactants of different chain lengths, head groups, and counterions. The observations have been attributed to the formation of closely packed dye surfactant ion pairs which is similar to nonionic surfactants in very dilute concentrations of the surfactant. These ion pairs dominate in the monolayer at the air-water interface of the aqueous dye surfactant solutions below the CMC of the pure surfactant. It has been shown that the dye in the ion pair deprotonates on micelle formation by the ion pair surfactants at near CMC but submicellar surfactant concentrations. The results of an equilibrium study at varying pH agree with the model of deprotonated 1:1 dye-surfactant ion pair formation in the near CMC submicellar solutions. At concentrations above the CMC of the cationic surfactant the dye is solubilized in normal micelles and the monolayer at the air-water interface consists of the cationic surfactant alone even in the presence of the dyes.
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Meena, Amanda H; Arai, Yuji
2016-01-01
Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Al Hasan, Naila M.; Johnson, Grant E.; Laskin, Julia
2013-07-02
Electrospray ionization mass spectrometry (ESI-MS) combined with in-source fragmentation and tandem mass spectrometry (MS/MS) experiments were used to generate a wide range of singly and multiply charged vanadium oxide cluster anions including V xO y n– and V xO yCl n– ions (x = 1–14, y = 2–36, n = 1–3), protonated clusters, and ligand-bound polyoxovanadate anions. The cluster anions were produced by electrospraying a solution of tetradecavanadate, V 14O 36Cl(L) 5 (L = Et 4N +, tetraethylammonium), in acetonitrile. Under mild source conditions, ESI-MS generates a distribution of doubly and triply charged V xO yCl n– and V xOmore » yCl(L) (n–1)– clusters predominantly containing 14 vanadium atoms as well as their protonated analogs. Accurate mass measurement using a high-resolution LTQ/Orbitrap mass spectrometer (m/Δm = 60,000 at m/z 410) enabled unambiguous assignment of the elemental composition of the majority of peaks in the ESI-MS spectrum. In addition, high-sensitivity mass spectrometry allowed the charge state of the cluster ions to be assigned based on the separation of the major from the much less abundant minor isotope of vanadium. In-source fragmentation resulted in facile formation of smaller V xO yCl (1–2)– and V xO y (1–2)– anions. Collision-induced dissociation (CID) experiments enabled systematic study of the gas-phase fragmentation pathways of the cluster anions originating from solution and from in-source CID. Surprisingly simple fragmentation patterns were obtained for all singly and doubly charged V xO yCl and V xO y species generated through multiple MS/MS experiments. In contrast, cluster anions originating directly from solution produced comparatively complex CID spectra. These results are consistent with the formation of more stable structures of V xO yCl and V xO y anions through low-energy CID. Finally and furthermore, our results demonstrate that solution-phase synthesis of one precursor cluster anion combined with gas-phase CID is an efficient approach for the top-down synthesis of a wide range of singly and multiply charged gas-phase metal oxide cluster anions for subsequent investigations of structure and reactivity using mass spectrometry and ion spectroscopy techniques.« less
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Electrodialysis potential for fractionation of multicomponent aqueous solutions
NASA Astrophysics Data System (ADS)
Grzegorzek, Martyna; Majewska-Nowak, Katarzyna
2017-11-01
The paper aimed at the evaluation of the batch electrodialysis (ED) run in the course of treatment and desalination of various aqueous mixtures containing both mineral (sodium fluoride, sodium chloride) and organic substances (dyes or humic acids). The commercial ED stack (PCCell Bed) equipped with standard anion-exchange and cation-exchange membranes or monovalent selective anion-exchange membranes was used. The ED experiments were performed at a constant current density (1.56 or 1.72 mA/cm2). The mechanism of ion migration as well as membrane deposition for variable solution composition and various membrane types was analyzed The calculated mass balance and electrical energy demand for each ED run were helpful in evaluating the membrane fouling intensity. It was found that the presence of organic substances in the treated solution had a minor impact on energy consumption, but rather strongly affected chloride flux. The extent of organics deposition was significantly lower for monovalent selective anion-exchange membranes than for classic anion-exchange membranes.
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Thermal unfolding of tetrameric melittin: comparison with the molten globule state of cytochrome c.
Hagihara, Y.; Oobatake, M.; Goto, Y.
1994-01-01
Whereas melittin at micromolar concentrations is unfolded under conditions of low salt at neutral pH, it transforms to a tetrameric alpha-helical structure under several conditions, such as high peptide concentration, high anion concentration, or alkaline pH. The anion- and pH-dependent stabilization of the tetrameric structure is similar to that of the molten globule state of several acid-denatured proteins, suggesting that tetrameric melittin might be a state similar to the molten globule state. To test this possibility, we studied the thermal unfolding of tetrameric melittin using far-UV CD and differential scanning calorimetry. The latter technique revealed a broad but distinct heat absorption peak. The heat absorption curves were consistent with the unfolding transition observed by CD and were explainable by a 2-state transition mechanism between the tetrameric alpha-helical state and the monomeric unfolded state. From the peptide or salt-concentration dependence of unfolding, the heat capacity change upon unfolding was estimated to be 5 kJ (mol of tetramer)-1 K-1 at 30 degrees C and decreased with increasing temperature. The observed change in heat capacity was much smaller than that predicted from the crystallographic structure (9.2 kJ (mol of tetramer)-1 K-1), suggesting that the hydrophobic residues of tetrameric melittin in solution are exposed in comparison with the crystallographic structure. However, the results also indicate that the structure is more ordered than that of a typical molten globule state. We consider that the conformation is intermediate between the molten globule state and the native state of globular proteins. PMID:7833804
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Ruiz-Angel, M J; Carda-Broch, S; García-Alvarez-Coque, M C; Berthod, A
2004-03-19
Logarithm of retention factors (log k) of a group of 14 ionizable diuretics were correlated with the molecular (log P o/w) and apparent (log P(app)) octanol-water partition coefficients. The compounds were chromatographed using aqueous-organic (reversed-phase liquid chromatography, RPLC) and micellar-organic mobile phases (micellar liquid chromatography, MLC) with the anionic surfactant sodium dodecyl sulfate (SDS), in the pH range 3-7, and a conventional octadecylsilane column. Acetonitrile was used as the organic modifier in both modes. The quality of the correlations obtained for log P(app) at varying ionization degree confirms that this correction is required in the aqueous-organic mixtures. The correlation is less improved with SDS micellar media because the acid-base equilibriums are shifted towards higher pH values for acidic compounds. In micellar chromatography, an electrostatic interaction with charged solutes is added to hydrophobic forces; consequently, different correlations should be established for neutral and acidic compounds, and for basic compounds. Correlations between log k and the isocratic descriptors log k(w), log k(wm) (extrapolated retention to pure water in the aqueous-organic and micellar-organic systems, respectively), and psi0 (extrapolated mobile phase composition giving a k = 1 retention factor or twice the dead time), and between these descriptors and log P(app) were also satisfactory, although poorer than those between log k and log P(app) due to the extrapolation. The study shows that, in the particular case of the ionizable diuretics studied, classical RPLC gives better results than MLC with SDS in the retention hydrophobicity correlations.
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Diseno de puertas moleculares controladas a nivel nanoscopico
NASA Astrophysics Data System (ADS)
Casasus Lis, Rosa
The present thesis has been developed between the frontiers of different disciplines such as Coordination and Supramolecular Chemistry and Material Science. The main objective has been the design and construction of nanosupramolecular gate-ensemble, which can be defined as a basis device that modulate the access to a certain site and whose state (opened or closed) can be controlled at will by certain external stimuli, for example ionically, electrochemically and photochemically. One of the most important ideas of this thesis is the development of molecular gates using organic-inorganic hybrid systems. We have been working with a mesoporous siliceous matrix MCM-41 type and UVM-7 that possesses preorganized cavities, in that sense the porous system are homogeneous in size even in shape and periodicity. Furthermore, it has been possible to obtain systems highly functionalized due to its high specific surfaces areas (internal and external). First of all, it has been studying the design of ionically-controlled nanoscopic molecular gates. The idealized open-closed mechanism would arise from simple interactions between amines (open-gate) and Coulombic repulsion between ammonium groups (closed-gate). When protonated the open-chain polyamines in the external surface would adopt a rigid-like conformation and would be pushed away towards the pore openings due to repulsion between ammonium groups charged positively. A fundamental aspect related to molecular gates was the demonstration of specific functions like "open-close" could be controlled wilfully by certain external stimuli. In this sense, we used two different approximations to prove how works the molecular machine: (a) detect the access (controlled by external stimuli) to the pores of certain species in solution and (b) study the release of some molecules entrapped from the pore voids into the bulk solution. The first approximation, the most difficult to control, has been carried out by using a coupled reaction that would give one observable and easy signal such as change of colour and even more the only way to occur was if the studied species came inside the nanometric porous. In second place it was reported a complete study of the behaviour of a pH-driven and anion-controlled nano-supramolecular gate-like ensemble obtained by anchoring suitable polyamines on the pore outlets of mesoporous materials of the type MCM-41. The release of an entrapped dye (Ru(bipy)3 2+) from the pore voids into the bulk solution allows us to study the gating effect. This study was carried out by monitoring the dye released from the pore voids of the solid at a certain pH in the presence of a range of anions with different structural dimensions and charges, including chloride, sulphate, phosphate, and ATP. The choice of a certain anionic guest results in a different gate-like ensemble behaviour, ranging from basically no action (chloride) to complete (ATP) or partial pore blockage, depending on the pH (sulphate and phosphate). Molecular dynamics simulations using force field methods have been carried out to explain the pH-driven open/close mechanism and selectivity patterns have been discussed in terms of kinetic rates of the liberation of the dye. Furthermore, it has been applied the potential use of molecular gatelike systems as a new strategy for the chromogenic signalling of the target anions in aqueous solutions. The idea involves molecular-recognition events coupled with the control of dye transport. It entails the use of solids with nanoscopic 3D organized surfaces (mesoporous solids) that have been functionalized at the outer surface with certain binding moieties (for example amines) and additionally the pores have been loaded with a suitable dye. In absence of any species to detect there is an opened gatelike system that is able to deliver the enclosed dye to the solution. The addition of a target anionic guest capable of forming a suitable complex with the binding site might "close the gate" which would lead to recognition, thus signalling the target anion by the inhibition of the mass-delivery process. In this work we have confirmed the ATP recognition and signalling by inhibiting dye release with nanoscopic supramolecular gatelike systems on mesoporous MCM-41 supports. Finally, a dual functional hybrid material was designed for the simultaneous chromo-fluorogenic detection and removal of Hg2+ in aqueous environment. The mesoporous solid is functionalized with thiol groups that have been further reacted with the squaraine dye, resulting in the formation of a 2,4-bis(4-dialkylaminophenyl)-3-hydroxy-4-alkylsulfanylcyclobut-2-enone (PAS) derivative being anchored to the inorganic silica matrix. When the species to detect, the Hg2+ cation, is present in the solution this reacts with the PAS fragment in the solid, releasing the squaraine dye to the solution that turned deep blue and highly fluorescent. This allows a straightforward "naked-eye" detection of Hg2+ employing an easy-to-use procedure.
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NASA Astrophysics Data System (ADS)
Alves, Leandro de Carvalho; Rubinger, Mayura Marques Magalhães; Tavares, Eder do Couto; Janczak, Jan; Pacheco, Elen Beatriz Acordi Vasques; Visconte, Leila Lea Yuan; Oliveira, Marcelo Ribeiro Leite
2013-09-01
The compounds (Bu4N)2[(4-RC6H4SO2NCS2)2] [Bu4N = tetrabutylammonium cation; R = H (1), F (2), Cl (3) and Br (4)] and (Ph4P)2[(4-RC6H4SO2NCS2)2]ṡH2O [Ph4P = tetraphenylphosphonium cation and R = I (5)] were synthesized by the reaction of the potassium dithiocarbimates (4-RC6H4SO2NCS2K2ṡ2H2O) with I2 and Bu4NBr or Ph4PCl. The IR data were consistent with the formation of the dithiocarbimatodisulfides anions. The NMR spectra showed the expected signals for the cations and anions in a 2:1 proportion. The structures of compounds 1-5 were determined by the single crystal X-ray diffraction. The compounds 2, 3 and 4 are isostructural and crystallise in the centrosymmetric space group C2/c of the monoclinic system. Compound 1 crystallises in the monoclinic system in the space group of P21/n and the compound 5 crystallises in the centrosymmetric space group P-1 of the triclinic system. The complex anions of compounds 2, 3 and 4 exhibit similar conformations having twofold symmetry, while in 1 and 5 the anions exhibit C1 symmetry. The activity of the new compounds in the vulcanization of the natural rubber was evaluated and compared to the commercial accelerators ZDMC, TBBS and TMTD. These studies confirm that the sulfonyldithiocarbimato disulfides anions are new vulcanization accelerators, being slower than the commercial accelerators, but producing a greater degree of crosslinking, and scorch time values compatible with good processing safety for industrial applications. The mechanical properties, stress and tear resistances were determined and compared to those obtained with the commercial accelerators.
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Suzuki, Y
2001-11-01
A methodology for selecting the measurement conditions in the dye-binding method for determining serum protein has been studied by a theoretical calculation. This calculation was based on the fact that a protein error occurs because of a reaction between the side chains of a positively charged amino acid residue in a protein molecule and a dissociated dye anion. The calculated characteristics of this method are summarized as follows: (1) Although the reaction between the dye and the protein occurs up to about pH 12, a change in the color shade, called protein error, is observed only in a pH region restricted within narrow limits. (2) Although the apparent absorbance (the absorbance of the test solution measured against a reagent blank) is lower than the true absorbance indicated by the formed dye-protein complex, the apparent absorbance correlates with the true absorbance with a correlation coefficient of 1.0. (3) At a higher dye concentration, the calibration curve is more linear at a higher pH than at a lower pH. Most of these characteristics were similarly observed experimentally in the reactions of BPB, BCG and BCP with human and bovine albumins. It is concluded that in order to ensure the linearity of the calibration curve, the measurement should be performed at a higher dye concentration and sufficiently high pH where the detection sensitivity is satisfied.
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Anirudhan, T S; Unnithan, Maya R
2007-01-01
The performance of a new anion exchanger (AE) prepared from coconut coir pith (CP), for the removal of arsenic(V) [As(V)] from aqueous solutions was evaluated in this study. The adsorbent (CP-AE) carrying dimethylaminohydroxypropyl weak base functional group was synthesized by the reaction of CP with epichlorohydrin and dimethylamine followed by treatment of hydrochloric acid. IR spectroscopy results confirm the presence of -NH(+)(CH(3))(2)Cl(-) group in the adsorbent. XRD studies confirm the decrease of crystallinity in CP-AE compared to CP, and it favours the protrusion of the functional group into the aqueous medium. Batch experiments were conducted to examine the efficiency of the adsorbent on As(V) removal. Maximum removal of 99.2% was obtained for an initial concentration of 1 mgl(-1) As(V) at pH 7.0 and an adsorbent dose of 2 gl(-1). The kinetics of sorption of As(V) onto CP-AE was described using the pseudo-second-order model. The equilibrium isotherms were determined for different temperatures and the results were analysed using the Langmuir equation. The temperature dependence indicates an exothermic process. Utility of the adsorbent was tested by removing As(V) from simulated groundwater. Regeneration studies were performed using 0.1N HCl. Batch adsorption-desorption studies illustrate that CP-AE could be used to remove As(V) from ground water and other industrial effluents.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Goldbach, A.; Johnson, J.; Meisel, D.
1999-05-12
The speciation of aqueous polyselenide solutions at high pH values has been investigated by Raman and Uv/vis absorption spectroscopy. Complementary, ab initio molecular orbital calculations at the HF/6-31+G{sup *} level of theory have been carried out on the vibrational frequencies of polyselenide dianions Se{sub x}{sup 2{minus}} (x = 2--4), polyselenide radical anions Se{sub x}{sup {minus}} (x = 2, 3), and protonated polyselenides HSe{sub x}{sup {minus}} (x = 1--3) in order to substantiate the assignment of the experimental Raman spectra. Although the optical spectra suggest the successive formation of Se{sub 2}{sup 2{minus}}, Se{sub 3}{sup 2{minus}}, and Se{sub 4}{sup 2{minus}} with progressivemore » oxidation of the solutions, only two characteristic Raman bands are observed at 269 and 324 cm{sup {minus}1}. A sequence of overtones of the 269 cm{sup {minus}1} band is observed after excitation with blue light. Likewise strong overtones of the 324 cm{sup {minus}1} band appear after excitation with green light. The 269 cm{sup {minus}1} features is assigned to Se{sub 4}{sup 2{minus}} while the 324 cm{sup {minus}1} band is attributed to the radical anion Se{sub 2}{sup {minus}}. The occurrence of polyselenide radicals in aqueous solution is without precedent, and the formation of Se{sub 2}{sup {minus}} is ascribed to a photolytic process in the electrolyte. The only protonated species observed in this study is HSe{sup {minus}}, which is characterized by a Raman band at 2,303 cm{sup {minus}1}.« less
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Pyromellitamide aggregates and their response to anion stimuli.
Webb, James E A; Crossley, Maxwell J; Turner, Peter; Thordarson, Pall
2007-06-06
The N,N',N'',N'''-1,2,4,5-tetra(ethylhexanoate) pyromellitamide is found to be capable of both intermolecular aggregation and binding to small anions. It is synthesized by aminolysis of pyromellitic anhydride with ethanolamine, followed by a reaction with hexanoyl chloride. The single-crystal X-ray structure of the pyromellitamide shows that it forms one-dimensional columnar stacks through an intermolecular hydrogen-bonding network. It also forms self-assembled gels in nonpolar solvents, presumably by a hydrogen-bonding network similar to the solid-state structure as shown by IR and XRD studies. Aggregation by intermolecular hydrogen bonding of the pyromellitamide is also observed by NMR and IR in solution. Fitting of NMR dilution data for pyromellitamide in d6-acetone to a cooperative aggregation model gave KE=232 M-1 and positive cooperativity of aggregation (rho=0.22). The pyromellitamide binds to a range of small anions with the binding strength decreasing in the order chloride>acetate>bromide>nitrate approximately iodide. The data indicate that the pyromellitamide binds two anions and that it displays negative cooperativity. The intermolecular aggregation of the pyromellitamide can also be altered using small anion stimuli; anion addition to preformed self-assembled pyromellitamide gels causes their collapse. The kinetics of anion-induced gel collapse are qualitatively correlated to the binding affinities of the same anions in solution. The cooperative anion binding properties and the sensitivity of the self-assembled gels formed by pyromellitamide toward anions could be useful in the development of sensors and switching/releasing devices.
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Melo, Menilla M A; Daniele-Silva, Alessandra; Teixeira, Diego G; Estrela, Andréia B; Melo, Karolline R T; Oliveira, Verônica S; Rocha, Hugo A O; Ferreira, Leandro de Santis; Pontes, Daniel L; Lima, João P M S; Silva-Júnior, Arnóbio A; Barbosa, Euzebio G; Carvalho, Eneas; Fernandes-Pedrosa, Matheus F
2017-08-01
Anionic Peptides are molecules rich in aspartic acid (Asp) and/or glutamic acid (Glu) residues in the primary structure. This work presents, for the first time, structural characterization and biological activity assays of an anionic peptide from the venom of the scorpion Tityus stigmurus, named TanP. The three-dimensional structure of TanP was obtained by computational modeling and refined by molecular dynamic (MD) simulations. Furthermore, we have performed circular dichroism (CD) analysis to predict TanP secondary structure, and UV-vis spectroscopy to evaluate its chelating activity. CD indicated predominance of random coil conformation in aqueous medium, as well as changes in structure depending on pH and temperature. TanP has chelating activity on copper ions, which modified the peptide's secondary structure. These results were corroborated by MD data. The molar ratio of binding (TanP:copper) depends on the concentration of peptide: at lower TanP concentration, the molar ratio was 1:5 (TanP:Cu 2+ ), whereas in concentrated TanP solution, the molar ratio was 1:3 (TanP:Cu 2+ ). TanP was not cytotoxic to non-neoplastic or cancer cell lines, and showed an ability to inhibit the in vitro release of nitric oxide by LPS-stimulated macrophages. Altogether, the results suggest TanP is a promising peptide for therapeutic application as a chelating agent. Copyright © 2017 Elsevier Inc. All rights reserved.
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Molecular dynamics simulations of the surface tension and structure of salt solutions and clusters.
Sun, Lu; Li, Xin; Hede, Thomas; Tu, Yaoquan; Leck, Caroline; Ågren, Hans
2012-03-15
Sodium halides, which are abundant in sea salt aerosols, affect the optical properties of aerosols and are active in heterogeneous reactions that cause ozone depletion and acid rain problems. Interfacial properties, including surface tension and halide anion distributions, are crucial issues in the study of the aerosols. We present results from molecular dynamics simulations of water solutions and clusters containing sodium halides with the interatomic interactions described by a conventional force field. The simulations reproduce experimental observations that sodium halides increase the surface tension with respect to pure water and that iodide anions reach the outermost layer of water clusters or solutions. It is found that the van der Waals interactions have an impact on the distribution of the halide anions and that a conventional force field with optimized parameters can model the surface tension of the salt solutions with reasonable accuracy. © 2012 American Chemical Society
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Rho, Hoon Suk; Hanke, Alexander Thomas; Ottens, Marcel; Gardeniers, Han J G E
2018-04-01
A microfluidic device for pH gradient chromatofocusing is presented, which performs creation of a micro-column, pH gradient generation, and fraction collection in a single device. Using a sieve micro-valve, anion exchange particles were packed into a microchannel in order to realize a solid-phase absorption column. To fractionate proteins according to their isoelectric points, elution buffer solutions with a stepwise pH gradient were prepared in 16 parallel mixing reactors and flowed through the micro-column, wherein a protein mixture was previously loaded. The volume of the column is only 20 nL, hence it allows extremely low sample consumption and fast analysis compared with a conventional system. We demonstrated separation of two proteins, albumin-fluorescein isothiocyanate conjugate (FITC-BSA) and R-Phycoerythrin (R-PE), by using a microcolumn of commercial charged polymeric particles (Source 15Q). The microfluidic device can be used as a rapid diagnostic tool to analyse crude mixtures of proteins or nucleic acids and determine adsorption/desorption characteristics of various biochemical products, which can be helpful for scientific fundamental understanding as well as instrumental in various industrial applications, especially in early stage screening and process development. © 2018 The Authors Electrophoresis Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Biswal, Jayashree; Paul, Jhimli; Naik, D. B.; Sarkar, S. K.; Sabharwal, S.
2013-04-01
The radiation induced degradation of 4-nitrophenol (4-NP) has been studied by gamma irradiation, while the reactivity and spectral features of the short lived transients formed by reaction with primary transient radicals at different pHs has been investigated by pulse radiolysis technique. In steady state radiolysis a dose of 4.4 k Gy is able to degrade 98% of 1×10-4 mol dm-3 4-NP. 4-NP has pKa at 7.1, above which it is present in the anionic form. At pH 5.2, •OH and N3• radicals were found to react with 4-NP with rate constants of 4.1×109 dm3 mol-1 s-1 and 2.8×108 dm3 mol-1 s-1, respectively. Differences in the absorption spectra of species formed in the reactions of 4-NP with •OH and N3• radicals suggested that •OH radicals add to the aromatic ring of 4-NP along with electron transfer reaction, whereas N3• radicals undergo only electron transfer reaction. At pH 9.2, rate constants for the reaction of •OH radicals with 4-NP was found to be higher by a factor of 2 compared to that at pH 5.2. This has been assigned to the deprotonation of 4-NP at pH 9.2.
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Seal, Rebecca P.; Shigeri, Yasushi; Eliasof, Scott; Leighton, Barbara H.; Amara, Susan G.
2001-01-01
Excitatory amino acid transporters (EAATs) buffer and remove synaptically released l-glutamate and maintain its concentrations below neurotoxic levels. EAATs also mediate a thermodynamically uncoupled substrate-gated anion conductance that may modulate cell excitability. Here, we demonstrate that modification of a cysteine substituted within a C-terminal domain of EAAT1 abolishes transport in both the forward and reverse directions without affecting activation of the anion conductance. EC50s for l-glutamate and sodium are significantly lower after modification, consistent with kinetic models of the transport cycle that link anion channel gating to an early step in substrate translocation. Also, decreasing the pH from 7.5 to 6.5 decreases the EC50 for l-glutamate to activate the anion conductance, without affecting the EC50 for the entire transport cycle. These findings demonstrate for the first time a structural separation of transport and the uncoupled anion flux. Moreover, they shed light on some controversial aspects of the EAAT transport cycle, including the kinetics of proton binding and anion conductance activation. PMID:11752470
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NASA Astrophysics Data System (ADS)
Gassara, S.; Abdelkafi, A.; Quémener, D.; Amar, R. Ben; Deratani, A.
2015-07-01
Poly(ether imide) (PEI) ultrafiltration membranes were chemically modified with branched poly(ethyleneimine) to obtain nanofiltration (NF) membrane Cat PEI with a positive charge in the pH range below 9. An oppositely charged polyelectrolyte layer was deposited on the resulting membrane surface by using sodium polystyrene sulfonate (PSSNa) and sodium polyvinyl sulfonate (PVSNa) to prepare a bipolar layered membrane NF Cat PEI_PSS and Cat PEI_PVS having a negatively charged surface and positively charged pores. Cat PEI exhibited good performance to remove multivalent cations (more than 90% of Ca2+) from single salt solutions except in presence of sulfate ions. Adding an anionic polyelectrolyte layer onto the positively charged surface resulted in a significant enhancement of rejection performance even in presence of sulfate anions. Application of the prepared membranes in water softening of natural complex mixtures was successful for the different studied membranes and a large decrease of hardness was obtained. Moreover, Cat PEI_PSS showed a good selectivity for nitrate removal. Fouling experiments were carried out with bovine serum albumin, as model protein foulant. Cat PEI_PSS showed much better fouling resistance than Cat PEI with a quantitative flux recovery ratio.
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Banerjee, Chiranjib; Mandal, Sarthak; Ghosh, Surajit; Rao, Vishal Govind; Sarkar, Nilmoni
2012-09-13
In this manuscript, we have modulated the location of an anionic probe, Coumarin-343 (C-343) in a zwitterionic (N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB-16)) micellar system by three different approaches. The effect of addition of the surfactant sodium dodecyl sulfate (SDS) and the room temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium octylsulfate (EmimOs) and N,N-dimethylethanol hexanoate (DAH), to the micellar solution has been studied. The effect of pH variation has been studied as well using solvent and rotational measurements. Migration of the anionic probe, C-343, from the palisade layer of SB-16 micelle to the bulk water has been observed to varying extents with the addition of SDS and EmimOs. The effect is much more pronounced in the presence of SDS and can be ascribed to the presence of the long alkyl (dodecyl) chain on SDS which can easily orient itself and fuse inside the SB-16 micelle and facilitate the observed migration of the probe molecule. This phenomenon is confirmed by faster solvation and rotational relaxation of the investigated probe molecule. The analogous fusion process is difficult in case of EmimOs and DAH because of their comparatively smaller alkyl (octyl and hexanoate) chain. However, the direction of C-343 migration is reversed with the decrease of pH of the SB-16 micellar medium. An increase in the average solvation and rotational relaxation time of the probe in acidic medium has been observed. Since experimental conditions are maintained such that the probe molecules and the zwitterionic SB-16 micelles remain oppositely charged, the observed results can be attributed to the increased electrostatic interaction (attractive) between them. Temperature dependent study also supports this finding.
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Qiu, Hongdeng; Jiang, Qiong; Wei, Zheng; Wang, Xusheng; Liu, Xia; Jiang, Shengxiang
2007-09-07
A new zwitterionic stationary phase based on silica bonded with 1-alkyl-3-(propyl-3-sulfonate) imidazolium was synthesized and characterized in this paper. The materials have been confirmed and evaluated by elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. Potassium and calcium were separated simultaneously with several common inorganic anions including an iodate, chloride, bromide, nitrate and iodide on the phase. The effects of the concentration, organic solvent and pH of the eluent on the separation of anions were studied. Operated in the anion-exchange mode, this new stationary phase shows considerable promise for the separation of anions. Bases, vitamins and three imidazolium ionic liquids with different alkyl chains are also separated successfully on this column. The stationary phase has multiple retention mechanisms, such as anion-exchange, electrostatic attraction and repulsion interactions, and hydrophobic interaction between the zwitterionic stationary phase and specimens.
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NASA Astrophysics Data System (ADS)
Zhang, Chang; Li, Yongqiu; Wang, Fenghua; Yu, Zhigang; Wei, Jingjing; Yang, Zhongzhu; Ma, Chi; Li, Zihao; Xu, ZiYi; Zeng, Guangming
2017-02-01
In this study, magnetic zirconium-iron oxide nanoparticles (MZION) of different Fe/Zr molar ratios were successfully prepared using the co-precipitation method, and their performance for phosphate removal was systematically evaluated. The as-obtained adsorbents were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Zeta potential analyzer, Fourier transform infrared spectroscopy (FT-IR) and Brunauer Emmett Teller (BET) specific surface area analysis. The effects of pH, ionic strength, and co-existing ions (including Cl-, SO42-, NO3- and HCO3-) were measured to evaluate the adsorption performance in batch experiments. The results showed that decreasing the Fe/Zr molar ratios increased the specific surface area that was propitious to adsorption process, but the adsorption capacity enhanced with the decrease of Fe/Zr molar ratios. Phosphate adsorption on MZION could be well described by the Freundlich equilibrium model and pseudo-second-order kinetics. The adsorption of phosphate was highly pH dependent and decreased with increasing pH from 1.5 to 10.0. The adsorption was slightly affected by ionic strength. With the exception of HCO3-, co-existing anions showed minimum or no effect on their adsorption performance. After adsorption, phosphate on these MZION could be easily desorbed by 0.1 M NaOH solution. The phosphate adsorption mechanism of MZION followed the inner-sphere complexing mechanism, and the surface sbnd OH groups played a significant role in the phosphate adsorption. Additionally, the main advantages of MZION consisted in its separation convenience and highly adsorption capacity compared to other adsorbents.
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8. VIEW OF GLOVE BOXES USED IN THE ANION EXCHANGE ...
8. VIEW OF GLOVE BOXES USED IN THE ANION EXCHANGE PROCESS. THE ANION EXCHANGE PROCESS PURIFIED AND CONCENTRATED PLUTONIUM-BEARING NITRIC ACID SOLUTIONS TO MAKE THEM ACCEPTABLE AS FEED FOR CONVERSION TO METAL. (6/20/60) - Rocky Flats Plant, Plutonium Recovery & Fabrication Facility, North-central section of plant, Golden, Jefferson County, CO
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Chaban, Vitaly
2015-07-01
Electrolyte solutions based on the propylene carbonate (PC)-dimethoxyethane (DME) mixtures are of significant importance and urgency due to emergence of lithium-ion batteries. Solvation and coordination of the lithium cation in these systems have been recently attended in detail. However, analogous information concerning anions (tetrafluoroborate, hexafluorophosphate) is still missed. This work reports PM7-MD simulations (electronic-structure level of description) to include finite-temperature effects on the anion solvation regularities in the PC-DME mixture. The reported result evidences that the anions appear weakly solvated. This observation is linked to the absence of suitable coordination sites in the solvent molecules. In the concentrated electrolyte solutions, both BF4(-) and PF6(-) prefer to exist as neutral ion pairs (LiBF4, LiPF6).
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Degradation of conazole fungicides in water by electrochemical oxidation.
Urzúa, J; González-Vargas, C; Sepúlveda, F; Ureta-Zañartu, M S; Salazar, R
2013-11-01
The electrochemical oxidation (EO) treatment in water of three conazole fungicides, myclobutanil, triadimefon and propiconazole, has been carried out at constant current using a BDD/SS system. First, solutions of each fungicide were electrolyzed to assess the effect of the experimental parameters such as current, pH and fungicide concentration on the decay of each compound and total organic carbon abatement. Then a careful analysis of the degradation by-products was made by high performance liquid chromatography, ion chromatography and gas chromatography coupled with mass spectrometry in order to provide a detailed discussion on the original reaction pathways. Thus, during the degradation of conazole fungicides by the electrochemical oxidation process, aromatic intermediates, aliphatic carboxylic acids and Cl(-) were detected prior to their complete mineralization to CO2 while NO3(-) anions remained in the treated solution. This is an essential preliminary step towards the applicability of the EO processes for the treatment of wastewater containing conazole fungicides. Copyright © 2013 Elsevier Ltd. All rights reserved.
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Bejaoui, Imen; Mouelhi, Meral; Hamrouni, Béchir
2017-01-01
Nanofiltration and reverse osmosis are investigated as a possible alternative to the conventional methods of Cr(VI) removal from model water and industrial effluent. The influences of feed concentration, water recovery, pH, and the coexisting anions were studied. The results have shown that retention rates of hexavalent chromium can reach 99.7% using nanofiltration membrane (NF-HL) and vary from 85 to 99.9% using reverse osmosis membrane (RO-SG) depending upon the composition of the solution and operating conditions. This work was also extended to investigate the separation of Cr(VI) from car shock absorber factory effluent. The use of these membranes is very promising for Cr(VI) water treatment and desalting industry effluent. Spiegler-Kedem model was applied to experimental results in the aim to determine phenomenological parameters, the reflection coefficient of the membrane (σ), and the solute permeability coefficient (Ps). The convective and diffusive parts of the mass transfer were quantified with predominance of the diffusive contribution. PMID:28819360
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Denning, A. Scott; Baron, Jill S.; Mast, M. Alisa; Arthur, Mary
1991-01-01
Intensive sampling of a stream draining an alpine-subalpine basin revealed that depressions in pH and acid neutralizing capacity (ANC) of surface water at the beginning of the spring snowmelt in 1987 and 1988 were not accompanied by increases in strong acid anions, and that surface waters did not become acidic (ANC<0). Samples of meltwater collected at the base of the snowpack in 1987 were acidic and exhibited distinct ‘pulses’ of nitrate and sulfate. Solutions collected with lysimeters in forest soils adjacent to the stream revealed high levels of dissolved organic carbon (DOC) and total Al. Peaks in concentration of DOC, Al, and nutrient species in the stream samples indicate a flush of soil solution into the surface water at the beginning of the melt. Infiltration of meltwater into soils and spatial heterogeneity in the timing of melting across the basin prevented stream and lake waters from becoming acidic.
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Kheriji, Jamel; Tabassi, Dorra; Hamrouni, Béchir
2015-01-01
Industrial effluents loaded with cadmium have contributed to the pollution of the environment and health troubles for humans. Therefore, these effluents need treatment to reduce cadmium concentration before releasing them to public sewage. The purpose of the research is to study the major role of reverse osmosis (RO) and nanofiltration (NF) processes, which can contribute to the removal of cadmium ions from model water and wastewater from the battery industry. For this reason, two RO and two nanofiltration membranes have been used. The effects of feed pressure, concentration, ionic strength, nature of anion associated with cadmium and pH on the retention of Cd(II) were studied with model solutions. Thereafter, NF and RO membranes were used to reduce cadmium ions and total salinity of battery industry effluent. Among these membranes, there are only three which eliminate more than 95% of cadmium. This was found to depend on operating conditions. It is worth noting that the Spiegler-Kedem model was applied to fit the experimental results.
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Process for removing sulfate anions from waste water
Nilsen, David N.; Galvan, Gloria J.; Hundley, Gary L.; Wright, John B.
1997-01-01
A liquid emulsion membrane process for removing sulfate anions from waste water is disclosed. The liquid emulsion membrane process includes the steps of: (a) providing a liquid emulsion formed from an aqueous strip solution and an organic phase that contains an extractant capable of removing sulfate anions from waste water; (b) dispersing the liquid emulsion in globule form into a quantity of waste water containing sulfate anions to allow the organic phase in each globule of the emulsion to extract and absorb sulfate anions from the waste water and (c) separating the emulsion including its organic phase and absorbed sulfate anions from the waste water to provide waste water containing substantially no sulfate anions.
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Villegas-Guzman, Paola; Hofer, Florian; Silva-Agredo, Javier; Torres-Palma, Ricardo A
2017-12-01
Taking ciprofloxacin (CIP) as a fluoroquinolone antibiotic model, this work explores the role of common anions (sulfate, nitrate, and chloride) during the application of photoelectro-Fenton (PEF) at natural pH to degrade this type of compound in water. The system was composed of an IrO 2 anode, Ti, or gas diffusion electrode (GDE) as cathode, Fe 2+ , and UV (254 nm). To determine the implications of these anions, the degradation pathway and efficiency of the PEF sub-processes (UV photolysis, anodic oxidation, and electro-Fenton at natural pH) were studied in the individual presence of the anions. The results highlight that degradation routes and kinetics are strongly dependent on electrolytes. When chloride and nitrate ions were present, indirect electro-chemical oxidation was identified by electro-generated HOCl and nitrogenated oxidative species, respectively. Additionally, direct photolysis and direct oxidation at the anode surface were identified as degradation routes. As a consequence of the different pathways, six primary CIP by-products were identified. Therefore, a scheme was proposed representing the pathways involved in the degradation of CIP when submitted to PEF in water with chloride, nitrate, and sulfate ions, showing the complexity of this process. Promoted by individual and synergistic actions of this process, the PEF system leads to a complete elimination of CIP with total removal of antibiotic activity against Staphylococcus aureus and Escherichia coli, and significant mineralization. Finally, the role of the anions was tested in seawater containing CIP, in which the positive contributions of the anions were partially suppressed by its OH radical scavenger action. The findings are of interest for the understanding of the degradation of antibiotics via the PEF process in different matrices containing sulfate, nitrate, and chloride ions.
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Ion-water wires in imidazolium-based ionic liquid/water solutions induce unique trends in density.
Ghoshdastidar, Debostuti; Senapati, Sanjib
2016-03-28
Ionic liquid/water binary mixtures are rapidly gaining popularity as solvents for dissolution of cellulose, nucleobases, and other poorly water-soluble biomolecules. Hence, several studies have focused on measuring the thermophysical properties of these versatile mixtures. Among these, 1-ethyl-3-methylimidazolium ([emim]) cation-based ILs containing different anions exhibit unique density behaviours upon addition of water. While [emim][acetate]/water binary mixtures display an unusual rise in density with the addition of low-to-moderate amounts of water, those containing the [trifluoroacetate] ([Tfa]) anion display a sluggish decrease in density. The density of [emim][tetrafluoroborate] ([emim][BF4])/water mixtures, on the other hand, declines rapidly in close accordance with the experimental reports. Here, we unravel the structural basis underlying this unique density behavior of [emim]-based IL/water mixtures using all-atom molecular dynamics (MD) simulations. The results revealed that the distinct nature of anion-water hydrogen bonded networks in the three systems was a key in modulating the observed unique density behaviour. Vast expanses of uninterrupted anion-water-anion H-bonded stretches, denoted here as anion-water wires, induced significant structuring in [emim][Ac]/water mixtures that resulted in the density rise. Conversely, the presence of intermittent large water clusters disintegrated the anion-water wires in [emim][Tfa]/water and [emim][BF4]/water mixtures to cause a monotonic density decrease. The differential nanostructuring affected the dynamics of the solutions proportionately, with the H-bond making and breaking dynamics found to be greatly retarded in [emim][Ac]/water mixtures, while it exhibited a faster relaxation in the other two binary solutions.
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Greenway, Hank; Kulichikhin, Konstantin Y.; Cawthray, Gregory R.; Colmer, Timothy D.
2012-01-01
During anoxia, cytoplasmic pH regulation is crucial. Mechanisms of pH regulation were studied in the coleoptile of rice exposed to anoxia and pH 3.5, resulting in H+ influx. Germinating rice seedlings survived a combination of anoxia and exposure to pH 3.5 for at least 4 d, although development was retarded and net K+ efflux was continuous. Further experiments used excised coleoptile tips (7–10 mm) in anoxia at pH 6.5 or 3.5, either without or with 0.2 mM NO3−, which distinguished two processes involved in pH regulation. Net H+ influx (μmol g−1 fresh weight h−1) for coleoptiles with NO3− was ∼1.55 over the first 24 h, being about twice that in the absence of NO3−, but then decreased to 0.5–0.9 as net NO3− uptake declined from ∼1.3 to 0.5, indicating reduced uptake via H+–NO3− symports. NO3− reduction presumably functioned as a biochemical pHstat. A second biochemical pHstat consisted of malate and succinate, and their concentrations decreased substantially with time after exposure to pH 3.5. In anoxic coleoptiles, K+ balancing the organic anions was effluxed to the medium as organic anions declined, and this efflux rate was independent of NO3− supply. Thus, biochemical pHstats and reduced net H+ influx across the plasma membrane are important features contributing to pH regulation in anoxia-tolerant rice coleoptiles at pH 3.5. PMID:22174442
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Colorimetric sensing of anions in water using ratiometric indicator-displacement assay.
Feng, Liang; Li, Hui; Li, Xiao; Chen, Liang; Shen, Zheng; Guan, Yafeng
2012-09-19
The analysis of anions in water presents a difficult challenge due to their low charge-to-radius ratio, and the ability to discriminate among similar anions often remains problematic. The use of a 3×6 ratiometric indicator-displacement assay (RIDA) array for the colorimetric detection and identification of ten anions in water is reported. The sensor array consists of different combinations of colorimetric indicators and metal cations. The colorimetric indicators chelate with metal cations, forming the color changes. Upon the addition of anions, anions compete with the indicator ligands according to solubility product constants (K(sp)). The indicator-metal chelate compound changes color back dramatically when the competition of anions wins. The color changes of the RIDA array were used as a digital representation of the array response and analyzed with standard statistical methods, including principal component analysis and hierarchical clustering analysis. No confusion or errors in classification by hierarchical clustering analysis were observed in 44 trials. The limit of detection was calculated approximately, and most limits of detections of anions are well below μM level using our RIDA array. The pH effect, temperature influence, interfering anions were also investigated, and the RIDA array shows the feasibility of real sample testing. Copyright © 2012 Elsevier B.V. All rights reserved.
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Eu(III) complexes as Anion-responsive Luminescent Sensors and PARACEST Agents
Hammell, Jacob; Buttarazzi, Leandro; Huang, Ching-Hui; Morrow, Janet R.
2011-01-01
The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the 1H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate and carbonate. These anions have weak dissociation constants that range from 19–38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at pH 6.5 or 7.2. This work shows that the Eu(S-THP) complex has unique selectivity toward binding of biologically relevant anions and that anion binding results in changes in both the luminescence and PARACEST spectra of the complex. PMID:21548563
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Hammell, Jacob; Buttarazzi, Leandro; Huang, Ching-Hui; Morrow, Janet R
2011-06-06
The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the (1)H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate, and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate, and carbonate. These anions have weak dissociation constants that range from 19 to 38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate, and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at pH 6.5 or 7.2. This work shows that the Eu(S-THP) complex has unique selectivity toward binding of biologically relevant anions and that anion binding results in changes in both the luminescence and the PARACEST spectra of the complex. © 2011 American Chemical Society
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Lauf, P K; Adragna, N C
1996-10-01
Swelling-induced human erythrocyte K-Cl cotransport is membrane potential independent and capable of uphill transport. However, a complete thermodynamic analysis of basal and stimulated K-Cl cotransport, at constant cell volume, is missing. This study was performed in low K sheep red blood cells before and after reducing cellular free Mg into the nanomolar range with the divalent cation ionophore A23187 and a chelator, an intervention known to stimulate K-Cl cotransport. The anion exchange inhibitor 4,4'diisothiocyanato-2,2'disulfonic stilbene was used to clamp intracellular pH and Cl or NO3 concentrations. Cell volume was maintained constant as external and internal pH differed by more than two units. K-Cl cotransport was calculated from the K effluxes and Rb (as K congener) influxes measured in Cl and NO3, at constant internal K and external anions, and variable concentrations of extracellular Rb and internal anions, respectively. The external Rb concentration at which net K-Cl cotransport is zero was defined as flux reversal point which changed with internal pH and hence Cl. Plots of the ratio of external Rb concentrations corresponding to the flux reversal points and the internal K concentration versus the ratio of the internal and external Cl concentrations (i.e., the Donnan ratio of the transported ions) yielded slopes near unity for both control and low internal Mg cells. Thus, basal as well as low internal Mg-stimulated net K-Cl cotransport depends on the electrochemical potential gradient of KCl.
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1996-01-01
Swelling-induced human erythrocyte K-Cl cotransport is membrane potential independent and capable of uphill transport. However, a complete thermodynamic analysis of basal and stimulated K-Cl cotransport, at constant cell volume, is missing. This study was performed in low K sheep red blood cells before and after reducing cellular free Mg into the nanomolar range with the divalent cation ionophore A23187 and a chelator, an intervention known to stimulate K- Cl cotransport. The anion exchange inhibitor 4,4'diisothiocyanato- 2,2'disulfonic stilbene was used to clamp intracellular pH and Cl or NO3 concentrations. Cell volume was maintained constant as external and internal pH differed by more than two units. K-Cl cotransport was calculated from the K effluxes and Rb (as K congener) influxes measured in Cl and NO3, at constant internal K and external anions, and variable concentrations of extracellular Rb and internal anions, respectively. The external Rb concentration at which net K-Cl cotransport is zero was defined as flux reversal point which changed with internal pH and hence Cl. Plots of the ratio of external Rb concentrations corresponding to the flux reversal points and the internal K concentration versus the ratio of the internal and external Cl concentrations (i.e., the Donnan ratio of the transported ions) yielded slopes near unity for both control and low internal Mg cells. Thus, basal as well as low internal Mg-stimulated net K-Cl cotransport depends on the electrochemical potential gradient of KCl. PMID:8894982