pH during non-synaptic epileptiform activity-computational simulations.

PubMed

Rodrigues, Antônio Márcio; Santos, Luiz Eduardo Canton; Covolan, Luciene; Hamani, Clement; de Almeida, Antônio-Carlos Guimarães

2015-09-02

The excitability of neuronal networks is strongly modulated by changes in pH. The origin of these changes, however, is still under debate. The high complexity of neural systems justifies the use of computational simulation to investigate mechanisms that are possibly involved. Simulated neuronal activity includes non-synaptic epileptiform events (NEA) induced in hippocampal slices perfused with high-K(+) and zero-Ca(2+), therefore in the absence of the synaptic circuitry. A network of functional units composes the NEA model. Each functional unit represents one interface of neuronal/extracellular space/glial segments. Each interface contains transmembrane ionic transports, such as ionic channels, cotransporters, exchangers and pumps. Neuronal interconnections are mediated by gap-junctions, electric field effects and extracellular ionic fluctuations modulated by extracellular electrodiffusion. Mechanisms investigated are those that change intracellular and extracellular ionic concentrations and are able to affect [H(+)]. Our simulations suggest that the intense fluctuations in intra and extracellular concentrations of Na(+), K(+) and Cl(-) that accompany NEA are able to affect the combined action of the Na(+)/H(+) exchanger (NHE), [HCO(-)(3)]/Cl(-) exchanger (HCE), H(+) pump and the catalytic activity of intra and extracellular carbonic anhydrase. Cellular volume changes and extracellular electrodiffusion are responsible for modulating pH.

Highly efficient micellar extraction of toxic picric acid into novel ionic liquid: Effect of parameters, solubilization isotherm, evaluation of thermodynamics and design parameters.

PubMed

Bhatt, Darshak R; Maheria, Kalpana C; Parikh, Jigisha K

2015-12-30

A simple and new approach in cloud point extraction (CPE) method was developed for removal of picric acid (PA) by the addition of N,N,N,N',N',N'-hexaethyl-ethane-1,2-diammonium dibromide ionic liquid (IL) in non-ionic surfactant Triton X-114 (TX-114). A significant increase in extraction efficiency was found upon the addition of dicationic ionic liquid (DIL) at both nearly neutral and high acidic pH. The effects of different operating parameters such as pH, temperature, time, concentration of surfactant, PA and DIL on extraction of PA were investigated and optimum conditions were established. The extraction mechanism was also proposed. A developed Langmuir isotherm was used to compute the feed surfactant concentration required for the removal of PA up to an extraction efficiency of 90%. The effects of temperature and concentration of surfactant on various thermodynamic parameters were examined. It was found that the values of ΔG° increased with temperature and decreased with surfactant concentration. The values of ΔH° and ΔS° increased with surfactant concentration. The developed approach for DIL mediated CPE has proved to be an efficient and green route for extraction of PA from water sample. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of rhamnolipid biosurfactant on solubilization of polycyclic aromatic hydrocarbons.

PubMed

Li, Shudong; Pi, Yongrui; Bao, Mutai; Zhang, Cong; Zhao, Dongwei; Li, Yiming; Sun, Peiyan; Lu, Jinren

2015-12-15

Rhamnolipid biosurfactant-producing bacteria, Bacillus Lz-2, was isolated from oil polluted water collected from Dongying Shengli oilfield, China. The factors that influence PAH solubilization such as biosurfactant concentration, pH, ionic strength and temperature were discussed. The results showed that the solubilities of naphthalene, phenanthrene and pyrene increased linearly with the rise of rhamnolipid biosurfactant dose above the biosurfactant critical micelle concentration (CMC). Furthermore, the molar solubilization ratio (MSR) values decreased in the following order: naphthalene>phenanthrene>pyrene. However, the solubility percentage increased and followed the opposite order: pyrene>phenanthrene>naphthalene. The solubilities of PAHs in rhamnolipid biosurfactant solution increased with the rise of pH and ionic strength, and reached the maximum values under the conditions of pH11 and NaCl concentration 8 g · L(-1). The solubility of phenanthrene and pyrene increased with the rise of temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

Changes in the quaternary structure of phosphoenolpyruvate carboxylase induced by ionic strength affect its catalytic activity.

PubMed

Wagner, R; Gonzalez, D H; Podesta, F E; Andreo, C S

1987-05-04

Phosphoenolpyruvate carboxylase from maize leaves dissociated into dimers and/or monomers when exposed to increasing ionic strength (e.g. 200-400 mM NaCl) as indicated by gel filtration experiments. Changes in the oligomerization state were dependent on pH, time of preincubation with salt and protein concentration. A dissociation into dimers and monomers was observed at pH 8, while at pH 7 dissociation into the dimeric form only was observed. Exposure of the enzyme to higher ionic strength decreased the activity in a time-dependent manner. Turnover conditions and glucose 6-phosphate protected the carboxylase from the decay in activity, which was faster at pH 7 than at pH 8. The results suggest that changes in activity of the enzyme, following exposure to high ionic strength, are the consequence of dissociation. Tetrameric and dimeric forms of the phosphoenolpyruvate carboxylase seemingly reveal different catalytic properties. We suggest that the distinct catalytic properties of the different oligomeric species of phosphoenolpyruvate carboxylase and changes in the equilibrium between them could be the molecular basis for an effective regulation of metabolite levels by this key enzyme of C4 plants.

Stability of Secondary and Tertiary Structures of Virus-Like Particles Representing Noroviruses: Effects of pH, Ionic Strength, and Temperature and Implications for Adhesion to Surfaces.

PubMed

Samandoulgou, Idrissa; Hammami, Riadh; Morales Rayas, Rocio; Fliss, Ismail; Jean, Julie

2015-11-01

Loss of ordered molecular structure in proteins is known to increase their adhesion to surfaces. The aim of this work was to study the stability of norovirus secondary and tertiary structures and its implications for viral adhesion to fresh foods and agrifood surfaces. The pH, ionic strength, and temperature conditions studied correspond to those prevalent in the principal vehicles of viral transmission (vomit and feces) and in the food processing and handling environment (pasteurization and refrigeration). The structures of virus-like particles representing GI.1, GII.4, and feline calicivirus (FCV) were studied using circular dichroism and intrinsic UV fluorescence. The particles were remarkably stable under most of the conditions. However, heating to 65°C caused losses of β-strand structure, notably in GI.1 and FCV, while at 75°C the α-helix content of GII.4 and FCV decreased and tertiary structures unfolded in all three cases. Combining temperature with pH or ionic strength caused variable losses of structure depending on the particle type. Regardless of pH, heating to pasteurization temperatures or higher would be required to increase GII.4 and FCV adhesion, while either low or high temperatures would favor GI.1 adhesion. Regardless of temperature, increased ionic strength would increase GII.4 adhesion but would decrease GI.1 adhesion. FCV adsorption would be greater at refrigeration, pasteurization, or high temperature combined with a low salt concentration or at a higher NaCl concentration regardless of temperature. Norovirus adhesion mediated by hydrophobic interaction may depend on hydrophobic residues normally exposed on the capsid surface at pH 3, pH 8, physiological ionic strength, and low temperature, while at pasteurization temperatures it may rely more on buried hydrophobic residues exposed upon structural rearrangement. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

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

PubMed

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

2009-08-15

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

A computer program for geochemical analysis of acid-rain and other low-ionic-strength, acidic waters

USGS Publications Warehouse

Johnsson, P.A.; Lord, D.G.

1987-01-01

ARCHEM, a computer program written in FORTRAN 77, is designed primarily for use in the routine geochemical interpretation of low-ionic-strength, acidic waters. On the basis of chemical analyses of the water, and either laboratory or field determinations of pH, temperature, and dissolved oxygen, the program calculates the equilibrium distribution of major inorganic aqueous species and of inorganic aluminum complexes. The concentration of the organic anion is estimated from the dissolved organic concentration. Ionic ferrous iron is calculated from the dissolved oxygen concentration. Ionic balances and comparisons of computed with measured specific conductances are performed as checks on the analytical accuracy of chemical analyses. ARCHEM may be tailored easily to fit different sampling protocols, and may be run on multiple sample analyses. (Author 's abstract)

Liquid-liquid extraction of neodymium(III) by dialkylphosphate ionic liquids from acidic medium: the importance of the ionic liquid cation.

PubMed

Rout, Alok; Kotlarska, Justyna; Dehaen, Wim; Binnemans, Koen

2013-10-21

The ionic liquids 1-hexyl-3-methylimidazolium bis(2-ethylhexyl)phosphate, [C6mim][DEHP], 1-hexyl-1-methylpyrrolidinium bis(2-ethylhexyl)phosphate, [C6mpyr][DEHP], and tetrabutylammonium bis(2-ethylhexyl)phosphate, [N4444][DEHP], were prepared and characterized using (1)H and (13)C NMR spectroscopy. The extraction behavior of neodymium(iii) from nitrate medium by these ionic liquids, diluted with the room temperature ionic liquids 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][NTf2], 1-hexyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C6mpyr][NTf2], and tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N1444][NTf2], was studied. The distribution ratio of neodymium(iii) was measured as a function of various parameters, such as pH, concentration of the ionic liquid extractant, nature of diluents, concentration of ionic liquid cations and nitrate anions in the aqueous phase. The extraction behavior was compared with that obtained for a solution of the molecular extractant bis(2-ethylhexyl)phosphoric acid (DEHPA) in an ionic liquid diluent. The extraction of neodymium(iii) in the ionic liquids [C6mim][DEHP] and [C6mpyr][DEHP] showed markedly different extraction properties in comparison with that of the quaternary ammonium analogue [N4444][DEHP], especially concerning the pH dependence of the extraction process. These results show that the extraction process can be tuned by the selection of the ionic liquid cation. The extraction experiments also included the trivalent rare-earth ions lanthanum(iii), cerium(iii), praseodymium(iii), ytterbium(iii) and yttrium(iii). Studies of the stripping behavior and the reusability of the ionic liquids were carried out, which indicate that the ionic liquids can be reused with no loss in activity.

Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

PubMed

Norkus, E; Vaskelis, A; Zakaite, I

1996-03-01

D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

Adsorption/Desorption Transition of Recombinant Human Neurotrophin 4: Physicochemical Characterization.

PubMed

Dąbkowska, Maria; Adamczak, Małgorzata; Barbasz, Jakub; Cieśla, Michał; Machaliński, Bogusław

2017-09-26

Bulk physicochemical properties of neurotrophin 4 (NT-4) in electrolyte solutions and its adsorption/desorption on/from mica surfaces have been studied using dynamic light scattering (DLS), microelectrophoresis, a solution depletion technique (enzyme-linked immunosorbent assay, ELISA), and AFM imaging. Our study presents a determination of the diffusion coefficient, hydrodynamic diameters, electrophoretic mobility, and isoelectric point of the NT-4 under various ionic strength and pH conditions. The size of the NT-4 homodimer for an ionic strength of 0.015 M was substantially independent of pH and equal to 5.1 nm. It has been found that the number of electrokinetic charges per NT-4 molecule was equal to zero for all studied ionic strengths at pH 8.1, which was identified as the isoelectric point (iep). The protein adsorption/desorption on/from mica surfaces was examined as a function of ionic strength and pH. The kinetics of neurotrophin adsorption/desorption were evaluated at pH 3.5, 7.4, and 11 by direct AFM imaging and the ELISA technique. A monotonic increase in the maximum coverage of adsorbed NT-4 molecules with ionic strength (up to 5.5 mg/m 2 ) was observed at pH 3.5. These results were interpreted in terms of the theoretical model postulating an irreversible adsorption of the protein governed by the random sequential adsorption (RSA). Our measurements revealed a significant role of ionic strength, pH, and electrolyte composition in the lateral electrostatic interactions among differently charged NT-4 molecules. The transition between adsorption/desorption processes is found for the region of high pH and low surface concentration of adsorbed neurotrophin molecules at constant ionic strength. Additionally, results presented in this work show that the adsorption behavior of neurotrophin molecules may be governed by intrasolvent electrostatic interactions yielding an aggregation process. Understanding polyvalent neurotrophin interactions may have an impact on the reversibility/irreversibility of adsorption, and hence they might be useful for obtaining well-ordered protein layers, targeting the future development of drug delivery systems for treating neurodegenerative diseases.

Measurements and theoretical interpretation of points of zero charge/potential of BSA protein.

PubMed

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

Effect of environmental factors on the kinetics of insulin fibril formation: elucidation of the molecular mechanism.

PubMed

Nielsen, L; Khurana, R; Coats, A; Frokjaer, S; Brange, J; Vyas, S; Uversky, V N; Fink, A L

2001-05-22

In the search for the molecular mechanism of insulin fibrillation, the kinetics of insulin fibril formation were studied under different conditions using the fluorescent dye thioflavin T (ThT). The effect of insulin concentration, agitation, pH, ionic strength, anions, seeding, and addition of 1-anilinonaphthalene-8-sulfonic acid (ANS), urea, TMAO, sucrose, and ThT on the kinetics of fibrillation was investigated. The kinetics of the fibrillation process could be described by the lag time for formation of stable nuclei (nucleation) and the apparent rate constant for the growth of fibrils (elongation). The addition of seeds eliminated the lag phase. An increase in insulin concentration resulted in shorter lag times and faster growth of fibrils. Shorter lag times and faster growth of fibrils were seen at acidic pH versus neutral pH, whereas an increase in ionic strength resulted in shorter lag times and slower growth of fibrils. There was no clear correlation between the rate of fibril elongation and ionic strength. Agitation during fibril formation attenuated the effects of insulin concentration and ionic strength on both lag times and fibril growth. The addition of ANS increased the lag time and decreased the apparent growth rate for insulin fibril formation. The ANS-induced inhibition appears to reflect the formation of amorphous aggregates. The denaturant, urea, decreased the lag time, whereas the stabilizers, trimethylamine N-oxide dihydrate (TMAO) and sucrose, increased the lag times. The results indicated that both nucleation and fibril growth were controlled by hydrophobic and electrostatic interactions. A kinetic model, involving the association of monomeric partially folded intermediates, whose concentration is stimulated by the air-water interface, leading to formation of the critical nucleus and thence fibrils, is proposed.

Influence of soil pH on the toxicity of zinc oxide nanoparticles to the terrestrial isopod Porcellionides pruinosus.

PubMed

Tourinho, Paula S; van Gestel, Cornelis A M; Lofts, Stephen; Soares, Amadeu M V M; Loureiro, Susana

2013-12-01

The effects of soil pH on the toxicity of ZnO nanoparticles (NPs) to the terrestrial isopod Porcellionides pruinosus were evaluated. Isopods were exposed to a natural soil amended with CaCO3 to reach 3 different pH(CaCl2) levels (4.5, 6.2, and 7.3) and to standard LUFA 2.2 soil (pH 5.5) spiked with ZnO NPs (30 nm), non-nano ZnO (200 nm), and ionic Zn as ZnCl₂. Toxicity was expressed based on total Zn concentration in soil, as well as total Zn and free Zn²⁺ ion concentrations in porewater. Compared with ZnO-spiked soils, the ZnCl₂-spiked soils had lower pH and higher porewater Ca²⁺ and Zn levels. Isopod survival did not differ between Zn forms and soils, but survival was higher for isopods exposed to ZnO NPs at pH 4.5. Median effect concentrations (EC50s) for biomass change showed similar trends for all Zn forms in all soils, with higher values at intermediate pH. Median lethal concentration (LC50) and EC50 values based on porewater Zn or free Zn ion concentrations were much lower for ZnO than for ionic zinc. Zn body concentrations increased in a dose-related manner, but no effect of soil pH was found. It is suggested not only that dissolved or free Zn in porewater contributed to uptake and toxicity, but also that oral uptake (i.e., ingestion of soil particles) could be an important additional route of exposure. © 2013 SETAC.

Effect of pH on ion current through conical nanopores

NASA Astrophysics Data System (ADS)

Chander, M.; Kumar, R.; Kumar, S.; Kumar, N.

2018-05-01

Here, we examined ionic current behavior of conical nanopores at different pH and a fixed ion concentration of potassium halide (KCl). Conical shaped nanopores have been developed by chemical etching technique in polyethylene terephthalate (PET) membrane/foil of thickness 12 micron. For this we employed a self-assembled electrochemical cell having two chambers and the foil was fitted in the centre of cell. The nanopores were produced in the foil using etching and stopping solutions. The experimental results show that ionic current rectification (ICR) occurs through synthesized conical nanopores. Further, ion current increases significantly with increase of voltage from the base side of nanopores to the tip side at fixed pH of electrolyte.

K-targeted strategy for isolation of phenolic alkaloids of Nelumbo nucifera Gaertn by counter-current chromatography using lysine as a pH regulator.

PubMed

Wang, Yanyan; Zhang, Lihong; Zhou, Hui; Guo, Xiuyun; Wu, Shihua

2017-03-24

Counter-current chromatography (CCC) is an efficient liquid-liquid partition chromatography technique without support matrix. Despite there are many significant advancements in the CCC separation of natural products especially for non-ionic neutral compounds, CCC isolation of ionic compounds including alkaloids is still a challenging process guide by classical partition coefficients (K) or distribution ratio (K C ) because their partition coefficient could not be equal to distribution ratio in common ionic conditions. Here, taking the extract of embryo of the seed of Nelumbo nucifera Gaertn as sample, we introduced a modified K-targeted strategy for isolation of phenolic alkaloids by use of lysine as a pH regulator. The results indicated that if the mass of basic regulators such as aqueous ammonia and lysine added into the solvent system were high enough to inhibit the ionization of the targeted alkaloids, the distribution ratio of targets with ionic and non-ionic molecular forms got stable and might not been changed as the concentration of the pH regulator. In this case, the distribution ratio of target was almost equal to the partition coefficient. Thus, the targets could be isolated by K-targeted CCC separation through adding a certain amount pH regulators into the solvent system. Further experiments also showed that the sample concentration was an important factor on the distribution ratio of targets. Meanwhile, CCC experiments indicated that lysine was more suitable than aqueous ammonia for the separation of phenolic alkaloids because the chemical property of lysine-target complex in the CCC fractions was more stable. Therefore, the preparative CCC separation was performed using 20mM lysine as a pH regulator with more than 800mg injection mass. After simple back-extraction with dichloromethane, the lysine in the CCC fraction was removed completely and pure isoliensinine and neferine were obtained. In summary, the whole results indicated that the modified K-targeted CCC strategy using lysine as the pH regulator was efficient for isolation of phenolic alkaloids from crude plant extracts. It not only provided a practical strategy for the isolation of neferine and its analogues, but also introduced a powerful method to resolve the peak skewing (leading or tailing) in CCC separation of ionic compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

Sorption of Th (IV) to silica as a function of pH, humic/fulvic acid, ionic strength, electrolyte type.

PubMed

Chen, Changlun; Wang, Xiangke

2007-02-01

The removal behavior of thorium (Th(IV)) has been investigated in multicomponent systems containing silica (SiO2) as the model of inorganic particles because of its widespread presence in the earth's crust and soil humic acid (HA)/fulvic acid (FA) by batch experiments. The influence of pH from 2 to 12, ionic strength from 0.02 to 0.2 M KNO3, soil HA/FA concentration from 8.3 to 22.5 mg/L, and foreign cations (Li+, Na+, K+) and anions (NO3(-), Cl-) on the sorption of Th(IV) onto SiO2 was also tested. The sorption isotherms of Th(IV) at approximately constant pH (3.50+/-0.02) were determined and analyzed regressively with three kinds of sorption isotherm models, i.e., linear, Langmuir, and Freundlich models. The results demonstrated that the sorption of Th(IV) onto SiO2 increased steeply with increasing pH from 2 to 4. Generally, humic substances (HSs) were shown to enhance Th(IV) sorption at low pH, but to reduce Th(IV) sorption at intermediate and high pH. It was a hypothesis that the significantly positive influence of HA/FA at pH from 2 to 4 on the sorption of Th(IV) onto SiO2 was attributed to strong surface binding of HA/FA on SiO2 and subsequently the formation of ternary surface complexes such as [triple bond]MO-O-HA-Th or [triple bond]MO-O-FA-Th. The results also demonstrated that the sorption was strongly dependent on the concentration of HA/FA, and independent of ionic strength and foreign ions under our experimental conditions.

The Influence of High Drug Loading in Xanthan Tablets and Media with Different Physiological pH and Ionic Strength on Swelling and Release.

PubMed

Mikac, Urša; Sepe, Ana; Baumgartner, Saša; Kristl, Julijana

2016-03-07

The formation of a gel coat around xanthan (Xan) tablets, empty or loaded with pentoxifylline (PF), and its release in media differing in pH and ionic strength by NMR, MR imaging, and two release methods were studied. The T1 and T2 NMR relaxation times in gels depend predominantly on Xan concentration; the presence of PF has negligible influence on them. It is interesting that the matrix swelling is primarily regulated by Xan despite high drug loading (25%, 50%). The gastric pH and high ionic strength of the media do not influence the position of the penetration and swelling fronts but do affect the erosion front and gel thickness. The different release profiles obtained in mixing and nonmixing in vitro methods are the consequence of matrix hydration level and erosion at the surface. In water and in diluted acid medium with low ionic strength, the main release mechanism is erosion, whereas in other media (pH 1.2, μ ≥ 0.20 M), anomalous transport dominates as was found out by fitting of measured data with theoretical model. Besides the in vitro investigation that mimics gastric conditions, mathematical modeling makes the product development more successful.

Study on the kinetic self-assembly of type I collagen from tilapia (Oreochromis niloticus) skin using the fluorescence probe thioflavin T.

PubMed

Yan, Mingyan; Wang, Xinping

2018-05-27

The kinetic self-assembly of type I collagen from tilapia (Oreochromis niloticus) skin was characterized by the fluorescence method based on thioflavin T (ThT). The fluorescence probe could bind to the active monomeric collagen with a higher ordered degree of molecule, which displayed the pH and ionic strength dependence, the binding constant higher at neutral pH and proportional to the NaCl concentration. Compared to the turbidity method, ThT was more suitable to characterize the nucleation phase of collagen self-assembly. The nucleus size was determined through the ThT fluorescence and linear-polymerization model. At various pH and ionic strength, the nucleus size was nearly identical, either one or two monomers, demonstrating that one or two active monomeric collagen formed into the nucleus and different pH and ionic strength didn't alter the self-assembly mechanism of collagen. This approach was beneficial to advance the understanding of the kinetic self-assembly of the fish-sourced collagen in vitro. Copyright © 2018 Elsevier B.V. All rights reserved.

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2004-01-01

Dissolution and precipitation rates of brucite (Mg(OH) 2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10 -4 to 3 M), saturation index (-12 < log Ω < 0.4) and aqueous magnesium concentrations (10 -6 to 5·10 -4 M). Brucite surface charge and isoelectric point (pH IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m 2) and lack of dependence on ionic strength predicts the dominance of >MgOH 2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO - as pH increases to 10-12. Rates are proportional to the square of >MgOH 2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH 2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: R=k Mg+ · {>MgOH 2+} 2 · (1-Ω 2) where kMg+ is the dissolution rate constant, {> i} is surface species concentration (mol/m 2), and Ω is the solution saturation index with respect to brucite. Measurements of nonsteady state brucite dissolution rates, in response to cycling the pH from 12 to 2 (pH-jump experiments), indicate the important role of surface hydroxylation — that leads to the formation of Mg oxo or -hydroxo complexes — in the formation of dissolution-active sites. Replacement of water molecules by these oxygen donor complexes in the Mg coordination sphere has a labilizing effect on the dynamics of the remaining water molecules and thus increases reaction rates.

Renewable energy powered membrane technology: Impact of pH and ionic strength on fluoride and natural organic matter removal.

PubMed

Owusu-Agyeman, Isaac; Shen, Junjie; Schäfer, Andrea Iris

2018-04-15

Real water pH and ionic strength vary greatly, which influences the performance of membrane processes such as nanofiltration (NF) and reverse osmosis (RO). Systematic variation of pH (3-12) and ionic strength (2-10g/L as total dissolved solids (TDS)) was undertaken with a real Tanzanian water to investigate how water quality affects retention mechanisms of fluoride (F) and natural organic matter (NOM). An autonomous solar powered NF/RO system driven by a solar array simulator was supplied with constant power from a generator. An open NF (NF270) and a brackish water RO (BW30) membrane were used. A surface water with a very high F (59.7mg/L) and NOM (110mgC/L) was used. Retention of F by NF270 was <20% at pH <6, increased to 40% at pH6, and 60-70% at pH7-12, indicating a dominance of charge repulsion while being ineffective in meeting the guideline of 1.5mg/L. Increase in ionic strength led to a significant decline in retention of F (from 70 to 50%) and electrical conductivity (from 60 to 10%) by NF270, presumably due to charge screening. In contrast, BW30 retained about 50% of F at pH3, >80% at pH4, and about 99% at pH >5, due to the smaller pore size and hence a more dominant size exclusion. In consequence, only little impact of ionic strength increase was observed for BW30. The concentration of NOM in permeates of both NF270 and BW30 were typically <2mg/L. This was not affected by pH or ionic strength due to the fact that the bulk of NOM was rejected by both membranes through size exclusion. The research is carried out in the context of providing safe drinking water for rural and remote communities where infrastructure is lacking, and water quality varies significantly. While other studies focus on energy fluctuations, this research emphasises on feed water quality that affects system performance and may alter due to a number of environmental factors. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrophoretic separations in poly(dimethylsiloxane) microchips using a mixture of ionic and zwitterionic surfactants

PubMed Central

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

Studies of bio-mimetic medium of ionic and non-ionic micelles by a simple charge transfer fluorescence probe N,N-dimethylaminonapthyl-(acrylo)-nitrile

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.

Polyvinyl alcohol-based nanocomposite hydrogels containing magnetic laponite RD to remove cadmium.

PubMed

Mola Ali Abasiyan, Sara; Mahdavinia, Gholam Reza

2018-05-01

In this study, magnetic nanocomposite hydrogels based on polyvinyl alcohol were synthesized. Magnetic polyvinyl alcohol/laponite RD (PVA-mLap) nanocomposites were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. The results indicated that PVA-mLap had desirable magnetic-sorption properties and magnetic-laponite nanoparticles were successfully synthesized and added to polyvinyl alcohol. The present nanocomposites were applied to remove Cd 2+ from aqueous solution. The influence of initial Cd 2+ concentration, magnetic-laponite concentration, pH, and ionic strength on adsorption isotherm was investigated. Heterogeneity of adsorption sites was intensified by increasing magnetic concentration of adsorbents and by rising pH value. Results of ionic strength studies indicated that by increasing ionic strength more than four times, the adsorption of Cd 2+ has only decreased around 15%. According to the results, the dominant mechanism of Cd 2+ sorption by the present adsorbents was determined chemical and specific sorption. Therefore, the use of the present nanocomposites as a powerful adsorbent of Cd 2+ in the wastewater treatment is suggested. Isotherm data were described by using Freundlich and Langmuir models, and better fitting was introduced Langmuir model.

Intermolecular Interactions and the Viscosity of Highly Concentrated Monoclonal Antibody Solutions.

PubMed

Binabaji, Elaheh; Ma, Junfen; Zydney, Andrew L

2015-09-01

The large increase in viscosity of highly concentrated monoclonal antibody solutions can be challenging for downstream processing, drug formulation, and delivery steps. The objective of this work was to examine the viscosity of highly concentrated solutions of a high purity IgG1 monoclonal antibody over a wide range of protein concentrations, solution pH, ionic strength, and in the presence / absence of different excipients. Experiments were performed with an IgG1 monoclonal antibody provided by Amgen. The steady-state viscosity was evaluated using a Rheometrics strain-controlled rotational rheometer with a concentric cylinder geometry. The viscosity data were well-described by the Mooney equation. The data were analyzed in terms of the antibody virial coefficients obtained from osmotic pressure data evaluated under the same conditions. The viscosity coefficient in the absence of excipients was well correlated with the third osmotic virial coefficient, which has a negative value (corresponding to short range attractive interactions) at the pH and ionic strength examined in this work. These results provide important insights into the effects of intermolecular protein-protein interactions on the behavior of highly concentrated antibody solutions.

EFFECT OF AQUEOUS PHASE PROPERTIES ON CLAY PARTICLE ZETA POTENTIAL AND ELECTRO-OSMOTIC PERMEABILITY: IMPLICATIONS FOR ELECTRO-KINETIC SOIL REMEDIATION PROCESSES

EPA Science Inventory

The influence of aqueous phase properties (pH, ionic strength and divalent metal ion concentration) on clay particle zeta potential and packed-bed electro-osmotic permeability was quantified. Although pH strongly altered the zeta potential of a Georgia kaolinite, it did not signi...

Interactions of lysozyme in concentrated electrolyte solutions from dynamic light-scattering measurements.

PubMed Central

Kuehner, D E; Heyer, C; Rämsch, C; Fornefeld, U M; Blanch, H W; Prausnitz, J M

1997-01-01

The diffusion of hen egg-white lysozyme has been studied by dynamic light scattering in aqueous solutions of ammonium sulfate as a function of protein concentration to 30 g/liter. Experiments were conducted under the following conditions: pH 4-7 and ionic strength 0.05-5.0 M. Diffusivity data for ionic strengths up to 0.5 M were interpreted in the context of a two-body interaction model for monomers. From this analysis, two potential-of-mean-force parameters, the effective monomer charge, and the Hamaker constant were obtained. At higher ionic strength, the data were analyzed using a model that describes the diffusion coefficient of a polydisperse system of interacting protein aggregates in terms of an isodesmic, indefinite aggregation equilibrium constant. Data analysis incorporated multicomponent virial and hydrodynamic effects. The resulting equilibrium constants indicate that lysozyme does not aggregate significantly as ionic strength increases, even at salt concentrations near the point of salting-out precipitation. PMID:9414232

Titanium dioxide nanoparticles: Impact of increasing ionic strength during synthesis, reflux, and hydrothermal aging

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

Isley, Sara L.; Jordan, David S.; Penn, R. Lee

2009-01-08

This work investigates the role of ionic strength during synthesis, reflux, and hydrothermal aging of sol-gel synthesized titanium dioxide. Research presented here uses X-ray diffraction data and Rietveld refinements to quantify anatase, brookite, and rutile phases as functions of synthetic and aging variables. In addition, the Scherrer equation is used to obtain average crystallite sizes for each phase quantified. Results presented in this work demonstrate that the most control over the sol-gel products can be obtained by modifying the pH during hydrolysis. In addition, while varying the ionic strength during reflux and hydrothermal aging can result in enhanced control overmore » the crystalline phase and crystallite size, the most control can be achieved by varying the ionic strength during synthesis. Finally, sol-gel synthesis at low pH (-0.6) and high-chloride concentration (3 M NaCl) produced a heterogeneous sample composed of nanocrystalline anatase (3.8 nm) and rutile (2.9 nm)« less

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

PubMed

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

2017-09-28

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

Sorption-desorption of fipronil in some soils, as influenced by ionic strength, pH and temperature.

PubMed

Singh, Anand; Srivastava, Anjana; Srivastava, Prakash C

2016-08-01

The sorption-desorpion of fipronil insecticide is influenced by soil properties and variables such as pH, ionic strength, temperature, etc. A better understanding of soil properties and these variables in sorption-desorption processes by quantification of fipronil using liquid chromatography may help to optimise suitable soil management to reduce contamination of surface and groundwaters. In the present investigation, the sorption-desorption of fipronil was studied in some soils at varying concentrations, ionic strengths, temperatures and pH values, and IR specta of fipronil sorbed onto soils were studied. The sorption of fipronil onto soils conformed to the Freundlich isotherm model. The sorption-desorption of fipronil varied with ionic strength in each of the soils. Sorption decreased but desorption increased with temperature. Sorption did not change with increasing pH, but for desorption there was no correlation. The cumulative desorption of fipronil from soil was significantly and inversely related to soil organic carbon content. IR spectra of sorbed fipronil showed the involvement of amino, nitrile, sulfone, chloro and fluoro groups and the pyrazole nucleus of the fipronil molecule. The sorption of fipronil onto soils appeared to be a physical process with the involvement of hydrogen bonding. An increase in soil organic carbon may help to reduce desorption of fipronil. High-temperature regimes are more conducive to the desorption. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Accurate and self-consistent procedure for determining pH in seawater desalination brines and its manifestation in reverse osmosis modeling.

PubMed

Nir, Oded; Marvin, Esra; Lahav, Ori

2014-11-01

Measuring and modeling pH in concentrated aqueous solutions in an accurate and consistent manner is of paramount importance to many R&D and industrial applications, including RO desalination. Nevertheless, unified definitions and standard procedures have yet to be developed for solutions with ionic strength higher than ∼0.7 M, while implementation of conventional pH determination approaches may lead to significant errors. In this work a systematic yet simple methodology for measuring pH in concentrated solutions (dominated by Na(+)/Cl(-)) was developed and evaluated, with the aim of achieving consistency with the Pitzer ion-interaction approach. Results indicate that the addition of 0.75 M of NaCl to NIST buffers, followed by assigning a new standard pH (calculated based on the Pitzer approach), enabled reducing measured errors to below 0.03 pH units in seawater RO brines (ionic strength up to 2 M). To facilitate its use, the method was developed to be both conceptually and practically analogous to the conventional pH measurement procedure. The method was used to measure the pH of seawater RO retentates obtained at varying recovery ratios. The results matched better the pH values predicted by an accurate RO transport model. Calibrating the model by the measured pH values enabled better boron transport prediction. A Donnan-induced phenomenon, affecting pH in both retentate and permeate streams, was identified and quantified. Copyright © 2014 Elsevier Ltd. All rights reserved.

A near infrared holographic glucose sensor.

PubMed

Vezouviou, Evangelia; Lowe, Christopher R

2015-06-15

Real-time glucose monitoring has been beneficial in reducing health complications associated with diabetes as well as a decrease in mortality. This report describes a novel holographic platform, fabricated via laser ablation on chitosan hydrogel with gold nanoparticles with a replaying in visible and near IR. The sensor responded with a 12 nm and 7 nm shift in wavelength at glucose concentrations in the 0-70 mM range and in the visible and near IR, respectively, at pH 7.4 and an ionic strength of 154 mM. The sensor did not respond to potential interferences found in the interstitial fluid, such as fructose, vitamin C and lactate, at their respective normal concentrations and was stable to fluctuations in temperature, pH and ionic strength. The characteristics of this sensor suggests that it may be applicable for use as an implanted device for the real time monitoring of glucose concentrations in the interstitial fluid using near IR as the interrogating medium. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation of magnetic chitosan and graphene oxide-functional guanidinium ionic liquid composite for the solid-phase extraction of protein.

PubMed

Ding, Xueqin; Wang, Yuzhi; Wang, Ying; Pan, Qi; Chen, Jing; Huang, Yanhua; Xu, Kaijia

2015-02-25

A series of novel cationic functional hexaalkylguanidinium ionic liquids and anionic functional tetraalkylguanidinium ionic liquids have been synthesized, and then magnetic chitosan graphene oxide (MCGO) composite has been prepared and coated with these functional guanidinium ionic liquids to extract protein by magnetic solid-phase extraction. MCGO-functional guanidinium ionic liquid has been characterized by vibrating sample magnetometer, field emission scanning electron microscopy, X-ray diffraction spectrometer and Fourier transform infrared spectrometer. After extraction, the concentrations of protein were determined by measuring the absorbance at 278 nm using an ultra violet visible spectrophotometer. The advantages of MCGO-functional guanidinium ionic liquid in protein extraction were compared with magnetic chitosan, graphene oxide, MCGO and MCGO-ordinary imidazolium ionic liquid. The proposed method has been applied to extract trypsin, lysozyme, ovalbumin and bovine serum albumin. A comprehensive study of the adsorption conditions such as the concentration of protein, the amount of MCGO-functional guanidinium ionic liquid, the pH, the temperature and the extraction time were also presented. Moreover, the MCGO-functional guanidinium ionic liquid can be easily regenerated, and the extraction capacity was about 94% of the initial one after being used three times. Copyright © 2015 Elsevier B.V. All rights reserved.

EFFECT OF pH, IONIC STRENGTH, DISSOLVED ORGANIC CARBON, TIME, AND PARTICLE SIZE ON METALS RELEASE FROM MINE DRAINAGE IMPACTED STREAMBED SEDIMENTS

EPA Science Inventory

Acid-mine drainage (AMD) input to a stream typically results in the stream having a reduced pH, increased concentrations of metals and salts, and decreased biological productivity. Removal and/or treatment of these AMD sources is desired to return the impacted stream(s) to initi...

Combined use of [TBA][L-ASP] and hydroxypropyl-β-cyclodextrin as selectors for separation of Cinchona alkaloids by capillary electrophoresis.

PubMed

Zhang, Yu; Yu, Haixia; Wu, Yujiao; Zhao, Wenyan; Yang, Min; Jing, Huanwang; Chen, Anjia

2014-10-01

In this paper, a new capillary electrophoresis (CE) separation and detection method was developed for the chiral separation of the four major Cinchona alkaloids (quinine/quinidine and cinchonine/cinchonidine) using hydroxypropyl-β-cyclodextrin (HP-β-CD) and chiral ionic liquid ([TBA][L-ASP]) as selectors. Separation parameters such as buffer concentrations, pH, HP-β-CD and chiral ionic liquid concentrations, capillary temperature, and separation voltage were investigated. After optimization of separation conditions, baseline separation of the three analytes (cinchonidine, quinine, cinchonine) was achieved in fewer than 7 min in ammonium acetate background electrolyte (pH 5.0) with the addition of HP-β-CD in a concentration of 40 mM and [TBA][L-ASP] of 14 mM, while the baseline separation of cinchonine and quinidine was not obtained. Therefore, the first-order derivative electropherogram was applied for resolving overlapping peaks. Regression equations revealed a good linear relationship between peak areas in first-order derivative electropherograms and concentrations of the two diastereomer pairs. The results not only indicated that the first-order derivative electropherogram was effective in determination of a low content component and of those not fully separated from adjacent ones, but also showed that the ionic liquid appeared to be a very promising chiral selector in CE. Copyright © 2014 Elsevier Inc. All rights reserved.

Ionic liquid as a mobile phase additive in high-performance liquid chromatography for the simultaneous determination of eleven fluorescent whitening agents in paper materials.

PubMed

Wang, Qing; Chen, Xianbo; Qiu, Bin; Zhou, Liang; Zhang, Hui; Xie, Juan; Luo, Yan; Wang, Bin

2016-04-01

In the present study, 11 4,4'-diaminostilbene-2,2'-disulfonic acid based fluorescent whitening agents with different numbers of sulfonic acid groups were separated by using an ionic liquid as a mobile phase additive in high-performance liquid chromatography with fluorescence detection. The effects of ionic liquid concentration, pH of mobile phase B, and composition of mobile phase A on the separation of fluorescent whitening agents were systematically investigated. The ionic liquid tetrabutylammonium tetrafluoroborate is superior to tetrabutylammomnium bromide for the separation of the fluorescent whitening agents. The optimal separation conditions were an ionic liquid concentration at 8 mM and the pH of mobile phase B at 8.5 with methanol as mobile phase A. The established method exhibited low limits of detection (0.04-0.07 ng/mL) and wide linearity ranges (0.30-20 ng/mL) with high linear correlation coefficients from 0.9994 to 0.9998. The optimized procedure was applied to analyze target analytes in paper samples with satisfactory results. Eleven target analytes were quantified, and the recoveries of spiked paper samples were in the range of 85-105% with the relative standard deviations from 2.1 to 5.1%. The obtained results indicated that the method was efficient for detection of 11 fluorescent whitening agents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of soil humic and fulvic acids, pH and ionic strength on Th(IV) sorption to TiO2 nanoparticles.

PubMed

Tan, Xiaoli; Wang, Xiangke; Chen, Changlun; Sun, Aihua

2007-04-01

Thorium is considered as a chemical analog of other tetravalent actinides. Herein, the sorption of Th(IV) on TiO(2) in the presence or absence of soil fulvic acid (FA)/humic acid (HA) as a function of pH, ionic strength and FA/HA concentration has been studied by a batch method. The morphology was characterized by scanning electron microscopy (SEM). The results indicate that sorption of Th(IV) on TiO(2) increases from 0% to approximately 94% at pH 1 approximately 4, and then maintains level with increasing pH values. Both FA and HA have a positive effect on Th(IV) sorption at low pH values and the contribution of FA on Th(IV) sorption is rather higher than that of HA at pH<4. The sorption is weakly dependent on the concentration of KNO(3) in solution, but the cations K(+), Na(+) and Li(+) influence Th(IV) sorption more obviously. The batch results indicate that the inner sphere complex formation is formed at bare surfaces or FA/HA-bound TiO(2) particle surfaces. Results of SEM analysis show that the particle sizes of TiO(2), Th-TiO(2) and Th-HA-TiO(2) colloids are quite different. Surface complexation may be considered as the main sorption mechanism.

Effects of Environmental Stresses and in Vitro Digestion on the Release of Tocotrienols Encapsulated Within Chitosan-Alginate Microcapsules.

PubMed

Tan, Phui Yee; Tan, Tai Boon; Chang, Hon Weng; Tey, Beng Ti; Chan, Eng Seng; Lai, Oi Ming; Sham Baharin, Badlishah; Nehdi, Imededdine Arbi; Tan, Chin Ping

2017-12-06

Considering the health benefits of tocotrienols, continuous works have been done on the encapsulation and delivery of these compounds. In this study, we encapsulated tocotrienols in chitosan-alginate microcapsules and evaluated their release profile. Generally, these tocotrienols microcapsules (TM) displayed high thermal stability. When subjected to pH adjustments (pH 1-9), we observed that the release of tocotrienols was the highest (33.78 ± 0.18%) under basic conditions. The TM were also unstable against the effect of ionic strength, with a high release (70.73 ± 0.04%) of tocotrienols even at a low sodium chloride concentration (50 mM). As for the individual isomers, δ-tocotrienol was the most sensitive to pH and ionic strength. In contrast, β-/γ-tocotrienols were the most ionic-stable isomers but more responsive toward thermal treatment. Simulated gastrointestinal model showed that the chitosan-alginate-based TM could be used to retain tocotrienols in the gastric and subsequently release them in the intestines for possible absorption.

Dispersion stability of a ceramic glaze achieved through ionic surfactant adsorption.

PubMed

Panya, Preecha; Arquero, Orn-anong; Franks, George V; Wanless, Erica J

2004-11-01

The adsorption of cetylpyridinium chloride (CPC) and sodium dodecylbenzenesulfonate (SDBS) onto a ceramic glaze mixture composed of limestone, feldspar, quartz, and kaolin has been investigated. Both adsorption isotherms and the average particle zeta potential have been studied in order to understand the suspension stability as a function of pH, ionic strength, and surfactant concentration. The adsorption of small amounts of cationic CPC onto the primarily negatively charged surfaces of the particles at pH 7 and 9 results in strong attraction and flocculation due to hydrophobic interactions. At higher surfactant concentrations a zeta potential of more than +60 mV results from the bilayered adsorbed surfactant, providing stability at salt concentrations < or = 0.01 M. At 0.1 M salt poor stability results despite substantial zeta potential values. Three mechanisms for SDBS adsorption have been identified. When anionic SDBS monomers either adsorb by electrostatic interactions with the few positive surface sites at high pH or adsorb onto like charged negative surface sites due to dispersion or hydrophobic interactions, the magnitude of the negative zeta potential increases slightly. At pH 9 this increase is enough to promote stability with an average zeta potential of more than -55 mV, whereas at pH 7 the zeta potential is lower at about -45 mV. The stability of suspensions at pH 7 is additionally due to steric repulsion caused by the adsorption of thick layers of neutrally charged Ca(DBS)2 complexes created when the surfactant interacts with dissolved calcium ions from the calcium carbonate component.

Potentiometric chip-based multipumping flow system for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples.

PubMed

Chango, Gabriela; Palacio, Edwin; Cerdà, Víctor

2018-08-15

A simple potentiometric chip-based multipumping flow system (MPFS) has been developed for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples. The proposed system was developed by using a poly(methyl methacrylate) chip microfluidic-conductor using the advantages of flow techniques with potentiometric detection. For this purpose, an automatic system has been designed and built by optimizing the variables involved in the process, such as: pH, ionic strength, stirring and sample volume. This system was applied successfully to water samples getting a versatile system with an analysis frequency of 12 samples per hour. Good correlation between chloride and fluoride concentration measured with ISE and ionic chromatography technique suggests satisfactory reliability of the system. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed Central

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

2017-01-01

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

Effect of surfactants on sorption of atrazine by soil

NASA Astrophysics Data System (ADS)

Abu-Zreig, Majed; Rudra, R. P.; Dickinson, W. T.; Evans, L. J.

1999-03-01

This study investigates the effect of synthetic wastewater containing surfactants on the sorption of atrazine using an equilibrium batch technique. Laboratory experiments were conducted on three soils with two non-ionic (Rexol and Rexonic) surfactants and one anionic (Sulphonic) surfactant, specifically manufactured for the detergent industry. Four sets of experiments were conducted to examine the influence of surfactants on the equilibrium time of atrazine sorption, to explore the effect of surfactant concentration, pH and type of surfactant on the amount of atrazine sorbed and to determine sorption isotherms of atrazine in the presence of surfactants. The results indicate that the application of Sulphonic results in dramatic increase in the adsorption of atrazine on to soils, the increase being directly proportional to the concentration of the surfactant. Application of the Sulphonic surfactants with a concentration of 3000 mg/l can result in a significant increase in Kd values of atrazine for loam and sandy loam soils. On the other hand, the effect of non-ionic surfactants depends on their concentration. Generally, non-ionic surfactants can result in a slight increase in atrazine sorption at high concentration, an exception being Rexol on sandy loam soil. At low concentrations, non-ionic surfactants have shown a tendency to decrease atrazine sorption.

Humic Acid Effects on the Transport of Colloidal Particles in Unsaturated Porous Media: Humic Acid Dosage, pH, and Ionic Strength Dependence

NASA Astrophysics Data System (ADS)

Morales, V. L.; Gao, B.; Steenhuis, T. S.

2008-12-01

Soil colloids and biocolloids can facilitate contaminant transport within the soil profile through the complexation of pollutants previously thought to have limited mobility. Dissolved organic substances are qualitatively known to alter the behavior of colloids and surface chemistry of soil particles in aquatic environments when adsorbed to their surfaces. Specifically, it has been observed that even small amounts of adsorbed humic acids result in a pronounced increase in colloid mobility in saturated porous systems, presumably by a combination of electrostatic and steric stabilization. However, the degree to which adsorbed humic acids stabilize colloidal suspension is highly sensitive to the system's solution chemistry; mainly in terms of pH, ionic strength, and metal ions present. The objective of this study is to expound quantitatively on the role that combined stabilizing and destabilizing solution chemistry components have on humic acid-colloid transport in unsaturated media by isolating experimentally some underlying mechanisms that regulate colloid transport in realistic aquatic systems. We hypothesize that in chemically heterogeneous porous media, with ionic strength values above 0 and pH ranges from 4 to 9, the effect of humic acid on colloid suspensions cannot be simply characterized by increased stability and mobility. That a critical salt concentration must exists for a given humic acid concentration and pH, above which the network of humic acid collapses by forming coordination complexes with other suspended or adsorbed humic acids, thus increasing greatly the retention of colloids in the porous medium by sweep flocculation. In addition, capillary forces in unsaturated media may contribute further to overcome repulsive forces that prevent flocculation of humic acid-colloid complexes. The experimental work in this study will include: jar tests to determine critical solution concentration combinations for desired coagulation/flocculation rates, column experiments to obtain effluent breakthrough data, in-situ visualization of internal processes with bright field microscopy, batch adsorption measurements, and changes in hydrophobic interaction energy of colloid and media surfaces for realistic aqueous ionic strength and pH ranges. Such experimental results are expected to provide sufficient evidence to corroborate our speculations that under natural soil water conditions, humic acids may greatly contribute to the immobilization of colloidal particles.

pH-dependent electron-transport properties of carbon nanotubes.

PubMed

Back, Ju Hee; Shim, Moonsub

2006-11-30

Carbon nanotube electrochemical transistors integrated with microfluidic channels are utilized to examine the effects of aqueous electrolyte solutions on the electron-transport properties of single isolated carbon nanotubes. In particular, pH and concentration of supporting inert electrolytes are examined. A systematic threshold voltage shift with pH is observed while the transconductance and subthreshold swing remain independent of pH and concentration. Decreasing pH leads to a negative shift of the threshold voltage, indicating that protonation does not lead to hole doping. Changing the type of contact metal does not alter the observed pH response. The pH-dependent charging of SiO2 substrate is ruled out as the origin based on measurements with suspended nanotube transistors. Increasing the ionic strength leads to reduced pH response. Contributions from possible surface chargeable chemical groups are considered.

Decreasing DOC trends in soil solution along the hillslopes at two IM sites in southern Sweden--geochemical modeling of organic matter solubility during acidification recovery.

PubMed

Löfgren, Stefan; Gustafsson, Jon Petter; Bringmark, Lage

2010-12-01

Numerous studies report increased concentrations of dissolved organic carbon (DOC) during the last two decades in boreal lakes and streams in Europe and North America. Recently, a hypothesis was presented on how various spatial and temporal factors affect the DOC dynamics. It was concluded that declining sulphur deposition and thereby increased DOC solubility, is the most important driver for the long-term DOC concentration trends in surface waters. If this recovery hypothesis is correct, the DOC levels should increase both in the soil solution as well as in the surrounding surface waters as soil pH rises and the ionic strength declines due to the reduced input of SO(4)(2-) ions. In this project a geochemical model was set up to calculate the net humic charge and DOC solubility trends in soils during the period 1996-2007 at two integrated monitoring sites in southern Sweden, showing clear signs of acidification recovery. The Stockholm Humic Model was used to investigate whether the observed DOC solubility is related to the humic charge and to examine how pH and ionic strength influence it. Soil water data from recharge and discharge areas, covering both podzols and riparian soils, were used. The model exercise showed that the increased net charge following the pH increase was in many cases counteracted by a decreased ionic strength, which acted to decrease the net charge and hence the DOC solubility. Thus, the recovery from acidification does not necessarily have to generate increasing DOC trends in soil solution. Depending on changes in pH, ionic strength and soil Al pools, the trends might be positive, negative or indifferent. Due to the high hydraulic connectivity with the streams, the explanations to the DOC trends in surface waters should be searched for in discharge areas and peat lands. Copyright © 2010 Elsevier B.V. All rights reserved.

Characterization of a supported ionic liquid membrane used for the removal of cyanide from wastewater.

PubMed

Xue, Juan Qin; Liu, Ni Na; Li, Guo Ping; Dang, Long Tao

2017-12-01

This work evaluated the performance of ionic liquids (ILs) in supported liquid membranes in the removal of total cyanide from wastewater. Membranes were characterized by scanning electron microscopy and contact angle measurements to study the membrane morphology and wetting ability. In particular, the effects of operational parameters such as membrane immersion time, feed-phase concentration, and pH on cyanide removal were investigated. ILs are organic salts that are entirely composed of organic cations and either organic or inorganic anions. Since their vapor pressure is negligible, they can be handled easily; this characteristic gives rise to their 'green' nature. In this study, a hydrophobic IL, 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF 6 ), was immobilized in the pores of a solid polymeric support made of polyvinylidene fluoride. The optimal conditions were as follows: 1 hour membrane immersion time, 312.24 mg/L feed-phase concentration, a feed-phase pH of 4, 3% NaOH solution, and 1 hour stirring time. The cyanide removal was 95.31%. The treatment of cyanide using supported ionic liquid membrane (SILM) technology is a method with potential applications in industry.

Human fibrinogen adsorption on positively charged latex particles.

PubMed

Zeliszewska, Paulina; Bratek-Skicki, Anna; Adamczyk, Zbigniew; Cieśla, Michał

2014-09-23

Fibrinogen (Fb) adsorption on positively charged latex particles (average diameter of 800 nm) was studied using the microelectrophoretic and the concentration depletion methods based on AFM imaging. Monolayers on latex were adsorbed from diluted bulk solutions at pH 7.4 and an ionic strength in the range of 10(-3) to 0.15 M where fibrinogen molecules exhibited an average negative charge. The electrophoretic mobility of the latex after controlled fibrinogen adsorption was systematically measured. A monotonic decrease in the electrophoretic mobility of fibrinogen-covered latex was observed for all ionic strengths. The results of these experiments were interpreted according to the three-dimensional electrokinetic model. It was also determined using the concentration depletion method that fibrinogen adsorption was irreversible and the maximum coverage was equal to 0.6 mg m(-2) for ionic strength 10(-3) M and 1.3 mg m(-2) for ionic strength 0.15 M. The increase of the maximum coverage was confirmed by theoretical modeling based on the random sequential adsorption approach. Paradoxically, the maximum coverage of fibrinogen on positively charged latex particles was more than two times lower than the maximum coverage obtained for negative latex particles (3.2 mg m(-2)) at pH 7.4 and ionic strength of 0.15 M. This was interpreted as a result of the side-on adsorption of fibrinogen molecules with their negatively charged core attached to the positively charged latex surface. The stability and acid base properties of fibrinogen monolayers on latex were also determined in pH cycling experiments where it was observed that there were no irreversible conformational changes in the fibrinogen monolayers. Additionally, the zeta potential of monolayers was more positive than the zeta potential of fibrinogen in the bulk, which proves a heterogeneous charge distribution. These experimental data reveal a new, side-on adsorption mechanism of fibrinogen on positively charged surfaces and confirmed the decisive role of electrostatic interactions in this process.

Cellulose ionics: switching ionic diode responses by surface charge in reconstituted cellulose films.

PubMed

Aaronson, Barak D B; Wigmore, David; Johns, Marcus A; Scott, Janet L; Polikarpov, Igor; Marken, Frank

2017-09-25

Cellulose films as well as chitosan-modified cellulose films of approximately 5 μm thickness, reconstituted from ionic liquid media onto a poly(ethylene-terephthalate) (PET, 6 μm thickness) film with a 5, 10, 20, or 40 μm diameter laser-drilled microhole, show significant current rectification in aqueous NaCl. Reconstituted α-cellulose films provide "cationic diodes" (due to predominant cation conductivity) whereas chitosan-doped cellulose shows "anionic diode" effects (due to predominant anion conductivity). The current rectification, or "ionic diode" behaviour, is investigated as a function of NaCl concentration, pH, microhole diameter, and molecular weight of the chitosan dopant. Future applications are envisaged exploiting the surface charge induced switching of diode currents for signal amplification in sensing.

Plasticizing Effects of Polyamines in Protein-Based Films

PubMed Central

Sabbah, Mohammed; Di Pierro, Prospero; Giosafatto, C. Valeria L.; Esposito, Marilena; Mariniello, Loredana; Regalado-Gonzales, Carlos; Porta, Raffaele

2017-01-01

Zeta potential and nanoparticle size were determined on film forming solutions of native and heat-denatured proteins of bitter vetch as a function of pH and of different concentrations of the polyamines spermidine and spermine, both in the absence and presence of the plasticizer glycerol. Our results showed that both polyamines decreased the negative zeta potential of all samples under pH 8.0 as a consequence of their ionic interaction with proteins. At the same time, they enhanced the dimension of nanoparticles under pH 8.0 as a result of macromolecular aggregations. By using native protein solutions, handleable films were obtained only from samples containing either a minimum of 33 mM glycerol or 4 mM spermidine, or both compounds together at lower glycerol concentrations. However, 2 mM spermidine was sufficient to obtain handleable film by using heat-treated samples without glycerol. Conversely, brittle materials were obtained by spermine alone, thus indicating that only spermidine was able to act as an ionic plasticizer. Lastly, both polyamines, mainly spermine, were found able to act as “glycerol-like” plasticizers at concentrations higher than 5 mM under experimental conditions at which their amino groups are undissociated. Our findings open new perspectives in obtaining protein-based films by using aliphatic polycations as components. PMID:28489025

Soil pH effects on the comparative toxicity of dissolved zinc, non-nano and nano ZnO to the earthworm Eisenia fetida.

PubMed

Heggelund, Laura R; Diez-Ortiz, Maria; Lofts, Stephen; Lahive, Elma; Jurkschat, Kerstin; Wojnarowicz, Jacek; Cedergreen, Nina; Spurgeon, David; Svendsen, Claus

2014-08-01

To determine how soil properties influence nanoparticle (NP) fate, bioavailability and toxicity, this study compared the toxicity of nano zinc oxide (ZnO NPs), non-nano ZnO and ionic ZnCl2 to the earthworm Eisenia fetida in a natural soil at three pH levels. NP characterisation indicated that reaction with the soil media greatly controls ZnO properties. Three main conclusions were drawn. First that Zn toxicity, especially for reproduction, was influenced by pH for all Zn forms. This can be linked to the influence of pH on Zn dissolution. Secondly, that ZnO fate, toxicity and bioaccumulation were similar (including relationships with pH) for both ZnO forms, indicating the absence of NP-specific effects. Finally, earthworm Zn concentrations were higher in worms exposed to ZnO compared to ZnCl2, despite the greater toxicity of the ionic form. This observation suggests the importance of considering the relationship between uptake and toxicity in nanotoxicology studies.

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

PubMed Central

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

2013-01-01

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

Counterion-induced swelling of ionic microgels

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Tang, Qiyun

2016-10-01

Ionic microgel particles, when dispersed in a solvent, swell to equilibrium sizes that are governed by a balance between electrostatic and elastic forces. Tuning of particle size by varying external stimuli, such as pH, salt concentration, and temperature, has relevance for drug delivery, microfluidics, and filtration. To model swelling of ionic microgels, we derive a statistical mechanical theorem, which proves exact within the cell model, for the electrostatic contribution to the osmotic pressure inside a permeable colloidal macroion. Applying the theorem, we demonstrate how the distribution of counterions within an ionic microgel determines the internal osmotic pressure. By combining the electrostatic pressure, which we compute via both Poisson-Boltzmann theory and molecular dynamics simulation, with the elastic pressure, modeled via the Flory-Rehner theory of swollen polymer networks, we show how deswelling of ionic microgels with increasing concentration of particles can result from a redistribution of counterions that reduces electrostatic pressure. A linearized approximation for the electrostatic pressure, which proves remarkably accurate, provides physical insight and greatly eases numerical calculations for practical applications. Comparing with experiments, we explain why soft particles in deionized suspensions deswell upon increasing concentration and why this effect may be suppressed at higher ionic strength. The failure of the uniform ideal-gas approximation to adequately account for counterion-induced deswelling below close packing of microgels is attributed to neglect of spatial variation of the counterion density profile and the electrostatic pressure of incompletely neutralized macroions.

Response surface optimization of pH and ionic strength for emulsion characteristics of egg yolk.

PubMed

Kurt, S; Zorba, O

2009-11-01

Effects of pH (3.5, 4.5, 6.0, 7.5, and 8.5) and ionic strength (0.05, 0.15, 0.30, 0.45, and 0.55 M NaCl) on emulsion capacity, emulsion stability (ES), apparent yield stress of emulsion (AYS), and emulsion density (ED) of egg yolk were studied by using a model system. Ionic strength and pH had significant (P < 0.01) effects on the emulsion characteristics of egg yolk. Their interaction effects also have been found significant on ES, AYS, and ED. Predicted solutions of ES, emulsion capacity, and ED were minimum. The critical point of ES was determined to be at pH 6.08 and an ionic strength of 0.49 (M NaCl). Predicted solution for AYS was a maximum, which was determined to be at pH 6.04 and an ionic strength of 0.29 (M NaCl). Optimum values of pH and ionic strenght were 4.61 to 7.43 and 0.10 to 0.47, respectively.

Kinetics of the oxidation of hydrogen sulfite by hydrogen peroxide in aqueous solution:. ionic strength effects and temperature dependence

NASA Astrophysics Data System (ADS)

Maaß, Frank; Elias, Horst; Wannowius, Klaus J.

Conductometry was used to study the kinetics of the oxidation of hydrogen sulfite, HSO -3, by hydrogen peroxide in aqueous non-buffered solution at the low concentration level of 10 -5-10 -6 M, typically found in cloud water. The kinetic data confirm that the rate law reported for the pH range 3-6 at higher concentration levels, rate= kH·[H +]·[HSO -3]·[H 2O 2], is valid at the low concentration level and at low ionic strength Ic. At 298 K and Ic=1.5×10 -4 M, third-order rate constant kH was found to be kH=(9.1±0.5)×10 7 M -2 s -1. The temperature dependence of kH led to an activation energy of Ea=29.7±0.9 kJ mol -1. The effect of the ionic strength (adjusted with NaCl) on rate constant kH was studied in the range Ic=2×10 -4-5.0 M at pH=4.5-5.2 by conductometry and stopped-flow spectrophotometry. The dependence of kH on Ic can be described with a semi-empirical relationship, which is useful for the purpose of comparison and extrapolation. The kinetic data obtained are critically compared with those reported earlier.

An empirical equation with tables of smoothed solubilities of methane in water and aqueous sodium chloride solutions up to 25 weight percent, 360 degrees C, and 138 MPa

USGS Publications Warehouse

Haas, John L.

1978-01-01

The total pressure for the system H2O-CH 4 is given by p(total) = P(H2O,t) + exp10[log x(CH 4) - a - b x(CH4)], where P(H2O,t) is the vapor pressure of H2O liquid at the temperature t (?C) and x(CH 4) is the molal concentration of methane in the solution. The terms a and b are functions of temperature only. Where the total pressure and temperature are known, the concentration of methane, x(CH4), is found by iteration. The concentration of methane in a sodium chloride brine, y(CH4), is estimated using the function log y(CH4) = log x(CH4) - A I, where A is the salting out constant and I is the ionic strength. For sodium chloride solutions, the ionic strength is equal to the molality of the salt. The equations are valid to 360?C, 138 MPa, and 25 weight percent sodium chloride.

The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

NASA Astrophysics Data System (ADS)

Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

2013-06-01

The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering capacity to previously studied non-halophilic bacteria. The titration data were used to determine the number of types, concentrations, and associated deprotonation constants of functional groups on the bacterial surface; the neptunium adsorption measurements were used to constrain binding constant values for the important neptunium (V)-bacterial surface species. Together, these results can be incorporated into geochemical speciation models to aid in the prediction of neptunium (V) mobility in complex bacteria-bearing geochemical systems.

Adsorption of polyelectrolyte-like proteins to silica surfaces and the impact of pH on the response to ionic strength. A Monte Carlo simulation and ellipsometry study.

PubMed

Hyltegren, Kristin; Skepö, Marie

2017-05-15

The adsorbed amount of the polyelectrolyte-like protein histatin 5 on a silica surface depends on the pH and the ionic strength of the solution. Interestingly, an increase in ionic strength affects the adsorbed amount differently depending on the pH of the solution, as shown by ellipsometry measurements (Hyltegren, 2016). We have tested the hypothesis that the same (qualitative) trends can be found also from a coarse-grained model that takes all charge-charge interactions into account within the frameworks of Gouy-Chapman and Debye-Hückel theories. Using the same coarse-grained model as in our previous Monte Carlo study of single protein adsorption (Hyltegren, 2016), simulations of systems with many histatin 5 molecules were performed and then compared with ellipsometry measurements. The strength of the short-ranged attractive interaction between the protein and the surface was varied. The coarse-grained model does not qualitatively reproduce the pH-dependence of the experimentally observed trends in adsorbed amount as a function of ionic strength. However, the simulations cast light on the balance between electrostatic attraction between protein and surface and electrostatic repulsion between adsorbed proteins, the deficiencies of the Langmuir isotherm, and the implications of protein charge regulation in concentrated systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Novel self-powered pH indicator using ionic polymeric gel muscles

NASA Astrophysics Data System (ADS)

Shahinpoor, Mohsen

1994-05-01

A novel design for a torsional spring-loaded pH indicator using ionic polymeric gel fibrous muscles is presented. The essential parts of the proposed self-powered pH indicator are a pair of co-axial and concentric cylinders, an assembly of fibrous polyacrylonitrile (PAN) muscles, a torsional spring, and a dial indicator. The two co-axial cylinders are such that the inner cylinder may pivotally rotate about the central rotation axis that is fixed to the inner bottom or side of the outer cylinder. The outer cylinder also serves as a reservoir for any liquid whose pH is to be determined either statically or dynamically. The internal cylindrical drum is further equipped with a dial indicator on one of its outer end caps such that when a pH environment is present the contraction or expansion of the PAN fibers cause the inner drum to rotate and thus give a reading of the dial indicator. The motion of the dial indicator may also be converted to an electrical signal (voltage) for digital electronics display and computer control. A mathematical model is also presented for the dynamic response of the self-powered pH indicator made with contractile PAN fiber bundle assemblies.

Regulating NH4+, N0-, and K+ concentration and proportions improves in vitro tissue growth.

USDA-ARS?s Scientific Manuscript database

A mixture-amount experiment that simultaneously varied both the ratios and total ionic concentration (from 20-100 mM) of NH4+, NO3+, and K+ was used to maximize sweet orange callus growth cv. ‘Hamlin.’ These experiments were free of ion confounding effects, i.e. ions added via pH adjustments and sa...

Phosphorylation and Ionic Strength Alter the LRAP-HAP Interface in the N-terminus

PubMed Central

Lu, Jun-xia; Xu, Yimin Sharon; Shaw, Wendy J.

2013-01-01

The conditions present during enamel crystallite development change dramatically as a function of time, including the pH, protein concentration, surface type and ionic strength. In this work, we investigate the role that two of these changing conditions, pH and ionic strength, have in modulating the interaction of the amelogenin, LRAP, with hydroxyapatite (HAP). Using solid state NMR dipolar recoupling and chemical shift data, we investigate the structure, orientation and dynamics of three regions in the N-terminus of the protein, L15 to V19, V19 to L23 and K24 to S28. These regions are also near the only phosphorylated residue in the protein, pS16, therefore, changes in the LRAP-HAP interaction as a function of phosphorylation (LRAP(−P) vs. LRAP(+P)) were also investigated. All of the regions and conditions studied for the surface immobilized proteins showed restricted motion, with indications of slightly more mobility under all conditions for L15(+P) and K24(−P). The structure and orientation of the LRAP-HAP interaction in the N-terminus of the phosphorylated protein is very stable to changing solution conditions. From REDOR dipolar recoupling data, the structure and orientation in the region L15V19(−P) did not change significantly as a function of pH or ionic strength. The structure and orientation of the region V19L23(+P) were also stable to changes in pH, with the only significant change observed at high ionic strength, where the region becomes extended, suggesting this may be an important region in regulating mineral development. Chemical shift studies also suggest minimal changes in all three regions studied for both LRAP(−P) and LRAP(+P) as a function of pH or ionic strength and reveal that K24 has multiple resolvable resonance, suggestive of two coexisting structures. Phosphorylation also alters the LRAP-HAP interface. All of the three residues investigated (L15, V19, and K24) are closer to the surface in LRAP(+P), but K24S28 also changes structure as a result of phosphorylation, from a random coil to a largely helical structure, and V19L23 becomes more extended at high ionic strength when phosphorylated. These observations suggest that ionic strength and dephosphorylation may provide switching mechanisms to trigger a change in the function of the N-terminus. PMID:23477367

Adsorption isotherm, kinetic and mechanism of expanded graphite for sulfadiazine antibiotics removal from aqueous solutions.

PubMed

Zhang, Ling; Wang, Yong; Jin, SuWan; Lu, QunZan; Ji, Jiang

2017-10-01

The adsorption of sulfadiazine from water by expanded graphite (EG), a low cost and environmental-friendly adsorbent, was investigated. Several adsorption parameters (including the initial sulfadiazine concentration, contact time, pH of solution, ionic strength and temperature) were studied. Results of equilibrium experiments indicated that adsorption of sulfadiazine onto EG were better described by the Langmuir and Tempkin models than by the Freundlich model. The maximum adsorption capacity is calculated to be 16.586 mg/g at 298 K. The kinetic data were analyzed by pseudo-first-order, pseudo-second-order and intraparticle models. The results indicated that the adsorption process followed pseudo-second-order kinetics and may be controlled by two steps. Moreover, the pH significantly influenced the adsorption process, with the relatively high adsorption capacity at pH 2-10. The electrostatic and hydrophobic interactions are manifested to be two main mechanisms for sulfadiazine adsorption of EG. Meanwhile, the ionic concentration of Cl - slightly impacted the removal of sulfadiazine. Results of thermodynamics analysis showed spontaneous and exothermic nature of sulfadiazine adsorption on EG. In addition, regeneration experiments imply that the saturated EG could be reused for sulfadiazine removal by immersing sodium hydroxide.

Application of an immobilized ionic liquid for the passive sampling of perfluorinated substances in water.

PubMed

Wang, Lei; Gong, Xinying; Wang, Ruonan; Gan, Zhiwei; Lu, Yuan; Sun, Hongwen

2017-09-15

Ionic liquids have been used to efficiently extract a wide range of polar and nonpolar organic contaminants from water. In this study, imidazole ionic liquids immobilized on silica gel were synthesized through a chemical bonding method, and the immobilized dodecylimidazolium ionic liquid was selected as the receiving phase material in a POCIS (polar organic chemical integrative sampler) like passive sampler to monitor five perfluoroalkyl substances (PFASs) in water. Twenty-one days of integrative accumulation was conducted in laboratory scale experiments, and the accumulated PFASs in the samplers were eluted and analyzed by high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The partitioning coefficients of most PFASs between sampler sorbents and water in the immobilized ionic liquid (IIL)-sampler were higher than those in the HLB-sampler, especially for compounds with shorter alkyl chains. The effects of flow velocity, temperature, dissolved organic matter (DOM) and pH on the uptake of these analytes were also evaluated. Under the experimental conditions, the uptake of PFASs in the IIL-sampler slightly increased with the flow velocity and temperature, while different influences of DOM and pH on the uptake of PFAS homologues with short or long chains were observed. The designed IIL-samplers were applied in the influent and effluent of a wastewater treatment plant. All five PFASs could be accumulated in the samplers, with concentrations ranging from 6.5×10 -3 -3.6×10 -1 nmol/L in the influent and from 1.3×10 -2 -2.2×10 -1 nmol/L in the effluent. The calculated time-weighted average concentrations of most PFASs fit well with the detected concentrations of the active sampling, indicating the applicability of the IIL-sampler in monitoring these compounds in water. Copyright © 2017 Elsevier B.V. All rights reserved.

Chiral separation of phenylalanine and tryptophan by capillary electrophoresis using a mixture of β-CD and chiral ionic liquid ([TBA] [L-ASP]) as selectors.

PubMed

Yujiao, Wu; Guoyan, Wang; Wenyan, Zhao; Hongfen, Zhang; Huanwang, Jing; Anjia, Chen

2014-05-01

In this paper, a simple, effective and green capillary electrophoresis separation and detection method was developed for the quantification of underivatized amino acids (dl-phenylalanine; dl-tryptophan) using β-Cyclodextrin and chiral ionic liquid ([TBA] [l-ASP]) as selectors. Separation parameters such as buffer concentrations, pH, β-CD and chiral ionic liquid concentrations and separation voltage were investigated for the enantioseparation in order to achieve the maximum possible resolution. A good separation was achieved in a background electrolyte composed of 15 mm sodium tetraborate, 5 mm β-CD and 4 mm chiral ionic liquid at pH 9.5, and an applied voltage of 10 kV. Under optimum conditions, linearity was achieved within concentration ranges from 0.08 to 10 µg/mL for the analytes with correlation coefficients from 0.9956 to 0.9998, and the analytes were separated in less than 6 min with efficiencies up to 970,000 plates/m. The proposed method was successfully applied to the determination of amino acid enantiomers in compound amino acids injections, such as 18AA-I, 18AA-II and 3AA.

Amperometric glucose biosensor with remarkable acid stability based on glucose oxidase entrapped in colloidal gold-modified carbon ionic liquid electrode.

PubMed

Liu, Xiaoying; Zeng, Xiandong; Mai, Nannan; Liu, Yong; Kong, Bo; Li, Yonghong; Wei, Wanzhi; Luo, Shenglian

2010-08-15

A colloidal gold-modified carbon ionic liquid electrode was constructed by mixing colloidal gold-modified graphite powder with a solid room temperature ionic liquid n-octyl-pyridinium hexafluorophosphate (OPPF(6)). Glucose oxidase (GOD) was entrapped in this composite matrix and maintained its bioactivity well and displayed excellent stability. The effect conditions of pH, applied potential and GOD loading were examined. Especially, the glucose oxidase entrapped in this carbon ionic liquid electrode fully retained its activity upon stressing in strongly acidic conditions (pH 2.0) for over one hour. The proposed biosensor responds to glucose linearly over concentration range of 5.0x10(-6) to 1.2x10(-3) and 2.6x10(-3) to 1.3x10(-2) M, and the detection limit is 3.5x10(-6) M. The response time of the biosensor is fast (within 10s), and the life time is over two months. The effects of electroactive interferents, such as ascorbic acid, uric acid, can be significantly reduced by a Nafion film casting on the surface of resulting biosensor. Copyright 2010 Elsevier B.V. All rights reserved.

Study of pH-responsive microgels containing methacrylic acid: effects of particle composition and added calcium.

PubMed

Dalmont, Helene; Pinprayoon, Orawan; Saunders, Brian R

2008-03-18

pH-responsive microgel dispersions contain cross-linked polymer particles that swell when the pH approaches the pKa of the ionic monomer incorporated within the particles. In recent work from our group, it was demonstrated that the mechanical properties of degenerated intervertebral discs (IVDs) could be restored to normal values by injection of pH-responsive microgel dispersions (Saunders, J. M.; Tong, T.; LeMaitre, C.; Freemont, A. J.; Saunders, B. R. Soft Matter 2007, 3, 486). These dispersions change from a fluid to a gel with increasing pH. The present work investigates the pH-dependent properties of dispersions of microgel particles containing MAA (methacrylic acid) and also the effects of added Ca2+. Two microgels are discussed: microgel A is poly(EA/MAA/AM) (EA and AM are ethyl acrylate and allyl methacrylate), and microgel B is poly(EA/MAA/BDDA) (butanediol diacrylate). The pH-dependent particle properties investigated include hydrodynamic diameters and electrophoretic mobilities. The critical coagulation concentrations (CCC) of dilute dispersions and the elastic modulus (G') of concentrated, gelled microgel dispersions were also investigated. In the absence of added Ca2+, the particle swelling and G' were smallest and largest, respectively, for microgel A. The changes in hydrodynamic diameter and mobility with pH were explained in terms of a core-shell swelling mechanism. Added Ca2+ was found to significantly decrease the CCCs, extents of particle swelling, and magnitude of the electrophoretic mobility. This was attributed to the ionic cross-linking of neighboring RCOO- groups by Ca2+. It is suggested that the formation of ionic cross-links is inefficient within the microgel particles because of the presence of covalent cross-links that oppose the large-scale conformational rearrangement of neighboring RCOO- groups. The effect of Ca2+ on the properties of the gelled dispersions is important from the viewpoint of potential application in vivo. Rheological studies of the gelled microgel dispersions showed that added Ca2+ did not have a specific influence on G'. The differences observed in the presence of Ca2+ were attributed to ionic strength effects (screening). The key parameter that controls G' of the gelled microgel dispersions is pH. The results from this work suggest that the elasticity of the gels would be slightly reduced in vivo as a consequence of the high ionic strength present.

Removal of Radionuclides from Waste Water at Fukushima Daiichi Nuclear Power Plant: Desalination and Adsorption Methods - 13126

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

Kani, Yuko; Kamosida, Mamoru; Watanabe, Daisuke

Waste water containing high levels of radionuclides due to the Fukushima Daiichi Nuclear Power Plant accident, has been treated by the adsorption removal and reverse-osmosis (RO) desalination to allow water re-use for cooling the reactors. Radionuclides in the waste water are collected in the adsorbent medium and the RO concentrate (RO brine) in the water treatment system currently operated at the Fukushima Daiichi site. In this paper, we have studied the behavior of radionuclides in the presently applied RO desalination system and the removal of radionuclides in possible additional adsorption systems for the Fukushima Daiichi waste water treatment. Regarding themore » RO desalination system, decontamination factors (DFs) of the elements present in the waste water were obtained by lab-scale testing using an RO unit and simulated waste water with non-radioactive elements. The results of the lab-scale testing using representative elements showed that the DF for each element depended on its hydrated ionic radius: the larger the hydrated ionic radius of the element, the higher its DF is. Thus, the DF of each element in the waste water could be estimated based on its hydrated ionic radius. For the adsorption system to remove radionuclides more effectively, we studied adsorption behavior of typical elements, such as radioactive cesium and strontium, by various kinds of adsorbents using batch and column testing. We used batch testing to measure distribution coefficients (K{sub d}s) for cesium and strontium onto adsorbents under different brine concentrations that simulated waste water conditions at the Fukushima Daiichi site. For cesium adsorbents, K{sub d}s with different dependency on the brine concentration were observed based on the mechanism of cesium adsorption. As for strontium, K{sub d}s decreased as the brine concentration increased for any adsorbents which adsorbed strontium by intercalation and by ion exchange. The adsorbent titanium oxide had higher K{sub d}s and it was used for the column testing to obtain breakthrough curves under various conditions of pH and brine concentration. The breakthrough point had a dependency on pH and the brine concentration. We found that when the pH was higher or the brine concentration was lower, the longer it took to reach the breakthrough point. The inhibition of strontium adsorption by alkali earth metals would be diminished for conditions of higher pH and lower brine concentration. (authors)« less

Origins--2.

ERIC Educational Resources Information Center

Fergusson, J. E.

1979-01-01

The abundance and distribution of the elements on the earth can, in part, be explained in terms of chemical properties such as reduction potentials, solubilities, ionic size, densities, melting points, and pH. The relative abundance of the elements, their distribution, and their concentration, particularly on the earth, are discussed. (Author/BB)

Application of ionic liquids based enzyme-assisted extraction of chlorogenic acid from Eucommia ulmoides leaves.

PubMed

Liu, Tingting; Sui, Xiaoyu; Li, Li; Zhang, Jie; Liang, Xin; Li, Wenjing; Zhang, Honglian; Fu, Shuang

2016-01-15

A new approach for ionic liquid based enzyme-assisted extraction (ILEAE) of chlorogenic acid (CGA) from Eucommia ulmoides is presented in which enzyme pretreatment was used in ionic liquids aqueous media to enhance extraction yield. For this purpose, the solubility of CGA and the activity of cellulase were investigated in eight 1-alkyl-3-methylimidazolium ionic liquids. Cellulase in 0.5 M [C6mim]Br aqueous solution was found to provide better performance in extraction. The factors of ILEAE procedures including extraction time, extraction phase pH, extraction temperatures and enzyme concentrations were investigated. Moreover, the novel developed approach offered advantages in term of yield and efficiency compared with other conventional extraction techniques. Scanning electronic microscopy of plant samples indicated that cellulase treated cell wall in ionic liquid solution was subjected to extract, which led to more efficient extraction by reducing mass transfer barrier. The proposed ILEAE method would develope a continuous process for enzyme-assisted extraction including enzyme incubation and solvent extraction process. In this research, we propose a novel view for enzyme-assisted extraction of plant active component, besides concentrating on enzyme facilitated cell wall degradation, focusing on improvement of bad permeability of ionic liquids solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Development of a downhole tool measuring real-time concentration of ionic tracers and pH in geothermal reservoirs

NASA Astrophysics Data System (ADS)

Hess, Ryan F.; Boyle, Timothy J.; Limmer, Steven; Yelton, William G.; Bingham, Samuel; Stillman, Greg; Lindblom, Scott; Cieslewski, Grzegorz

2014-06-01

For enhanced or Engineered Geothermal Systems (EGS) geothermal brine is pumped to the surface via the production wells, the heat extracted to turn a turbine to generate electricity, and the spent brine re-injected via injection wells back underground. If designed properly, the subsurface rock formations will lead this water back to the extraction well as heated brine. Proper monitoring of these geothermal reservoirs is essential for developing and maintaining the necessary level of productivity of the field. Chemical tracers are commonly used to characterize the fracture network and determine the connectivity between the injection and production wells. Currently, most tracer experiments involve injecting the tracer at the injection well, manually collecting liquid samples at the wellhead of the production well, and sending the samples off for laboratory analysis. While this method provides accurate tracer concentration data at very low levels of detection, it does not provide information regarding the location of the fractures which were conducting the tracer between wellbores. Sandia is developing a high-temperature electrochemical sensor capable of measuring tracer concentrations and pH downhole on a wireline tool. The goal of this effort is to collect real-time pH and ionic tracer concentration data at temperatures up to 225 °C and pressures up to 3000 psi. In this paper, a prototype electrochemical sensor and the initial data obtained will be presented detailing the measurement of iodide tracer concentrations at high temperature and pressure in a newly developed laboratory scale autoclave.

Efficient Removal of Tetracycline from Aqueous Media with a Fe3O4 Nanoparticles@graphene Oxide Nanosheets Assembly

PubMed Central

Hu, Xinjiang; Zhao, Yunlin; Wang, Hui; Tan, Xiaofei; Yang, Yuanxiu; Liu, Yunguo

2017-01-01

A readily separated composite was prepared via direct assembly of Fe3O4 magnetic nanoparticles onto the surface of graphene oxide (GO) (labeled as Fe3O4@GO) and used as an adsorbent for the removal of tetracycline (TC) from wastewater. The effects of external environmental conditions, such as pH, ionic strength, humic acid (HA), TC concentration, and temperature, on the adsorption process were studied. The adsorption data were analyzed by kinetics and isothermal models. The results show that the Fe3O4@GO composite has excellent sorptive properties and can efficiently remove TC. At low pH, the adsorption capacity of Fe3O4@GO toward TC decreases slowly with increasing pH value, while the adsorption capacity decreases rapidly at higher pH values. The ionic strength has insignificant effect on TC adsorption. The presence of HA affects the affinity of Fe3O4@GO to TC. The pseudo-second-order kinetics model and Langmuir model fit the adsorption data well. When the initial concentration of TC is 100 mg/L, a slow adsorption process dominates. Film diffusion is the rate limiting step of the adsorption. Importantly, Fe3O4@GO has good regeneration performance. The above results are of great significance to promote the application of Fe3O4@GO in the treatment of antibiotic wastewater. PMID:29194395

Quantification of surface charge density and its effect on boundary slip.

PubMed

Jing, Dalei; Bhushan, Bharat

2013-06-11

Reduction of fluid drag is important in the micro-/nanofluidic systems. Surface charge and boundary slip can affect the fluid drag, and surface charge is also believed to affect boundary slip. The quantification of surface charge and boundary slip at a solid-liquid interface has been widely studied, but there is a lack of understanding of the effect of surface charge on boundary slip. In this paper, the surface charge density of borosilicate glass and octadecyltrichlorosilane (OTS) surfaces immersed in saline solutions with two ionic concentrations and deionized (DI) water with different pH values and electric field values is quantified by fitting experimental atomic force microscopy (AFM) electrostatic force data using a theoretical model relating the surface charge density and electrostatic force. Results show that pH and electric field can affect the surface charge density of glass and OTS surfaces immersed in saline solutions and DI water. The mechanisms of the effect of pH and electric field on the surface charge density are discussed. The slip length of the OTS surface immersed in saline solutions with two ionic concentrations and DI water with different pH values and electric field values is measured, and their effects on the slip length are analyzed from the point of surface charge. Results show that a larger absolute value of surface charge density leads to a smaller slip length for the OTS surface.

Imaging of pH in vivo using hyperpolarized 13C-labelled zymonic acid

PubMed Central

Düwel, Stephan; Hundshammer, Christian; Gersch, Malte; Feuerecker, Benedikt; Steiger, Katja; Buck, Achim; Walch, Axel; Haase, Axel; Glaser, Steffen J.; Schwaiger, Markus; Schilling, Franz

2017-01-01

Natural pH regulatory mechanisms can be overruled during several pathologies such as cancer, inflammation and ischaemia, leading to local pH changes in the human body. Here we demonstrate that 13C-labelled zymonic acid (ZA) can be used as hyperpolarized magnetic resonance pH imaging sensor. ZA is synthesized from [1-13C]pyruvic acid and its 13C resonance frequencies shift up to 3.0 p.p.m. per pH unit in the physiological pH range. The long lifetime of the hyperpolarized signal enhancement enables monitoring of pH, independent of concentration, temperature, ionic strength and protein concentration. We show in vivo pH maps within rat kidneys and subcutaneously inoculated tumours derived from a mammary adenocarcinoma cell line and characterize ZA as non-toxic compound predominantly present in the extracellular space. We suggest that ZA represents a reliable and non-invasive extracellular imaging sensor to localize and quantify pH, with the potential to improve understanding, diagnosis and therapy of diseases characterized by aberrant acid-base balance. PMID:28492229

ELECTROPHORETIC MOBILITIES OF ESCHERICHIA COLI 0157:H7 AND WILD-TYPE ESCHERICHIA COLI STRAINS

EPA Science Inventory

The electrophoretic mobility (EPM) of a number of human-virulent and "wild-type" Escherichia coli strains in phosphate buffered water was measured. The impact of pH, ionic strength, cation type (valence) and concentration, and bacterial strain on the EPM was investigated. Resul...

Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

NASA Astrophysics Data System (ADS)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

Retention and transport of graphene oxide in water-saturated limestone media.

PubMed

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.

The binding of glucose to yeast hexokinase monomers is independent of ionic strength.

PubMed

Mayes, E L; Hoggett, J G; Kellett, G L

1982-05-01

Hoggett & Kellett [Eur. J. Biochem. 66, 65-77 (1976)] have reported that the binding of glucose to the monomer of hexokinase PII isoenzyme is independent of ionic strength, in contrast to the subsequent claim of Feldman & Kramp [Biochemistry 17, 1541-1547 (1978)] that the binding is strongly dependent on ionic strength. Since measurements with native hexokinase P forms are complicated by the fact that the enzyme exists in a monomer-dimer association-dissociation equilibrium, we have now studied the binding of glucose to the proteolytically-modified S forms which are monomeric. At pH 8.5, the affinity of glucose for both SI and SII monomers is independent of salt concentration over the range of KCl concentrations 0-1.0 mol . dm-3 and is in good agreement with that of the corresponding P forms in both low and high salt. These observations confirm that the binding of glucose to hexokinase P monomers is independent of ionic strength and that the affinity of glucose for the hexokinase PII monomer is about an order of magnitude greater than that for the dimer.

The binding of glucose to yeast hexokinase monomers is independent of ionic strength.

PubMed Central

Mayes, E L; Hoggett, J G; Kellett, G L

1982-01-01

Hoggett & Kellett [Eur. J. Biochem. 66, 65-77 (1976)] have reported that the binding of glucose to the monomer of hexokinase PII isoenzyme is independent of ionic strength, in contrast to the subsequent claim of Feldman & Kramp [Biochemistry 17, 1541-1547 (1978)] that the binding is strongly dependent on ionic strength. Since measurements with native hexokinase P forms are complicated by the fact that the enzyme exists in a monomer-dimer association-dissociation equilibrium, we have now studied the binding of glucose to the proteolytically-modified S forms which are monomeric. At pH 8.5, the affinity of glucose for both SI and SII monomers is independent of salt concentration over the range of KCl concentrations 0-1.0 mol . dm-3 and is in good agreement with that of the corresponding P forms in both low and high salt. These observations confirm that the binding of glucose to hexokinase P monomers is independent of ionic strength and that the affinity of glucose for the hexokinase PII monomer is about an order of magnitude greater than that for the dimer. PMID:7052060

Effects of Solution Chemistry on Nano-Bubbles Transport in Saturated Porous Media

NASA Astrophysics Data System (ADS)

Hamamoto, S.; Takemura, T.; Suzuki, K.; Nihei, N.; Nishimura, T.

2017-12-01

Nano-bubbles (NBs) have a considerable potential for the remediation of soil and groundwater contaminated by organic compounds, especially when used in conjunction with bioremediation technologies. Understanding the transport mechanisms of NBs in soils is essential to optimize NB-based remediation techniques. In this study, one-dimensional column transport experiments using glass beads with 0.1 mm size were conducted, where NBs created by oxygen gas at different pH and ionic strength were injected to the column at the constant flow rate. The NBs concentration in the effluent was quantified using a resonant mass measurement technique. Effects of solution chemistry of the NBs water on NB transport in the porous media were investigated. The results showed that attachment of NBs was enhanced under higher ionic strength and lower pH conditions, caused by the reduced repulsive force between NBs and glass beads. In addition, bubble size distributions in the effluents showed that relatively larger NBs were retained in the column. This trend was more significant at lower pH condition.

Removal of trace metal contaminants from potable water by electrocoagulation.

PubMed

Heffron, Joe; Marhefke, Matt; Mayer, Brooke K

2016-06-21

This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency.

Removal of trace metal contaminants from potable water by electrocoagulation

NASA Astrophysics Data System (ADS)

Heffron, Joe; Marhefke, Matt; Mayer, Brooke K.

2016-06-01

This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency.

Chemical factors influencing colloid-facilitated transport of contaminants in porous media

USGS Publications Warehouse

Roy, Sujoy B.; Dzombak, David A.

1997-01-01

The effects of colloids on the transport of two strongly sorbing solutesa hydrophobic organic compound, phenanthrene, and a metal ion, Ni2+were studied in sand-packed laboratory columns under different pH and ionic strength conditions. Two types of column experiments were performed as follows:  (i) sorption/mobilization experiments where the contaminant was first sorbed in the column under conditions where no colloids were released and mobilized under conditions where colloids were released as a result of ionic strength reduction in the influent; and (ii) transport experiments where the contaminant, dissolved or sorbed on colloids, was injected into columns packed with a strongly sorbing porous medium. In the first type of experiment, contaminant mobilization was significant only when all releasable colloids were flushed from the column. In all other cases, although high colloid particle concentrations were encountered, there was no marked effect on total contaminant concentrations. In the second type of experiment, colloid deposition efficiencies were shown to control the enhancement of transport. The deposition efficiency was a function of the pH (for a high organic content sand) and of the contaminant concentration (for a charged species such as Ni2+).

Struvite formation and decomposition characteristics for ammonia and phosphorus recovery: A review of magnesium-ammonia-phosphate interactions.

PubMed

Tansel, Berrin; Lunn, Griffin; Monje, Oscar

2018-03-01

Struvite (MgNH 4 PO 4 ·6H 2 O) forms in aqueous systems with high ammonia and phosphate concentrations. However, conditions that result into struvite formation are highly dependent on the ionic compositions, temperature, pH, and ion speciation characteristics. The primary ions involved in struvite formation have complex interactions and can form different crystals depending on the ionic levels, pH and temperature. Struvite as well as struvite analogues (with substitution of monovalent cations for NH 4 + or divalent cations for Mg 2+ ) as well as other crystals can form simultaneously and result in changes in crystal morphology during crystal growth. This review provides the results from experimental and theoretical studies on struvite formation and decomposition studies. Characteristics of NH 4 + or divalent cations for Mg 2+ were evaluated in comparison to monovalent and divalent ions for formation of struvite and its analogues. Struvite crystals forming in wastewater systems are likely to contain crystals other than struvite due to ionic interactions, pH changes, temperature effects and clustering of ions during nucleation and crystal growth. Decomposition of struvite occurs following a series of reactions depending on the rate of heating, temperature and availability of water during heating. Copyright © 2017 Elsevier Ltd. All rights reserved.

The effect of humic acid on the aggregation of titanium dioxide nanoparticles under different pH and ionic strengths.

PubMed

Zhu, Miao; Wang, Hongtao; Keller, Arturo A; Wang, Tao; Li, Fengting

2014-07-15

With the increasingly widespread use of titanium dioxide nanoparticles (TiO2 NPs), the particles' environmental impacts have attracted concern, making it necessary to understand the fate and transport of TiO2 NPs in aqueous media. In this study, we investigated TiO2 NP aggregation caused by the effects of humic acid (HA), ionic strength (IS) and different pH using dynamic light scattering (DLS) to monitor the size distribution of the TiO2 NPs continuously. It was determined that HA can influence the stability of TiO2 NPs through charge neutralization, steric hindrance and bridging effects. In the absence of IS, aggregation was promoted by adding HA only when the pH (pH=4) is less than the point of zero charge for the TiO2 NPs (pHPZC≈6) because HA reduces the zeta potential of the TiO2 NPs via charge neutralization. At pH=4 and when the concentration of HA is 94.5 μg/L, the zeta potential of TiO2 NPs is close to zero, and they reach an aggregation maximum. A higher concentration of HA results in more negatively charged TiO2 NP surfaces, which hinder their aggregation. When the pH is 5.8, HA enhances the negative zeta potential of the TiO2 NPs and increases their stability via electrostatic repulsion and steric hindrance. When the pH (pH=8) is greater than pHpzc, the zeta potential of the TiO2 NPs is high (~40 mV), and it barely changes with increasing HA concentration. Thus, the TiO2 NPs are notably stable, and their size does not grow at pH8. The increase in the critical coagulation concentration (CCC) of TiO2 NPs indicated that there is steric hindrance after the addition of HA. HA can enhance the coagulation of TiO2 NPs, primarily due to bridging effect. These findings are useful in understanding the size change of TiO2 NPs, as well as the removal of TiO2 NPs and HA from aqueous media. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation of Chitosan Nanoparticles: A Study of Influencing Factors

NASA Astrophysics Data System (ADS)

Thakur, Anupama; Taranjit

2011-12-01

Chitosan (CS), a cationic polysaccharide, offers great advantages for ionic interactions with negatively charged species such as sodium tripolyphosphate (STPP) leading to the formation of biocompatible crosslinked chitosan nanoparticles In the present work, an attempt has been made to systematically study the following factors influencing the ionotropic gelation of chitosan with STPP to produce CS nanoparticles: effect of pH of solution, CS concentration, STPP concentration and CS/STPP ratio. The results show that with the increase in CS concentration, the yield of the nanoparticle decreases whereas size increases. The mean size of the prepared nanoparticles varied between 120 to 720 nm and zeta potential between +14 mV to +53 mV . Nanoparticle size and yield was found to be strongly dependent on solution pH. Nanoparticle size decreased with increase in solution pH from 4 to 5 and yield was found to be maximum at pH = 5. With increase in STPP concentration, the size and yield of the nanoparticle increased. The potential of CS nanoparticles to trap amoxicillin trihydrate, taken as the model drug, was also studied. The maximum drug loading capacity was found to be 35% at a solution pH = 5 for 0.2% CS and 0.086% STPP.

Adsorption removal of tannic acid from aqueous solution by polyaniline: Analysis of operating parameters and mechanism.

PubMed

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.

Colloid-probe AFM studies of the interaction forces of proteins adsorbed on colloidal crystals.

PubMed

Singh, Gurvinder; Bremmell, Kristen E; Griesser, Hans J; Kingshott, Peter

2015-04-28

In recent years, colloid-probe AFM has been used to measure the direct interaction forces between colloidal particles of different size or surface functionality in aqueous media, as one can study different forces in symmerical systems (i.e., sphere-sphere geometry). The present study investigates the interaction between protein coatings on colloid probes and hydrophilic surfaces decorated with hexagonally close packed single particle layers that are either uncoated or coated with proteins. Controlled solvent evaporation from aqueous suspensions of colloidal particles (coated with or without lysozyme and albumin) produces single layers of close-packed colloidal crystals over large areas on a solid support. The measurements have been carried out in an aqueous medium at different salt concentrations and pH values. The results show changes in the interaction forces as the surface charge of the unmodified or modified particles, and ionic strength or pH of the solution is altered. At high ionic strength or pH, electrostatic interactions are screened, and a strong repulsive force at short separation below 5 nm dominates, suggesting structural changes in the absorbed protein layer on the particles. We also study the force of adhesion, which decreases with an increment in the salt concentration, and the interaction between two different proteins indicating a repulsive interaction on approach and adhesion on retraction.

Adsorption of malachite green from aqueous solution by using novel chitosan ionic liquid beads.

PubMed

Naseeruteen, Faizah; Hamid, Nur Shahirah Abdul; Suah, Faiz Bukhari Mohd; Ngah, Wan Saime Wan; Mehamod, Faizatul Shimal

2018-02-01

Chitosan ionic liquid beads were prepared from chitosan and 1-butyl-3-methylimidazolium based ionic liquids to remove Malachite Green (MG) from aqueous solutions. Batch adsorption experiments were carried out as a function of initial pH, adsorbent dosage, agitation time and initial MG concentration. The optimum conditions were obtained at pH 4.0, 0.008g of adsorbent dosage and 20min of agitation time were utilized in the kinetic and isotherm studies. Three kinetic models were applied to analyze the kinetic data and pseudo-second order was found to be the best fitted model with R 2 >0.999. In order to determine the adsorption capacity, the sorption data were analyzed using the linear form of Langmuir, Freundlich and Temkin equations. The isotherm was best fitted by Langmuir isotherm model. The maximum adsorption capacity (q max ) obtained from Langmuir isotherm for two chitosan beads 1-butyl-3-methylimidazolium acetate A and 1-butyl-3-methylimidazolium B are 8.07mgg -1 and 0.24mgg -1 respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

1998-05-01

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

Effects of low-level radioactive-waste disposal on water chemistry in the unsaturated zone at a site near Sheffield, Illinois, 1982-84

USGS Publications Warehouse

Peters, C.A.; Striegl, Robert G.; Mills, P.C.; Healy, R.W.

1992-01-01

A 1982-84 field study defined the chemistry of water collected from the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Ill. Chemical data were evaluated to determine the principal, naturally occurring geochemical reactions in the unsaturated zone and to evaluate waste-induced effects on pore-water chemistry. Samples of precipitation, unsaturated-zone pore water, and saturated-zone water were analyzed for specific conductance, pH, alkalinity, major cations and anions, dissolved organic carbon, gross alpha and beta radiation, and tritium. Little change in concentration of most major constituents in the unsaturated-zone water was observed with respect to depth or distance from disposal trenches. Tritium and dissolved organic carbon concentrations were, however, dependent on proximity to trenches. The primary reactions, both on-site and off-site, were carbonate and clay dissolution, cation exchange, and the oxidation of pyrite. The major difference between on-site and off-site inorganic water chemistry resulted from the removal of the Roxana Silt and the Radnor Till Member of the Glasford Formation from on-site. Off-site, the Roxana Silt contributed substantial quantities of sodium to solution from montmorillonite dissolution and associated cation-exchange reactions. The Radnor Till Member provided exchange surfaces for magnesium. Precipitation at the site had an ionic composition of calcium zinc sulfate and an average pH of 4.6. Within 0.3 meter of the land surface, infiltrating rainwater or snowmelt changed to an ionic composition of calcium sulfate off-site and calcium bicarbonate on-site and had an average pH of 7.9; below that depth, pH averaged 7.5 and the ionic composition generally was calcium magnesium bicarbonate. Alkalinity and specific conductance differed primarily according to composition of geologic materials. Tritium concentrations ranged from 0.2 (detection limit) to 1,380 nanocuries per liter. The methods of constructing, installing, and sampling with lysimeters were evaluated to ensure data reliability. These evaluations indicate that, with respect to most constituents, the samples retrieved from the lysimeters accurately represented pore-water chemistry.

Effects of low-level radioactive-waste disposal on water chemistry in the unsaturated zone at a site near Sheffield, Illinois, 1982-84

USGS Publications Warehouse

Peters, C.A.; Striegl, Robert G.; Mills, P.C.; Healy, R.W.

1992-01-01

A 1982-84 field study defined the chemistry of water collected from the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois. Chemical data were evaluated to determine the principal naturally occurring geochemical reactions in the unsaturated zone and to evaluate waste-induced effects on pore-water chemistry. Samples of precipitation, unsaturated-zone pore water, and saturated-zone water were analyzed for specific conductance, pH, alkalinity, major cations and anions, dissolved organic carbon, gross alpha and beta radiation, and tritium. Little change in concentration of most major constituents in the unsaturated-zone water was observed with respect to depth or distance from disposal trenches. Tritium and dissolved organic carbon concentrations were, however, dependent on proximity to trenches. The primary reactions, both on- site and off-site, were carbonate and clay dissolution, cation exchange, and the oxidation of pyrite. The major difference between on-site and off-site inorganic water chemistry resulted from the removal of the Roxana Silt and the Radnor Till Member of the Glasford Formation from on-site. Off-site, the Roxana Silt contributed substantial quantities of sodium to solution from montmorillonite dissolution and associated cation-exchange reactions. The Radnor Till Member provided exchange surfaces for magnesium. Precipitation at the site had an ionic composition of calcium zinc sulfate and an average pH of 4.6. Within 0.3 meter of the land surface, infiltrating rain water or snowmelt changed to an ionic canposition of calcium sulfate off-site and calcium bicarbonate on-site and had an average pH of 7.9; below that depth, pH averaged 7.5 and the ionic composition generally was calcium magnesium bicarbonate. Alkalinity and specific conductance differed primarily according to composition of geologic materials. Tritium concentrations ranged from 0.2 (detection limit) to 1,380 nanocuries per liter. The methods of constructing, installing, and sampling with lysimeters were evaluated to ensure data reliability. These evaluations indicate that, with respect to most constituents, the samples retrieved from the lysimeters accurately represented pore-water chemistry.

Fate and Transport of Elemental Copper (Cu0) Nanoparticles through Saturated Porous Media in the Presence of Organic Materials

EPA Science Inventory

Column experiments were performed to assess the fate and transport of nanoscale elemental copper (Cu0) particles in saturated quartz sands. Both effluent concentrations and retention profiles were measured over a broad range of physicochemical conditions, which included pH, ionic...

Solvent extraction separation of Th-227 and Ac-225 in room temperature ionic liquids

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

Bell, Jason R; Boll, Rose Ann; Dai, Sheng

2012-01-01

The solvent extractions of Th-227 and Ac-225 from the aqueous phase into ionic liquids (ILs) were investigated by using N,N,N ,N - tetraoctyldiglycolamide (TODGA) or di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant. Four ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]), 1-butyl-3-methylimidazolium bis(perfluoroethanesulfonyl)imide ([C4mim][BETI]), 1-butyl-2,3-trimethyleneimidazolium (trifluoromethanesulfonyl)imide [BuI5][NTf2], and 1-benzyl pyridinium bis(trifluoromethanesulfonyl)imide ([PhCH2Py][NTf2]) were used as extraction solvents for separation of Th-227 and Ac-225 in this study. Excellent extraction efficiencies and selectivities were found for Th-227/Ac-225 when HDEHP was used as an extractant in these ionic liquids. The effects of different extractant concentrations in ionic liquids and acidities of the aqueous phase on extraction efficienciesmore » and selectivities of Th-227/Ac-225 are also presented in this article.« less

Polymerized PolyHEMA photonic crystals: pH and ethanol sensor materials.

PubMed

Xu, Xiangling; Goponenko, Alexander V; Asher, Sanford A

2008-03-12

The surface of monodisperse silica particles synthesized using the Stober process were coated with a thin layer of polystyrene. Surface charge groups were attached by a grafting polymerization of styrene sulfonate. The resulting highly charged monodisperse silica particles self-assemble into crystalline colloidal arrays (CCA) in deionized water. We polymerized hydroxyethyl methacrylate (HEMA) around the CCA to form a HEMA-polymerized crystalline colloidal array (PCCA). Hydrofluoric acid was utilized to etch out the silica particles to produce a three-dimensional periodic array of voids in the HEMA PCCA. The diffraction from the embedded CCA sensitively monitors the concentration of ethanol in water because the HEMA PCCA shows a large volume dependence on ethanol due to a decreased Flory-Huggins mixing parameter. Between pure water and 40% ethanol the diffraction shifts across the entire visible spectral region. We accurately modeled the dependence of the diffraction wavelength on ethanol concentration using Flory theory. We also fabricated a PCCA (which responds to pH changes in both low and high ionic strength solutions) by utilizing a second polymerization to incorporate carboxyl groups into the HEMA PCCA. We were also able to model the pH dependence of diffraction of the HEMA PCCA by using Flory theory. An unusual feature of the pH response is a hysteresis in response to titration to higher and lower pH. This hysteresis results from the formation of a Donnan potential at high pH which shifts the ionic equilibrium. The kinetics of equilibration is very slow due to the ultralow diffusion constant of protons in the carboxylated PCCA as predicted earlier by the Tanaka group.

Ionic imbalance induced self-propulsion of liquid metals

PubMed Central

Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F.; O'Mullane, Anthony P.; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-zadeh, Kourosh

2016-01-01

Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems. PMID:27488954

Ionic imbalance induced self-propulsion of liquid metals.

PubMed

Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F; O'Mullane, Anthony P; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-Zadeh, Kourosh

2016-08-04

Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems.

Ionic imbalance induced self-propulsion of liquid metals

NASA Astrophysics Data System (ADS)

Zavabeti, Ali; Daeneke, Torben; Chrimes, Adam F.; O'Mullane, Anthony P.; Zhen Ou, Jian; Mitchell, Arnan; Khoshmanesh, Khashayar; Kalantar-Zadeh, Kourosh

2016-08-01

Components with self-propelling abilities are important building blocks of small autonomous systems and the characteristics of liquid metals are capable of fulfilling self-propulsion criteria. To date, there has been no exploration regarding the effect of electrolyte ionic content surrounding a liquid metal for symmetry breaking that generates motion. Here we show the controlled actuation of liquid metal droplets using only the ionic properties of the aqueous electrolyte. We demonstrate that pH or ionic concentration gradients across a liquid metal droplet induce both deformation and surface Marangoni flow. We show that the Lippmann dominated deformation results in maximum velocity for the self-propulsion of liquid metal droplets and illustrate several key applications, which take advantage of such electrolyte-induced motion. With this finding, it is possible to conceive the propulsion of small entities that are constructed and controlled entirely with fluids, progressing towards more advanced soft systems.

Enhancing Natural Attenuation through Bioaugmentation with Aerobic Bacteria that Degrade cis-1,2-Dichloroethene

DTIC Science & Technology

2010-01-01

mg/L; low ionic strength (conductivity ᝿ milliSiemens per centimeter [mS/cm]); a pH of 6.5 to 8; and relatively low concentrations of TCE, 1,2-DCA...include: • Groundwater dissolved oxygen (DO) levels as low as 0.01 mg/L and as high as 8 mg/L; • Groundwater with low ionic strength (conductivity ᝿...held at 980°C. The chlorinated ethene was oxidized in the oven to CO2 and water. The water was removed via a Nafion ™ membrane water trap and the CO2

Thiacarbocyanine as ligand in dye-affinity chromatography for protein purification. II. Dynamic binding capacity using lysozyme as a model.

PubMed

Boto, R E F; Anyanwu, U; Sousa, F; Almeida, P; Queiroz, J A

2009-09-01

A constant development of dye-affinity chromatography to replace more traditional techniques is verified, with the aim of increasing specificity in the purification of biomolecules. The establishment of a new dye-affinity chromatographic support imposes their complete characterization, namely with relation to the binding capacity for proteins, in order to evaluate its applicability on global purification processes. Following previous studies, the adsorption of lysozyme onto a thiacarbocyanine dye immobilized on beaded cellulose was investigated. The effect of different parameters, such as temperature, ionic strength, pH, protein concentration and flow rate, on the dynamic binding capacity of the support to retain lysozyme was also studied. Increasing the temperature and the lysozyme concentration had a positive effect on the dynamic binding capacity (DBC), whereas increasing the ionic strength and the flow rate resulted in the opposite. It was also discovered that the pH used had an important impact on the lysozyme binding onto the immobilized dye. The maximum DBC value obtained for lysozyme was 8.6 mg/mL, which was achieved at 30 degrees C and pH 9 with a protein concentration of 0.5 mg/mL and a flow rate of 0.05 mL/min. The dissociation constant (K(d)) obtained was 2.61 +/- 0.36 x 10(-5 )m, proving the affinity interaction between the thiacarbocyanine dye ligand and the lysozyme. Copyright (c) 2009 John Wiley & Sons, Ltd.

A comparative study for adsorption of lysozyme from aqueous samples onto Fe3O4 magnetic nanoparticles using different ionic liquids as modifier.

PubMed

Kamran, Sedigheh; Absalan, Ghodratollah; Asadi, Mozaffar

2015-12-01

In this paper, nanoparticles of Fe3O4 as well as their modified forms with different ionic liquids (IL-Fe3O4) were prepared and used for adsorption of lysozyme. The mean size and the surface morphology of the nanoparticles were characterized by TEM, XRD and FTIR techniques. Adsorption studies of lysozyme were performed under different experimental conditions in batch system on different modified magnetic nanoparticles such as, lysozyme concentration, pH of the solution, and contact time. Experimental results were obtained under the optimum operational conditions of pH 9.0 and a contact time of 10 min when initial protein concentrations of 0.05-2.0 mg mL(-1) were used. The isotherm evaluations revealed that the Langmuir model attained better fits to the equilibrium data than the Freundlich model. The maximum obtained adsorption capacities were 370.4, 400.0 500.0 and 526.3 mg of lysozyme for adsorption onto Fe3O4 and modified magnetic nanoparticles by [C4MIM][Br], [C6MIM][Br] and [C8MIM][Br] per gram of adsorbent, respectively. The Langmuir adsorption constants were 0.004, 0.019, 0.024 and 0.012 L mg(-1) for adsorptions of lysozyme onto Fe3O4 and modified magnetic nanoparticles by [C4MIM][Br], [C6MIM][Br] and [C8MIM][Br], respectively. The adsorption capacity of lysozyme was found to be dependent on its chemical structure, pH of the solution, temperature and type of ionic liquid as modifier. The applicability of two kinetic models including pseudo-first order and pseudo-second order model was estimated. Furthermore, the thermodynamic parameters were calculated. Protein could desorb from IL-Fe3O4 nanoparticles by using NaCl solution at pH 9.5 and was reused.

Multiple functional ionic liquids based dispersive liquid-liquid microextraction combined with high performance chromatography for the determination of phenolic compounds in water samples.

PubMed

Sun, Jian-Nan; Chen, Juan; Shi, Yan-Ping

2014-07-01

A new mode of ionic liquid based dispersive liquid-liquid microextraction (IL-DLLME) is developed. In this work, [C6MIm][PF6] was chosen as the extraction solvent, and two kinds of hydrophilic ionic liquids, [EMIm][BF4] and [BSO3HMIm][OTf], functioned as the dispersive solvent. So in the whole extraction procedure, no organic solvent was used. With the aid of SO3H group, the acidic compound was extracted from the sample solution without pH adjustment. Two phenolic compounds, namely, 2-naphthol and 4-nitrophenol were chosen as the target analytes. Important parameters affecting the extraction efficiency, such as the type of hydrophilic ionic liquids, the volume ratio of [EMIm][BF4] to [BSO3HMIm][OTf], type and volume of extraction solvent, pH value of sample solution, sonication time, extraction time and centrifugation time were investigated and optimized. Under the optimized extraction conditions, the method exhibited good sensitivity with the limits of detection (LODs) at 5.5 μg L(-1)and 10.0 μg L(-1) for 4-nitrophenol and 2-naphthol, respectively. Good linearity over the concentration ranges of 24-384 μg L(-1) for 4-nitrophenol and 28-336 μg L(-1) for 2-naphthol was obtained with correlation coefficients of 0.9998 and 0.9961, respectively. The proposed method can directly extract acidic compound from environmental sample or even more complex sample matrix without any pH adjustment procedure. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrostatic Interactions Influence Protein Adsorption (but Not Desorption) at the Silica-Aqueous Interface.

PubMed

McUmber, Aaron C; Randolph, Theodore W; Schwartz, Daniel K

2015-07-02

High-throughput single-molecule total internal reflection fluorescence microscopy was used to investigate the effects of pH and ionic strength on bovine serum albumin (BSA) adsorption, desorption, and interfacial diffusion at the aqueous-fused silica interface. At high pH and low ionic strength, negatively charged BSA adsorbed slowly to the negatively charged fused silica surface. At low pH and low ionic strength, where BSA was positively charged, or in solutions at higher ionic strength, adsorption was approximately 1000 times faster. Interestingly, neither surface residence times nor the interfacial diffusion coefficients of BSA were influenced by pH or ionic strength. These findings suggested that adsorption kinetics were dominated by energy barriers associated with electrostatic interactions, but once adsorbed, protein-surface interactions were dominated by short-range nonelectrostatic interactions. These results highlight the ability of single-molecule techniques to isolate elementary processes (e.g., adsorption and desorption) under steady-state conditions, which would be impossible to measure using ensemble-averaging methods.

Ions, metabolites, and cells: Water as a reporter of surface conditions during bacterial growth.

PubMed

Jarisz, Tasha A; Lane, Sarah; Gozdzialski, Lea; Hore, Dennis K

2018-06-14

Surface-specific nonlinear vibrational spectroscopy, combined with bulk solution measurements and imaging, is used to study the surface conditions during the growth of E. coli. As a result of the silica high surface charge density, the water structure at the silica-aqueous interface is known to be especially sensitive to pH and ionic strength, and surface concentration profiles develop that can be appreciably different from the bulk solution conditions. We illustrate that, in the presence of growing cells, a unique surface micro-environment is established as a result of metabolites accumulating on the silica surface. Even in the subsequent absence of the cells, this surface layer works to reduce the interfacial ionic strength as revealed by the enhanced signal from surface water molecules. In the presence of growing cells, an additional boost in surface water signal is attributed to a local pH that is higher than that of the bulk solution.

Ions, metabolites, and cells: Water as a reporter of surface conditions during bacterial growth

NASA Astrophysics Data System (ADS)

Jarisz, Tasha A.; Lane, Sarah; Gozdzialski, Lea; Hore, Dennis K.

2018-06-01

Surface-specific nonlinear vibrational spectroscopy, combined with bulk solution measurements and imaging, is used to study the surface conditions during the growth of E. coli. As a result of the silica high surface charge density, the water structure at the silica-aqueous interface is known to be especially sensitive to pH and ionic strength, and surface concentration profiles develop that can be appreciably different from the bulk solution conditions. We illustrate that, in the presence of growing cells, a unique surface micro-environment is established as a result of metabolites accumulating on the silica surface. Even in the subsequent absence of the cells, this surface layer works to reduce the interfacial ionic strength as revealed by the enhanced signal from surface water molecules. In the presence of growing cells, an additional boost in surface water signal is attributed to a local pH that is higher than that of the bulk solution.

The effect of pH and ionic strength of dissolution media on in-vitro release of two model drugs of different solubilities from HPMC matrices.

PubMed

Asare-Addo, Kofi; Conway, Barbara R; Larhrib, Hassan; Levina, Marina; Rajabi-Siahboomi, Ali R; Tetteh, John; Boateng, Joshua; Nokhodchi, Ali

2013-11-01

The evaluation of the effects of different media ionic strengths and pH on the release of hydrochlorothiazide, a poorly soluble drug, and diltiazem hydrochloride, a cationic and soluble drug, from a gel forming hydrophilic polymeric matrix was the objective of this study. The drug to polymer ratio of formulated tablets was 4:1. Hydrochlorothiazide or diltiazem HCl extended release (ER) matrices containing hypromellose (hydroxypropyl methylcellulose (HPMC)) were evaluated in media with a pH range of 1.2-7.5, using an automated USP type III, Bio-Dis dissolution apparatus. The ionic strength of the media was varied over a range of 0-0.4M to simulate the gastrointestinal fed and fasted states and various physiological pH conditions. Sodium chloride was used for ionic regulation due to its ability to salt out polymers in the midrange of the lyotropic series. The results showed that the ionic strength had a profound effect on the drug release from the diltiazem HCl K100LV matrices. The K4M, K15M and K100M tablets however withstood the effects of media ionic strength and showed a decrease in drug release to occur with an increase in ionic strength. For example, drug release after the 1h mark for the K100M matrices in water was 36%. Drug release in pH 1.2 after 1h was 30%. An increase of the pH 1.2 ionic strength to 0.4M saw a reduction of drug release to 26%. This was the general trend for the K4M and K15M matrices as well. The similarity factor f2 was calculated using drug release in water as a reference. Despite similarity occurring for all the diltiazem HCl matrices in the pH 1.2 media (f2=64-72), increases of ionic strength at 0.2M and 0.4M brought about dissimilarity. The hydrochlorothiazide tablet matrices showed similarity at all the ionic strength tested for all polymers (f2=56-81). The values of f2 however reduced with increasing ionic strengths. DSC hydration results explained the hydrochlorothiazide release from their HPMC matrices. There was an increase in bound water as ionic strengths increased. Texture analysis was employed to determine the gel strength and also to explain the drug release for the diltiazem hydrochloride. This methodology can be used as a valuable tool for predicting potential ionic effects related to in vivo fed and fasted states on drug release from hydrophilic ER matrices. Copyright © 2013 Elsevier B.V. All rights reserved.

THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS.

PubMed

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.

pH-Dependent Binding of Chloride to a Marine Alkaline Phosphatase Affects the Catalysis, Active Site Stability, and Dimer Equilibrium.

PubMed

Hjörleifsson, Jens G; Ásgeirsson, Bjarni

2017-09-26

The effect of ionic strength on enzyme activity and stability varies considerably between enzymes. Ionic strength is known to affect the catalytic activity of some alkaline phosphatases (APs), such as Escherichia coli AP, but how ions affect APs is debated. Here, we studied the effect of various ions on a cold-adapted AP from Vibrio splendidus (VAP). Previously, we have found that the active form of VAP is extremely unstable at low ionic strengths. Here we show that NaCl increased the activity and stability of VAP and that the effect was pH-dependent in the range of pH 7-10. The activity profile as a function of pH formed two maxima, indicating a possible conformational change. Bringing the pH from the neutral to the alkaline range was accompanied by a large increase in both the K i for inorganic phosphate (product inhibition) and the K M for p-nitrophenyl phosphate. The activity transitions observed as the pH was varied correlated with structural changes as monitored by tryptophan fluorescence. Thermal and urea-induced inactivation was shown to be accompanied by neither dissociation of the active site metal ions nor dimer dissociation. This would suggest that the inactivation involved subtle changes in active site conformation. Furthermore, the VAP dimer equilibrium was studied for the first time and shown to highly favor dimerization, which was dependent on pH and NaCl concentration. Taken together, the data support a model in which anions bind to some specific acceptor in the active site of VAP, resulting in great stabilization and catalytic rate enhancement, presumably through a different mechanism.

Aggregation of asbestos fibers in water: role of solution chemistry

NASA Astrophysics Data System (ADS)

Wu, L.; Ortiz, C. P.; Jerolmack, D. J.

2016-12-01

Aggregation kinetics and stability of colloidal particles have been extensively studied using bulk techniques such as dynamic light scattering; these techniques involve large ensembles of particles and interpretation of results is difficult when particles are non-spherical and poorly characterized, as is always the case with non-ideal natural hazardous materials such as asbestos fibers. These difficulties hinder greatly progress on fundamental understanding of whether the classic colloidal aggregation theories can be applied to natural materials and how the heterogeneity of particles (e.g., shape) affects the colloidal aggregation kinetics and structure. By using in-situ microscopy and particle tracking techniques, we were able to observe the particle-by-particle growth of aggregated formed by elongated particles (synthetic glass rods and natural asbestos fibers) and demonstrated the rod-shaped geometry induced novel structures and growth dynamics that challenge existing theory. In this study, we continue to use asbestos as model system of elongated colloidal contaminant, and investigate the effects of changing solution chemistry (e.g., ionic strength, pH, and natural organic matter (NOM)), on growth dynamics and aggregates structure. The results show that aggregate growth curves are self-similar with a characteristic timescale that increases with increasing pH. By varying ionic strength for fixed pH values, we determine that the ccc is sensitive to pH. Fractal dimension decreases slightly with increasing pH and decreasing ionic strength, indicating that stronger inter-particle repulsion create sparser aggregates; however, the magnitude of the solution chemistry effects is much smaller than that of colloid shape. In monovalent solutions, regardless of their concentration, HA drastically reduces the aggregation kinetics of asbestos fiber. This work may lead to enhanced prediction of the colloidal contaminants' mobility in the environment, bioavailability, and toxicity to organisms.

Assessment of solubilization characteristics of different surfactants for carvedilol phosphate as a function of pH.

PubMed

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.

Removal of trace metal contaminants from potable water by electrocoagulation

PubMed Central

Heffron, Joe; Marhefke, Matt; Mayer, Brooke K.

2016-01-01

This study investigated the effects of four operational and environmental variables on the removal of trace metal contaminants from drinking water by electrocoagulation (EC). Removal efficiencies for five metals (arsenic, cadmium, chromium, lead and nickel) were compared under varying combinations of electrode material, post-treatment, water composition and pH. Iron electrodes out-performed aluminum electrodes in removing chromium and arsenic. At pH 6.5, aluminum electrodes were slightly more effective at removing nickel and cadmium, while at pH 8.5, iron electrodes were more effective for these metals. Regardless of electrode, cadmium and nickel removal efficiencies were higher at pH 8.5 than at pH 6.5. Post-EC treatment using membrane filtration (0.45 μm) enhanced contaminant removal for all metals but nickel. With the exception of lead, all metals exhibited poorer removal efficiencies as the ionic strength of the background electrolyte increased, particularly in the very high-solids synthetic groundwaters. Residual aluminum concentrations were lowest at pH 6.5, while iron residuals were lowest in low ionic strength waters. Both aluminum and iron residuals required post-treatment filtration to meet drinking water standards. EC with post-treatment filtration appears to effectively remove trace metal contaminants to potable water standards, but both reactor and source water parameters critically impact removal efficiency. PMID:27324564

Scaling Behavior for Ionic Transport and its Fluctuations in Individual Carbon Nanotubes.

PubMed

Secchi, Eleonora; Niguès, Antoine; Jubin, Laetitia; Siria, Alessandro; Bocquet, Lydéric

2016-04-15

In this Letter, we perform an experimental study of ionic transport and current fluctuations inside individual carbon nanotubes (CNTs). The conductance exhibits a power law behavior at low salinity, with an exponent close to 1/3 versus the salt concentration in this regime. This behavior is rationalized in terms of a salinity dependent surface charge, which is accounted for on the basis of a model for hydroxide adsorption at the (hydrophobic) carbon surface. This is in contrast to boron nitride nanotubes which exhibit a constant surface conductance. Further, we measure the low frequency noise of the ionic current in CNTs and show that the amplitude of the noise scales with the surface charge, with data collapsing on a master curve for the various studied CNTs at a given pH.

The effect of Ca2+ ions and ionic strength on Mn(II) oxidation by spores of the marine Bacillus sp. SG-1

PubMed Central

Tebo, Bradley M.

2017-01-01

Manganese(IV) oxides, believed to form primarily through microbial activities, are extremely important mineral phases in marine environments where they scavenge a variety of trace elements and thereby control their distributions. The presence of various ions common in seawater are known to influence Mn oxide mineralogy yet little is known about the effect of these ions on the kinetics of bacterial Mn(II) oxidation and Mn oxide formation. We examined factors affecting bacterial Mn(II) oxidation by spores of the marine Bacillus sp. strain SG-1 in natural and artificial seawater of varying ionic conditions. Ca2+ concentration dramatically affected Mn(II) oxidation, while Mg2+, Sr2+, K+, Na+ and NO3− ions had no effect. The rate of Mn(II) oxidation at 10mM Ca2+ (seawater composition) was four or five times that without Ca2+. The relationship between Ca2+ content and oxidation rate demonstrates that the equilibrium constant is small (on the order of 0.1) and the binding coefficient is 0.5. The pH optimum for Mn(II) oxidation changed depending on the amount of Ca2+ present, suggesting that Ca2+ exerts a direct effect on the enzyme perhaps as a stabilizing bridge between polypeptide components. We also examined the effect of varying concentrations of NaCl or KNO3 (0 mM – 2000 mM) on the kinetics of Mn(II) oxidation in solutions containing 10 mM Ca2+. Mn(II) oxidation was unaffected by changes in ionic strength (I) below 0.2, but it was inhibited by increasing salt concentrations above this value. Our results suggest that the critical coagulation concentration is around 200 mM of salt (I = ca. 0.2), and that the ionic strength of seawater (I > 0.2) accelerates the precipitation of Mn oxides around the spores. Under these conditions, the aggregation of Mn oxides reduces the supply of dissolved O2 and/or Mn2+ and inhibits the Mn(II) -> Mn(III) step controlling the enzymatic oxidation of Mn(II). Our results suggest that the hardness and ionic strength of the aquatic environment at circumneutral pH strongly influences the rate of biologically mediated Mn(II) oxidation. PMID:29176910

The pH of chemistry assays plays an important role in monoclonal immunoglobulin interferences.

PubMed

Alberti, Michael O; Drake, Thomas A; Song, Lu

2015-12-01

Immunoglobulin paraproteins can interfere with multiple chemistry assays. We want to investigate the mechanisms of immunoglobulin interference. Serum samples containing paraproteins from the index patient and eight additional patients were used to investigate the interference with the creatinine and total protein assays on the Beckman Coulter AU5400/2700 analyzer, and to determine the effects of pH and ionic strength on the precipitation of different immunoglobulins in these patient samples. The paraprotein interference with the creatinine and total protein assays was caused by the precipitation of IgM paraprotein in the index patient's samples under alkaline assay conditions. At extremely high pH (12-13) and extremely low pH (1-2) and low ionic strength, paraprotein formed large aggregates in samples from the index patient but not from other patients. The pH and ionic strength are the key factors that contribute to protein aggregation and precipitation which interfere with the creatinine and total protein measurements on AU5400/2700. The different amino acid sequence of each monoclonal paraprotein will determine the pH and ionic strength at which the paraprotein will precipitate.

Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

USGS Publications Warehouse

Kim, Sang-Tae; Gebbinck, Christa Klein; Mucci, Alfonso; Coplen, Tyler B.

2014-01-01

To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

Adsorption of gentian violet dyes in aqueous solution on microporous AlPOs molecular sieves synthesized by ionothermal method

NASA Astrophysics Data System (ADS)

Fortas, W.; Djelad, A.; Hasnaoui, M. A.; Sassi, M.; Bengueddach, A.

2018-02-01

In this work, AlPO-34, like-chabazite (CHA) zeolite, was ionothermally prepared using the ionic liquid (IL), 1-ethyl-3-methylimidazolium chloride [EMIMCl], as solvent. The solids obtained were characterized by x-ray powder diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FTIR), thermal analysis (TG) and nitrogen adsorption/desorption at 77.3 K. The results show that the ionic liquid is occluded in the AlPO-34 framework and consequently it acts also as a structure-directing agent. The variation of chemical composition led to AlPO-34 materials with different crystal sizes and morphologies. The well crystallized AlPO-34 material was used as adsorbent for Crystal Violet (CV) dye removal from aqueous solutions. The effect of adsorption parameters such as pH and initial concentration were investigated. It was found that adsorption dyes is favorable at pH = 6. The adsorption isotherm data follow the Langmuir equation in which parameters are calculated. The selected AlPO-34 sample exhibited a high crystal violet dye removal of 46.08 mg g-1 at pH = 6.

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading

NASA Astrophysics Data System (ADS)

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-12-01

This paper reports the synthetic route of 3-D network shape α-Fe2O3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe2O3, particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe2O3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil.

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading

PubMed Central

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-01-01

This paper reports the synthetic route of 3-D network shape α-Fe2O3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe2O3, particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe2O3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil. PMID:27966663

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading.

PubMed

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-12-14

This paper reports the synthetic route of 3-D network shape α-Fe 2 O 3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe 2 O 3 , particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe 2 O 3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil.

The hydrophilicity vs. ion interaction selectivity plot revisited: The effect of mobile phase pH and buffer concentration on hydrophilic interaction liquid chromatography selectivity behavior.

PubMed

Iverson, Chad D; Gu, Xinyun; Lucy, Charles A

2016-08-05

This work systematically investigates the selectivity changes on many HILIC phases from w(w)pH 3.7-6.8, at 5 and 25mM buffer concentrations. Hydrophilicity (kcytosine/kuracil) vs. ion interaction (kBTMA/kuracil) selectivity plots developed by Ibrahim et al. (J. Chromatogr. A 1260 (2012) 126-131) are used to investigate the effect of mobile phase changes on the selectivity of 18 HILIC columns from various classes. "Selectivity change plots" focus on the change in hydrophilicity and ion interaction that the columns exhibit upon changing mobile phase conditions. In general, the selectivity behavior of most HILIC columns is dominated by silanol activity. Minimal changes in selectivity are observed upon changing pH between w(w)pH 5 and 6.8. However, a reduction in ionic interaction is observed when the buffer concentration is increased at w(w)pH≥5.0 due to ionic shielding. Reduction of the w(w)pH to<5.0 results in decreasing cation exchange activity due to silanol protonation. Under all eluent conditions, the majority of phases show little change in their hydrophilicity. Copyright © 2016 Elsevier B.V. All rights reserved.

Biotoxicity of TiO2 Nanoparticles on Raphidocelis subcapitata Microalgae Exemplified by Membrane Deformation

PubMed Central

Ozkaleli, Merve; Erdem, Ayca

2018-01-01

TiO2 nanoparticles (NPs), which are mainly used in consumer products (mostly cosmetics), have been found to cause ecotoxic effects in the aquatic environment. The green algae Raphidocelis subcapitata, as a representative of primary producers of the freshwater ecosystem, has been frequently used to study the effects of metal oxide NPs. An ecotoxicity study was conducted herein to investigate the effects of TiO2 NPs on survival and membrane deformation of algal cells. Five different concentrations of nano-TiO2 particles (1, 10, 50, 100 and 500 mg/L) were prepared in synthetic surface water samples with five different water quality characteristics (pH 6.4–8.4, hardness 10–320 mg CaCO3/L, ionic strength 0.2–8 mM, and alkalinity 10–245 mg CaCO3/L). Results showed a significant increase in the hydrodynamic diameter of NPs with respect to both NP concentrations and ionic content of the test system. A soft synthetic freshwater system at pH 7.3 ± 0.2 appeared to provide the most effective water type, with more than 95% algal mortality observed at 50, 100 and 500 mg/L NP concentrations. At high exposure concentrations, increased malondialdehyde formations were observed. Moreover, due to membrane deformation, TEM images correlated the uptake of the NPs. PMID:29495534

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

PubMed

Gall, B; Scheer, H

1998-07-17

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

Characterization of phthalocyanine functionalized quantum dots by dynamic light scattering, laser Doppler, and capillary electrophoresis.

PubMed

Ramírez-García, Gonzalo; Oluwole, David O; Nxele, Siphesihle Robin; d'Orlyé, Fanny; Nyokong, Tebello; Bedioui, Fethi; Varenne, Anne

2017-02-01

In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy. Graphical Abstract Schematic illustration of the phthalocyanine capped QDs nanoconjugates and the capillary electrophoresis methods applied for size and ζ-potential characterization.

Effect of environmental factors on the complexation of iron and humic acid.

PubMed

Fang, Kai; Yuan, Dongxing; Zhang, Lei; Feng, Lifeng; Chen, Yaojin; Wang, Yuzhou

2015-01-01

A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron (Fe) and humic acid (HA) in a water environment. The factors affecting the complexation of Fe and HA, such as ionic strength, pH, temperature and UV radiation, were investigated. The Fe-HA complex residence time was also studied. Experimental results showed that pH could influence the deprotonation of HA and hydrolysis of Fe, and thus affected the complexation of Fe and HA. The complexation was greatly disrupted by the presence of NaCl. Temperature had some influence on the complexation. The yield of Fe-HA complexes showed a small decrease at high levels of UV radiation, but the effect of UV radiation on Fe-HA complex formation at natural levels could be neglected. It took about 10 hr for the complexation to reach equilibrium, and the Fe-HA complex residence time was about 20 hr. Complexation of Fe and HA reached a maximum level under the conditions of pH 6, very low ionic strength, in the dark and at a water temperature of about 25°C, for 10 hr. It was suggested that the Fe-HA complex could form mainly in freshwater bodies and reach high levels in the warm season with mild sunlight radiation. With changing environmental parameters, such as at lower temperature in winter or higher pH and ionic strength in an estuary, the concentration of the Fe-HA complex would decrease. Copyright © 2014. Published by Elsevier B.V.

Sorption of metals on humic acid

NASA Astrophysics Data System (ADS)

Kerndorff, H.; Schnitzer, M.

1980-11-01

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg≫ Fe≫ Pb≫ CuAl ≫ Ni ≫ CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO 2H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation Y = 100/[1 + exp - (A + BX)], where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.

A novel pH optical sensor using methyl orange based on triacetylcellulose membranes as support.

PubMed

Hosseini, Mohammad; Heydari, Rouhollah; Alimoradi, Mohammad

2014-07-15

A novel pH optical sensor based on triacetylcellulose membrane as solid support was developed by using immobilization of methyl orange indicator. The prepared optical sensor was fixed into a flow cell for on-line pH monitoring. Variables affecting sensor performance, such as pH of dye bonding to triacetylcellulose membrane and dye concentration have been fully evaluated and optimized. The calibration curve showed good behavior and precision (RSD<0.4%) in the pH range of 4.0-12.0. No significant variation was observed on sensor response with increasing the ionic strength in the range of 0.0-0.5M of sodium chloride. Determination of pH by using the proposed optical sensor is on-line, quick, inexpensive, selective and sensitive in the pH range of 4.0-12.0. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface Complexation Modeling of Fluoride Adsorption by Soil and the Role of Dissolved Aluminum on Adsorption

NASA Astrophysics Data System (ADS)

Padhi, S.; Tokunaga, T.

2017-12-01

Adsorption of fluoride (F) on soil can control the mobility of F and subsequent contamination of groundwater. Hence, accurate evaluation of adsorption equilibrium is a prerequisite for understanding transport and fate of F in the subsurface. While there have been studies for the adsorption behavior of F with respect to single mineral constituents based on surface complexation models (SCM), F adsorption to natural soil in the presence of complexing agents needs much investigation. We evaluated the adsorption processes of F on a natural granitic soil from Tsukuba, Japan, as a function of initial F concentration, ionic strength, and initial pH. A SCM was developed to model F adsorption behavior. Four possible surface complexation reactions were postulated with and without including dissolved aluminum (Al) and Al-F complex sorption. Decrease in F adsorption with the increase in initial pH was observed in between the initial pH range of 4 to 9, and a decrease in the rate of the reduction of adsorbed F with respect to the increase in the initial pH was observed in the initial pH range of 5 to 7. Ionic strength variation in the range of 0 to 100mM had insignificant effect on F removal. Changes in solution pH were observed by comparing the solution before and after F adsorption experiments. At acidic pH, the solution pH increased, whereas at alkaline pH, the solution pH decreased after equilibrium. The SCM including dissolved Al and the adsorption of Al-F complex can simulate the experimental results quite successfully. Also, including dissolved Al and the adsorption of Al-F complex to the model explained the change in solution pH after F adsorption.

Modeling solubility, acid-base properties and activity coefficients of amoxicillin, ampicillin and (+)6-aminopenicillanic acid, in NaCl(aq) at different ionic strengths and temperatures.

PubMed

Crea, Francesco; Cucinotta, Daniela; De Stefano, Concetta; Milea, Demetrio; Sammartano, Silvio; Vianelli, Giuseppina

2012-11-20

The total solubility of three penicillin derivatives was determined, in pure water and NaCl aqueous solutions at different salt concentrations (from ∼0.15 to 1.0 mol L(-1) for ampicillin and amoxicillin, and from ∼0.05 to 2.0 mol L(-1) for (+)6-aminopenicillanic acid), using the shake-flask method for generating the saturated solutions, followed by potentiometric analysis. The knowledge of the pH of solubilization and of the protonation constants determined in the same experimental conditions, allowed us to calculate, by means of the mass balance equations, the solubility of the neutral species at different ionic strength values, to model its dependence on the salt concentration and to determine the corresponding values at infinite dilution. The salting parameter and the activity coefficients of the neutral species were calculated by the Setschenow equation. The protonation constants of ampicillin and amoxicillin, determined at different temperatures (from T=288.15 to 318.15K), from potentiometric and spectrophotometric measurements, were used to calculate, by means of the Van't Hoff equation, the temperature coefficients at different ionic strength values and the corresponding protonation entropies. The protonation enthalpies of the (+)6-aminopenicillanic acid were determined by isoperibol calorimetric titrations at T=298.15K and up to I=2.0 mol L(-1). The dependence of the protonation constants on ionic strength was modeled by means of the Debye-Hückel and SIT (Specific ion Interaction Theory) approaches, and the specific interaction parameters of the ionic species were determined. The hydrolysis of the β-lactam ring was studied by spectrophotometric and H NMR investigations as a function of pH, ionic strength and time. Potentiometric measurements carried out on the hydrolyzed (+)6-aminopenicillanic acid allowed us to highlight that the opened and the closed β-lactam forms of the (+)6-aminopenicillanic acid have quite different acid-base properties. An analysis of literature solubility, protonation constants, enthalpies and activity coefficients is reported too. Copyright © 2012 Elsevier B.V. All rights reserved.

A Facile pH Controlled Citrate-Based Reduction Method for Gold Nanoparticle Synthesis at Room Temperature.

PubMed

Tyagi, Himanshu; Kushwaha, Ajay; Kumar, Anshuman; Aslam, Mohammed

2016-12-01

The synthesis of gold nanoparticles using citrate reduction process has been revisited. A simplified room temperature approach to standard Turkevich synthesis is employed to obtain fairly monodisperse gold nanoparticles. The role of initial pH alongside the concentration ratio of reactants is explored for the size control of Au nanoparticles. The particle size distribution has been investigated using UV-vis spectroscopy and transmission electron microscope (TEM). At optimal pH of 5, gold nanoparticles obtained are highly monodisperse and spherical in shape and have narrower size distribution (sharp surface plasmon at 520 nm). For other pH conditions, particles are non-uniform and polydisperse, showing a red-shift in plasmon peak due to aggregation and large particle size distribution. The room temperature approach results in highly stable "colloidal" suspension of gold nanoparticles. The stability test through absorption spectroscopy indicates no sign of aggregation for a month. The rate of reduction of auric ionic species by citrate ions is determined via UV absorbance studies. The size of nanoparticles under various conditions is thus predicted using a theoretical model that incorporates nucleation, growth, and aggregation processes. The faster rate of reduction yields better size distribution for optimized pH and reactant concentrations. The model involves solving population balance equation for continuously evolving particle size distribution by discretization techniques. The particle sizes estimated from the simulations (13 to 25 nm) are close to the experimental ones (10 to 32 nm) and corroborate the similarity of reaction processes at 300 and 373 K (classical Turkevich reaction). Thus, substitution of experimentally measured rate of disappearance of auric ionic species into theoretical model enables us to capture the unusual experimental observations.

Silver Sucrose Octasulfate (IASOS™) as a Valid Active Ingredient into a Novel Vaginal Gel against Human Vaginal Pathogens: In Vitro Antimicrobial Activity Assessment

PubMed Central

Marianelli, Cinzia; Petrucci, Paola; Comelli, Maria Cristina; Calderini, Gabriella

2014-01-01

This in vitro study assessed the antimicrobial properties of a novel octasilver salt of Sucrose Octasulfate (IASOS) as well as of an innovative vaginal gel containing IASOS (SilSOS Femme), against bacterial and yeast pathogens isolated from human clinical cases of symptomatic vaginal infections. In BHI and LAPT culture media, different ionic silver concentrations and different pHs were tested. IASOS exerted a strong antimicrobial activity towards all the pathogens tested in both culture media. The results demonstrated that salts and organic compounds present in the culture media influenced IASOS efficacy only to a moderate extent. Whereas comparable MBCs (Minimal Bactericidal Concentrations) were observed for G. vaginalis (10 mg/L Ag+), E. coli and E. aerogenes (25 mg/L Ag+) in both media, higher MBCs were found for S. aureus and S. agalactiae in LAPT cultures (50 mg/L Ag+ versus 25 mg/L Ag+). No minimal concentration totally inhibiting the growth of C. albicans was found. Nevertheless, in both media at the highest ionic silver concentrations (50–200 mg/L Ag+), a significant 34–52% drop in Candida growth was observed. pH differently affected the antimicrobial properties of IASOS against bacteria or yeasts; however, a stronger antimicrobial activity at pH higher than the physiological pH was generally observed. It can be therefore concluded that IASOS exerts a bactericidal action against all the tested bacteria and a clear fungistatic action against C. albicans. The antimicrobial activity of the whole vaginal gel SilSOS Femme further confirmed the antimicrobial activity of IASOS. Overall, our findings support IASOS as a valid active ingredient into a vaginal gel. PMID:24897299

Assessing the suitability of the OECD 29 guidance document to investigate the transformation and dissolution of silver nanoparticles in aqueous media.

PubMed

Wasmuth, Claus; Rüdel, Heinz; Düring, Rolf-Alexander; Klawonn, Thorsten

2016-02-01

The OECD guidance document No. 29 was designed to determine the rate and extend to which metals can produce soluble available ionic metal species. This transformation/dissolution protocol was applied to silver nanomaterials. The results prove that concentrations of released Ag(+) at pH 8 were nearly similar at all three different loadings. At pH 6, the concentration of Ag(+) was almost the same at loadings of 10 and 100 mg L(-1) AgNPs. However, the study showed changes in concentrations of nanoparticles and aggregates (operationally defined as the fraction passing a 0.2 µm filter). At the higher pH both the concentrations in the test medium of Ag(+) and of AgNPs (fraction < 0.2 µm) decreased. After 7 days of test duration, 71 µg L(-1) of Ag(+) was found in pH 6 medium (initial loading of 100 mg L(-1)). In pH 8 medium a maximum concentration of 29 µg L(-1) Ag(+) was measured (initial loading of 10 mg L(-1)). The maximum transformation from AgNPs to Ag(+) was 2.7% (27 µg L(-1)) in pH 8 medium (loading of 1 mg L(-1)) after 7 days. At an initial loading of 100 mg L(-1) AgNPs in medium at pH 8, only 0.03% (30 µg L(-1)) were transformed to Ag(+) after 7 days. At the loading of 1 mg L(-1) AgNPs all silver concentrations remain relatively constant for the duration of the test after 7 until 28 days. The results reveal that only low concentrations of Ag(+) are released from AgNPs under the applied conditions. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Formation of positively charged gold nanoparticle monolayers on silica sensors.

PubMed

Oćwieja, Magdalena; Maciejewska-Prończuk, Julia; Adamczyk, Zbigniew; Roman, Maciej

2017-09-01

Formation of positively charged gold nanoparticle monolayers on the Si/SiO 2 was studied under in situ conditions using quartz microbalance (QCM). The gold nanoparticles were synthesized in a chemical reduction method using sodium borohydride as reducing agent. Cysteamine hydrochloride was applied to generate a positive surface charge of nanoparticles. The micrographs obtained from transmission electron microscopy (TEM) revealed that the average size of nanoparticles was equal to 12±3nm. The stability of nanoparticle suspensions under controlled pH and ionic strength was determined by dynamic light scattering (DLS). The electrophoretic mobility measurements showed that the zeta potential of nanoparticles was positive, decreasing with ionic strength and pH from 56mV at pH 4.2 and I=10 -4 M to 22mV at pH 8.3 and I=3×10 -3 M. The surface enhanced Raman spectroscopy (SERS) confirmed chemisorption of cysteamine on nanoparticles and the contribution of amine moieties in the generation of nanoparticle charge. The influence of suspension concentration, ionic strength and flow rate on the kinetics of nanoparticle deposition on the sensors was quantitatively determined. It was confirmed that the deposition for the low coverage regime is governed by the bulk mass transfer that results in a linear increase of the coverage with time. The significant increase in the maximum coverage of gold monolayers with ionic strength was interpreted as due to the decreasing range of the electrostatic interactions among deposited particles. Moreover, the hydratation of formed monolayers, their structure and the stability were determined by the comparison of the QCM results with those obtained by AFM and SEM. The experimental data were adequately interpreted in terms of the extended random sequential adsorption (eRSA) model that considers the bulk and surface transfer steps in a rigorous way. The obtained results are useful for a facile fabrication of gold nanoparticle-based biosensors capable to bind target molecules via available amine moieties. Copyright © 2017 Elsevier Inc. All rights reserved.

Theory and practice in the electrometric determination of pH in precipitation

NASA Astrophysics Data System (ADS)

Brennan, Carla Jo; Peden, Mark E.

Basic theory and laboratory investigations have been applied to the electrometric determination of pH in precipitation samples in an effort to improve the reliability of the results obtained from these low ionic strength samples. The theoretical problems inherent in the measurement of pH in rain have been examined using natural precipitation samples with varying ionic strengths and pH values. The importance of electrode design and construction has been stressed. The proper choice of electrode can minimize or eliminate problems arising from residual liquid junction potentials, streaming potentials and temperature differences. Reliable pH measurements can be made in precipitation samples using commercially available calibration buffers providing low ionic strength quality control solutions are routinely used to verify electrode and meter performance.

Simultaneous extraction and HPLC determination of 3-indole butyric acid and 3-indole acetic acid in pea plant by using ionic liquid-modified silica as sorbent.

PubMed

Sheikhian, Leila; Bina, Sedigheh

2016-01-15

In this study, ionic liquid-modified silica was used as sorbent for simultaneous extraction and preconcentration of 3-indole butyric acid and 3-indole acetic acid in pea plants. The effect of some parameters such as pH and ionic strength of sample solution, amount of sorbent, flow rate of aqueous sample solution and eluent solution, concentration of eluent solution, and temperature were studied for each hormone solution. Percent extraction of 3-indole butyric acid and 3-indole acetic acid was strongly affected by pH of aqueous sample solution. Ionic strength of aqueous phase and temperature showed no serious effects on extraction efficiency of studied plant hormones. Obtained breakthrough volume was 200mL for each of studied hormones. Preconcentration factor for spectroscopic and chromatographic determination of studied hormones was 100 and 4.0×10(3) respectively. Each solid sorbent phase was reusable for almost 10 times of extraction/stripping procedure. Relative standard deviations of extraction/stripping processes of 3-indole butyric acid and 3-indole acetic acid were 2.79% and 3.66% respectively. The calculated limit of detections for IBA and IAA were 9.1×10(-2)mgL(-1) and 1.6×10(-1)mgL(-1) respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Structure of the Stern layer in Phospholipid Systems

NASA Astrophysics Data System (ADS)

Vangaveti, Sweta; Travesset, Alex

2011-03-01

The structure of the Stern layer in Phospholipid Systems results from a subtle competition of salt concentration, ionic valence, specific ionic-phospolipid interactions and pH. It becomes very challenging to develop a rigorous theory that encompasses all these effects, yet its understanding is extremely relevant for both model and biological systems, as the structure of the Stern layer determines the interactions of phospholipids with proteins or electrostatic phase separation (rafts). In this talk we will present our theoretical model for the Stern Layer and discuss how all these effects are included. Particularly emphasis is made to Phosphoinositides and Phosphatidic acid. This work is supported by grant NSF DMR-0748475.

Monitoring of fogwater chemistry in the gulf coast urban industrial corridor: Baton Rouge (louisiana).

PubMed

Raja, S; Ravikrishna, R; Kommalapati, R R; Valsaraj, K T

2005-11-01

Seventeen fog events were sampled in Baton Rouge, Louisiana during 2002-2004 as part of characterizing wet deposition by fogwater in the heavily industrialized corridor along the Louisiana Gulf Coast in the United States. These samples were analyzed for chemical characteristics such as pH, conductivity, total organic and inorganic carbon, total metals and the principal ion concentrations. The dominant ionic species in all samples were NH4+, NO3-, Cl- and SO4(2-). The pH of the fogwater sampled had a mean value of 6.7 with two cases of acidic pH of 4.7. Rainwater and fogwater pH were similar in this region. The acidity of fogwater was a result of NO3- but partly offset by high NH4+. The measured gaseous SO2 accounted for a small percentage of the observed sulfate concentration, indicating additional gas-to-particle conversion of SO2 to sulfate in fogwater. The gaseous NOx accounted for most of the dissolved nitrate and nitrite concentration in fogwater. The high chloride concentration was attributable to the degradation of chlorinated organics in the atmosphere. The metal composition was traced directly to soil-derived aerosol precursors in the air. The major metals observed in fogwater were Na, K, Ca, Fe, Al, Mg and Zn. Of these Na, K, Ca and Mg were predominant with mean concentrations > 100 microM. Al, Fe and Zn were present in the samples, at mean concentrations < 100 microM. Small concentrations of Mn (7.8 microM), Cu (2 microM), Pb (0.07 microM) and As (0.32 microM) were also observed in the fogwaters, and these were shown to result from particulates (PM2.5) in the atmosphere. The contribution to both ions and metals from the marine sources in the Louisiana Gulf Coast was minimal. The concentrations of all principal ionic species and metals in fogwater were 1-2 orders of magnitude larger than in rainwater. Several linear alkane organic compounds were observed in the fogwater, representing the contributions from petroleum products at concentrations far exceeding their aqueous solubility. A pesticide (atrazine) was also observed in fogwater, representing the contribution from the agricultural activities nearby.

Determination of sulfonamides in butter samples by ionic liquid magnetic bar liquid-phase microextraction high-performance liquid chromatography.

PubMed

Wu, Lijie; Song, Ying; Hu, Mingzhu; Xu, Xu; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

2015-01-01

A novel, simple, and environmentally friendly pretreatment method, ionic liquid magnetic bar liquid-phase microextraction, was developed for the determination of sulfonamides in butter samples by high-performance liquid chromatography. The ionic liquid magnetic bar was prepared by inserting a stainless steel wire into the hollow of a hollow fiber and immobilizing ionic liquid in the micropores of the hollow fiber. In the extraction process, the ionic liquid magnetic bars were used to stir the mixture of sample and extraction solvent and enrich the sulfonamides in the mixture. After extraction, the analyte-adsorbed ionic liquid magnetic bars were readily isolated with a magnet from the extraction system. It is notable that the present method was environmentally friendly since water and only several microliters of ionic liquid were used in the whole extraction process. Several parameters affecting the extraction efficiency were investigated and optimized, including the type of ionic liquid, sample-to-extraction solvent ratio, the number of ionic liquid magnetic bars, extraction temperature, extraction time, salt concentration, stirring speed, pH of the extraction solvent, and desorption conditions. The recoveries were in the range of 73.25-103.85 % and the relative standard deviations were lower than 6.84 %. The experiment results indicated that the present method was effective for the extraction of sulfonamides in high-fat content samples.

Extraction of trivalent rare-earth metal nitrates by solutions of tributyl phosphate and diisooctylmethylphosphonate in kerosene

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

Pyartman, A.K.; Puzikov, E.A.; Kopyrin, A.A.

1995-01-01

Isotherms of extraction of trivalent rare-earth metal nitrates in the series lanthanum-lutetium, yttrium by 0.5-2.5 M solutions of tri-n-buty1 phosphate and diisooctyl methylphosphonate in kerosene at 298.15 K, pH 2 are presented. The influence of the ionic strength of aqueous phase and extractant concentration on the concentration extraction constants in the case of formation of metal(III) trisolvates in organic phase is given by equation.

Assembly properties of the Bacillus subtilis actin, MreB.

PubMed

Mayer, Joshua A; Amann, Kurt J

2009-02-01

The bacterial actin MreB has been implicated in a variety of cellular roles including cell shape determination, cell wall synthesis, chromosome condensation and segregation, and the establishment and maintenance of cell polarity. Toward elucidating a clearer understanding of how MreB functions inside the bacterial cell, we investigated biochemically the polymerization of MreB from Bacillus subtilis. Light scattering and sedimentation assays revealed pH-, ionic-, cationic-, and temperature-dependent behavior. B. subtilis MreB polymerizes in the presence of millimolar divalent cations in a protein concentration-dependent manner. Polymerization is favored by decreasing pH and inhibited by monovalent salts and low temperatures. Although B. subtilis MreB binds and hydrolyzes both ATP and GTP, it does not require a bound nucleotide for assembly and polymerizes indistinguishably regardless of the nucleotide species bound, with a critical concentration of approximately 900 nM. A number of the presently reported properties of B. subtilis MreB differ significantly from those of T. maritima MreB1 (Bean and Amann [2008]: Biochemistry 47: 826-835), including the nucleotide requirements and temperature and ionic effects on polymerization state. These observations collectively suggest that additional factors interact with MreB to account for its complex dynamic behavior in cells.

Study on the inclusion complex between β-cyclodextrin derivatives and flurbiprofen by spectrofluorometric

NASA Astrophysics Data System (ADS)

Miao, Jiabing; Guo, Zhaohua; Wang, Yongwang; Chen, Dong; Li, Yifan; Zhang, Feng

2017-08-01

The inclusion behavior between β-cyclodextrin derivatives (β-CDs) and flurbiprofen had been studied by fluorescence spectrophotometry. The effects of type and concentration of β-CDs; ionic strength; pH as well as temperature on inclusion behavior were investigated. And then the thermodynamic parameters ΔH/ΔS and ΔG of the inclusion complex of flurbiprofen and HP-β-CD were calculated, the driving force of the inclusion reaction had been also certified. The experimental results indicate, the fluorescence intensity (F) of flurbiprofen increases with the raising of β-CDs concentration, among the studied types of β-cyclodextrin derivatives, hydroxypropy l-β-cyclodextrin (HP-β-CD) has the most obvious enhancement, namely HP-β-CD has the strongest ability to complex with flurbiprofen. Plot of 1/ (F-F0) against 1/ [β-CD] yields a straight line, indicating 1:1 stoichiometric complex formed between β-CDs and flurbiprofen. Inclusion constant is enhanced with the increase in ionic strength of solution, whereas followes an opposite tendency with the rise of pH value. In the inclusive process, under normal temperature ΔG<0, it illustrates that this process is spontaneous, and the driving force is the change of enthalpy.

Carbon monoxide photoproduction: implications for photoreactivity of Arctic permafrost-derived soil dissolved organic matter.

PubMed

Hong, Jun; Xie, Huixiang; Guo, Laodong; Song, Guisheng

2014-08-19

Apparent quantum yields of carbon monoxide (CO) photoproduction (AQY(CO)) for permafrost-derived soil dissolved organic matter (SDOM) from the Yukon River Basin and Alaska coast were determined to examine the dependences of AQY(CO) on temperature, ionic strength, pH, and SDOM concentration. SDOM from different locations and soil depths all exhibited similar AQY(CO) spectra irrespective of soil age. AQY(CO) increased by 68% for a 20 °C warming, decreased by 25% from ionic strength 0 to 0.7 mol L(-1), and dropped by 25-38% from pH 4 to 8. These effects combined together could reduce AQY(CO) by up to 72% when SDOM transits from terrestrial environemnts to open-ocean conditions during summer in the Arctic. A Michaelis-Menten kinetics characterized the influence of SDOM dilution on AQY(CO) with a very low substrate half-saturation concentration. Generalized global-scale relationships between AQY(CO) and salinity and absorbance demostrate that the CO-based photoreactivity of ancient permaforst SDOM is comparable to that of modern riverine DOM and that the effects of the physicochemical variables revealed here alone could account for the seaward decline of AQY(CO) observed in diverse estuarine and coastal water bodies.

Study of the Effect of Surfactants on Extraction and Determination of Polyphenolic Compounds and Antioxidant Capacity of Fruits Extracts

PubMed Central

Hosseinzadeh, Reza; Khorsandi, Khatereh; Hemmaty, Syavash

2013-01-01

Micelle/water mixed solutions of different surface active agents were studied for their effectiveness in the extraction of polyphenolic compounds from various varieties of apples from west Azerbaijan province in Iran. The total content of polyphenolic compound in fruit extracts were determined using ferrous tartrate and Folin–Ciocalteu assays methods and chromatographic methods and compared with theme. High performance liquid chromatography is one of the most common and important methods in biochemical compound identification. The effect of pH, ionic strength, surfactant type, surfactant concentration, extraction time and common organic solvent in the apple polyphenolics extractions was studied using HPLC-DAD. Mixtures of surfactants, water and methanol at various ratios were examined and micellar-water solutions of Brij surfactant showed the highest polyphenol extraction efficiency. Optimum conditions for the extraction of polyphenolic compounds from apple occurred at 7 mM Brij35, pH 3. Effect of ionic strength on extraction was determined and 2% (W/V) potassium Chloride was determined to be the optimum salt concentration. The procedure worked well with an ultrasound bath. Total antioxidant capacity also was determined in this study. The method can be safely scaled up for pharmaceutical applications. PMID:23472082

Copper removal by algae Gelidium, agar extraction algal waste and granulated algal waste: kinetics and equilibrium.

PubMed

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

2008-03-01

Biosorption of copper ions by an industrial algal waste, from agar extraction industry has been studied in a batch system. This biosorbent was compared with the algae Gelidium itself, which is the raw material for agar extraction, and the industrial waste immobilized with polyacrylonitrile (composite material). The effects of contact time, pH, ionic strength (IS) and temperature on the biosorption process have been studied. Equilibrium data follow both Langmuir and Langmuir-Freundlich models. The parameters of Langmuir equilibrium model were: q(max)=33.0mgg(-1), K(L)=0.015mgl(-1); q(max)=16.7mgg(-1), K(L)=0.028mgl(-1) and q(max)=10.3mgg(-1), K(L)=0.160mgl(-1) respectively for Gelidium, algal waste and composite material at pH=5.3, T=20 degrees C and IS=0.001M. Increasing the pH, the number of deprotonated active sites increases and so the uptake capacity of copper ions. In the case of high ionic strengths, the contribution of the electrostatic component to the overall binding decreases, and so the uptake capacity. The temperature has little influence on the uptake capacity principally for low equilibrium copper concentrations. Changes in standard enthalpy, Gibbs energy and entropy during biosorption were determined. Kinetic data at different solution pH (3, 4 and 5.3) were fitted to pseudo-first-order and pseudo-second-order models. The adsorptive behaviour of biosorbent particles was modelled using a batch reactor mass transfer kinetic model, which successfully predicts Cu(II) concentration profiles.

Liquid-liquid phase separation causes high turbidity and pressure during low pH elution process in Protein A chromatography.

PubMed

Luo, Haibin; Lee, Nacole; Wang, Xiangyang; Li, Yuling; Schmelzer, Albert; Hunter, Alan K; Pabst, Timothy; Wang, William K

2017-03-10

Turbid elution pools and high column back pressure are common during elution of monoclonal antibodies (mAbs) by acidic pH in Protein A chromatography. This phenomenon has been historically attributed to acid-induced precipitation of incorrectly folded or pH-sensitive mAbs and host cell proteins (HCPs). In this work, we propose a new mechanism that may account for some observations of elution turbidity in Protein A chromatography. We report several examples of turbidity and high column back pressure occurring transiently under a short course of neutral conditions during Protein A elution. A systematic study of three mAbs displaying this behavior revealed phase separation characterized by liquid drops under certain conditions including neutral pH, low ionic strength, and high protein concentration. These liquid droplets caused solution turbidity and exhibited extremely high viscosity, resulting in high column back pressure. We found out that the droplets were formed through liquid-liquid phase separation (LLPS) as a result of protein self-association. We also found multiple factors, including pH, temperature, ionic strength, and protein concentration can affect LLPS behaviors. Careful selection of process parameters during protein A elution, including temperature, flow rate, buffer, and salt can inhibit formation of a dense liquid phase, reducing both turbidity (by 90%) and column back pressure (below 20 pounds per square inch). These findings provide both mechanistic insight and practical mitigation strategies for Protein A chromatography induced LLPS. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Magnetical hollow fiber bar collection of extract in homogenous ionic liquid microextraction of triazine herbicides in water samples.

PubMed

Wang, Kun; Jiang, Jia; Kang, Mingqin; Li, Dan; Zang, Shuang; Tian, Sizhu; Zhang, Hanqi; Yu, Aimin; Zhang, Ziwei

2017-04-01

The homogeneous ionic liquid microextraction combined with magnetical hollow fiber bar collection was developed for extracting triazine herbicides from water samples. These analytes were separated and determined by high performance liquid chromatography. The triazines were quickly extracted into ionic liquid microdroplets dispersed in solution, and then these microdroplets were completely collected with magnetical hollow fiber bars; the pores of which were impregnated with hydrophobic ionic liquid, which makes the phase separation simplified with no need of centrifugation. Some experimental parameters, such as the type of ionic liquid, ultrasonic immersion time of hollow fiber, pH of sample solution, volume of hydrophilic ionic liquid, amount of ion-pairing agent NH 4 PF 6 , NaCl concentration, number of magnetical hollow fiber bar, stirring rate, and collection time were investigated and optimized. When the present method was applied to the analysis of real water samples, the precision and recoveries of six triazine herbicides vary from 0.1 to 9.2% and 73.4 to 118.5%, respectively. The detection limits for terbumeton, ametryn, prometryn, terbutryn, trietazine, and dimethametryn were 0.48, 0.15, 0.15, 0.14, 0.35, and 0.16 μg L -1 , respectively.

Multiple environmental factors regulate the expression of the carbohydrate-selective OprB porin of Pseudomonas aeruginosa.

PubMed

Adewoye, L O; Worobec, E A

1999-12-01

In response to low extracellular glucose concentration, Pseudomonas aeruginosa induces the expression of the outer membrane carbohydrate-selective OprB porin. The promoter region of the oprB gene was cloned into a lacZ transcriptional fusion vector, and the construct was mobilized into P. aeruginosa OprB-deficient strain, WW100, to evaluate additional environmental factors that influence OprB porin gene expression. Growth temperature, pH of the growth medium, salicylate concentration, and carbohydrate source were found to differentially influence porin expression. This expression pattern was compared to those of whole-cell [14C]glucose uptake under conditions of high osmolarity, ionicity, variable pH, growth temperatures, and carbohydrate source. These studies revealed that the high-affinity glucose transport genes are down-regulated by salicylic acid, differentially regulated by pH and temperature, and are specifically responsive to exogenous glucose induction.

Scaling Behavior for Ionic Transport and its Fluctuations in Individual Carbon Nanotubes

PubMed Central

Secchi, Eleonora; Niguès, Antoine; Jubin, Laetitia; Siria, Alessandro; Bocquet, Lydéric

2016-01-01

In this Letter, we perform an experimental study of ionic transport and current fluctuations inside individual carbon nanotubes (CNTs). The conductance exhibits a power law behavior at low salinity, with an exponent close to 1/3 versus the salt concentration in this regime. This behavior is rationalized in terms of a salinity dependent surface charge, which is accounted for on the basis of a model for hydroxide adsorption at the (hydrophobic) carbon surface. This is in contrast to boron nitride nanotubes which exhibit a constant surface conductance. Further, we measure the low frequency noise of the ionic current in CNTs and show that the amplitude of the noise scales with the surface charge, with data collapsing on a master curve for the various studied CNTs at a given pH. PMID:27127970

Drag reducing properties of microalgal exopolymers.

PubMed

Ramus, J; Kenney, B E; Shaughnessy, E J

1989-01-25

Dilute aqueous solutions of polymers released by marine phytoplankton (microalgae) were shown to effectively reduce drag in capillary pipe flow. Tests were performed in a capillary turbulent flow viscometer which extruded small samples under high pressures. In all, 22 species were screened, and the products of one chlorophyte and four rhodophyte species proved especially effective. The viscoelastic polymers produced by these species delayed the transition from laminar to turbulent flow to significantly higher Re. In general, polymeric regime segments come off the maximum drag reduction asymptote at characteristic retro-onset points, and come to lie approximately parallel to, but displaced upwards from the Prandtl-von Karman line. The delay to transition was shown to be dependent on additive polymer concentration, capillary diameter, and temperature. Ionic concentration, ionic composition, or pH had little effect on drag reducing properties.

THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS

PubMed Central

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

Binding mechanisms for histamine and agmatine ligands in plasmid deoxyribonucleic acid purifications.

PubMed

Sousa, Ângela; Pereira, Patrícia; Sousa, Fani; Queiroz, João A

2014-10-31

Histamine and agmatine amino acid derivatives were immobilized into monolithic disks, in order to combine the specificity and selectivity of the ligand with the high mass transfer and binding capacity offered by monolithic supports, to purify potential plasmid DNA biopharmaceuticals. Different elution strategies were explored by changing the type and salt concentration, as well as the pH, in order to understand the retention pattern of different plasmids isoforms The pVAX1-LacZ supercoiled isoform was isolated from a mixture of pDNA isoforms by using NaCl increasing stepwise gradient and also by ammonium sulfate decreasing stepwise gradient, in both histamine and agmatine monoliths. Acidic pH in the binding buffer mainly strengthened ionic interactions with both ligands in the presence of sodium chloride. Otherwise, for histamine ligand, pH values higher than 7 intensified hydrophobic interactions in the presence of ammonium sulfate. In addition, circular dichroism spectroscopy studies revealed that the binding and elution chromatographic conditions, such as the combination of high ionic strength with extreme pH values can reversibly influence the structural stability of the target nucleic acid. Therefore, ascending sodium chloride gradients with pH manipulation can be preferable chromatographic conditions to be explored in the purification of plasmid DNA biopharmaceuticals, in order to avoid the environmental impact of ammonium sulfate. Copyright © 2014. Published by Elsevier B.V.

Determining fluoride ions in ammonium desulfurization slurry using an ion selective electrode method

NASA Astrophysics Data System (ADS)

Luo, Zhengwei; Guo, Mulin; Chen, Huihui; Lian, Zhouyang; Wei, Wuji

2018-02-01

Determining fluoride ions in ammonia desulphurization slurry using a fluoride ion selective electrode (ISE) is investigated. The influence of pH was studied and the appropriate total ionic strength adjustment buffer and its dosage were optimized. The impact of Fe3+ concentration on the detection results was analyzed under preferable conditions, and the error analysis of the ISE method’s accuracy and precision for measuring fluoride ion concentration in the range of 0.5-2000 mg/L was conducted. The quantitative recovery of F- in ammonium sulfate slurry was assessed. The results showed that when pH ranged from 5.5˜6 and the Fe3+ concentration was less than 750 mg/L, the accuracy and precision test results with quantitative recovery rates of 92.0%-104.2% were obtained.

The role of graphene oxide and graphene oxide-based nanomaterials in the removal of pharmaceuticals from aqueous media: a review.

PubMed

Khan, Ayub; Wang, Jian; Li, Jun; Wang, Xiangxue; Chen, Zhongshan; Alsaedi, Ahmed; Hayat, Tasawar; Chen, Yuantao; Wang, Xiangke

2017-03-01

In this review paper, the ill effects of pharmaceuticals (PhAs) on the environment and their adsorption on graphene oxide (GO) and graphene oxide-based (GO-based) nanomaterials have been summarised and discussed. The adsorption of prominent PhAs discussed herein includes beta-blockers (atenolol and propranolol), antibiotics (tetracycline, ciprofloxacin and sulfamethoxazole), pharmaceutically active compounds (carbamazepine) and analgesics such as diclofenac. The adsorption of PhAs strictly depends upon the experimental conditions such as pH, adsorbent and adsorbate concentrations, temperature, ionic strength, etc. To understand the adsorption mechanism and feasibility of the adsorption process, the adsorption isotherms, thermodynamics and kinetic studies were also considered. Except for some cases, GO and its derivatives show excellent adsorption capacities for PhAs, which is crucial for their applications in the environmental pollution cleanup.

Utilization of a modified special-cubic design and an electronic tongue for bitterness masking formulation optimization.

PubMed

Li, Lianli; Naini, Venkatesh; Ahmed, Salah U

2007-10-01

A unique modification of simplex design was applied to an electronic tongue (E-Tongue) analysis in bitterness masking formulation optimization. Three formulation variables were evaluated in the simplex design, i.e. concentrations of two taste masking polymers, Amberlite and Carbopol, and pH of the granulating fluid. Response of the design was a bitterness distance measured using an E-Tongue by applying a principle component analysis, which represents taste masking efficiency of the formulation. The smaller the distance, the better the bitterness masking effect. Contour plots and polynomial equations of the bitterness distance response were generated as a function of formulation composition and pH. It was found that interactions between polymer and pH reduced the bitterness of the formulation, attributed to pH-dependent ionization and complexation properties of the ionic polymers, thus keeping the drug out of solution and unavailable to bitterness perception. At pH 4.9 and an Amberlite/Carbopol ratio of 1.4:1 (w/w), the optimal taste masking formulation was achieved and in agreement with human gustatory sensation study results. Therefore, adopting a modified simplex experimental design on response measured using an E-Tongue provided an efficient approach to taste masking formulation optimization using ionic binding polymers. (c) 2007 Wiley-Liss, Inc.

An evaluation of soluble cations and anions on the conductivity and rate of flocculation of kaolins

NASA Astrophysics Data System (ADS)

Fulton, Deborah Lee

1998-10-01

The focus of this project was to learn how ionic concentrations and their contributions to electric conductivity influence the flocculation behavior of kaolin/water suspensions. Sodium silicate, calcium chloride, and magnesium sulfate were used as chemical additives. The specific surface areas, particle size distributions, and methylene blue indices for two kaolins were measured. The SSA and MBI for these kaolins indicated that they possessed inherent differences in SSA and flocculation behaviors. Rheological studies were also performed. Testing included simultaneous gelation, deflocculation, and pH tests. Viscosity, pH, temperature, and chemical additive concentrations were monitored at each point. Testing was performed at 45/55 wt% solids. Effects of additions of various levels of deflocculant and flocculant to each of the kaolin/water suspensions were studied by making several suspensions from each kaolin. The concentrations of dispersant, and flocculant levels and types were varied to produce suspensions with different chemical additive "histories," but all with similar final apparent viscosities. Slurry filtrates were analyzed for conductivity, pH, temperature, and ion concentrations of (Al3+, Fe2+,3+, Ca 2+, Mg+, Na+, SO4 2--, and Cl--). Plastic properties were calculated to determine how variations in suspension histories affected conductivities, pH, and detectable ion contents of the suspensions. These analyses were performed on starting slurries which were under-, completely-, and over-deflocculated before further additions of flocculants and deflocculant were added to tune the slurries to the final, constant, target viscosity. Results showed that rates of flocculation and conductivities increased as concentrations of ions increased. By increasing conductivity correlations with increases in flocculation occurs, which yields higher rates of buildup, or RBU [1]. This is the single most important slip control property in the whitewares industry. Shear-thinning behavior of the bodies also increased with increases in ion concentrations and conductivities. Bingham viscosities decreased as ionic concentrations increased. Brookfield buildup (BBU), plasticity index, yield stress, and pseudoplastic index generally increased as chemical additions increased. Softness and plastic behavior of the bodies increased with increasing concentrations of additive chemicals and with increasing conductivity. Calcium, sodium, and sulfate ions were primarily responsible for increasing conductivity. Calcium chloride was a more effective flocculant than magnesium sulfate.

pH regulation of the kinetic stability of the lipase from Thermomyces lanuginosus.

PubMed

Wang, H; Andersen, K K; Sehgal, P; Hagedorn, J; Westh, P; Borch, K; Otzen, D E

2013-01-08

Thermomyces lanuginosus lipase (TlL) is a kinetically stable protein, resistant toward both denaturation and refolding in the presence of the ionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant decyl maltoside (DecM). We investigate the pH dependence of this kinetic stability. At pH 8, TlL remains folded and enzymatically active at multimillimolar surfactant concentrations but fails to refold from the acid urea-denatured state at submillimolar concentrations of SDS and DecM, indicating a broad concentration range of kinetic trapping or hysteresis. At pH 8, very few SDS molecules bind to TlL. The hysteresis SDS concentration range shrinks when moving to pH 4-6; in this pH range, SDS binds as micellelike clusters. Although hysteresis can be eliminated by reducing disulfide bonds, destabilizing the native state, and lowering the unfolding activation barrier, SDS sensitivity is not directly linked to intrinsic kinetic stability [its resistance to the general chemical denaturant guanidinium chloride (GdmCl)], because TlL unfolds more slowly in GdmCl at pH 6.0 than at pH 8.0. However, the estimated net charge drops from approximately -12 to approximately -5 between pH 8 and 6. SDS denatures TlL at pH 6.0 by nucleating via a critical number of bound SDS molecules on the surface of native TlL to form clusters. These results imply that SDS sensitivity is connected to the availability of appropriately charged regions on the protein. We suggest that conformational rigidity is a necessary but not sufficient feature of SDS resistance, because this has to be combined with sufficient negative electrostatic potential to avoid extensive SDS binding.

The pH and ionic composition of stratiform cloud water

NASA Astrophysics Data System (ADS)

Castillo, Raymond A.; Jiusto, James E.; Mclaren, Eugene

Over 50 cloud water samples were collected during five comprehensive case studies of the water chemistry of stratiform clouds at Whiteface Mountain, New York. The water samples were analyzed for pH, conductivity and ions of sodium, potassium, magnesium, calcium, ammonium, sulfate, chloride and nitrate. Trajectory analyses and cloud condensation nucleus concentrations at 0.5 % confirmed that the air masses in all five of these cases represented continental air that was relatively clean (low aerosol concentration) for the northeystern United States. The major ions related to cloud water pH were found to be sulfate, nitrate, potassium, ammonium and calcium. The results revealed a mean hydrogen ion concentration [ H+] = 0.239 meq ℓ -1 ( σ = ± 0.21) which converts to a mean pH = 3.6 for all collected cloud samples. The low pH values are related to a normal background of nitrate ions found in the rural continental air masses plus sulfate ions largely from the industrial emissions of the midwestern United States. The [NO -3], in two of the three cases presented, demonstrates the importance of the nitrate ions' contribution to the pH of cloud water. A dependent means analysis of 40 events yielded a significant difference (0.04 level of significance), with the mean pH of precipitation (4.2) being greater than the mean pH of cloud water (4.0) for event samples. The ion concentrations indicated that the cloud rainout process contributed from 67 % to almost 100% of the total ion concentration of the precipitation. The washout process, i.e. precipitation scavenging below the cloud base, contributed considerably less than the cloud/rainout process of those total precipitation anions associated with air pollution.

Distinct structural changes detected by X-ray fiber diffraction in stabilization of F-actin by lowering pH and increasing ionic strength.

PubMed

Oda, T; Makino, K; Yamashita, I; Namba, K; Maéda, Y

2001-02-01

Lowering pH or raising salt concentration stabilizes the F-actin structure by increasing the free energy change associated with its polymerization. To understand the F-actin stabilization mechanism, we studied the effect of pH, salt concentration, and cation species on the F-actin structure. X-ray fiber diffraction patterns recorded from highly ordered F-actin sols at high density enabled us to detect minute changes of diffraction intensities and to precisely determine the helical parameters. F-actin in a solution containing 30 mM NaCl at pH 8 was taken as the control. F-actin at pH 8, 30 to 90 mM NaCl or 30 mM KCl showed a helical symmetry of 2.161 subunits per turn of the 1-start helix (12.968 subunits/6 turns). Lowering pH from 8 to 6 or replacing NaCl by LiCl altered the helical symmetry to 2.159 subunits per turn (12.952/6). The diffraction intensity associated with the 27-A meridional layer-line increased as the pH decreased but decreased as the NaCl concentration increased. None of the solvent conditions tested gave rise to significant changes in the pitch of the left-handed 1-start helix (approximately 59.8 A). The present results indicate that the two factors that stabilize F-actin, relatively low pH and high salt concentration, have distinct effects on the F-actin structure. Possible mechanisms will be discussed to understand how F-actin is stabilized under these conditions.

The role of electrostatics in protein-protein interactions of a monoclonal antibody.

PubMed

Roberts, D; Keeling, R; Tracka, M; van der Walle, C F; Uddin, S; Warwicker, J; Curtis, R

2014-07-07

Understanding how protein-protein interactions depend on the choice of buffer, salt, ionic strength, and pH is needed to have better control over protein solution behavior. Here, we have characterized the pH and ionic strength dependence of protein-protein interactions in terms of an interaction parameter kD obtained from dynamic light scattering and the osmotic second virial coefficient B22 measured by static light scattering. A simplified protein-protein interaction model based on a Baxter adhesive potential and an electric double layer force is used to separate out the contributions of longer-ranged electrostatic interactions from short-ranged attractive forces. The ionic strength dependence of protein-protein interactions for solutions at pH 6.5 and below can be accurately captured using a Deryaguin-Landau-Verwey-Overbeek (DLVO) potential to describe the double layer forces. In solutions at pH 9, attractive electrostatics occur over the ionic strength range of 5-275 mM. At intermediate pH values (7.25 to 8.5), there is a crossover effect characterized by a nonmonotonic ionic strength dependence of protein-protein interactions, which can be rationalized by the competing effects of long-ranged repulsive double layer forces at low ionic strength and a shorter ranged electrostatic attraction, which dominates above a critical ionic strength. The change of interactions from repulsive to attractive indicates a concomitant change in the angular dependence of protein-protein interaction from isotropic to anisotropic. In the second part of the paper, we show how the Baxter adhesive potential can be used to predict values of kD from fitting to B22 measurements, thus providing a molecular basis for the linear correlation between the two protein-protein interaction parameters.

Polyelectrolyte multilayer assembly as a function of pH and ionic strength using the polysaccharides chitosan and heparin.

PubMed

Boddohi, Soheil; Killingsworth, Christopher E; Kipper, Matt J

2008-07-01

The goal of this work is to explore the effects of solution ionic strength and pH on polyelectrolyte multilayer (PEM) assembly, using biologically derived polysaccharides as the polyelectrolytes. We used the layer-by-layer (LBL) technique to assemble PEM of the polysaccharides heparin (a strong polyanion) and chitosan (a weak polycation) and characterized the sensitivity of the PEM composition and layer thickness to changes in processing parameters. Fourier-transform surface plasmon resonance (FT-SPR) and spectroscopic ellipsometry provided in situ and ex situ measurements of the PEM thickness, respectively. Vibrational spectroscopy and X-ray photoelectron spectroscopy (XPS) provided details of the chemistry (i.e., composition, electrostatic interactions) of the PEM. We found that when PEM were assembled from 0.2 M buffer, the PEM thickness could be increased from less than 2 nm per bilayer to greater than 4 nm per bilayer by changing the solution pH; higher and lower ionic strength buffer solutions resulted in narrower ranges of accessible thickness. Molar composition of the PEM was not very sensitive to solution pH or ionic strength, but pH did affect the interactions between the sulfonates in heparin and amines in chitosan when PEM were assembled from 0.2 M buffer. Changes in the PEM thickness with pH and ionic strength can be interpreted through descriptions of the charge density and conformation of the polyelectrolyte chains in solution.

Interaction of a novel peptoid enhancer--arginine oligomer with bovine submaxillary mucin.

PubMed

Liang, Wei; Davalian, Dariush; Torchilin, Vladimir P

2004-12-01

To determine the thermodynamics of binding reaction of arginine oligomer (R8) to bovine submaxillary mucin (BSM) in order to provide the foundation for understanding the influence of mucin on transport of macromolecules through mucosa mediated by arginine oligomer. Ultracentrifugation sedimentation was employed to investigate the interaction of BSM-R8. The mixtures of R8 with variable concentration and constant volume of BSM were placed on a shaker under oscillation at 25 degrees C to achieve equilibriums of binding reaction, and then centrifuged. The fluorescence intensity of the supernatant was measured by spectrofluorometer. The data were described by two types of binding sites model, the binding parameters of BSM-R8 were obtained by Scatchard plots. At the low pH values < or = 4.5 and ionic strength > or = 0.2 mol x L(-1), the BSM-R8 interaction was principally electrostatic interaction, the five primary binding sites (n1) predominantly were supplied by sulfate groups, the secondary binding sites apparently depended on pH, in that percent ionization of sialic acid residues (n2) in BSM. At the low ionic strength < or = 0.2 mol x L(-1) and pH 7.0, the BSM-R8 interaction was exceedingly complex, hydrogen bonds, hydrophobic interaction and electrostatic forces were involved in the interaction between R8 and BSM, the binding sites of BSM bound R8 were markedly increased. There existed evidence that R8 interacted with BSM. The pH and the ionic strength of the binding solution strongly affected the interaction of BSM with R8. The results suggested that the enhancing efficacy of the arginine oligomer for the transport of macromolecules through different site mucosa in body might be variable.

Electrostatically Driven Assembly of Charged Amphiphiles Forming Crystallized Membranes, Vesicles and Nanofiber Arrays

NASA Astrophysics Data System (ADS)

Leung, Cheuk Yui Curtis

Charged amphiphilic molecules can self-assemble into a large variety of objects including membranes, vesicles and fibers. These micro to nano-scale structures have been drawing increasing attention due to their broad applications, especially in biotechnology and biomedicine. In this dissertation, three self-assembled systems were investigated: +3/-1 self-assembled catanionic membranes, +2/-1 self-assembled catanionic membranes and +1 self-assembled nanofibers. Transmission electron microscopy (TEM) combined with synchrotron small and wide angle x-ray scattering (SAXS and WAXS) were used to characterize the coassembled structures from the mesoscopic to nanometer scale. We designed a system of +3 and -1 ionic amphiphiles that coassemble into crystalline ionic bilayer vesicles with large variety of geometries that resemble polyhedral cellular crystalline shells and archaea wall envelopes. The degree of ionization of the amphiphiles and their intermolecular electrostatic interactions can be controlled by varying pH. The molecular packing of these membranes showed a hexagonal to rectangular-C to hexagonal phase transition with increasing pH, resulting in significant changes to the membrane morphology. A similar mixture of +2 and -1 ionic amphiphiles was also investigated. In addition to varying pH, which controls the headgroup attractions, we also adjust the tail length of the amphiphiles to control the van der Waals interactions between the tails. A 2D phase diagram was developed to show how pH and tail length can be used to control the intermolecular packing within the membranes. Another system of self-assembled nanofiber network formed by positively charged amphiphiles was also studied. These highly charged fibers repel each other and are packed in hexagonal lattice with lattice constant at least eight times of the fiber diameter. The d-spacing and the crystal structure can be controlled by varying the solution concentration and temperature.

Electroosmotic pump performance is affected by concentration polarizations of both electrodes and pump

PubMed Central

Suss, Matthew E.; Mani, Ali; Zangle, Thomas A.; Santiago, Juan G.

2010-01-01

Current methods of optimizing electroosmotic (EO) pump performance include reducing pore diameter and reducing ionic strength of the pumped electrolyte. However, these approaches each increase the fraction of total ionic current carried by diffuse electric double layer (EDL) counterions. When this fraction becomes significant, concentration polarization (CP) effects become important, and traditional EO pump models are no longer valid. We here report on the first simultaneous concentration field measurements, pH visualizations, flow rate, and voltage measurements on such systems. Together, these measurements elucidate key parameters affecting EO pump performance in the CP dominated regime. Concentration field visualizations show propagating CP enrichment and depletion fronts sourced by our pump substrate and traveling at order mm/min velocities through millimeter-scale channels connected serially to our pump. The observed propagation in millimeter-scale channels is not explained by current propagating CP models. Additionally, visualizations show that CP fronts are sourced by and propagate from the electrodes of our system, and then interact with the EO pump-generated CP zones. With pH visualizations, we directly detect that electrolyte properties vary sharply across the anode enrichment front interface. Our observations lead us to hypothesize possible mechanisms for the propagation of both pump- and electrode-sourced CP zones. Lastly, our experiments show the dynamics associated with the interaction of electrode and membrane CP fronts, and we describe the effect of these phenomena on EO pump flow rates and applied voltages under galvanostatic conditions. PMID:21516230

Gold Nanoparticle-Quantum Dot Fluorescent Nanohybrid: Application for Localized Surface Plasmon Resonance-induced Molecular Beacon Ultrasensitive DNA Detection

NASA Astrophysics Data System (ADS)

Adegoke, Oluwasesan; Park, Enoch Y.

2016-11-01

In biosensor design, localized surface plasmon resonance (LSPR)-induced signal from gold nanoparticle (AuNP)-conjugated reporter can produce highly sensitive nanohybrid systems. In order to retain the physicochemical properties of AuNPs upon conjugation, high colloidal stability in aqueous solution is needed. In this work, the colloidal stability with respect to the zeta potential (ZP) of four negatively charged thiol-functionalized AuNPs, thioglycolic (TGA)-AuNPs, 3-mercaptopropionic acid (MPA)-AuNPs, l-cysteine-AuNPs and l-glutathione (GSH)-AuNPs, and a cationic cyteamine-capped AuNPs was studied at various pHs, ionic strength, and NP concentration. A strong dependence of the ZP charge on the nanoparticle (NP) concentration was observed. High colloidal stability was exhibited between pH 3 and 9 for the negatively charged AuNPs and between pH 3 and 7 for the cationic AuNPs. With respect to the ionic strength, high colloidal stability was exhibited at ≤104 μM for TGA-AuNPs, l-cysteine-AuNPs, and GSH-AuNPs, whereas ≤103 μM is recommended for MPA-AuNPs. For the cationic AuNPs, very low ionic strength of ≤10 μM is recommended due to deprotonation at higher concentration. GSH-AuNPs were thereafter bonded to SiO2-functionalized alloyed CdZnSeS/ZnSe1.0S1.3 quantum dots (SiO2-Qdots) to form a plasmon-enhanced AuNP-SiO2-Qdots fluorescent nanohybrid. The AuNP-SiO2-Qdots conjugate was afterward conjugated to a molecular beacon (MB), thus forming an ultrasensitive LSPR-induced SiO2-Qdots-MB biosensor probe that detected a perfect nucleotide DNA sequence at a concentration as low as 10 fg/mL. The limit of detection was 11 fg/mL (1.4 fM) while the biosensor probe efficiently distinguished between single-base mismatch and noncomplementary sequence target.

Expanding the range of free calcium regulation in biological solutions.

PubMed

Dweck, David; Reyes-Alfonso, Avelino; Potter, James D

2005-12-15

Many biological systems use ethylene glycol bis (beta-aminoethylether)-N,N,N',N'-tetraacetic acid (EGTA) to regulate the free calcium concentration ([Ca(2+)](free)) in the presence of physiological levels of free Mg(2+) ([Mg(2+)](free)). Frequently, it is necessary to work at [Ca(2+)](free) beyond EGTA's buffering capabilities. Therefore, we have developed methods to extend the buffering range by adding nitrilotriacetic acid (NTA) to solutions containing EGTA. This extension results from NTA having a lower K'(dCa) than EGTA. Such equilibria are solved by pCa Calculator, a computer program designed to aid in the study of Ca(2+)-dependent physiological processes while accounting for the effects of pH, temperature, and ionic strength. With multiple chelators and pH buffers from which to choose, pCa Calculator calculates the total concentration of each species required to achieve specified free concentrations of Ca(2+), ATP, and Mg(2+). The program is intuitive, user-friendly, and flexible enough to fix or vary the [Mg-ATP(2-)] and ionic strength. Moreover, it can account for increases in experimental volume from calcium addition. A comparative analysis is reported for testing solutions in the presence and absence of NTA by measuring the calcium binding affinity of fluorescent cardiac troponin C. These findings demonstrate that EGTA, when used in conjunction with NTA, improves and expands the regulation of free calcium in solution.

Pore-Scale Transport of Strontium During Dynamic Water Content Changes in the Unsaturated Zone

NASA Astrophysics Data System (ADS)

Weaver, W.; Kibbey, T. C. G.; Papelis, C.

2016-12-01

Dynamic water content changes in the unsaturated zone caused by natural and manmade processes, such as evaporation, rainfall, and irrigation, have an effect on contaminant mobility. In general, in the unsaturated zone, evaporation causes an increase in contaminant concentrations, potentially leading to sorption of contaminants on aquifer materials or precipitation of crystalline or amorphous phases. On the other hand, increase of water content may result in dissolution of precipitated phases and increased mobility of contaminants. The objective of this study was to develop a quantitative model for the transport of strontium through sand under dynamic water content conditions, as a function of strontium concentration, pH, and ionic strength. Strontium was selected as a surrogate for strontium-90, a by-product of nuclear reactions. The dynamic water content was determined using an automated device for rapidly measuring the hysteretic capillary pressure—saturation relationship, followed by ambient air evaporation, and gravimetric water content measurement. Strontium concentrations were measured using inductively coupled plasma mass spectrometry (ICP-MS). Flow interruption experiments were conducted to determine whether equilibrium conditions existed for a given flowrate. Scanning electron microscopy (SEM) was used to visualize the treated quartz sand particles and the distribution of strontium on sand grains was determined using elemental maps created by energy-dispersive x-ray spectroscopy (EDX). Strontium behavior appears to be pH dependent as well as ionic strength dependent under these conditions.

Encapsulation of ascorbyl palmitate in chitosan nanoparticles by oil-in-water emulsion and ionic gelation processes.

PubMed

Yoksan, Rangrong; Jirawutthiwongchai, Jatesuda; Arpo, Kridsada

2010-03-01

The encapsulation of ascorbyl palmitate (AP) in chitosan particles was carried out by droplet formation via an oil-in-water emulsion, followed by droplet solidification via ionic gelation using sodium triphosphate pentabasic (TPP) as a cross-linking agent. The success of AP encapsulation was confirmed by FT-IR, UV-vis spectrophotometry, TGA, and XRD techniques. The obtained AP-loaded chitosan particles were spherical in shape with an average diameter of 30-100nm as observed by SEM and TEM. Loading capacity (LC) and encapsulation efficiency (EE) of AP in the nanoparticles were about 8-20% and 39-77%, respectively, when the initial AP concentration was in the range of 25-150% (w/w) of chitosan. Augmentation of the initial AP concentration led to an increase of LC and a reduction of EE. The amount of AP released from the nanoparticles in ethanol and tris buffer (pH approximately 8.0) increased with increasing LC and decreasing TPP concentration.

pH effects on the hyaluronan hydrolysis catalysed by hyaluronidase in the presence of proteins: Part I. Dual aspect of the pH-dependence.

PubMed

Lenormand, Hélène; Deschrevel, Brigitte; Vincent, Jean-Claude

2010-05-01

Hyaluronan (HA) hydrolysis catalysed by hyaluronidase (HAase) is strongly inhibited when performed at a low ratio of HAase to HA concentrations and at low ionic strength. This is because long HA chains can form non-active complexes with HAase. Bovine serum albumin (BSA) is able to compete with HAase to form electrostatic complexes with HA so freeing HAase which then recovers its catalytic activity. This BSA-dependence is characterised by two main domains separated by the optimal BSA concentration: below this concentration the HAase activity increases when the BSA concentration is increased, above this concentration the HAase activity decreases. This occurs provided that HA is negatively charged and BSA is positively charged, i.e. in a pH range from 3 to 5.25. The higher the pH value the higher the optimal BSA concentration. Other proteins can also modulate HAase activity. Lysozyme, which has a pI higher than that of BSA, is also able to compete with HAase to form electrostatic complexes with HA and liberate HAase. This occurs over a wider pH range that extends from 3 to 9. These results mean that HAase can form complexes with HA and recover its enzymatic activity at pH as high as 9, consistent with HAase having either a high pI value or positively charged patches on its surface at high pH. Finally, the pH-dependence of HAase activity, which results from the influence of pH on both the intrinsic HAase activity and the formation of complexes between HAase and HA, shows a maximum at pH 4 and a significant activity up to pH 9. Copyright 2009 International Society of Matrix Biology. Published by Elsevier B.V. All rights reserved.

Heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride degradation.

PubMed

Meijide, Jessica; Pazos, Marta; Sanromán, Maria Ángeles

2017-10-15

The application of the electro-Fenton process for organic compound mineralisation has been widely reported over the past years. However, operational problems related to the use of soluble iron salt as a homogeneous catalyst involve the development of novel catalysts that are able to operate in a wide pH range. For this purpose, polyvinyl alcohol-alginate beads, containing goethite as iron, were synthesised and evaluated as heterogeneous electro-Fenton catalyst for 1-butylpyridinium chloride mineralisation. The influence of catalyst dosage and pH solution on ionic liquid degradation was analysed, achieving almost total oxidation after 60 min under optimal conditions (2 g/L catalyst concentration and pH 3). The results showed good catalyst stability and reusability, although its effectiveness decreases slightly after three successive cycles. Furthermore, a plausible mineralisation pathway was proposed based on the oxidation byproducts determined by chromatographic techniques. Finally, the Microtox® test revealed notable detoxification after treatment which demonstrates high catalyst ability for pyridinium-based ionic liquid degradation by the electro-Fenton process.

Osmotic pressures and second virial coefficients for aqueous saline solutions of lysozyme

DOE PAGES

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

Extraction of acetanilides in rice using ionic liquid-based matrix solid phase dispersion-solvent flotation.

PubMed

Zhang, Liyuan; Wang, Changyuan; Li, Zuotong; Zhao, Changjiang; Zhang, Hanqi; Zhang, Dongjie

2018-04-15

Ionic liquid-based matrix solid phase dispersion-solvent flotation coupled with high performance liquid chromatography was developed for the determination of the acetanilide herbicides, including metazachlor, propanil, alachlor, propisochlor, pretilachlor, and butachlor in rice samples. Some experimental parameters, including the type of dispersant, the mass ratio of dispersant to sample, pH of sample solution, the type of extraction solvent, the type of ionic liquid, flotation time, and flow rate of N 2 were optimized. The average recoveries of the acetanilide herbicides at spiked concentrations of 50, 125, and 250 µg/kg ranged from 89.4% to 108.7%, and relative standard deviations were equal to or lower than 7.1%, the limits of quantification were in the range of 38.0 to 84.7 µg/kg. Copyright © 2017 Elsevier Ltd. All rights reserved.

Coagulation removal of humic acid-stabilized carbon nanotubes from water by PACl: influences of hydraulic condition and water chemistry.

PubMed

Ma, Si; Liu, Changli; Yang, Kun; Lin, Daohui

2012-11-15

Discharged carbon nanotubes (CNTs) can adsorb the widely-distributed humic acid (HA) in aquatic environments and thus be stabilized. HA-stabilized CNTs can find their way into and challenge the potable water treatment system. This study investigated the efficiency of coagulation and sedimentation techniques in the removal of the HA-stabilized multi-walled carbon nanotubes (MWCNTs) using polyaluminum chloride (PACl) as a coagulant, with a focus on the effects of hydraulic conditions and water chemistry. Stirring speeds in the mixing and reacting stages were gradually changed to examine the effect of the hydraulic conditions on the removal rate. The stirring speed in the reacting stage affected floc formation and thereby had a greater impact on the removal rate than the stirring speed in the mixing stage. Water chemistry factors such as pH and ionic strength had a significant effect on the stability of MWCNT suspension and the removal efficiency. Low pH (4-7) was favorable for saving the coagulant and maintaining high removal efficiency. High ionic strength facilitated the destabilization of the HA-stabilized MWCNTs and thereby lowered the required PACl dosage for the coagulation. However, excessively high ionic strength (higher than the critical coagulation concentration) decreased the maximum removal rate, probably by inhibiting ionic activity of PACl hydrolyzate in water. These results are expected to shed light on the potential improvement of coagulation removal of aqueous stabilized MWCNTs in water treatment systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Theoretical and experimental adsorption studies of sulfamethoxazole and ketoprofen on synthesized ionic liquids modified CNTs.

PubMed

Lawal, Isiaka A; Lawal, Monsurat M; Akpotu, Samson O; Azeez, Mayowa A; Ndungu, Patrick; Moodley, Brenda

2018-06-18

The adsorption of sulfamethoxazole (SMZ) and ketoprofen (KET) using carbon nanotubes (CNTs) and CNTs modified with ionic liquids (ILs) was investigated. Two ionic liquids (1-benzyl, 3-hexyl imidazolium, IL1 and 1-benzyl, 3-decahexyl imidazolium, IL2) were synthesized, and characterized by nuclear magnetic resonance ( 1 H and 13 C NMR) and high resolution-mass spectrometry (HR-MS). CNTs and modified CNTs were characterized using FT-IR, X-ray diffraction (XRD), surface area and porosity analysis, thermal gravimetric analysis (TGA), Zeta potential, Raman and scanning electron microscopy (SEM). Kinetics, isotherm and computational studies were carried out to determine the efficiency and adsorption mechanism of SMZ and KET on modified CNTs. A density functional theory (DFT) method was applied to shed more light on the interactions between the pharmaceutical compounds and the adsorbents at the molecular level. The effects of adsorbent dosage, concentration, solution pH, energetics and contact time of SMZ and KET on the adsorption process were investigated. The adsorption of SMZ and KET on CNTs and modified CNTs were pH dependent, and adsorption was best described by pseudo-second-order kinetics and the Freundlich adsorption isotherm. Ionic liquid modified CNTs showed improved adsorption capacities compared to the unmodified ones for both SMZ and KET, which is in line with the computational results showing performance order; CNT+KET/SMZ < CNT-ILs+SMZ < CNT-ILs+KET. Copyright © 2018 Elsevier Inc. All rights reserved.

Gas-assisted dispersive liquid-phase microextraction using ionic liquid as extracting solvent for spectrophotometric speciation of copper.

PubMed

Akhond, Morteza; Absalan, Ghodratollah; Pourshamsi, Tayebe; Ramezani, Amir M

2016-07-01

Gas-assisted dispersive liquid-phase microextraction (GA-DLPME) has been developed for preconcentration and spectrophotometric determination of copper ion in different water samples. The ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate and argon gas, respectively, were used as the extracting solvent and disperser. The procedure was based on direct reduction of Cu(II) to Cu(I) by hydroxylamine hydrochloride, followed by extracting Cu(I) into ionic liquid phase by using neocuproine as the chelating agent. Several experimental variables that affected the GA-DLPME efficiency were investigated and optimized. Under the optimum experimental conditions (IL volume, 50µL; pH, 6.0; acetate buffer, 1.5molL(-1); reducing agent concentration, 0.2molL(-1); NC concentration, 120µgmL(-1); Ar gas bubbling time, 6min; argon flow rate, 1Lmin(-1); NaCl concentration, 6% w/w; and centrifugation time, 3min), the calibration graph was linear over the concentration range of 0.30-2.00µgmL(-1) copper ion with a limit of detection of 0.07µgmL(-1). Relative standard deviation for five replicate determinations of 1.0µgmL(-1) copper ion was found to be 3.9%. The developed method was successfully applied to determination of both Cu(I) and Cu(II) species in water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Micro-rheology on (polymer-grafted) colloids using optical tweezers.

PubMed

Gutsche, C; Elmahdy, M M; Kegler, K; Semenov, I; Stangner, T; Otto, O; Ueberschär, O; Keyser, U F; Krueger, M; Rauscher, M; Weeber, R; Harting, J; Kim, Y W; Lobaskin, V; Netz, R R; Kremer, F

2011-05-11

Optical tweezers are experimental tools with extraordinary resolution in positioning (± 1 nm) a micron-sized colloid and in the measurement of forces (± 50 fN) acting on it-without any mechanical contact. This enables one to carry out a multitude of novel experiments in nano- and microfluidics, of which the following will be presented in this review: (i) forces within single pairs of colloids in media of varying concentration and valency of the surrounding ionic solution, (ii) measurements of the electrophoretic mobility of single colloids in different solvents (concentration, valency of the ionic solution and pH), (iii) similar experiments as in (i) with DNA-grafted colloids, (iv) the nonlinear response of single DNA-grafted colloids in shear flow and (v) the drag force on single colloids pulled through a polymer solution. The experiments will be described in detail and their analysis discussed.

EFFECTS OF PH, SOLID/SOLUTION RATIO, IONIC STRENGTH, AND ORGANIC ACIDS ON PB AND CD SOPRTION ON KAOLINITE

EPA Science Inventory

Potentiometric and ion-selective electrode titrations together with batch sorption/desorption experiments, were performed to explain the aqueous and surface complexation reactions between kaolinite, Pb, Cd and three organic acids. Variables included pH, ionic strength, metal conc...

Characterization of morphological response of red cells in a sucrose solution.

PubMed

Rudenko, Sergey V

2009-01-01

The dynamics of red cell shape changes following transfer into sucrose media having a low chloride content was studied. Based on a large number of measurements, six types of morphological response (MR), differing both in the degree of shape changes and the time course of the process, were identified. The most prominent type of response is a triphasic sequence of shape changes consisting of a fast transformation into a sphere (phase 1), followed by restoration of the discoid shape (phase 2) and final transformation into spherostomatocytes (phase 3), with individual parameters which could vary significantly. It was found that individual morphological response exhibited day to day variations, depending on the initial state of the red blood cells and the donor, but to a larger extent depended on the composition of the sucrose solution, such as concentration and type of buffers, the presence of EDTA, calcium, as well as very small amounts of extracellular hemoglobin. MR shows strong pH and ionic strength dependence. Low pH inhibited phase 1 and high pH changed dramatically the time course of the response. Increasing ionic strength inhibited all phases of MR, and at concentrations above 10-20 mM NaCl it was fully suppressed. Tris and phosphate were also inhibitory whereas HEPES, MOPS and Tricine were less effective. MR occurred also in hypertonic or hypotonic sucrose solutions, with exception of extreme hypotonicity due to volume restrictions. It is concluded that strong membrane depolarization per se is not a causal factor leading to MR, and its different phases could be regulated independently. For some types of morphological response the fast shape transformation from sphere to disc and back to sphere occurs within a 10 s time interval and could be accelerated several fold in the presence of a small amount of hemoglobin. It is suggested that MR represents a type of general cell reaction that occurs upon exposure to low ionic strength.

Compatible intracellular ion composition of the host improves carbon assimilation by zooxanthellae in mutualistic symbioses.

PubMed

Seibt, C; Schlichter, D

2001-09-01

Cytosymbiotic algae within the host's plasma are exposed to completely different ionic conditions than microalgae living in the sea. The altered ionic gradients, in particular, could be the reason for higher in hospite carbon assimilation levels. To study the effect of varying extracellular ionic conditions on isolated zooxanthellae, their photosynthetic capacity in pure seawater was compared to that in a test medium in which the concentrations of the major inorganic ions, the pH and the osmolality were adjusted to the conditions measured in the host cytoplasm. In this test medium the ratio between oxygen evolution and carbon fixation was 1.2:1.0; in contrast, zooxanthellae in the hyperionic seawater medium showed a comparatively higher oxygen production (2.6:1.0). These results are attributed to a higher energy demand for ion regulation of the isolated algae in the hyperionic medium. Isolated cytosymbionts in seawater need more energy both for the readjustment to the original intracellular ion concentration within the host cell and also for the maintenance of a much steeper gradient during incubation under hyperionic conditions outside the host. The particular intracellular ion concentration of the host cells could have been a decisive evolutionary factor for the very successful establishment of the mutualistic symbioses between anthozoans and dinoflagellates more than 200 million years ago.

Mobilization of natural colloids from an iron oxide-coated sand aquifer--Effect of pH and ionic strength

USGS Publications Warehouse

Bunn, Rebecca A.; Magelky, Robin D.; Ryan, Joseph N.; Elimelech, Menachem

2002-01-01

Field and laboratory column experiments were performed to assess the effect of elevated pH and reduced ionic strength on the mobilization of natural colloids in a ferric oxyhydroxide-coated aquifer sediment. The field experiments were conducted as natural gradient injections of groundwater amended by sodium hydroxide additions. The laboratory experiments were conducted in columns of undisturbed, oriented sediments and disturbed, disoriented sediments. In the field, the breakthrough of released colloids coincided with the pH pulse breakthrough and lagged the bromide tracer breakthrough. The breakthrough behavior suggested that the progress of the elevated pH front controlled the transport of the mobilized colloids. In the laboratory, about twice as much colloid release occurred in the disturbed sediments as in the undisturbed sediments. The field and laboratory experiments both showed that the total mass of colloid release increased with increasing pH until the concurrent increase in ionic strength limited release. A decrease in ionic strength did not mobilize significant amounts of colloids in the field. The amount of colloids released normalized to the mass of the sediments was similar for the field and the undisturbed laboratory experiments.

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

PubMed

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

2016-04-01

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

Interactions between a poorly soluble cationic drug and sodium dodecyl sulfate in dissolution medium and their impact on in vitro dissolution behavior.

PubMed

Huang, Zongyun; Parikh, Shuchi; Fish, William P

2018-01-15

In the pharmaceutical industry, in vitro dissolution testing ofsolid oral dosage forms is a very important tool for drug development and quality control. However, ion-pairing interaction between the ionic drugand surfactants in dissolution medium often occurs, resulting in inconsistent and incomplete drug release. The aim of this study is toevaluate the effects ofsodium dodecyl sulfate (SDS) mediated medium onthe dissolution behaviors of a poorly soluble cationic drug (Drug B). The study was carried out by measuring solubility of Drug B substance and dissolution rate of Drug B product in media containing SDS.Desolubilization of Drug B substance was observed at pH 4.5 in the presence of SDS at concentrations below critical micelle concentration (CMC) which is attributed to the formation of an insoluble di-dodecyl sulfate salt between SDS and Drug B. This ion-pairing effect is less significant with increasing medium pH where Drug B is less ionized and CMC of SDS is lower. In medium at pH 4.5, dissolution of Drug B product was found incomplete with SDS concentration below CMC due to the desolubilization of Drug B substance. In media with SDS level above CMC, the dissolution rate is rather slower with higher inter-vessel variations compared to that obtained in pH 4.5 medium without SDS. The dissolution results demonstrate that the presence of SDS in medium generates unexpected irregular dissolution profiles for Drug B which are attributed to incompatible dissolution medium for this particular drug. Therefore, non-ionic surfactant was selected for Drug B product dissolution method and ion-pairing effect in SDS mediated medium should be evaluated when developing a dissolution method for any poorly soluble cationic drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

Release of major ions during rigor mortis development in kid Longissimus dorsi muscle.

PubMed

Feidt, C; Brun-Bellut, J

1999-01-01

Ionic strength plays an important role in post mortem muscle changes. Its increase is due to ion release during the development of rigor mortis. Twelve alpine kids were used to study the effects of chilling and meat pH on ion release. Free ions were measured in Longissimus dorsi muscle by capillary electrophoresis after water extraction. All free ion concentrations increased after death, but there were differences between ions. Temperature was not a factor affecting ion release in contrast to ultimate pH value. Three release mechanisms are believed to coexist: a passive binding to proteins, which stops as pH decreases, an active segregation which stops as ATP disappears and the production of metabolites due to anaerobic glycolysis.

Use of a chemical equilibrium model to describe surface properties and uptake of cadmium, strontium, and lead by Chlorella (UTEX 252)

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

Hassett, J.M.

1988-01-01

Metal-aquatic biota interactions are important in both natural and engineered systems. In this study, the uptake of cadmium, strontium and lead by the unicellular green alga Chlorella (UTEX 252) was investigated. Variables included metal concentration, pH, and ionic strength. Data gathered included dry weights (mg/l), cell counts (cells/ml), electrophoretic mobilities (EPMs, {mu}m/sec/V/cm) of metal-free and metal-exposed cells, and metal uptake - difference in concentration in filtrate of cell-metal and cell-free metal solutions. Derived data included cell volumes and surface area, uptake on a {mu}M/m{sup 2} basis, {zeta}-potentials, diffuse layer potentials and charge densities. Typical uptake values were 1.1, 5.2, andmore » 6 {mu}M/m{sup 2} for Cd, Pb, and Sr, respectively, from solutions of pH 6, ionic strength 0.02M, and metal concentration 10{sup {minus}4} M. Cell EPMs were insensitive to metal; under certain conditions, however, (pM > 4, pH > 8), cadmium exposed cells exhibited a reversal in surface charge from negative to positive. The chemical equilibrium model MINEQL1 + STANFORD was used to model algal surface properties and metal uptake. Input data included site pK, density, and {Delta}pK, estimated from EPM-pH data. The model described surface properties of Chlorella (UTEX 252) as judged by a close fit of {zeta}-potentials and model-derived diffuse layer potentials. Metal uptake was modelled by adjusting site density and/or metal-surface site equilibrium constants. Attempts to model surface properties and metal uptake simultaneously were not successful.« less

Effects of starvation on the transport of Escherichia coli K12 in saturated porous media are dependent on pH and ionic strength

NASA Astrophysics Data System (ADS)

Xu, S.; Walczak, J. J.; Wang, L.; Bardy, S. L.; Li, J.

2010-12-01

In this research, we investigate the effects of starvation on the transport of E. coli K12 in saturated porous media. Particularly, we examine the relationship between such effects and the pH and ionic strength of the electrolyte solutions that were used to suspend bacterial cells. E. coli K12 (ATCC 10798) cells were cultured using either Luria-Bertani Miller (LB-Miller) broth (10 g trypton, 5 g yeast extract and 10 g NaCl in 1 L of deionized water) or LB-Luria broth (10 g tryptone, 5 g yeast extract and 0.5 g NaCl in 1 L of deionized water). Both broths had similar pH (~7.1) but differed in ionic strength (LB-Miller: ~170 mM, LB-Luria: ~ 8 mM). The bacterial cells were then harvested and suspended using one of the following electrolyte solutions: phosphate buffered saline (PBS) (pH ~7.2; ionic strength ~170 mM), 168 mM NaCl (pH ~5.7), 5% of PBS (pH ~ 7.2; ionic strength ~ 8 mM) and 8 mM NaCl (pH ~ 5.7). Column transport experiments were performed at 0, 21 and 48 hours following cell harvesting to evaluate the change in cell mobility over time under “starvation” conditions. Our results showed that 1) starvation increased the mobility of E. coli K12 cells; 2) the most significant change in mobility occurred when bacterial cells were suspended in an electrolyte solution that had different pH and ionic strength (i.e., LB-Miller culture suspended in 8 mM NaCl and LB-Luria culture suspended in 168 mM Nacl); and 3) the change in cell mobility primarily occurred within the first 21 hours. The size of the bacterial cells was measured and the surface properties (e.g., zeta potential, hydrophobicity, cell-bound protein, LPS sugar content, outer membrane protein profiles) of the bacterial cells were characterized. We found that the measured cell surface properties could not fully explain the observed changes in cell mobility caused by starvation.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Individual and Co Transport Study of Titanium Dioxide NPs and Zinc Oxide NPs in Porous Media

PubMed Central

Kumari, Jyoti; Mathur, Ankita; Rajeshwari, A.; Venkatesan, Arthi; S, Satyavati; Pulimi, Mrudula; Chandrasekaran, Natarajan; Nagarajan, R.; Mukherjee, Amitava

2015-01-01

The impact of pH and ionic strength on the mobility (individual and co-transport) and deposition kinetics of TiO2 and ZnO NPs in porous media was systematically investigated in this study. Packed column experiments were performed over a series of environmentally relevant ionic strengths with both NaCl (0.1−10 mM) and CaCl2 (0.01–0.1mM) solutions and at pH 5, 7, and 9. The transport of TiO2 NPs at pH 5 was not significantly affected by ZnO NPs in solution. At pH 7, a decrease in TiO2 NP transport was noted with co-existence of ZnO NPs, while at pH 9 an increase in the transport was observed. At pH 5 and 7, the transport of ZnO NPs was decreased when TiO2 NPs was present in the solution, and at pH 9, an increase was noted. The breakthrough curves (BTC) were noted to be sensitive to the solution chemistries; the decrease in the breakthrough plateau with increasing ionic strength was observed under all examined pH (5, 7, and 9). The retention profiles were the inverse of the plateaus of BTCs, as expected from mass balance considerations. Overall, the results from this study suggest that solution chemistries (ionic strength and pH) are likely the key factors that govern the individual and co-transport behavior of TiO2 and ZnO NPs in sand. PMID:26252479

Kinetics of binding of chicken cystatin to papain.

PubMed

Björk, I; Alriksson, E; Ylinenjärvi, K

1989-02-21

The kinetics of binding of chicken cystatin to papain were studied by stopped-flow fluorometry under pseudo-first-order conditions, i.e., with an excess of inhibitor. All reactions showed first-order behavior, and the observed pseudo-first-order rate constant increased linearly with the cystatin concentration up to the highest concentration that could be studied, 35 microM. The analyses thus provided no evidence for a limiting rate resulting from a conformational change stabilizing an initial encounter complex, in contrast with previous studies of reactions between serine proteinases and their protein inhibitors. The second-order association rate constant for complex formation was 9.9 X 10(6) M-1 s-1 at 25 degrees C, pH 7.4, I = 0.15, for both forms of cystatin, 1 and 2. This value approaches that expected for a diffusion-controlled rate. The temperature dependence of the association rate constant gave an enthalpy of activation at 25 degrees C of 31.5 kJ mol-1 and an entropy of activation at 25 degrees C of -7 J K-1 mol-1, compatible with no appreciable conformational change during the reaction. The association rate constant was independent of pH between pH 6 and 8 but decreased at lower and higher pH in a manner consistent with involvement of an unprotonated acid group with a pKa of 4-4.5 and a protonated basic group with a pKa of 9-9.5 in the interaction. The association rate constant was unaffected by ionic strengths between 0.15 and 1.0 but decreased somewhat at lower ionic strengths. Incubation of the complex between cystatin 2 and papain with an excess of cystatin 1 resulted in slow displacement of cystatin 2 from the complex.(ABSTRACT TRUNCATED AT 250 WORDS)

Quantification of amino acids and peptides in an ionic liquid based aqueous two-phase system by LC-MS analysis.

PubMed

Oppermann, Sebastian; Oppermann, Christina; Böhm, Miriam; Kühl, Toni; Imhof, Diana; Kragl, Udo

2018-04-25

Aqueous two-phase systems (ATPS) occur by the mixture of two polymers or a polymer and an inorganic salt in water. It was shown that not only polymers but also ionic liquids in combination with inorganic cosmotrophic salts are able to build ATPS. Suitable for the formation of ionic liquid-based ATPS systems are hydrophilic water miscible ionic liquids. To understand the driving force for amino acid and peptide distribution in IL-ATPS at different pH values, the ionic liquid Ammoeng 110™ and K 2 HPO 4 have been chosen as a test system. To quantify the concentration of amino acids and peptides in the different phases, liquid chromatography and mass spectrometry (LC-MS) technologies were used. Therefore the peptides and amino acids have been processed with EZ:faast™-Kit from Phenomenex for an easy and reliable quantification method even in complex sample matrices. Partitioning is a surface-dependent phenomenon, investigations were focused on surface-related amino acid respectively peptide properties such as charge and hydrophobicity. Only a very low dependence between the amino acids or peptides hydrophobicity and the partition coefficient was found. Nevertheless, the presented results show that electrostatic respectively ionic interactions between the ionic liquid and the amino acids or peptides have a strong impact on their partitioning behavior.

Impact of Environmental Conditions (pH, Ionic Strength, And Electrolyte Type) On The Surface Charge And Aggregation Of Silver Nanoparticles Suspensions

EPA Science Inventory

The impact of capping agents and environmental conditions (pH, ionic strength, and background electrolytes) on surface charge and aggregation potential of silver nanoparticles (AgNPs) suspensions were investigated. Capping agents are chemicals used in the synthesis of nanopartic...

Effect of various pH values, ionic strength, and temperature on papain hydrolysis of salivary film.

PubMed

Yao, Jiang-Wu; Xiao, Yin; Lin, Feng

2012-04-01

Stimulated human whole saliva (WS) was used to study the dynamics of papain hydrolysis at defined pH, ionic strength, and temperature with the view of reducing an acquired pellicle. A quartz crystal microbalance with dissipation (QCM-D) was used to monitor the changes in frequency caused by enzyme hydrolysis of WS films, and the hydrolytic parameters were calculated using an empirical model. The morphological and conformational changes of the salivary films before and after enzymatic hydrolysis were characterized by atomic force microscopy (AFM) imaging and grazing-angle Fourier transform infrared (GA-FTIR ) spectra, respectively. The characteristics of papain hydrolysis of WS films were pH-, ionic strength-, and temperature-dependent. The WS films were partially removed by the action of papain, resulting in thinner and smoother surfaces. The infrared data suggested that hydrolysis-induced deformation did not occur on the remnants of salivary films. The processes of papain hydrolysis of WS films can be controlled by properly regulating pH, ionic strength, and temperature. © 2012 Eur J Oral Sci.

NADP-dependent malate dehydrogenase (decarboxylating) from sugar cane leaves. Kinetic properties of different oligomeric structures.

PubMed

Iglesias, A A; Andreo, C S

1990-09-24

NADP-dependent malate dehydrogenase (decarboxylating) from sugar cane leaves was inhibited by increasing the ionic strength in the assay medium. The inhibitory effect was higher at pH 7.0 than 8.0, with median inhibitory concentrations (IC50) of 89 mM and 160 mM respectively, for inhibition by NaCl. Gel-filtration experiments indicated that the enzyme dissociated into dimers and monomers when exposed to high ionic strength (0.3 M NaCl). By using the enzyme-dilution approach in the absence and presence of 0.3 M NaCl, the kinetic properties of each oligomeric species of the protein was determined at pH 7.0 and 8.0. Tetrameric, dimeric and monomeric structures were shown to be active but with different V and Km values. The catalytic efficiency of the oligomers was tetramer greater than dimer greater than monomer, and each quaternary structure exhibited higher activity at pH 8.0 than 7.0. Dissociation constants for the equilibria between the different oligomeric forms of the enzyme were determined. It was established that Kd values were affected by pH and Mg2+ levels in the medium. Results suggest that the distinct catalytic properties of the different oligomeric forms of NADP-dependent malate dehydrogenase and changes in their equilibrium could be the molecular basis for an efficient physiological regulation of the decarboxylation step of C4 metabolism.

The Influence of Formulation and Manufacturing Process Parameters on the Characteristics of Lyophilized Orally Disintegrating Tablets

PubMed Central

Jones, Rhys J.; Rajabi-Siahboomi, Ali; Levina, Marina; Perrie, Yvonne; Mohammed, Afzal R.

2011-01-01

Gelatin is a principal excipient used as a binder in the formulation of lyophilized orally disintegrating tablets. The current study focuses on exploiting the physicochemical properties of gelatin by varying formulation parameters to determine their influence on orally disintegrating tablet (ODT) characteristics. Process parameters, namely pH and ionic strength of the formulations, and ball milling were investigated to observe their effects on excipient characteristics and tablet formation. The properties and characteristics of the formulations and tablets which were investigated included: glass transition temperature, wettability, porosity, mechanical properties, disintegration time, morphology of the internal structure of the freeze-dried tablets, and drug dissolution. The results from the pH study revealed that adjusting the pH of the formulation away from the isoelectric point of gelatin, resulted in an improvement in tablet disintegration time possibly due to increase in gelatin swelling resulting in greater tablet porosity. The results from the ionic strength study revealed that the inclusion of sodium chloride influenced tablet porosity, tablet morphology and the glass transition temperature of the formulations. Data from the milling study showed that milling the excipients influenced formulation characteristics, namely wettability and powder porosity. The study concludes that alterations of simple parameters such as pH and salt concentration have a significant influence on formulation of ODT. PMID:24310589

Interaction of copper and fulvic acid at the hematite-water interface

NASA Astrophysics Data System (ADS)

Christl, Iso; Kretzschmar, Ruben

2001-10-01

The influence of surface-bound fulvic acid on the sorption of Cu(II) to colloidal hematite particles was studied experimentally and the results were compared with model calculations based on the linear additivity assumption. In the first step, proton and Cu binding to colloidal hematite particles and to purified fulvic acid was studied by batch equilibration and ion-selective electrode titration experiments, respectively. The sorption data for these binary systems were modeled with a basic Stern surface complexation model for hematite and the NICA-Donnan model for fulvic acid. In the second step, pH-dependent sorption of Cu and fulvic acid in ternary systems containing Cu, hematite, and fulvic acid in NaNO3 electrolyte solutions was investigated in batch sorption experiments. Sorption of fulvic acid to the hematite decreased with increasing pH (pH 3-10) and decreasing ionic strength (0.01-0.1 M NaNO3), while the presence of 22 μM Cu had a small effect on fulvic acid sorption, only detectable at low ionic strength (0.01 M). Sorption of Cu to the solid phase separated by centrifugation was strongly affected by the presence of fulvic acid. Below pH 6, sorption of Cu to the solid phase increased by up to 40% compared with the pure hematite. Above pH 6, the presence of fulvic acid resulted in a decrease in Cu sorption due to increasing concentrations of dissolved metal-organic complexes. At low ionic strength (0.01 M), the effects of fulvic acid on Cu sorption to the solid phase were more pronounced than at higher ionic strength (0.1 M). Comparison of the experimental data with model calculations shows that Cu sorption in ternary hematite-fulvic acid systems is systematically underestimated by up to 30% using the linear additivity assumption. Therefore, specific interactions between organic matter and trace metal cations at mineral surfaces must be taken into account when applying surface complexation models to soils or sediments which contain oxides and natural organic matter.

In-vitro investigations of a pH- and ionic-strength-responsive polyelectrolytic hydrogel using a piezoresistive microsensor

PubMed Central

Schulz, Volker; Guenther, Margarita; Gerlach, Gerald; Magda, Jules J.; Tathireddy, Prashant; Rieth, Loren; Solzbacher, Florian

2010-01-01

Environmental responsive or smart hydrogels show a volume phase transition due to changes of external stimuli such as pH or ionic strength of an ambient solution. Thus, they are able to convert reversibly chemical energy into mechanical energy and therefore they are suitable as sensitive material for integration in biochemical microsensors and MEMS devices. In this work, micro-fabricated silicon pressure sensor chips with integrated piezoresistors were used as transducers for the conversion of mechanical work into an appropriate electrical output signal due to the deflection of a thin silicon bending plate. Within this work two different sensor designs have been studied. The biocompatible poly(hydroxypropyl methacrylate-N,N-dimethylaminoethyl methacrylate-tetra-ethyleneglycol dimethacrylate) (HPMA-DMA-TEGDMA) was used as an environmental sensitive element in piezoresistive biochemical sensors. This polyelectrolytic hydrogel shows a very sharp volume phase transition at pH values below about 7.4 which is in the range of the physiological pH. The sensor's characteristic response was measured in-vitro for changes in pH of PBS buffer solution at fixed ionic strength. The experimental data was applied to the Hill equation and the sensor sensitivity as a function of pH was calculated out of it. The time-dependent sensor response was measured for small changes in pH, whereas different time constants have been observed. The same sensor principal was used for sensing of ionic strength. The time-dependent electrical sensor signal of both sensors was measured for variations in ionic strength at fixed pH value using PBS buffer solution. Both sensor types showed an asymmetric swelling behavior between the swelling and the deswelling cycle as well as different time constants, which was attributed to the different nature of mechanical hydrogel-confinement inside the sensor. PMID:21152365

Biochemical thermodynamics: applications of Mathematica.

PubMed

Alberty, Robert A

2006-01-01

The most efficient way to store thermodynamic data on enzyme-catalyzed reactions is to use matrices of species properties. Since equilibrium in enzyme-catalyzed reactions is reached at specified pH values, the thermodynamics of the reactions is discussed in terms of transformed thermodynamic properties. These transformed thermodynamic properties are complicated functions of temperature, pH, and ionic strength that can be calculated from the matrices of species values. The most important of these transformed thermodynamic properties is the standard transformed Gibbs energy of formation of a reactant (sum of species). It is the most important because when this function of temperature, pH, and ionic strength is known, all the other standard transformed properties can be calculated by taking partial derivatives. The species database in this package contains data matrices for 199 reactants. For 94 of these reactants, standard enthalpies of formation of species are known, and so standard transformed Gibbs energies, standard transformed enthalpies, standard transformed entropies, and average numbers of hydrogen atoms can be calculated as functions of temperature, pH, and ionic strength. For reactions between these 94 reactants, the changes in these properties can be calculated over a range of temperatures, pHs, and ionic strengths, and so can apparent equilibrium constants. For the other 105 reactants, only standard transformed Gibbs energies of formation and average numbers of hydrogen atoms at 298.15 K can be calculated. The loading of this package provides functions of pH and ionic strength at 298.15 K for standard transformed Gibbs energies of formation and average numbers of hydrogen atoms for 199 reactants. It also provides functions of temperature, pH, and ionic strength for the standard transformed Gibbs energies of formation, standard transformed enthalpies of formation, standard transformed entropies of formation, and average numbers of hydrogen atoms for 94 reactants. Thus loading this package makes available 774 mathematical functions for these properties. These functions can be added and subtracted to obtain changes in these properties in biochemical reactions and apparent equilibrium constants.

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

Sawyer, Thomas W., E-mail: Thomas.Sawyer@drdc-rddc.gc.ca; Nelson, Peggy; Bjarnason, Stephen

The effect of ionic environment on sulphur mustard (bis 2-chloroethyl sulphide; HD) toxicity was examined in CHO-K1 cells. Cultures were treated with HD in different ionic environments at constant osmolar conditions (320 mOsM, pH 7.4). The cultures were refed with fresh culture medium 1 h after HD exposure, and viability was assessed. Little toxicity was apparent when HD exposures were carried out in ion-free sucrose buffer compared to LC{sub 50} values of {approx} 100-150 {mu}M when the cultures were treated with HD in culture medium. Addition of NaCl to the buffer increased HD toxicity in a salt concentration-dependent manner tomore » values similar to those obtained in culture medium. HD toxicity was dependent on both cationic and anionic species with anionic environment playing a much larger role in determining toxicity. Substitution of NaI for NaCl in the treatment buffers increased HD toxicity by over 1000%. The activity of the sodium hydrogen exchanger (NHE) in recovering from cytosolic acidification in salt-free and in different chloride salts did not correlate with the HD-induced toxicity in these buffers. However, the inhibition by HD of intracellular pH regulation correlated with its toxicity in NaCl, NaI and sucrose buffers. Analytical chemical studies and the toxicity of the iodine mustard derivative ruled out the role of chemical reactions yielding differentially toxic species as being responsible for the differences in HD toxicity observed. This work demonstrates that the early events that HD sets into motion to cause toxicity are dependent on ionic environment, possibly due to intracellular pH deregulation.« less

Polyelectrolyte brushes in mixed ionic medium studied via intermolecular forces

NASA Astrophysics Data System (ADS)

Farina, Robert; Laugel, Nicolas; Pincus, Philip; Tirrell, Matthew

2011-03-01

The vast uses and applications of polyelectrolyte brushes make them an attractive field of research especially with the growing interest in responsive materials. Polymers which respond via changes in temperature, pH, and ionic strength are increasingly being used for applications in drug delivery, chemical gating, etc. When polyelectrolyte brushes are found in either nature (e.g., surfaces of cartilage and mammalian lung interiors) or commercially (e.g., skin care products, shampoo, and surfaces of medical devices) they are always surrounded by mixed ionic medium. This makes the study of these brushes in varying ionic environments extremely relevant for both current and future potential applications. The polyelectrolyte brushes in this work are diblock co-polymers of poly-styrene sulfonate (N=420) and poly-t-butyl styrene (N=20) which tethers to a hydrophobic surface allowing for a purely thermodynamic study of the polyelectrolyte chains. Intermolecular forces between two brushes are measured using the SFA. As multi-valent concentrations are increased, the brushes collapse internally and form strong adhesion between one another after contact (properties not seen in a purely mono-valent environment).

Novel functionalized fluorescent polymeric nanoparticles for immobilization of biomolecules

NASA Astrophysics Data System (ADS)

Jain, Swati; Chattopadhyay, Sruti; Jackeray, Richa; Abid, C. K. V. Zainul; Singh, Harpal

2013-07-01

Novel, size controlled fluorescent polymeric nanoparticles (FPNP) were synthesized having acetoacetoxy functionality on the surface for immobilization of biomolecules which can be utilized as biomarkers and labels in fluoroimmunoassays. Core-shell nanoparticles of poly(styrene, St-methyl methacrylate, MMA-acetoacetoxy ethyl methacrylate, AAEM), stabilized by various concentrations of surfactant, sodium lauryl sulphate (SLS), were obtained by facile miniemulsion co-polymerization encapsulated with pyrene molecules in their hydrophobic core. Analytical, spectroscopic and imaging characterization techniques revealed the formation of stable, monodisperse, spherical nano sized particles exhibiting high luminescence properties. Particles with 1% SLS (S1) showed good dispersion stability and fluorescence intensity and were chosen as ideal candidates for further immobilization studies. Steady state fluorescence studies showed 10 times higher fluorescence intensity of S1 nanoparticles than that of pyrene solution in solvent-toluene at the same concentration. Environmental factors such as pH, ionic strength and time were found to have no effect on fluorescence intensity of FPNPs. Surface β-di-ketone groups were utilized for the covalent immobilization of enzyme conjugated antibodies without any activation or pre-treatment of nanoparticles.Novel, size controlled fluorescent polymeric nanoparticles (FPNP) were synthesized having acetoacetoxy functionality on the surface for immobilization of biomolecules which can be utilized as biomarkers and labels in fluoroimmunoassays. Core-shell nanoparticles of poly(styrene, St-methyl methacrylate, MMA-acetoacetoxy ethyl methacrylate, AAEM), stabilized by various concentrations of surfactant, sodium lauryl sulphate (SLS), were obtained by facile miniemulsion co-polymerization encapsulated with pyrene molecules in their hydrophobic core. Analytical, spectroscopic and imaging characterization techniques revealed the formation of stable, monodisperse, spherical nano sized particles exhibiting high luminescence properties. Particles with 1% SLS (S1) showed good dispersion stability and fluorescence intensity and were chosen as ideal candidates for further immobilization studies. Steady state fluorescence studies showed 10 times higher fluorescence intensity of S1 nanoparticles than that of pyrene solution in solvent-toluene at the same concentration. Environmental factors such as pH, ionic strength and time were found to have no effect on fluorescence intensity of FPNPs. Surface β-di-ketone groups were utilized for the covalent immobilization of enzyme conjugated antibodies without any activation or pre-treatment of nanoparticles. Electronic supplementary information (ESI) available: Resulting ATR-FTIR spectrum and procedure to study fluorescence of nanoparticles, effect of particle size, concentration, pH, ionic strength and time on Fl intensity of FPNP. See DOI: 10.1039/c3nr34100c

Magnetomotive room temperature dicationic ionic liquid: a new concept toward centrifuge-less dispersive liquid-liquid microextraction.

PubMed

Beiraghi, Asadollah; Shokri, Masood; Seidi, Shahram; Godajdar, Bijan Mombani

2015-01-09

A new centrifuge-less dispersive liquid-liquid microextraction technique based on application of magnetomotive room temperature dicationic ionic liquid followed by electrothermal atomic absorption spectrometry (ETAAS) was developed for preconcentration and determination of trace amount of gold and silver in water and ore samples, for the first time. Magnetic ionic liquids not only have the excellent properties of ionic liquids but also exhibit strong response to an external magnetic field. These properties provide more advantages and potential application prospects for magnetic ionic liquids than conventional ones in the fields of extraction processes. In this work, thio-Michler's ketone (TMK) was used as chelating agent to form Ag/Au-TMK complexes. Several important factors affecting extraction efficiency including extraction time, rate of vortex agitator, pH of sample solution, concentration of the chelating agent, volume of ionic liquid as well as effects of interfering species were investigated and optimized. Under the optimal conditions, the limits of detection (LOD) were 3.2 and 7.3ngL(-1) with the preconcentration factors of 245 and 240 for Au and Ag, respectively. The precision values (RSD%, n=7) were 5.3% and 5.8% at the concentration level of 0.05μgL(-1) for Au and Ag, respectively. The relative recoveries for the spiked samples were in the acceptable range of 96-104.5%. The results demonstrated that except Hg(2+), no remarkable interferences are created by other various ions in the determination of Au and Ag, so that the tolerance limits (WIon/WAu or Ag) of major cations and anions were in the range of 250-1000. The validated method was successfully applied for the analysis of Au and Ag in some water and ore samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Design of an optically stable pH sensor based on immobilization of Giemsa on triacetylcellulose membrane.

PubMed

Khodadoust, Saeid; Kouri, Narges Cham; Talebiyanpoor, Mohammad Sharif; Deris, Jamile; Pebdani, Arezou Amiri

2015-12-01

In this work a simple, inexpensive, and sensitive optical sensor based on triacetylcellulose membrane as solid support was developed by using immobilization of Giemsa indicator for pH measurement. In this method, the influence variables on the membrane performance including pH concentration of indicator, response time, ionic strength, and reversibility were investigated. At optimum values of all variables the response of optical pH sensor is linear in the pH range of 3.0-12.0. This optical sensor was produced through simultaneous binding of the Giemsa on the activated triacetylcellulose membrane which responded to the pH changes in a broader linear range within less than 2.0 min and suitable reproducibility (RSD<5%). Stability results showed that this sensor was stable after 6 months of storage in the water/ethanol (50:50, v/v) solution without any measurable divergence in response properties (less than 5% RSD). Copyright © 2015 Elsevier B.V. All rights reserved.

Thermodynamic considerations on the role of heat and mass transfer in biochemical causes of carcinogenesis

NASA Astrophysics Data System (ADS)

Lucia, Umberto; Grisolia, Giulia; Ponzetto, Antonio; Deisboeck, Thomas S.

2018-01-01

Cellular homoeostasis involves a continuous interaction between the cell and its microenvironment. As such, active and passive transport of ions, nutrients, molecules and water are the basis for biochemical-physical cell life. These transport phenomena change the internal and external ionic concentrations, and, as a consequence, the cell membrane's electric potential and the pH. In this paper we focus on the relationship between these ion transport-induced pH and membrane voltage changes to highlight their impact on carcinogenesis. The preliminary results suggest a critical role for Cl- in driving tumour transformation towards a more malignant phenotype.

A reagent strip for measuring the specific gravity of urine.

PubMed

Burkhardt, A E; Johnston, K G; Waszak, C E; Jackson, C E; Shafer, S R

1982-10-01

A solid-phase reagent for determination of urinary specific gravity (relative density) is described. This reagent strip, similar to others in the "N-Multistix" series (Ames), contains a polyacid whose acidity is sensitive to the ionic concentration in the urine in which it is immersed. As the acidity of the polyacid changes, pH changes are detected by a pH indicator within the reagent strip. In comparison studies, 84.4% of relative densities as measured with these reagent strips were within 0.005 of the corresponding results with a total-solids meter, and 89.9% were within 0.005 of the corresponding urinometer results. Adding a correction of +0.005 to the reagent-strip results for urines with high pH increased the percentage of results within 0.005 of the comparison method to 90.7% (TS meter) and 92.9% (urinometer). Lot-to-lot variability and reader-to-reader variability were both low. Reagent strip results are not affected by glucose, may be increased by albumin, and correlate with urea concentrations.

A de novo designed 11 kDa polypeptide: model for amyloidogenic intrinsically disordered proteins.

PubMed

Topilina, Natalya I; Ermolenkov, Vladimir V; Sikirzhytski, Vitali; Higashiya, Seiichiro; Lednev, Igor K; Welch, John T

2010-07-01

A de novo polypeptide GH(6)[(GA)(3)GY(GA)(3)GE](8)GAH(6) (YE8) has a significant number of identical weakly interacting beta-strands with the turns and termini functionalized by charged amino acids to control polypeptide folding and aggregation. YE8 exists in a soluble, disordered form at neutral pH but is responsive to changes in pH and ionic strength. The evolution of YE8 secondary structure has been successfully quantified during all stages of polypeptide fibrillation by deep UV resonance Raman (DUVRR) spectroscopy combined with other morphological, structural, spectral, and tinctorial characterization. The YE8 folding kinetics at pH 3.5 are strongly dependent on polypeptide concentration with a lag phase that can be eliminated by seeding with a solution of folded fibrillar YE8. The lag phase of polypeptide folding is concentration dependent leading to the conclusion that beta-sheet folding of the 11-kDa amyloidogenic polypeptide is completely aggregation driven.

A solid-state pH sensor for nonaqueous media including ionic liquids.

PubMed

Thompson, Brianna C; Winther-Jensen, Orawan; Winther-Jensen, Bjorn; MacFarlane, Douglas R

2013-04-02

We describe a solid state electrode structure based on a biologically derived proton-active redox center, riboflavin (RFN). The redox reaction of RFN is a pH-dependent process that requires no water. The electrode was fabricated using our previously described 'stuffing' method to entrap RFN into vapor phase polymerized poly(3,4-ethylenedioxythiophene). The electrode is shown to be capable of measuring the proton activity in the form of an effective pH over a range of different water contents including nonaqueous systems and ionic liquids (ILs). This demonstrates that the entrapment of the redox center facilitates direct electron communication with the polymer. This work provides a miniaturizable system to determine pH (effective) in nonaqueous systems as well as in ionic liquids. The ability to measure pH (effective) is an important step toward the ability to customize ILs with suitable pH (effective) for catalytic reactions and biotechnology applications such as protein preservation.

The rate of sulfide oxidation by δMnO 2 in seawater

NASA Astrophysics Data System (ADS)

Yao, Wensheng; Millero, Frank J.

1993-07-01

The rate of oxidation of hydrogen sulfide by manganese dioxide in seawater was determined as a function of pH (2.0-9.0), temperature (5-45°C), and ionic strength (0-4 M). The overall rate constant, k, in seawater at pH = 8.17 was found to be first order with respect to both sulfide and manganese dioxide: - d[H 2S] T/dt = k[H 2S] τ[MnO 2] . The rate constant, k, for seawater (S = 35.8, pH = 8.17) at 25°C was found to be 436 M -1 min -1, or 0.0244 m -2 1 min -1 when [MnO 2] is expressed in surface area (m 2/L). The energies of activation were found to be 14 ± 1 KJ mol -1 and 10 ± 1 KJ mol -1, respectively, for pH = 8.2 and pH = 5.0 in seawater (S = 35). The rate increased from pH 2.0 to a maximum at a pH of about 5.0 and decreased at higher pH. This pH dependence was attributed to formation of a surface complex between >MnO - and H 2S. As the concentration of HS - increases above pH = 5 the rate of the reaction decreases. The rate of sulfide oxidation by MnO 2 is not strongly dependent on ionic strength. The rates in 0.57 M NaCl were found to be slightly higher than the rates in seawater. Measurements made in solutions of the major sea salts indicated that Ca 2+ and Mg 2+ caused the rates to decrease, apparently by absorbing on the surface of manganese dioxide. Measurements made in artificial seawater (Na +, Mg 2+, Ca 2+, Cl -, and SO 2-4) were found to be in good agreement with the measurements in actual seawater. Phosphate was found to inhibit the reaction significantly.

Behavior of engineered nanoparticles in aqueous solutions and porous media: Connecting experimentation to probabilistic analysis

NASA Astrophysics Data System (ADS)

Contreras, Carolina

2011-12-01

Engineered nanoparticles have enhanced products and services in the fields of medicine, energy, engineering, communications, personal care, environmental treatment, and many others. The increased use of engineered nanoparticles in consumer products will lead to these materials in natural systems, inevitably becoming a potential source of pollution. The study of the stability and mobility of these materials is fundamental to understand their behavior in natural systems and predict possible health and environmental implications. In addition, the use of probabilistic methods such as sensitivity analysis applied to the parameters controlling their behavior is useful in providing support in performing a risk assessment. This research investigated the stability and mobility of two types of metal oxide nanoparticles (aluminum oxide and titanium dioxide). The stability studies tested the effect of sand, pH 4, 7, and 10, and the NaCl in concentrations of 10mM, 25mM, 50mM, and 75mM. The mobility was tested using saturated quartz sand columns and nanoparticles suspension at pH 4 and 7 and in the presence of NaCl and CaCl2 in concentrations of 0.1mM, 1mM, and 10mM. Additionally, this work performed a sensitivity analysis of physical parameters used in mobility experiment performed for titanium dioxide and in mobility experiments taken from the literature for zero valent iron nanoparticles and fluorescent colloids to determine their effect on the value C/Co of by applying qualitative and quantitative methods. The results from the stability studies showed that titanium dioxide nanoparticles (TiO2) could remain suspended in solution for up to seven days at pH 10 and pH 7 even after settling of the sand; while for pH 4 solutions titanium settled along with the sand and after seven days no particles were observed in suspension. Other stability studies showed that nanoparticle aluminum oxide (Al2O3) and titanium dioxide (TiO2) size increased with increasing ionic strength (10 to 75 mM NaCl). The results from the mobility experiments showed that ionic strength has more effect on aluminum oxide nanoparticles mobility than on titanium oxide nanoparticles mobility. For Al2O3 25% of the initial concentration was obtained in the effluent whereas for TiO2 less than the 10% of the initial concentration was observed. In general, when the ionic strength was increased the effluent of nanoparticles decreased. Collision efficiencies calculated base on the colloid filtration theory were consistent with the mobility experiments. Results from sensitivity analysis showed that for zero valent iron nanoparticles and fluorescent colloids porous medium diameter and porosity were the parameters that most influenced the variability of C/Co whereas for titanium dioxide nanoparticles C/Co was more sensitive to column length and pore water velocity.

Determination of Surface Charge of Titanium Dioxide (Anatase) at High Ionic Strength

NASA Astrophysics Data System (ADS)

Schoonen, M. A.; Strongin, D. R.

2014-12-01

Charge development on mineral surfaces is an important control on the fate of minor and trace elements in a wide range of environments, including in possible radioactive waste repositories. Formation waters have often a high ionic strength. In this study, we determined the zeta potential (ζ) of anatase in potassium chloride solutions with concentrations up to 3M (25°C). The zeta potential is the potential at the hydrodynamic shear plane. In this study, we made use of the electro-acoustic effect. This effect is based on the development of a measureable potential/current when the electrical double layer outside the shearplane is separated from a charged particle through rapid oscillation induced by a sound wave. The advantage of this type of measurement is that the particles are not subjected to a high electric field (common to typical zeta potential measurements), which leads to electrode reactions and a shift of solution pH. Measurements were collected by subtracting the ion vibration current (IVI) due to the presence of potassium and chloride ions from the CVI. The correction is necessary for measurements in solutions with I > 0.25 M. This subtraction was done at each of the measurement conditions by centrifuging the slurrly, measuring the IVI of the supernatant, reconstituting the slurry, and then measuring CVI of the slurry. Subtraction of IVI at each condition is critical because IVI changes with pH and accounts for most of raw signal. The results show that the anatase isoelectric point shifts from a pH ~6.5 to a value of ~4.5 at 1M KCl. At ionic strength in excess of 1 M KCl, the surface appears to be slightly negatively charged accross the pH range accessible by this technique (pH 2.5-10). The loss of an isoelectric point suggests that KCl is no longer an indifferent electrolyte at 1 M KCl and higher. The results are in disagreement with earlier measurements in which anatase was shown to have a positive charge at high ionic strength across the pH scale. The difference between the current and earlier work is likely a result of the IVI correction. While anatase is unlikely to be of importance in a waste environment, the work provides a method to determine charge on more relevant mineral surfaces. This can then lead to a better representation of the fate for radionuclides in the subsurface.

Buffer capacity of biologics--from buffer salts to buffering by antibodies.

PubMed

Karow, Anne R; Bahrenburg, Sven; Garidel, Patrick

2013-01-01

Controlling pH is essential for a variety of biopharmaceutical process steps. The chemical stability of biologics such as monoclonal antibodies is pH-dependent and slightly acidic conditions are favorable for stability in a number of cases. Since control of pH is widely provided by added buffer salts, the current study summarizes the buffer characteristics of acetate, citrate, histidine, succinate, and phosphate buffers. Experimentally derived values largely coincide with values calculated from a model that had been proposed in 1922 by van Slyke. As high concentrated protein formulations become more and more prevalent for biologics, the self-buffering potential of proteins becomes of relevance. The current study provides information on buffer characteristics for pH ranges down to 4.0 and up to 8.0 and shows that a monoclonal antibody at 50 mg/mL exhibits similar buffer capacity as 6 mM citrate or 14 mM histidine (pH 5.0-6.0). Buffer capacity of antibody solutions scales linearly with protein concentration up to more than 200 mg/mL. At a protein concentration of 220 mg/mL, the buffer capacity resembles the buffer capacity of 30 mM citrate or 50 mM histidine (pH 5.0-6.0). The buffer capacity of monoclonal antibodies is practically identical at the process relevant temperatures 5, 25, and 40°C. Changes in ionic strength of ΔI=0.15, in contrast, can alter the buffer capacity up to 35%. In conclusion, due to efficient self-buffering by antibodies in the pH range of favored chemical stability, conventional buffer excipients could be dispensable for pH stabilization of high concentrated protein solutions. Copyright © 2013 American Institute of Chemical Engineers.

Effect of salts on the kinetic parameters and thermal stability of bovine brain acid phosphatase.

PubMed

Bittencourt, H M; Chaimovich, H

1976-08-01

Bovine brain acid phosphatase is inhibited, at any pH, by an increase in ionic strength. The rate decrease is associated at pH 5, with a marked decrease in Km and, at pH 8, with a noticeable decrease in Vm. The rate of thermal inactivation of the enzyme is unaffected by increasing ionic strength up to 300 mM. These results are discussed in terms of interactions at the active site of the enzyme.

Harvesting Chlorella vulgaris by natural increase in pH: effect of medium composition.

PubMed

Nguyen, Thi Dong Phuong; Frappart, Matthieu; Jaouen, Pascal; Pruvost, Jérémy; Bourseau, Patrick

2014-01-01

The freshwater microalga Chlorella vulgaris was harvested by autoflocculation resulting from the precipitation of magnesium or calcium compounds induced by a slow increase in pH in the absence of CO2 input. Autoflocculation was tested in two culture media with, respectively, ammonium (NH4+) and nitrate (NO3-) ions as nitrogen source. The culture pH increased because of photosynthesis and CO2 stripping. pH rose to 11 after 8 h in the NO3- medium, but did not exceed 9 in the NH4+ medium. No flocculation took place in any of the media. Autoflocculation tests were repeated in the NO(3-)-based culture medium by progressively increasing the concentrations of Ca2+ and Mg2+ until inorganic compounds precipitated and flocculated microalgae. The minimal concentrations for flocculation were found to be 120 mg Ca2 L(-1) and 1000 mg Mg2+ L(-1). These values were, respectively, 3.5 times and 20 times higher than those allowing flocculation by NaOH addition. Energy-dispersive X-ray spectroscopy, zeta potential measurement, and ionic chromatography suggest that the mechanisms involved are different. The rate of cell removal was close to 90% in both cases, but cells were more concentrated in the aggregates obtained by magnesium compound precipitation, with an estimated concentration close to 33 g (dry matter) L(-1), against 19 g L(-1) for calcium phosphates.

Are clinical findings of systemic titanium dispersion following implantation explained by available in vitro evidence? An evidence-based analysis.

PubMed

Curtin, Justin Paul; Wang, Minji

2017-08-01

Although the presence of titanium wear particles released into tissues is known to induce local inflammation following the therapeutic implantation of titanium devices into humans, the role that titanium ions play in adverse tissue responses has received little attention. Support that ongoing titanium ion release occurs is evidenced by the presence of ionic titanium bound to transferrin in blood, and ongoing excretion in the urine of patients with titanium devices. However, as reports documenting the presence of titanium within tissues do not distinguish between particulate and ionic forms due to technical challenges, the degree to which ionic titanium is released into tissues is unknown. To determine the potential for titanium ion release into tissues, this study evaluates available in vitro evidence relating to the release of ionic titanium under physiological conditions. This is a systematic literature review of studies reporting titanium ion release into solutions from titanium devices under conditions replicating the interstitial pH and constituents. Inclusion and exclusion criteria were defined. Of 452 articles identified, titanium ions were reported in nine media relevant to human biology in seventeen studies. Only one study, using human serum replicated both physiological pH and the concentration of constituents while reporting the presence of titanium ions. While there is insufficient information to explain the factors that contribute to the presence of titanium ions in serum of humans implanted with titanium devices, currently available information suggests that areas of future inquiry include the role of transferrin and organic acids.

Interactions in Undersaturated and Supersaturated Lysozyme Solutions: Static and Dynamic Light Scattering Results

NASA Technical Reports Server (NTRS)

Muschol, Martin; Rosenberger, Franz

1995-01-01

We have performed multiangle static and dynamic light scattering studies of lysozyme solutions at pH=4.7. The Rayleigh ratio R(sub g) and the collective diffusion coefficient D(sub c) were determined as function of both protein concentration c(sub p) and salt concentration c(sub s) with two different salts. At low salt concentrations, the scattering ratio K(sub c)(sub p)/R(sub theta) and diffusivity increased with protein concentration above the values for a monomeric, ideal solution. With increasing salt concentration this trend was eventually reversed. The hydrodynamic interactions of lysozyme in solution, extracted from the combination of static and dynamic scattering data, decreased significantly with increasing salt concentration. These observations reflect changes in protein interactions, in response to increased salt screening, from net repulsion to net attraction. Both salts had the same qualitative effect, but the quantitative behavior did not scale with the ionic strength of the solution. This indicates the presence of salt specific effects. At low protein concentrations, the slopes of K(sub c)(sub p)/R(sub theta) and D(sub c) vs c(sub p) were obtained. The dependence of the slopes on ionic strength was modeled using a DLVO potential for colloidal interactions of two spheres, with the net protein charge Z(sub e) and Hamaker constant A(sub H) as fitting parameters. The model reproduces the observed variations with ionic strength quite well. Independent fits to the static and dynamic data, however, led to different values of the fitting parameters. These and other shortcomings suggest that colloidal interaction models alone are insufficient to explain protein interactions in solutions.

Effects of altered groundwater chemistry upon the pH-dependency and magnitude of bacterial attachment during transport within an organically contaminated sandy aquifer

USGS Publications Warehouse

Harvey, Ronald W.; Metge, David W.; Barber, Larry B.; Aiken, George R.

2010-01-01

The effects of a dilute (ionic strength = 5 ?? 10-3 M) plume of treated sewage, with elevated levels (3.9 mg/L) of dissolved organic carbon (DOC), upon the pH-dependency and magnitude of bacterial transport through an iron-laden, quartz sand aquifer (Cape Cod, MA) were evaluated using sets of replicate, static minicolumns. Compared with uncontaminated groundwater, the plume chemistry diminished bacterial attachment under mildly acidic (pH 5.0-6.5) in-situ conditions, in spite of the 5-fold increase in ionic strength and substantively enhanced attachment under more alkaline conditions. The effects of the hydrophobic neutral and total fractions of the plume DOC; modest concentrations of fulvic and humic acids (1.5 mg/L); linear alkyl benzene sulfonate (LAS) (25 mg/L); Imbentin (200 ??g/L), a model nonionic surfactant; sulfate (28 mg/L); and calcium (20 mg/L) varied sharply in response to relatively small changes in pH, although the plume constituents collectively decreased the pH-dependency of bacterial attachment. LAS and other hydrophobic neutrals (collectively representing only ???3% of the plume DOC) had a disproportionately large effect upon bacterial attachment, as did the elevated concentrations of sulfate within the plume. The findings further suggest that the roles of organic plume constituents in transport or bacteria through acidic aquifer sediments can be very different than would be predicted from column studies performed at circumneutral pH and that the inorganic constituents within the plume cannot be ignored.

Th(IV) Adsorption onto Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated Fullerene and Carboxylated Fullerene

PubMed Central

Wang, Jing; Liu, Peng; Li, Zhan; Qi, Wei; Lu, Yan; Wu, Wangsuo

2013-01-01

The adsorption of Th(IV) onto the surface of oxidized multi-walled carbon nanotubes (oMWCNTs) in the absence and presence of hydroxylated fullerene (C60(OH)n) and carboxylated fullerene (C60(C(COOH)2)n) has been investigated. C60(OH)n, C60(C(COOH)2)n and oMWCNTs have been chosen as model phases because of their representative in carbon nano-materials family. Adsorption experiments were performed by batch procedure as a function of contact time, pH, ionic strength, and temperature. The results demonstrated that the adsorption of Th(IV) was rapidly reached equilibrium and the kinetic process could be described by a pseudo-second-order rate model very well. Th(IV) adsorption on oMWCNTs was dependent on pH but independent on ionic strength. Adsorption isotherms were correlated better with the Langmuir model than with the Freundlich model. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Th(IV) adsorption on oMWCNTs was spontaneous and endothermic. Compared with the adsorption of Th(IV) on the same oMWCNTs free of C60(OH)n or C60(C(COOH)2)n, the study of a ternary system showed the inhibition effect of C60(OH)n at high concentration on the adsorption of Th(IV) in a pH range from neutral to slightly alkaline; whereas the promotion effect of C60(C(COOH)2)n, even at its low concentration, on Th(IV) adsorption was observed in acid medium. PMID:28788324

Th(IV) Adsorption onto Oxidized Multi-Walled Carbon Nanotubes in the Presence of Hydroxylated Fullerene and Carboxylated Fullerene.

PubMed

Wang, Jing; Liu, Peng; Li, Zhan; Qi, Wei; Lu, Yan; Wu, Wangsuo

2013-09-17

The adsorption of Th(IV) onto the surface of oxidized multi-walled carbon nanotubes (oMWCNTs) in the absence and presence of hydroxylated fullerene (C 60 (OH) n ) and carboxylated fullerene (C 60 (C(COOH)₂) n ) has been investigated. C 60 (OH) n , C 60 (C(COOH)₂) n and oMWCNTs have been chosen as model phases because of their representative in carbon nano-materials family. Adsorption experiments were performed by batch procedure as a function of contact time, pH, ionic strength, and temperature. The results demonstrated that the adsorption of Th(IV) was rapidly reached equilibrium and the kinetic process could be described by a pseudo-second-order rate model very well. Th(IV) adsorption on oMWCNTs was dependent on pH but independent on ionic strength. Adsorption isotherms were correlated better with the Langmuir model than with the Freundlich model. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Th(IV) adsorption on oMWCNTs was spontaneous and endothermic. Compared with the adsorption of Th(IV) on the same oMWCNTs free of C 60 (OH) n or C 60 (C(COOH)₂) n , the study of a ternary system showed the inhibition effect of C 60 (OH) n at high concentration on the adsorption of Th(IV) in a pH range from neutral to slightly alkaline; whereas the promotion effect of C 60 (C(COOH)₂) n , even at its low concentration, on Th(IV) adsorption was observed in acid medium.

Macroscopic and molecular approaches of enrofloxacin retention in soils in presence of Cu(II).

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2013-10-15

The co-adsorption of copper and the fluoroquinolone antibiotic enrofloxacin (ENR) at the water-soil interface was studied by means of batch adsorption experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The system was investigated over a pH range between 6 and 10, at different contact times, ionic strengths, and ENR concentrations. Adsorption coefficient - Kd - was determined at relevant environmental concentrations and the value obtained in water at a ionic strength imposed by the soil and at soil natural pH was equal to 0.66Lg(-1). ENR adsorption onto the soil showed strong pH dependence illustrating the influence of the electrostatic interactions in the sorption processes. The simultaneous co-adsorption of ENR and Cu(II) on the soil was also investigated. The presence of Cu(II) strongly influenced the retention of the antibiotic, leading to an increase up to 35% of adsorbed ENR amount. The combined quantitative and spectroscopic results showed that Cu(II) and ENR directly interacted at the water-soil interface to form ternary surface complexes. Cu K-edge EXAFS data indicated a molecular structure where the carboxylate and carbonyl groups of ENR coordinate to Cu(II) to form a 6-membered chelate ring and where Cu(II) bridges between ENR and the soil surface sites. Cu(II) bonds bidentately to the surface in an inner-sphere mode. Thus, the spectroscopic data allowed us to propose the formation of ternary surface complexes with the molecular architecture soil-Cu(II)-ENR. Copyright © 2013 Elsevier Inc. All rights reserved.

Intrinsic electric fields and proton diffusion in immobilized protein membranes. Effects of electrolytes and buffers.

PubMed Central

Zabusky, N J; Deem, G S

1979-01-01

We present a theory for proton diffusion through an immobilized protein membrane perfused with an electrolyte and a buffer. Using a Nernst-Planck equation for each species and assuming local charge neutrality, we obtain two coupled nonlinear diffusion equations with new diffusion coefficients dependent on the concentration of all species, the diffusion constants or mobilities of the buffers and salts, the pH-derivative of the titration curves of the mobile buffer and the immobilized protein, and the derivative with respect to ionic strength of the protein titration curve. Transient time scales are locally pH-dependent because of protonation-deprotonation reactions with the fixed protein and are ionic strength-dependent because salts provide charge carriers to shield internal electric fields. Intrinsic electric fields arise proportional to the gradient of an "effective" charge concentration. The field may reverse locally if buffer concentrations are large (greater to or equal to 0.1 M) and if the diffusivity of the electrolyte species is sufficiently small. The "ideal" electrolyte case (where each species has the same diffusivity) reduces to a simple form. We apply these theoretical considerations to membranes composed of papain and bovine serum albumin (BSA) and show that intrinsic electric fields greatly enhance the mobility of protons when the ionic strength of the salts is smaller than 0.1 M. These results are consistent with experiments where pH changes are observed to depend strongly on buffer, salt, and proton concentrations in baths adjacent to the membranes. PMID:233570

Removal of reactive red-120 and 4-(2-pyridylazo) resorcinol from aqueous samples by Fe3O4 magnetic nanoparticles using ionic liquid as modifier.

PubMed

Absalan, Ghodratollah; Asadi, Mozaffar; Kamran, Sedigheh; Sheikhian, Leila; Goltz, Douglas M

2011-08-30

The nanoparticles of Fe(3)O(4) as well as the binary nanoparticles of ionic liquid and Fe(3)O(4) (IL-Fe(3)O(4)) were synthesized for removal of reactive red 120 (RR-120) and 4-(2-pyridylazo) resorcinol (PAR) as model azo dyes from aqueous solutions. The mean size and the surface morphology of the nanoparticles were characterized by TEM, DLS, XRD, FTIR and TGA techniques. Adsorption of RR-120 and PAR was studied in a batch reactor at different experimental conditions such as nanoparticle dosage, dye concentration, pH of the solution, ionic strength, and contact time. Experimental results indicated that the IL-Fe(3)O(4) nanoparticles had removed more than 98% of both dyes under the optimum operational conditions of a dosage of 60mg, a pH of 2.5, and a contact time of 2min when initial dyes concentrations of 10-200mg L(-1) were used. The maximum adsorption capacity of IL-Fe(3)O(4) was 166.67 and 49.26mg g(-1) for RR-120 and PAR, respectively. The isotherm experiments revealed that the Langmuir model attained better fits to the equilibrium data than the Freundlich model. The Langmuir adsorption constants were 5.99 and 3.62L mg(-1) for adsorptions of RR-120 and PAR, respectively. Both adsorption processes were endothermic and dyes could be desorbed from IL-Fe(3)O(4) by using a mixed NaCl-acetone solution and adsorbent was reusable. Copyright © 2011 Elsevier B.V. All rights reserved.

Transport and deposition of Suwannee River Humic Acid/Natural Organic Matter formed silver nanoparticles on silica matrices: the influence of solution pH and ionic strength.

PubMed

Akaighe, Nelson; Depner, Sean W; Banerjee, Sarbajit; Sohn, Mary

2013-07-01

The transport and deposition of silver nanoparticles (AgNPs) formed from Ag(+) reduction by Suwannee River Humic Acid (SRHA) and Suwannee River Natural Organic Matter (SRNOM) utilizing a silica matrix is reported. The morphology and stability of the AgNPs was analyzed by transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential measurements. The percentage conversion of the initial [Ag(+)] to [AgNPs] was determined from a combination of atomic absorption (AAS) and UV-Vis spectroscopy, and centrifugation techniques. The results indicate higher AgNP transport and consequently low deposition in the porous media at basic pH conditions and low ionic strength. However, at low acidic pH and high ionic strength, especially with the divalent metallic cations, the mobility of the AgNPs in the porous media was very low, most likely due to NP aggregation. Overall, the results suggest the potential for AgNP contamination of subsurface soils and groundwater aquifers is mostly dependent on their aggregation state, controlled by the soil water and sediment ionic strength and pH. Copyright © 2013 Elsevier Ltd. All rights reserved.

Source of Sustained Voltage Difference between the Xylem of a Potted Ficus benjamina Tree and Its Soil

PubMed Central

Love, Christopher J.; Zhang, Shuguang; Mershin, Andreas

2008-01-01

It has long been known that there is a sustained electrical potential (voltage) difference between the xylem of many plants and their surrounding soil, but the mechanism behind this voltage has remained controversial. After eliminating any extraneous capacitive or inductive couplings and ground-mediated electric current flows, we have measured sustained differences of 50–200 mV between the xylem region of a Faraday-caged, intact, potted Ficus benjamina tree and its soil, as well as between its cut branches and soils and ionic solutions standardized to various pH values. Using identical platinum electrodes, no correlation between the voltage and time of day, illumination, sap flow, electrode elevation, or ionic composition of soil was found, suggesting no direct connection to simple dissimilar-metal redox reactions or transpirational activity. Instead, a clear relationship between the voltage polarity and magnitude and the pH difference between xylem and soil was observed. We attribute these sustained voltages to a biological concentration cell likely set up by the homeostatic mechanisms of the tree. Potential applications of this finding are briefly explored. PMID:18698415

Physicochemical properties and storage stability of soybean protein nanoemulsions prepared by ultra-high pressure homogenization.

PubMed

Xu, Jing; Mukherjee, Dipaloke; Chang, Sam K C

2018-02-01

This study investigated the effects of the ultrahigh pressure homogenization (pressure, protein concentration, oil phase fraction, pH, temperature, and ionic strength) and storage on the properties of nanoemulsions (100-500nm range), which were stabilized by laboratory-prepared soybean protein isolate (SPI), β-conglycinin (7S) and glycinin (11S). The nanoemulsions made with SPI, 7S and 11S proteins exhibited considerable stability over various ionic strengths (0-500mM NaCl), pH (<4 or >7), thermal treatments (30-60°C) and storage (0-45days). The far-UV spectra of SPI, 7S, 11S dispersions, and SPI-, 7S-, 11S protein-stabilized nanoemulsions were analyzed for the protein structural changes following lipid removal. The ultra-high pressure homogenization changed the secondary structure of SPI, 7S, 11S proteins in the nanoemulsions, and enhanced their stability. This study demonstrated that SPI, 7S, and 11S proteins can be used as effective emulsifiers in nanoemulsions prepared by ultra-high pressure homogenization. Copyright © 2017. Published by Elsevier Ltd.

Determination of microcystin-LR in drinking water using UPLC tandem mass spectrometry-matrix effects and measurement.

PubMed

Li, Wei; Duan, Jinming; Niu, Chaoying; Qiang, Naichen; Mulcahy, Dennis

2011-10-01

A simple detection method using ultra-performance liquid chromatography electrospray ionisation tandem mass spectrometry (UPLC-ESI-MS-MS) coupled with the sample dilution method for determining trace microcystin-LR (MC-LR) in drinking water is presented. The limit of detection (LOD) was 0.04 µg/L and the limit of quantitation (LOQ) was 0.1 µg/L. Water matrix effects of ionic strength, dissolved organic carbon (DOC) and pH were examined. The results indicate that signal detection intensity for MC-LR was significantly suppressed as the ionic strength increased from ultrapure water condition, whereas it increased slightly with solution pH and DOC at low concentrations. However, addition of methanol (MeOH) into the sample was able to counter the signal suppression effects. In this study, dilution of the tap water sample by adding 4% MeOH (v/v) was observed to be adequate to compensate for the signal suppression. The recoveries of the samples fortified with MC-LR (0.2, 1, and 10 µg/L) for three different tap water samples ranged from 84.4% to 112.9%.

Halloysite nanotubule clay for efficient water purification.

PubMed

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.

New Culture Medium Containing Ionic Concentrations of Nutrients Similar to Concentrations Found in the Soil Solution †

PubMed Central

Angle, J. Scott; McGrath, Stephen P.; Chaney, Rufus L.

1991-01-01

A new growth medium which closely approximates the composition of the soil solution is presented. This soil solution equivalent (SSE) medium contains the following components (millimolar): NO3, 2.5; NH4, 2.5; HPO4, 0.005; Na, 2.5; Ca, 4.0; Mg, 2.0; K, 0.503; Cl, 4.0; SO4, 5.0; ethylenediamine-di(o-hydroxyphenylacetic acid), 0.02; and MES [2-(N-morpholino)ethanesulfonic acid] (to maintain the pH at 6.0), 10, plus 0.1% arabinose. The advantages of the SSE medium are discussed. PMID:16348614

Study of surface-bonded dicationic ionic liquids as stationary phases for hydrophilic interaction chromatography.

PubMed

Qiao, Lizhen; Li, Hua; Shan, Yuanhong; Wang, Shuangyuan; Shi, Xianzhe; Lu, Xin; Xu, Guowang

2014-02-21

In the present study, several geminal dicationic ionic liquids based on 1,4-bis(3-allylimidazolium)butane and 1,8-bis(3-allylimidazolium)octane in combination with different anions bromide and bis(trifluoromethanesulphonyl)imide were prepared and then bonded to the surface of 3-mercaptopropyl modified silica materials through the "thiol-ene" click chemistry as stationary phases for hydrophilic interaction chromatography (HILIC). Compared with their monocationic analogues, the dicationic ionic liquids stationary phases presented effective retention and good selectivity for typical hydrophilic compounds under HILIC mode with the column efficiency as high as 130,000 plates/m. Moreover, the influence of different alkyl chain spacer between dications and combined anions on the retention behavior and selectivity of the dicationic ionic liquids stationary phases under HILIC mode was displayed. The results indicated that the longer linkage chain would decrease the hydrophilicity and retention on the dicationic ionic liquid stationary phase, and while differently combined anions had no difference due to the exchangeability under the common HILIC mobile phase with buffer salt. Finally, the retention mechanism was investigated by evaluating the effect of chromatographic factors on retention, including the water content in the mobile phase, the mobile phase pH and buffer salt concentration. The results showed that the dicationic ionic liquids stationary phases presented a mixed-mode retention behavior with HILIC mechanism and anion exchange. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanomechanics of layer-by-layer polyelectrolyte complexes: a manifestation of ionic cross-links and fixed charges.

PubMed

Han, Biao; Chery, Daphney R; Yin, Jie; Lu, X Lucas; Lee, Daeyeon; Han, Lin

2016-01-28

This study investigates the roles of two distinct features of ionically cross-linked polyelectrolyte networks - ionic cross-links and fixed charges - in determining their nanomechanical properties. The layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) network is used as the model material. The densities of ionic cross-links and fixed charges are modulated through solution pH and ionic strength (IS), and the swelling ratio, elastic and viscoelastic properties are quantified via an array of atomic force microscopy (AFM)-based nanomechanical tools. The roles of ionic cross-links are underscored by the distinctive elastic and viscoelastic nanomechanical characters observed here. First, as ionic cross-links are highly sensitive to solution conditions, the instantaneous modulus, E0, exhibits orders-of-magnitude changes upon pH- and IS-governed swelling, distinctive from the rubber elasticity prediction based on permanent covalent cross-links. Second, ionic cross-links can break and self-re-form, and this mechanism dominates force relaxation of PAH/PAA under a constant indentation depth. In most states, the degree of relaxation is >90%, independent of ionic cross-link density. The importance of fixed charges is highlighted by the unexpectedly more elastic nature of the network despite low ionic cross-link density at pH 2.0, IS 0.01 M. Here, the complex is a net charged, loosely cross-linked, where the degree of relaxation is attenuated to ≈50% due to increased elastic contribution arising from fixed charge-induced Donnan osmotic pressure. In addition, this study develops a new method for quantifying the thickness of highly swollen polymer hydrogel films. It also underscores important technical considerations when performing nanomechanical tests on highly rate-dependent polymer hydrogel networks. These results provide new insights into the nanomechanical characters of ionic polyelectrolyte complexes, and lay the ground for further investigation of their unique time-dependent properties.

Long-chain ionic liquid based mixed hemimicelles and magnetic dispersed solid-phase extraction for the extraction of fluorescent whitening agents in paper materials.

PubMed

Wang, Qing; Qiu, Bin; Chen, Xianbo; Wang, Bin; Zhang, Hui; Zhang, Xiaoyuan

2017-06-01

A novel mixed hemimicelles and magnetic dispersive solid-phase extraction method based on long-chain ionic liquids for the extraction of five fluorescent whitening agents was established. The factors influenced on extraction efficiency were investigated. Under the optimal conditions, namely, the pH of sample solution at 8.0, the concentration of long chain ionic liquid at 0.5 mmol/L, the amount of Fe 3 O 4 nanoparticle at 12 mg, extraction time at 10 min, pH 6.0 of methanol as eluent, and the desorption time at 1 min, satisfactory results were obtained. Wide linear ranges (0.02-10 ng/mL) and good linearity were attained (0.9997-0.9999). The intraday and interday RSDs were 2.1-8.3%. Limits of detection were 0.004-0.01 ng/mL, which were decreased by almost an order of magnitude compared to direct detection without extraction. The present method was applied to extract the fluorescent whitening agents in two kinds of paper samples, obtaining satisfactory results. All showed results illustrated that the detection sensitivity was improved and the proposed method was a good choice for the enriching and monitoring of trace fluorescent whitening agents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Jones, T.P.

Sensors for the determination of pH have been developed which are based on the immobilization of direct dyes at hydrolyzed cellulosic films. The performance and structural characteristics of the sensors were investigated by a variety of spectroscopic methods, and applications for remote sensing were developed. Films of cellulose acetate were base hydrolyzed in 0.07 M KOH to yield a porous support structure. The structural changes resulting from the hydrolysis on cellulose acetate were probed with infrared internal reflectance spectroscopy. The progress of the hydrolysis reaction was monitored by the changes in vibrational modes of the acetyl group, and other spectralmore » changes indicated changes in film thickness as a result of solvent incorporation. Direct dyes, including Congo Red and C. I. Direct Blue 8, were then immobilized at these porous cellulosic films. The optical response characteristics of the Congo Red pH sensor were characterized, including the UV-visible absorption spectra as a function of pH, the response time as a function of ionic strength and ionic size of electrolyte, the long-term stability of the sensor, the effects of metal-ion interference, and the concentration of Congo Red in the polymer film. The structural characteristics of the sensor were investigated by internal reflectance spectroscopy and resonance-enhanced Raman spectroscopy, and the protonation sites were identified as the two azo groups of Congo Red. Infrared internal reflection spectra of immobilized Congo Red led to the development of a sensor for pH based on infrared spectroscopy. Finally, a two-wavelength fiber-optic photometer, which is based on solid-state sources and detectors, and a fiber-optic photometer, which is based on solid-state sources and detectors, and a fiber-optic probe were developed for pH determinations using Congo Red and C. I. Direct Blue 8 pH sensors.« less

Regulation of the Activity of Lactate Dehydrogenases from Four Lactic Acid Bacteria*

PubMed Central

Feldman-Salit, Anna; Hering, Silvio; Messiha, Hanan L.; Veith, Nadine; Cojocaru, Vlad; Sieg, Antje; Westerhoff, Hans V.; Kreikemeyer, Bernd; Wade, Rebecca C.; Fiedler, Tomas

2013-01-01

Despite high similarity in sequence and catalytic properties, the l-lactate dehydrogenases (LDHs) in lactic acid bacteria (LAB) display differences in their regulation that may arise from their adaptation to different habitats. We combined experimental and computational approaches to investigate the effects of fructose 1,6-bisphosphate (FBP), phosphate (Pi), and ionic strength (NaCl concentration) on six LDHs from four LABs studied at pH 6 and pH 7. We found that 1) the extent of activation by FBP (Kact) differs. Lactobacillus plantarum LDH is not regulated by FBP, but the other LDHs are activated with increasing sensitivity in the following order: Enterococcus faecalis LDH2 ≤ Lactococcus lactis LDH2 < E. faecalis LDH1 < L. lactis LDH1 ≤ Streptococcus pyogenes LDH. This trend reflects the electrostatic properties in the allosteric binding site of the LDH enzymes. 2) For L. plantarum, S. pyogenes, and E. faecalis, the effects of Pi are distinguishable from the effect of changing ionic strength by adding NaCl. 3) Addition of Pi inhibits E. faecalis LDH2, whereas in the absence of FBP, Pi is an activator of S. pyogenes LDH, E. faecalis LDH1, and L. lactis LDH1 and LDH2 at pH 6. These effects can be interpreted by considering the computed binding affinities of Pi to the catalytic and allosteric binding sites of the enzymes modeled in protonation states corresponding to pH 6 and pH 7. Overall, the results show a subtle interplay among the effects of Pi, FBP, and pH that results in different regulatory effects on the LDHs of different LABs. PMID:23720742

Simultaneous Determination of Oxygen and pH Inside Microfluidic Devices Using Core-Shell Nanosensors.

PubMed

Ehgartner, Josef; Strobl, Martin; Bolivar, Juan M; Rabl, Dominik; Rothbauer, Mario; Ertl, Peter; Borisov, Sergey M; Mayr, Torsten

2016-10-04

A powerful online analysis setup for the simultaneous detection of oxygen and pH is presented. It features core-shell nanosensors, which enable contactless and inexpensive read-out using adapted oxygen meters via modified dual lifetime referencing in the frequency domain (phase shift measurements). Lipophilic indicator dyes were incorporated into core-shell structured poly(styrene-block-vinylpyrrolidone) nanoparticles (average diameter = 180 nm) yielding oxygen nanosensors and pH nanosensors by applying different preparation protocols. The oxygen indicator platinum(II) meso-tetra(4-fluorophenyl) tetrabenzoporphyrin (PtTPTBPF) was entrapped into the polystyrene core (oxygen nanosensors) and a pH sensitive BF 2 -chelated tetraarylazadipyrromethene dye (aza-BODIPY) was incorporated into the polyvinylpyrrolidone shell (pH nanosensors). The brightness of the pH nanoparticles was increased by more than 3 times using a light harvesting system. The nanosensors have several advantages such as being excitable with red light, emitting in the near-infrared spectral region, showing a high stability in aqueous media even at high particle concentrations, high ionic strength, or high protein concentrations and are spectrally compatible with the used read-out device. The resolution for oxygen of the setup is 0.5-2.0 hPa (approximately 0.02-0.08 mg/L of dissolved oxygen) at low oxygen concentrations (<50 hPa) and 4-8 hPa (approximately 0.16-0.32 mg/L of dissolved oxygen) at ambient air oxygen concentrations (approximately 200 hPa at 980 mbar air pressure) at room temperature. The pH resolution is 0.03-0.1 pH units within the dynamic range (apparent pK a 7.23 ± 1.0) of the nanosensors. The sensors were used for online monitoring of pH changes during the enzymatic transformation of Penicillin G to 6-aminopenicillanic acid catalyzed by Penicillin G acylase in miniaturized stirred batch reactors or continuous flow microreactors.

Potentiometric study of binary complexes of 3-[(1 R)-1-hydroxy-2-(methylamino)ethyl]phenol hydrochloride with some lanthanide ions in aqueous and mixed solutions

NASA Astrophysics Data System (ADS)

Sharma, S. S.; Kadia, M. V.

2014-12-01

The complexation of lanthanide ions (Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Gd3+, Tb3+, and Dy3+) with 3-[(1 R)-1-hydroxy-2-(methylamino)ethyl]phenol hydrochloride was studied at different temperatures and different ionic strengths in aqueous solutions by Irving-Rossotti pH titration technique. Stepwise calculation, PKAS and BEST Fortran IV computer programs were used for determination of proton-ligand and metal-ligand stability constants. The formation of species like MA, MA2, and MA(OH) is considered in SPEPLOT. Thermodynamic parameters of complex formation (Δ G, Δ H, and Δ S) are also evaluated. Negative Δ G and Δ H values indicate that complex formation is favourable in these experimental conditions. The stability of complexes is also studied at in different solvent-aqueous (vol/vol). The stability series of lanthanide complexes has shown to have the "gadolinium break." Stability of complexes decreases with increase in ionic strength and temperature. Effect of systematic errors like effect of dissolved carbon dioxide, concentration of alkali, concentration of acid, concentration of ligand and concentration of metal have also been explained.

Improving clarity and stability of skim milk powder dispersions by dissociation of casein micelles at pH 11.0 and acidification with citric acid.

PubMed

Pan, Kang; Zhong, Qixin

2013-09-25

Casein micelles in milk cause turbidity and have poor stability at acidic conditions. In this study, skim milk powder dispersions were alkalized to pH 10.0 or 11.0, corresponding to reduced particle mass. In the following acidification with hydrochloric or citric acid, the re-formation of casein particles was observed. The combination of treatment at pH 11.0 and acidification with citric acid resulted in dispersions with the lowest turbidity and smallest particles, which enabled translucent dispersions at pH 5.5-7.0, corresponding to discrete nanoparticles. The concentration of ionic calcium was lower when acidified with citric acid than hydrochloric acid, corresponding to smaller particles with less negative zeta potential. The pH 11.0 treatment followed by acidification with citric acid also resulted in smaller particles than the simple chelating effects (directly implementing sodium citrate). The produced casein nanoparticles with reduced dimensions can be used for beverage and other novel applications.

Combinatorial ligand libraries as a two-dimensional method for proteome analysis.

PubMed

Santucci, Laura; Candiano, Giovanni; Petretto, Andrea; Lavarello, Chiara; Bruschi, Maurizio; Ghiggeri, Gian Marco; Citterio, Attilio; Righetti, Pier Giorgio

2013-07-05

The present report tries to assess the possibility of performing capture of proteomes via combinatorial peptide ligand libraries (CPLL) in a two-dimensional (2D) mode, i.e. via orthogonal complementarity in the capture phase. To that aim, serum proteins are captured at physiological pH either at low ionic strength (25mM NaCl) or at high concentrations of lyotropic salts of the Hofmeister series (1M ammonium sulphate) favouring hydrophobic interaction. Indeed such 2D mechanisms seems to be operative, since 52% of the captured proteins are common to the two capture modes, 20% are specific only of the "ionic" interaction mode and 28% are found only in the "hydrophobically" driven interaction. As an additional bonus, losses of protein species from the initial sample, one of the major drawbacks of CPLLs, are diminished to about 5% and are found only in the ionic capture, whereas the hydrophobically engendered capture is loss-free. Copyright © 2013 Elsevier B.V. All rights reserved.

Metal and anion composition of two biopolymeric chemical stabilizers and toxicity risk implication for the environment.

PubMed

Ndibewu, P P; Mgangira, M B; Cingo, N; McCrindle, R I

2010-01-01

The objective of this study was to (1) measure the concentration of four anions (Cl(-), F(-), [image omitted], and [image omitted]) and nine other elements (Al, Ba, Ca, K, Mg, Mn, Fe, Ni, and Si) in two nontraditional biopolymeric chemical stabilizers (EBCS1 and EBCS2), (2) investigate consequent environmental toxicity risk implications, and (3) create awareness regarding environmental health issues associated with metal concentration levels in enzyme-based chemical stabilizers that are now gaining widespread application in road construction and other concrete materials. Potential ecotoxicity impacts were studied on aqueous extracts of EBCS1 and EBCS2 using two thermodynamic properties models: the Pitzer-Mayorga model (calculation of the electrolyte activity coefficients) and the Millero-Pitzer model (calculation of the ionic activity coefficients). Results showed not only high concentrations of a variety of metal ions and inorganic anions, but also a significant variation between two chemical stabilizing mixtures. The mixture (EBCS2) with the lower pH value was richer in all the cationic and anionic species than (EBCS1). Sulfate (SO(2-)(4)) concentrations were found to be higher in EBCS2 than in EBCS1. There was no correlation between electrolyte activity and presence of the ionic species, which may be linked to a possible high ionic environmental activity. The concentrations of trace metals found (Mn, Fe, and Ni) were low compared to those of earth metals (Ba, Ca, K, and Mg). The metal concentrations were higher in EBCS1 than in EBCS2. Data suggest that specific studies are needed to establish "zero" permissible metal ecotoxicity values for elements and anions in any such strong polyelectrolytic enzyme-based chemical stabilizers.

Solubility and dissolution improvement of ketoprofen by emulsification ionic gelation

NASA Astrophysics Data System (ADS)

Rachmaniar, Revika; Tristiyanti, Deby; Hamdani, Syarif; Afifah

2018-02-01

Ketoprofen or [2-(3-benzoylphenyl) propionic acid] is non-steroidal anti-inflammatory (NSAID) and an analgesic which has high permeability and low solubility. The purpose of this work was to improve the solubility and dissolution of poorly water-soluble ketoprofen prepared by emulsification ionic gelation method and utilizing polymer (chitosan) and cross linker (tripolyphosphate, TPP) for particles formulation. The results show that increasing pH value of TPP, higher solubility and dissolution of as-prepared ketoprofen-chitosan was obtained. The solubility in water of ketoprofen-chitosan with pH 6 for TPP increased 2.71-fold compared to untreated ketoprofen. While the dissolution of ketoprofen-chitosan with pH 6 of TPP in simulated gastric fluid without enzyme (0.1 N HCl), pH 4.5 buffer and simulated intestinal fluid without enzyme (phosphate buffer pH 6.8) was increased 1.9-fold, 1.6-fold and 1.2-fold compared to untreated ketoprofen for dissolution time of 30 minutes, respectively. It could be concluded that chitosan and TPP in the emulsification ionic gelation method for ketoprofen preparation effectively increases solubility and dissolution of poorly water-soluble ketoprofen.

Sorption properties of Th(IV) on the raw diatomite--effects of contact time, pH, ionic strength and temperature.

PubMed

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.

Stability and electrostatics of mercaptoundecanoic acid-capped gold nanoparticles with varying counterion size.

PubMed

Laaksonen, Timo; Ahonen, Päivi; Johans, Christoffer; Kontturi, Kyösti

2006-10-13

The solubility of charged nanoparticles is critically dependent on pH. However, the concentration range available with bases such as NaOH is quite narrow, since the particles precipitate due to compression of the electric double layer when the ionic strength is increased. The stability of mercaptoundecanoic acid-capped Au nanoparticles is studied at a set pH using the hydroxide as base and different cations of various sizes. The counterions used are sodium (Na(+)), tetramethylammonium (TMA(+)), tetraethylammonium (TEA(+)), and tetrabutylammonium (TBA(+)). The particles precipitate in the 70-90 mM range with Na(+) as the counterion, but with quaternary ammonium hydroxides the particles are stable even in concentrations exceeding 1 M. The change in solubility is linked to a strongly adsorbed layer on the surface of the ligand shell of the nanoparticles. The increased concentration range obtained with TEAOH is further used to facilitate thiol exchange which occurs at a greater extent than would be achieved in NaOH solution.

Acid-base properties of brown seaweed biomass considered as a Donnan gel. A model reflecting electrostatic effects and chemical heterogeneity.

PubMed

Rey-Castro, Carlos; Lodeiro, Pablo; Herrero, Roberto; Sastre de Vicente, Manuel E

2003-11-15

Brown seaweeds are interesting materials to be used as biosorbents for heavy metals due to their high binding ability and low cost. The study of the passive biosorption of protons on this kind of materials and its dependency on pH, ionic strength, and medium composition is essential for the practical application of brown algae in wastewater treatment. This work reports the results of the study of the proton binding equilibria of dead biomass from the seaweeds Sargassum muticum, Cystoseira baccata, and Saccorhiza polyschides by potentiometric titration with a glass electrode in the pH range between 2 and 8. Two different salts, NaCl and KNO3, in concentrations ranging from 0.05 to 2 mol x L(-1), were used as background electrolytes. The influence of the ionic strength was accounted for by means of the Donnan model in combination with the master curve approach. Different empirical expressions to describe the swelling behavior of the biosorbent were tested. On the basis of the intrinsic affinity distribution analysis a unimodal Langmuir-Freundlich isotherm was selected to describe the proton binding properties. The results show very little influence of the type of salt. The ionic strength dependency of the proton binding is very similar for the three species, and average empirical expressions of the Donnan volume are proposed. The maximum proton binding capacities obtained ranged between 2.4 and 2.9 mol x kg(-1), with average intrinsic proton affinity constants between 3.1 and 3.3, and heterogeneity parameters of ca. 0.5 for S. muticum and C. baccata, and slightly higher (ca. 0.7) for S. polyschides. The combined Langmuir-Freundlich equation and Donnan model allowed a good description of the experimental charge vs pH curves obtained.

Acid-base titrations of functional groups on the surface of the thermophilic bacterium Anoxybacillus flavithermus: comparing a chemical equilibrium model with ATR-IR spectroscopic data.

PubMed

Heinrich, Hannah T M; Bremer, Phil J; Daughney, Christopher J; McQuillan, A James

2007-02-27

Acid-base functional groups at the surface of Anoxybacillus flavithermus (AF) were assigned from the modeling of batch titration data of bacterial suspensions and compared with those determined from in situ infrared spectroscopic titration analysis. The computer program FITMOD was used to generate a two-site Donnan model (site 1: pKa = 3.26, wet concn = 2.46 x 10(-4) mol g(-1); site 2: pKa = 6.12, wet concn = 6.55 x 10(-5) mol g(-1)), which was able to describe data for whole exponential phase cells from both batch acid-base titrations at 0.01 M ionic strength and electrophoretic mobility measurements over a range of different pH values and ionic strengths. In agreement with information on the composition of bacterial cell walls and a considerable body of modeling literature, site 1 of the model was assigned to carboxyl groups, and site 2 was assigned to amino groups. pH difference IR spectra acquired by in situ attenuated total reflection infrared (ATR-IR) spectroscopy confirmed the presence of carboxyl groups. The spectra appear to show a carboxyl pKa in the 3.3-4.0 range. Further peaks were assigned to phosphodiester groups, which deprotonated at slightly lower pH. The presence of amino groups could not be confirmed or discounted by IR spectroscopy, but a positively charged group corresponding to site 2 was implicated by electrophoretic mobility data. Carboxyl group speciation over a pH range of 2.3-10.3 at two different ionic strengths was further compared to modeling predictions. While model predictions were strongly influenced by the ionic strength change, pH difference IR data showed no significant change. This meant that modeling predictions agreed reasonably well with the IR data for 0.5 M ionic strength but not for 0.01 M ionic strength.

Removal of Mercury from Chloralkali Electrolysis Wastewater by a Mercury-Resistant Pseudomonas putida Strain

PubMed Central

von Canstein, H.; Li, Y.; Timmis, K. N.; Deckwer, W.-D.; Wagner-Döbler, I.

1999-01-01

A mercury-resistant bacterial strain which is able to reduce ionic mercury to metallic mercury was used to remediate in laboratory columns mercury-containing wastewater produced during electrolytic production of chlorine. Factory effluents from several chloralkali plants in Europe were analyzed, and these effluents contained total mercury concentrations between 1.6 and 7.6 mg/liter and high chloride concentrations (up to 25 g/liter) and had pH values which were either acidic (pH 2.4) or alkaline (pH 13.0). A mercury-resistant bacterial strain, Pseudomonas putida Spi3, was isolated from polluted river sediments. Biofilms of P. putida Spi3 were grown on porous carrier material in laboratory column bioreactors. The bioreactors were continuously fed with sterile synthetic model wastewater or nonsterile, neutralized, aerated chloralkali wastewater. We found that sodium chloride concentrations up to 24 g/liter did not inhibit microbial mercury retention and that mercury concentrations up to 7 mg/liter could be treated with the bacterial biofilm with no loss of activity. When wastewater samples from three different chloralkali plants in Europe were used, levels of mercury retention efficiency between 90 and 98% were obtained. Thus, microbial mercury removal is a potential biological treatment for chloralkali electrolysis wastewater. PMID:10583977

Study on Enhancement Principle and Stabilization for the Luminol-H2O2-HRP Chemiluminescence System

PubMed Central

Yang, Lihua; Jin, Maojun; Du, Pengfei; Chen, Ge; Zhang, Chan; Wang, Jian; Jin, Fen; Shao, Hua; She, Yongxin; Wang, Shanshan; Zheng, Lufei; Wang, Jing

2015-01-01

A luminol-H2O2-HRP chemiluminescence system with high relative luminescent intensity (RLU) and long stabilization time was investigated. First, the comparative study on the enhancement effect of ten compounds as enhancers to the luminol-H2O2-HRP chemiluminescence system was carried out, and the results showed that 4-(imidazol-1-yl)phenol (4-IMP), 4-iodophenol (4-IOP), 4-bromophenol (4-BOP) and 4-hydroxy-4’-iodobiphenyl (HIOP) had the best performance. Based on the experiment, the four enhancers were dissolved in acetone, acetonitrile, methanol, and dimethylformamide (DMF) with various concentrations, the results indicated that 4-IMP, 4-IOP, 4-BOP and HIOP dissolved in DMF with the concentrations of 0.2%, 3.2%, 1.6% and 3.2% could get the highest RLU values. Subsequently, the influences of pH, ionic strength, HRP, 4-IMP, 4-IOP, 4-BOP, HIOP, H2O2 and luminol on the stabilization of the luminol-H2O2-HRP chemiluminescence system were studied, and we found that pH value, ionic strength, 4-IMP, 4-IOP, 4-BOP, HIOP, H2O2 and luminol have little influence on luminescent stabilization, while HRP has a great influence. In different ranges of HRP concentration, different enhancers should be selected. When the concentration is within the range of 0~6 ng/mL, 4-IMP should be selected. When the concentration of HRP ranges from 6 to 25ng/mL, 4-IOP was the best choice. And when the concentration is within the range of 25~80 ng/mL, HIOP should be selected as the enhancer. Finally, the three well-performing chemiluminescent enhanced solutions (CESs) have been further optimized according to the three enhancers (4-IMP, 4-IOP and HIOP) in their utilized HRP concentration ranges. PMID:26154162

Study on Enhancement Principle and Stabilization for the Luminol-H2O2-HRP Chemiluminescence System.

PubMed

Yang, Lihua; Jin, Maojun; Du, Pengfei; Chen, Ge; Zhang, Chan; Wang, Jian; Jin, Fen; Shao, Hua; She, Yongxin; Wang, Shanshan; Zheng, Lufei; Wang, Jing

2015-01-01

A luminol-H2O2-HRP chemiluminescence system with high relative luminescent intensity (RLU) and long stabilization time was investigated. First, the comparative study on the enhancement effect of ten compounds as enhancers to the luminol-H2O2-HRP chemiluminescence system was carried out, and the results showed that 4-(imidazol-1-yl)phenol (4-IMP), 4-iodophenol (4-IOP), 4-bromophenol (4-BOP) and 4-hydroxy-4'-iodobiphenyl (HIOP) had the best performance. Based on the experiment, the four enhancers were dissolved in acetone, acetonitrile, methanol, and dimethylformamide (DMF) with various concentrations, the results indicated that 4-IMP, 4-IOP, 4-BOP and HIOP dissolved in DMF with the concentrations of 0.2%, 3.2%, 1.6% and 3.2% could get the highest RLU values. Subsequently, the influences of pH, ionic strength, HRP, 4-IMP, 4-IOP, 4-BOP, HIOP, H2O2 and luminol on the stabilization of the luminol-H2O2-HRP chemiluminescence system were studied, and we found that pH value, ionic strength, 4-IMP, 4-IOP, 4-BOP, HIOP, H2O2 and luminol have little influence on luminescent stabilization, while HRP has a great influence. In different ranges of HRP concentration, different enhancers should be selected. When the concentration is within the range of 0~6 ng/mL, 4-IMP should be selected. When the concentration of HRP ranges from 6 to 25 ng/mL, 4-IOP was the best choice. And when the concentration is within the range of 25~80 ng/mL, HIOP should be selected as the enhancer. Finally, the three well-performing chemiluminescent enhanced solutions (CESs) have been further optimized according to the three enhancers (4-IMP, 4-IOP and HIOP) in their utilized HRP concentration ranges.

Solubility of aluminum in the presence of hydroxide, fluoride, and sulfate

USGS Publications Warehouse

Roberson, Charles Elmer; Hem, John David

1969-01-01

The total concentration of aqueous dissolved species of aluminum that will be present in equilibrium with microcrystalline gibbsite at various levels of complexing ligand concentration are shown graphically. The graphs can be used to estimate aluminum solubility, at 25?C and 1 atmosphere total pressure, when the pH of the solution, its ionic strength, and the total sulfate and fluoride concentrations are known. The standard free energy of formation of cryolite calculated from solubility experiments is --745.4 ? 1.0 kcal per mole at 25?C. Diagrams are included showing the solubility of cryolite in terms of aluminum, fluoride, and sodium concentrations. The stability fields of cryolite and microcrystalline gibbsite and their solubilities also are shown on pH-[F] diagrams.

Temperature and substrate chemistry as major drivers of interregional variability of leaf microbial decomposition and cellulolytic activity in headwater streams.

PubMed

Fenoy, Encarnación; Casas, J Jesús; Díaz-López, Manuel; Rubio, Juan; Guil-Guerrero, J Luís; Moyano-López, Francisco J

2016-11-01

Abiotic factors, substrate chemistry and decomposers community composition are primary drivers of leaf litter decomposition. In soil, much of the variation in litter decomposition is explained by climate and substrate chemistry, but with a significant contribution of the specialisation of decomposer communities to degrade specific substrates (home-field advantage, HFA). In streams, however, HFA effects on litter decomposition have not been explicitly tested. We evaluated responses of microbial decomposition and β-glucosidase activity to abiotic factors, substrate and decomposer assemblages, using a reciprocal litter transplant experiment: 'ecosystem type' (mountain vs lowland streams) × 'litter chemistry' (alder vs reed). Temperature, pH and ionic concentration were higher in lowland streams. Decomposition for both species was faster in lowland streams. Decomposition of reed was more accelerated in lowland compared with mountain streams than that of alder, suggesting higher temperature sensitivity of decomposition in reed. Q10 (5°C-15°C) values of β-glucosidase activity were over 2. The alkaline pH and high ionic concentration of lowland streams depleted enzyme activity. We found similar relationships of decomposition or enzyme activity with abiotic factors for both species, suggesting limited support to the HFA hypothesis. Overall, our results suggest a prime role of temperature interacting with substrate chemistry on litter decomposition. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Sorption-desorption of carbamazepine by palygorskite-montmorillonite (PM) filter medium.

PubMed

Berhane, Tedros M; Levy, Jonathan; Krekeler, Mark P S; Danielson, Neil D; Stalcup, Apryll

2015-01-23

Palygorskite-montmorillonite (PM) was studied as a potential sewage treatment effluent filter material for carbamazepine. Batch sorption experiments were conducted as a function of granule size (0.3-0.6, 1.7-2.0 and 2.8mm) and different sewage effluent conditions (pH, ionic strength and temperature). Results showed PM had a mix of fibrous and plate-like morphologies. Sorption and desorption isotherms were fitted to the Freundlich model. Sorption is granule size-dependent and the medium granule size would be an appropriate size for optimizing both flow and carbamazepine retention. Highest and lowest sorption capacities corresponded to the smallest and the largest granule sizes, respectively. The lowest and the highest equilibrium aqueous (Ce) and sorbed (qe) carbamazepine concentrations were 0.4 mg L(-1) and 4.5 mg L(-1), and 0.6 mg kg(-1) and 411.8 mg kg(-1), respectively. Observed higher relative sorption at elevated concentrations with a Freundlich exponent greater than one, indicated cooperative sorption. The sorption-desorption hysteresis (isotherm non-singularity) indicated irreversible sorption. Higher sorption observed at higher rather than at lower ionic strength conditions is likely due to a salting-out effect. Negative free energy and the inverse sorption capacity-temperature relationship indicated the carbamazepine sorption process was favorable or spontaneous. Solution pH had little effect on sorption. Copyright © 2014 Elsevier B.V. All rights reserved.

Adsorption Removal of 17β-Estradiol from Water by Rice Straw-Derived Biochar with Special Attention to Pyrolysis Temperature and Background Chemistry.

PubMed

Wang, Xiaohua; Liu, Ni; Liu, Yunguo; Jiang, Luhua; Zeng, Guangming; Tan, Xiaofei; Liu, Shaobo; Yin, Zhihong; Tian, Sirong; Li, Jiang

2017-10-11

Rice straw biochar that produced at three pyrolysis temperatures (400, 500 and 600 °C) were used to investigate the adsorption properties of 17β-estradiol (E2). The biochar samples were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), elemental analysis and BET surface area measurements. The influences of pyrolysis temperature, E2 concentration, pH, ionic strength, background electrolyte and humic acid were studied. Kinetic and isotherm results illustrated that the adsorption process could be well described by pseudo-second-order and Freundlich models. Experimental results showed that ionic strength had less influence on the adsorption of E2 by 500 and 600 °C rice straw biochar. Further, multivalent ions had positive impact on E2 removal than monovalent ions and the influence of the pyrolysis temperature was unremarkable when background electrolyte existed in solutions. The adsorption capacity of E2 decreased with the pH ranged from 3.0 to 12.0 and the humic acid concentration from 2 to 10 mg L -1 . Electrostatic attractions and π-π interaction were involved in the adsorption mechanisms. Compared to low-temperature biochar, high-temperature biochar exhibited a better adsorption capacity for E2 in aqueous solution, indicated it had a greater potential for E2 pollution control.

Adsorption Removal of 17β-Estradiol from Water by Rice Straw-Derived Biochar with Special Attention to Pyrolysis Temperature and Background Chemistry

PubMed Central

Wang, Xiaohua; Liu, Ni; Liu, Yunguo; Jiang, Luhua; Zeng, Guangming; Tan, Xiaofei; Liu, Shaobo; Yin, Zhihong; Tian, Sirong; Li, Jiang

2017-01-01

Rice straw biochar that produced at three pyrolysis temperatures (400, 500 and 600 °C) were used to investigate the adsorption properties of 17β-estradiol (E2). The biochar samples were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), elemental analysis and BET surface area measurements. The influences of pyrolysis temperature, E2 concentration, pH, ionic strength, background electrolyte and humic acid were studied. Kinetic and isotherm results illustrated that the adsorption process could be well described by pseudo-second-order and Freundlich models. Experimental results showed that ionic strength had less influence on the adsorption of E2 by 500 and 600 °C rice straw biochar. Further, multivalent ions had positive impact on E2 removal than monovalent ions and the influence of the pyrolysis temperature was unremarkable when background electrolyte existed in solutions. The adsorption capacity of E2 decreased with the pH ranged from 3.0 to 12.0 and the humic acid concentration from 2 to 10 mg L−1. Electrostatic attractions and π-π interaction were involved in the adsorption mechanisms. Compared to low-temperature biochar, high-temperature biochar exhibited a better adsorption capacity for E2 in aqueous solution, indicated it had a greater potential for E2 pollution control. PMID:29019933

Arginine inactivates human herpesvirus 2 and inhibits genital herpesvirus infection.

PubMed

Ikeda, Keiko; Yamasaki, Hisashi; Minami, Sawako; Suzuki, Yukiko; Tsujimoto, Kazuko; Sekino, Yoshihisa; Irie, Hiroshi; Arakawa, Tsutomu; Koyama, A Hajime

2012-12-01

Arginine, among the amino acids, has demonstrated unique properties, including suppression of protein-protein interactions and virus inactivation. We investigated the effects of arginine on the infectivity of human herpesvirus 2 (HHV-2) and the potential application of arginine as a chemotherapeutic agent against genital herpes. Arginine directly inactivated HHV-2 and characterization of the inactivation demonstrated that 1 M arginine at pH 4.3 inactivated the virus more efficiently compared to 0.1 M citrate or 1 M sodium chloride, indicating that neither acidic pH nor ionic strength alone is sufficient for virus inactivation. The effect of arginine was rapid and concentration-dependent. Although virus inactivation was efficient at an acidic pH, arginine inactivated the virus even at a neutral pH, provided that a higher arginine concentration and prolonged incubation time were used. In addition, arginine suppressed the multiplication of HHV-2 under the conditions at which its effect on cell viability was insignificant. Pilot mouse model studies revealed a marked suppression of death by arginine when the mice were infected with HHV-2 through the vaginal route, followed by an intermittent application of acidic arginine by vaginal instillation.

In vitro nonenzymatic glycation of DNA nucleobases: an evaluation of advanced glycation end products under alkaline pH.

PubMed

Dutta, Udayan; Cohenford, Menashi A; Guha, Madhumita; Dain, Joel A

2006-11-01

The advanced glycation end products (AGEs) of DNA nucleobases have received little attention, perhaps due to the fact that adenine, guanine, cytosine and thymine do not dissolve under mild pH conditions. To maintain nucleobases in solution, alkaline pH conditions are typically required. The objectives of this investigation were twofold: to study the susceptibility of DNA nucleobases to nonenzymatic attack by different sugars, and to evaluate the factors that influence the formation of nucleobase AGEs at pH 12, i.e., in an alkaline environment that promotes the aldo-keto isomerization and epimerization of sugars. Varying concentrations of adenine, guanine, thymine and cytosine were incubated over time with constant concentrations of D-glucose, D-galactose or D/L-glyceraldehyde under different conditions of temperature and ionic strength. Incubation of the nucleobases with the sugars resulted in a heterogeneous assembly of AGEs whose formation was monitored by UV/fluorescence spectroscopy. Capillary electrophoresis and HPLC were used to resolve the AGEs of the DNA adducts and provided a powerful tool for following the extent of glycation in each of the DNA nucleobases. Mass spectrometry studies of DNA adducts of guanine established that glycation at pH 12 proceeded through an Amadori intermediate.

Sorghum Roots are Inefficient in Uptake of EDTA-chelated Lead

PubMed Central

Xu, Yong; Yamaji, Naoki; Shen, Renfang; Ma, Jian Feng

2007-01-01

Background and Aims Ethylene diamine tetraacetic acid (EDTA)-assisted phytoremediation has been developed to clean up lead (Pb)-contaminated soil; however, the mechanism responsible for the uptake of EDTA–Pb complex is not well understood. In this study, the accumulation process of Pb from EDTA–Pb is characterized in comparison to ionic Pb [Pb(NO3)2] in sorghum (Sorghum bicolor). Methods Sorghum seedlings were exposed to a 0·5 mm CaCl2 (pH 5·0) solution containing 0, 1 mm Pb(NO3)2 or EDTA–Pb complexes at a molar ratio of 1:0·5, 1:1, 1:2 and 1:4 (Pb:EDTA). The root elongation of sorghum at different ratios of Pb:EDTA was measured. Xylem sap was collected after the stem was severed at different times. The concentration of Pb in the shoots and roots were determined by an atomic absorption spectrometer. In addition, the roots were stained with Fluostain I for observation of the root structure. Key Results Lead accumulation in the shoots of the plants exposed to EDTA–Pb at 1:1 ratio was only one-fifth of that exposed to ionic Pb at the same concentration. Lead accumulation decreased when transpiration was suppressed. The concentration of Pb in the xylem sap from the EDTA–Pb-treated plants was about 1/25 000 of that in the external solution. Root elongation was severely inhibited by ionic Pb, but not by EDTA–Pb at a 1:1 ratio. Root staining showed that a physiological barrier was damaged in the roots exposed to ionic Pb, but not in the roots exposed to EDTA–Pb. Conclusions All these results suggest that sorghum roots are inefficient in uptake of EDTA-chelated Pb and that enhanced Pb accumulation from ionic Pb was attributed to the damaged structure of the roots. PMID:17452378

The sulphation of chondroitin sulphate in embryonic chicken cartilage

PubMed Central

Robinson, H. C.

1969-01-01

1. Whole tissue preparations and subcellular fractions from embryonic chicken cartilage were used to measure the rate of incorporation of inorganic sulphate into chondroitin sulphate in vitro. 2. In cartilage from 14-day-old embryos, [35S]sulphate is incorporated to an equal extent into chondroitin 4-sulphate and chondroitin 6-sulphate at a rate of 1·5nmoles of sulphate/hr./mg. dry wt. of cartilage. 3. Microsomal and soluble enzyme preparations from embryonic cartilage catalyse the transfer of sulphate from adenosine 3′-phosphate 5′-sulphatophosphate into both chondroitin 4-sulphate and chondroitin 6-sulphate. 4. The effects of pH, ionic strength, adenosine 3′-phosphate 5′-sulphatophosphate concentration and acceptor chondroitin sulphate concentration on the soluble sulphotransferase activity were examined. These factors all influence the activity of the sulphotransferase, and pH and incubation time also influence the percentage of chondroitin 4-sulphate formed. PMID:5807213

Influence of reaction conditions on formation of ionic liquid-based nanostructured Bi2O3 as an efficient visible-light-driven photocatalyst

NASA Astrophysics Data System (ADS)

Bagheri, Mozhgan; Heydari, Mojgan; Vaezi, Mohammad Reza

2018-01-01

In this study, nanostructured bismuth oxide was synthesized based on the chemical reaction of bismuth nitrate and NaOH in the ionic liquid 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) under ultrasonic irradiation. The effect of sodium hydroxide with a different molar ratio of NaOH to bismuth in the range of 3-10 was investigated. The results of fourier-transform infrared spectroscopy (FT-IR) and X-ray powder diffraction (XRD) showed that NaOH has a critical role in the formation of pure α-Bi2O3. So, at high concentrations of NaOH (NaOH:Bi ≥ 7.5), the chloride anion from the ionic liquid cannot be entered into the crystalline structure of bismuth oxide, which resulted in the formation of pure bismuth oxide, while at lower concentrations of NaOH (NaOH:Bi ≤ 5), Bi3O4Cl was formed with a layered structure. The XRD results revealed that the synthesized α-Bi2O3 has a monoclinic structure and scanning electron microscopy (SEM) images showed that the sample consists of needle like particles with an average thickness of 50 nm. The ionic liquid has an important role in the prevention of an agglomeration of particles in the Bi2O3 sample. The photocatalytic activity of the synthesized Bi2O3 was investigated to study the degradation of malachite green dye as a model pollutant under visible light. The effects of various parameters such as the pH, concentration of the dye, and the catalyst on the degradation of malachite green were also investigated.

IgG1 adsorption to siliconized glass vials-influence of pH, ionic strength, and nonionic surfactants.

PubMed

Höger, Kerstin; Mathes, Johannes; Frieß, Wolfgang

2015-01-01

In this study, the adsorption of an IgG1 antibody to siliconized vials was investigated with focus on the formulation parameters pH, ionic strength, and nonionic surfactants. Electrophoretic mobility measurements were performed to investigate the charge characteristics of protein and siliconized glass particles at different pH values. Calculation of the electrokinetic charge density allowed further insight into the energetic conditions in the protein-sorbent interface. Maximum adsorption of IgG1 was found at acidic pH values and could be correlated with energetically favorable minimal ion incorporation into the interface. The importance of electrostatic interactions for IgG1 adsorption at acidic pH values was also confirmed by the efficient adsorption reduction at decreased solution ionic strength. A second adsorption maximum around the pI of the protein was assigned to hydrophobic interactions with the siliconized surface. Addition of the nonionic surfactants poloxamer 188 or polysorbate 80 resulted in almost complete suppression of adsorption at pH 7.2, and a strong but less efficient effect at pH 4 on siliconized glass vials. This adsorption suppression was much less pronounced on borosilicate glass vials. From these results, it can be concluded that electrostatic interactions contribute substantially to IgG1 adsorption to siliconized glass vials especially at acidic formulation pH. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

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.

Impact of noncovalent interactions between apple condensed tannins and cell walls on their transfer from fruit to juice: studies in model suspensions and application.

PubMed

Le Bourvellec, Carine; Le Quere, Jean-Michel; Renard, Catherine M G C

2007-09-19

The adsorption of procyanidins (condensed tannins) on cell-wall material was quantified by bringing into contact solutions of procyanidins and suspensions of cell-wall material. A model was developed on the basis of the Langmuir isotherm formulation and a factorial experimental design. The parameters that influenced the adsorption were the concentration and molecular weight of the procyanidins, the ionic strength of the solution, the temperature, and the apple cell-wall concentration. The model was applied to partitioning of procyanidins from apple between juice and mash. The parameters to be taken into account are the composition of the apples and, specifically, (i) the concentration and molecular weight of the procyanidins, (ii) their acidity and pH as a determinant of the ionic strength, and (iii) their cell-wall content and the temperature at pressing. To estimate the ability of the model to relate procyanidin concentrations in the juice to their concentration in the apple, apples of three varieties of widely different procyanidin compositions were pressed in conditions that prevent oxidation. In these conditions, yields in the juice were >80% for phenolic acids or catechin monomers but <50% for procyanidins, with the lowest rates obtained for the higher polymers in accordance with the model.

Development and optimization of a naphthoic acid-based ionic liquid as a "non-organic solvent microextraction" for the determination of tetracycline antibiotics in milk and chicken eggs.

PubMed

Gao, Jiajia; Wang, Hui; Qu, Jingang; Wang, Huili; Wang, Xuedong

2017-01-15

In traditional ionic liquids (ILs)-based microextraction, ILs are often used as extraction and dispersive solvents; however, their functional effects are not fully utilized. Herein, we developed a novel ionic liquid 1-butyl-3-methylimidazolium naphthoic acid salt ([C4MIM][NPA]) with strong acidity. It was used as a mixed dispersive solvent with conventional [C2MIM][BF4] in "functionalized ionic liquid-based non-organic solvent microextraction (FIL-NOSM)" for determination of tetracycline antibiotics (TCs) in milk and eggs. Utilization of [C4MIM][NPA] in FIL-NOSM method increased extraction recoveries (ERs) of TCs by more than 20% and eliminated the pH adjustment step because of its strong acidity. Under optimized conditions based on central composite design, the ERs of four TCs were 94.1-102.1%, and the limitsofdetection were 0.08-1.12μgkg(-1) in milk and egg samples. This proposed method provides high extraction efficiency, less pretreatment time and requires non-organic solvents for determination of trace TC concentrations in complex animal-based food matrices. Copyright © 2016 Elsevier Ltd. All rights reserved.

A simple, rapid and green ultrasound assisted and ionic liquid dispersive microextraction procedure for the determination of tin in foods employing ETAAS.

PubMed

Tuzen, Mustafa; Uluozlu, Ozgur Dogan; Mendil, Durali; Soylak, Mustafa; Machado, Luana O R; Dos Santos, Walter N L; Ferreira, Sergio L C

2018-04-15

This paper proposes a simple, rapid and green ultrasound assisted and ionic liquid dispersive microextraction procedure using pyrocatechol violet (PV) as complexing reagent and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide [C 6 MIM][Tf 2 N] as ionic liquid for the detection of tin employing electrothermal atomic absorption spectrometry (ETAAS). The optimization step was performed using a two-level full factorial design involving the following factors: pH of the working media, amount reagents, ionic liquid volume and extraction time and the chemometric response was tin recovery. The procedure allowed the determination of tin with limits of detection and quantification of 3.4 and 11.3 ng L -1 , respectively. The relative standard deviation was 4.5% for a tin solution of 0.50 µg L -1 . The validation method was confirmed by analysis of rice flour certified reference material. The method was applied for the quantification of tin in several food samples. The concentration range found varied from 0.10 to 1.50 µg g -1 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Vanadium Uptake by Plants

PubMed Central

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

Determining pH at elevated pressure and temperature using in situ ¹³C NMR.

PubMed

Surface, J Andrew; Wang, Fei; Zhu, Yanzhe; Hayes, Sophia E; Giammar, Daniel E; Conradi, Mark S

2015-02-03

We have developed an approach for determining pH at elevated pressures and temperatures by using (13)C NMR measurements of inorganic carbon species together with a geochemical equilibrium model. The approach can determine in situ pH with precision better than 0.1 pH units at pressures, temperatures, and ionic strengths typical of geologic carbon sequestration systems. A custom-built high pressure NMR probe was used to collect (13)C NMR spectra of (13)C-labeled CO2 reactions with NaOH solutions and Mg(OH)2 suspensions at pressures up to 107 bar and temperatures of 80 °C. The quantitative nature of NMR spectroscopy allows the concentration ratio [CO2]/[HCO3(-)] to be experimentally determined. This ratio is then used with equilibrium constants calculated for the specific pressure and temperature conditions and appropriate activity coefficients for the solutes to calculate the in situ pH. The experimentally determined [CO2]/[HCO3(-)] ratios agree well with the predicted values for experiments performed with three different concentrations of NaOH and equilibration with multiple pressures of CO2. The approach was then applied to experiments with Mg(OH)2 slurries in which the change in pH could track the dissolution of CO2 into solution, rapid initial Mg(OH)2 dissolution, and onset of magnesium carbonate precipitation.

Colloid mobilization and heavy metal transport in the sampling of soil solution from Duckum soil in South Korea.

PubMed

Lee, Seyong; Ko, Il-Won; Yoon, In-Ho; Kim, Dong-Wook; Kim, Kyoung-Woong

2018-03-24

Colloid mobilization is a significant process governing colloid-associated transport of heavy metals in subsurface environments. It has been studied for the last three decades to understand this process. However, colloid mobilization and heavy metal transport in soil solutions have rarely been studied using soils in South Korea. We investigated the colloid mobilization in a variety of flow rates during sampling soil solutions in sand columns. The colloid concentrations were increased at low flow rates and in saturated regimes. Colloid concentrations increased 1000-fold higher at pH 9.2 than at pH 7.3 in the absence of 10 mM NaCl solution. In addition, those were fourfold higher in the absence than in the presence of the NaCl solution at pH 9.2. It was suggested that the mobility of colloids should be enhanced in porous media under the basic conditions and the low ionic strength. In real field soils, the concentrations of As, Cr, and Pb in soil solutions increased with the increase in colloid concentrations at initial momentarily changed soil water pressure, whereas the concentrations of Cd, Cu, Fe, Ni, Al, and Co lagged behind the colloid release. Therefore, physicochemical changes and heavy metal characteristics have important implications for colloid-facilitated transport during sampling soil solutions.

Amaranth proteins foaming properties: Film rheology and foam stability - Part 2.

PubMed

Bolontrade, Agustín J; Scilingo, Adriana A; Añón, María C

2016-05-01

In this work the influence of pH and ionic strength on the stability of foams prepared with amaranth protein isolate was analyzed. The behaviour observed was related to the physico-chemical and structural changes undergone by amaranth protein as a result of those treatments. The results obtained show that foams prepared at acidic pH were more stable than the corresponding to alkaline pH. At pH 2.0 the foams presented higher times and more volumes of drainage. This behaviour is consistent with the characteristics of the interfacial film, which showed a higher viscoelasticity and a greater flexibility at acidic pH than alkaline pH value, which in turn increased by increasing the concentration of proteins in the foaming solution. It is also important to note that the presence of insoluble protein is not necessarily detrimental to the properties of the foam. Detected changes in the characteristics of the interfacial film as in the foam stability have been attributed to the increased unfolding, greater flexibility and net charge of amaranth proteins at acidic conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and characterization of goethite and goethite-hematite composite: experimental study and literature survey.

PubMed

Kosmulski, Marek; Maczka, Edward; Jartych, Elzbieta; Rosenholm, Jarl B

2003-03-19

Aging of synthetic goethite at 140 degrees C overnight leads to a composite material in which hematite is detectable by Mössbauer spectroscopy, but X-ray diffraction does not reveal any hematite peaks. The pristine point of zero charge (PZC) of synthetic goethite was found at pH 9.4 as the common intersection point of potentiometric titration curves at different ionic strengths and the isoelectric point (IEP). For the goethite-hematite composite, the common intersection point (pH 9.4), and the IEP (pH 8.8) do not match. The electrokinetic potential of goethite at ionic strengths up to 1 mol dm(-3) was determined. Unlike metal oxides, for which the electrokinetic potential is reversed to positive over the entire pH range at sufficiently high ionic strength, the IEP of goethite is rather insensitive to the ionic strength. A literature survey of published PZC/IEP values of iron oxides and hydroxides indicated that the average PZC/IEP does not depend on the degree of hydration (oxide or hydroxide). Our material showed a higher PZC and IEP than most published results. The present results confirm the allegation that electroacoustic measurements produce a higher IEP than the average IEP obtained by means of classical electrokinetic methods.

A batch adsorption study on bentonite clay Pertinence to transport modeling?

NASA Astrophysics Data System (ADS)

BOURG, I.; BOURG, A. C.; SPOSITO, G.

2001-12-01

Bentonite clay is often used as a component of engineered barriers for the isolation of high-level toxic wastes. This swelling clay is used for its physical (impermeability, self-healing) but also for its chemical properties, mostly a high cation exchange capacity (CEC). The adsorbed cations being temporarily immobilized, this should slow down the release of cations from the waste to the surrounding environment. In order to assess the performance of the engineered barrier, the partitioning of solutes between the liquid and solid phases needs to be quantified for use in transport models. The usual method for characterizing the adsorption is through batch adsorption experiments on dispersed suspensions of the solid, yielding an adsorption isotherm (adsorbed concentration vs. dissolved concentration). This isotherm however should be a function of various environmental variables (e.g., pH, ionic strength, concentrations of various ligands and competing adsorbents), so that extrapolation of lab data to performance assessment in the field is problematic. We present results from a study of the adsorption of cesium, strontium, cadmium and lead on dispersed suspensions of the standard BX-80 bentonite. Through a wide range of experimental parameters (pH, ionic strength, reaction time, reactor open or closed to the atmosphere, study of a range of cations of differing properties), we seek a mechanistic interpretation of the results instead of an empirical determination of adsorption parameters. Depending on the mechanisms that control the adsorption in different experimental ranges, we discuss the degree to which the partitioning coefficient (Kd) obtained in the lab can be extrapolated to a transport model through compacted bentonite in a natural environment.

[Characteristics of Adsorption Leaching and Influencing Factors of Dimethyl Phthalate in Purple Soil].

PubMed

Wang, Qiang; Song, Jiao-yan; Zeng, Wei; Wang, Fa

2016-02-15

The typical soil-purple soil in Three Gorges Reservoir was the tested soil, the characteristics of adsorption leaching of dimethyl phthalate (DMP) in contaminated water by the soil, and the influencing factors in the process were conducted using soil column leaching experiment. The results showed that the parabolic equation was the best equation describing adsorption kinetics of DMP by soils. The concentration of DMP in the leaching solution had significant effect on the adsorption amounts of DMP. With the increasing concentration of DMP in the leaching solution, the adsorption capacities of DMP by purple soil increased linearly. The ionic strength and pH in leaching solution had significant effects on adsorption of DMP. On the whole, increasing of the ionic strength restrained the adsorption. The adsorption amounts at pH 5.0-7.0 were more than those under other pH condition. The addition of exogenous organic matter (OM) in purple soil increased the adsorption amount of DMP by purple soil. However, the adsorption amount was less than those with other addition amounts of exogenous OM when the addition of exogenous OM was too high (> or = 30 g x kg(-1)). The addition of surfactant sodium dodecylbenzene sulfonic acid (SDBS) in purple soil increased the adsorption amount of DMP by purple soil. The adsorption amount was maximal when the addition amount of SDBS was 50 mg x kg(-1). However, the adsorption amounts decreased with increasing addition amounts of SDBS although the adsorption amounts were still more than that of the control group, and the adsorption amount was almost equal to that of the control group when the addition amount of SDBS was 800 mg x kg(-1). Continuous leaching time affected the vertical distribution of DMP in the soil column. When the leaching time was shorter, the upper soil column adsorbed more DMP, while the DMP concentrations in upper and lower soil columns became similar with the extension of leaching time.

Liquid Crystalline Properties of Amyloid Protein Fibers in Water

NASA Astrophysics Data System (ADS)

Mezzenga, Raffaele; Jung, Jin-Mi

2010-03-01

We have studied the liquid crystalline features of two colloidal systems consisting of food protein amyloid fibrils in water, obtained by heat-denaturation and aggregation of β-lactoglobulin, a globular dairy protein. The resulting fibrils, have a monodisperse cross section of about 4 nm and two groups of polydisperse contour lengths: (i) fibrils 1-10 μm long, showing semiflexible polyeletrolyte-like behaviour and (ii) rigid rods 100-200 nm long. In both systems, the fibers are highly charged (+5 e/nm) and stable in water at low ionic strength (0.01 M) and low pH (pH 2). The physical properties of these systems are studied using a polymer physics approach and phase diagrams of these two systems are obtained by changing concentration and pH. Both systems exhibit rich phase behaviours. Interestingly, the experimentally measured isotropic-nematic phase transition was found to occur at concentrations more than one order of magnitude lower than what expected based on Onsager theory. Experimental results are revisited in terms of the Flory theory developed for rigid polymers in solvent of varying conditions.

Electrochromatographic retention of peptides on strong cation-exchange stationary phases.

PubMed

Nischang, Ivo; Höltzel, Alexandra; Tallarek, Ulrich

2010-03-01

We analyze the systematic and substantial electrical field-dependence of electrochromatographic retention for four counterionic peptides ([Met5]enkephalin, oxytocin, [Arg8]vasopressin, and luteinizing hormone releasing hormone (LHRH) ) on a strong cation-exchange (SCX) stationary phase. Our experiments show that retention behavior in the studied system depends on the charge-selectivity of the stationary phase particles, the applied voltage, and the peptides' net charge. Retention factors of twice positively charged peptides ([Arg8]vasopressin and LHRH at pH 2.7) decrease with increasing applied voltage, whereas lower charged peptides (oxytocin and [Met5]enkephalin at pH 2.7, [Arg8]vasopressin and LHRH at pH 7.0) show a concomitant increase in their retention factors. The observed behavior is explained on the basis of electrical field-induced concentration polarization (CP) that develops around the SCX particles of the packing. The intraparticle concentration of charged species (buffer ions, peptides) increases with increasing applied voltage due to diffusive backflux from the enriched CP zone associated with each SCX particle. For twice charged and on the SCX phase strongly retained peptides the local increase in mobile phase ionic strength reduces the electrostatic interactions with the stationary phase, which explains the decrease of retention factors with increasing applied voltage and CP intensity. Lower charged and weaker retained peptides experience a much stronger relative intraparticle enrichment than the twice-charged peptides, which results in a net increase of retention factors with increasing applied voltage. The CP-related contribution to electrochromatographic retention of peptides on the SCX stationary phase is modulated by the applied voltage, the mobile phase ionic strength, and the peptides' net charge and could be used for selectivity tuning in difficult separations.

Single-channel measurements of an N-acetylneuraminic acid-inducible outer membrane channel in Escherichia coli

PubMed Central

Giri, Janhavi; Tang, John M.; Wirth, Christophe; Peneff, Caroline M.

2012-01-01

NanC is an Escherichia coli outer membrane protein involved in sialic acid (Neu5Ac, i.e., N-acetylneuraminic acid) uptake. Expression of the NanC gene is induced and controlled by Neu5Ac. The transport mechanism of Neu5Ac is not known. The structure of NanC was recently solved (PDB code: 2WJQ) and includes a unique arrangement of positively charged (basic) side chains consistent with a role in acidic sugar transport. However, initial functional measurements of NanC failed to find its role in the transport of sialic acids, perhaps because of the ionic conditions used in the experiments. We show here that the ionic conditions generally preferred for measuring the function of outer-membrane porins are not appropriate for NanC. Single channels of NanC at pH 7.0 have: (1) conductance 100 pS to 800 pS in 100 mM KCl to 3 M KCl), (2) anion over cation selectivity (Vreversal = +16 mV in 250 mM KCl || 1 M KCl), and (3) two forms of voltage-dependent gating (channel closures above ±200 mV). Single-channel conductance decreases by 50% when HEPES concentration is increased from 100 μM to 100 mM in 250 mM KCl at pH 7.4, consistent with the two HEPES binding sites observed in the crystal structure. Studying alternative buffers, we find that phosphate interferes with the channel conductance. Single-channel conductance decreases by 19% when phosphate concentration is increased from 0 mM to 5 mM in 250 mM KCl at pH 8.0. Surprisingly, TRIS in the baths reacts with Ag|AgCl electrodes, producing artifacts even when the electrodes are on the far side of agar–KCl bridges. A suitable baseline solution for NanC is 250 mM KCl adjusted to pH 7.0 without buffer. PMID:22246445

Functional properties of protein from frozen mantle and fin of jumbo squid Dosidicus gigas in function of pH and ionic strength.

PubMed

Rocha-Estrada, J G; Córdova-Murueta, J H; García-Carreño, F L

2010-10-01

Functional properties of protein from mantle and fin of the jumbo squid Dosidicus gigas were explained based on microscopic muscle fiber and protein fractions profiles as observed in SDS-PAGE. Fin has higher content of connective tissue and complex fiber arrangement, and we observed higher hardness of fin gels as expected. Myosin heavy chain (MHC) was found in sarcoplasmic, myofibril and soluble-in-alkali fractions of mantle and only in sarcoplasmic and soluble-in-alkali fractions of fin. An additive effect of salt concentration and pH affected the solubility and foaming properties. Fin and mantle proteins yielded similar results in solubility tests, but significant differences occurred for specific pH and concentrations of salt. Foaming capacity was proportional to solubility; foam stability was also affected by pH and salt concentration. Hardness and fracture strength of fin gels were significantly higher than mantle gels; gels from proteins of both tissues reached the highest level in the folding test. Structural and molecular properties, such as MHC and paramyosin solubility, arrangement of muscle fibers and the content of connective tissue were useful to explain the differences observed in these protein properties. High-strength gels can be formed from squid mantle or fin muscle. Fin displayed similar or better properties than mantle in all tests.

Influence of naturally occurring dissolved organic matter, colloids, and cations on nanofiltration of pharmaceutically active and endocrine disrupting compounds.

PubMed

Sadmani, A H M Anwar; Andrews, Robert C; Bagley, David M

2014-12-01

This study examined the rejection of selected pharmaceutically active (PhAC) and endocrine disrupting compounds (EDCs) when using nanofiltration as a function of naturally occurring dissolved organic matter (DOM), colloidal particles, cations and their interactions. Lake Ontario water served as a source of natural DOM and colloidal particles. PhAC/EDC rejection experiments were conducted using raw Lake Ontario water and Lake Ontario water that was pre-treated with either ultrafiltration to remove colloidal particles, or fluidized ion exchange resins to remove DOM. Additionally, the concentration of cations (Ca(2+), Mg(2+), and Na(+)) in the raw and pre-treated water matrices was varied. While ionic PhACs and EDCs exhibited high rejections from all the water matrices examined, neutral compounds were most effectively rejected in water containing DOM and no colloids, and least effectively rejected from colloid-containing water with increased cations but no DOM. The presence of DOM significantly improved compound rejection and the increase in cation concentration significantly decreased rejection. The presence of colloids had comparatively little effect except to mitigate the impact of increased cation concentration, apparently providing some cation-buffering capacity. The sequence in which constituents are removed from waters during treatment may significantly impact PhAC and EDC removal, especially of neutral compounds. Copyright © 2014 Elsevier Ltd. All rights reserved.

Wintertime water-soluble aerosol composition and particle water content in Fresno, California

NASA Astrophysics Data System (ADS)

Parworth, Caroline L.; Young, Dominique E.; Kim, Hwajin; Zhang, Xiaolu; Cappa, Christopher D.; Collier, Sonya; Zhang, Qi

2017-03-01

The composition and concentrations of water-soluble gases and ionic aerosol components were measured from January to February 2013 in Fresno, CA, with a particle-into-liquid sampler with ion chromatography and annular denuders. The average (±1σ) ionic aerosol mass concentration was 15.0 (±9.4) µg m-3, and dominated by nitrate (61%), followed by ammonium, sulfate, chloride, potassium, nitrite, and sodium. Aerosol-phase organic acids, including formate and glycolate, and amines including methylaminium, triethanolaminium, ethanolaminium, dimethylaminium, and ethylaminium were also detected. Although the dominant species all came from secondary aerosol formation, there were primary sources of ionic aerosols as well, including biomass burning for potassium and glycolate, sea spray for sodium, chloride, and dimethylamine, and vehicles for formate. Particulate methanesulfonic acid was also detected and mainly associated with terrestrial sources. On average, the molar concentration of ammonia was 49 times greater than nitric acid, indicating that ammonium nitrate formation was limited by nitric acid availability. Particle water was calculated based on the Extended Aerosol Inorganics Model (E-AIM) thermodynamic prediction of inorganic particle water and κ-Köhler theory approximation of organic particle water. The average (±1σ) particle water concentration was 19.2 (±18.6) µg m-3, of which 90% was attributed to inorganic species. The fractional contribution of particle water to total fine particle mass averaged at 36% during this study and was greatest during early morning and night and least during the day. Based on aqueous-phase concentrations of ions calculated by using E-AIM, the average (±1σ) pH of particles in Fresno during the winter was estimated to be 4.2 (±0.2).

Estimating Concentrations of Road-Salt Constituents in Highway-Runoff from Measurements of Specific Conductance

USGS Publications Warehouse

Granato, Gregory E.; Smith, Kirk P.

1999-01-01

Discrete or composite samples of highway runoff may not adequately represent in-storm water-quality fluctuations because continuous records of water stage, specific conductance, pH, and temperature of the runoff indicate that these properties fluctuate substantially during a storm. Continuous records of water-quality properties can be used to maximize the information obtained about the stormwater runoff system being studied and can provide the context needed to interpret analyses of water samples. Concentrations of the road-salt constituents calcium, sodium, and chloride in highway runoff were estimated from theoretical and empirical relations between specific conductance and the concentrations of these ions. These relations were examined using the analysis of 233 highwayrunoff samples collected from August 1988 through March 1995 at four highway-drainage monitoring stations along State Route 25 in southeastern Massachusetts. Theoretically, the specific conductance of a water sample is the sum of the individual conductances attributed to each ionic species in solution-the product of the concentrations of each ion in milliequivalents per liter (meq/L) multiplied by the equivalent ionic conductance at infinite dilution-thereby establishing the principle of superposition. Superposition provides an estimate of actual specific conductance that is within measurement error throughout the conductance range of many natural waters, with errors of less than ?5 percent below 1,000 microsiemens per centimeter (?S/cm) and ?10 percent between 1,000 and 4,000 ?S/cm if all major ionic constituents are accounted for. A semi-empirical method (adjusted superposition) was used to adjust for concentration effects-superposition-method prediction errors at high and low concentrations-and to relate measured specific conductance to that calculated using superposition. The adjusted superposition method, which was developed to interpret the State Route 25 highway-runoff records, accounts for contributions of constituents other than calcium, sodium, and chloride in dilute waters. The adjusted superposition method also accounts for the attenuation of each constituent's contribution to conductance as ionic strength increases. Use of the adjusted superposition method generally reduced predictive error to within measurement error throughout the range of specific conductance (from 37 to 51,500 ?S/cm) in the highway runoff samples. The effects of pH, temperature, and organic constituents on the relation between concentrations of dissolved constituents and measured specific conductance were examined but these properties did not substantially affect interpretation of the Route 25 data set. Predictive abilities of the adjusted superposition method were similar to results obtained by standard regression techniques, but the adjusted superposition method has several advantages. Adjusted superposition can be applied using available published data about the constituents in precipitation, highway runoff, and the deicing chemicals applied to a highway. This semi-empirical method can be used as a predictive and diagnostic tool before a substantial number of samples are collected, but the power of the regression method is based upon a large number of water-quality analyses that may be affected by a bias in the data.

Interaction of diazepam with surfactants. Spectrophotometric and spectrofluorometric study

NASA Astrophysics Data System (ADS)

De La Guardia, M.; Rodilla, F.

1986-03-01

The interaction of diazepam with non-ionic, anionic and cationic surfactants has been studied spectrophotometrically and fluorometrically. It has been verified that the absorption spectrum of diazepam is not modified in micellar medium. However, a dramatic five-fold increase in fluorescence sensitivity is observed in the presence of sodium lauryl sulphate (SDS). The experimental conditions, temperature, pH and surfactant concentration have been optimized to improve the fluorometric determination of diazepam and a detection limit of 0,04 ppmhas been obtained.

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

USGS Publications Warehouse

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

1999-01-01

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

Highly selective adsorption of hydroquinone by hydroxyethyl cellulose functionalized with magnetic/ionic liquid.

PubMed

Ding, Chaofan; Li, Yue; Wang, Yanhui; Li, Jianbo; Sun, Yuanling; Lin, Yanna; Sun, Weiyan; Luo, Chuannan

2018-02-01

Magnetic hydroxyethyl cellulose/ionic liquid (MHEC/IL) materials were fabricated through a facile and fast process and their application as excellent adsorbents for hydroquinone was also demonstrated. The thermal stability, chemical structure and magnetic property of the MHEC/IL were characterized by the Scanning electron microscope (SEM), Transmission Electron Microscope (TEM), Fourier transform infrared spectrometer (FT-IR) and X-ray diffraction (XRD), respectively. The adsorbents were used for the removal of hydroquinone from simulated wastewater with a fast solid-liquid separation in the presence of external magnetic field. The influence of various analytical parameters on the adsorption of hydroquinone such as pH, contact time and initial ion concentration were studied in detail. The results showed that the maximum adsorption capacity was 335.68mgg -1 , observed at pH 5 and temperature 30°C. Equilibrium adsorption was achieved within 30min. The kinetic data, obtained at the optimum pH 5, could be fitted with a pseudo-second order equation. Adsorption process could be well described by Freundlich adsorption isotherms. The obtained results indicated that the impregnation of the room temperature IL significantly enhances the removal efficiency of hydroquinone. The MHEC/IL may be suitable materials in phenols pollution cleanup if they are synthesized in largescale and at low price in near future. Copyright © 2017 Elsevier B.V. All rights reserved.

The fate and transport of RDX, HMX, TNT and DNT in the volcanic soils of Hawaii: a laboratory and modeling study.

PubMed

Alavi, Ghasem; Chung, Mel; Lichwa, Joseph; D'Alessio, Matteo; Ray, Chittaranjan

2011-01-30

The adsorption and degradation behavior of RDX, HMX, TNT and DNT and the impact of pH, ionic strength and dissolved organic matter on sorption were examined for two volcanic soils of a former military training area on Hawaii Island, Hawaii, USA. The transport of these chemicals in the soil was also studied in small packed columns and simulated using a water-flow and solute-transport model, HYDRUS_1D. The results show that HMX and RDX are both significantly more mobile than TNT and DNT. The adsorbability of the four chemicals was ranked as: RDXRDX>DNT>TNT. No significant trend was observed for the effect of ionic strength, pH and dissolved organic carbon (DOC) on the adsorption of explosive compounds within the concentrations and pH ranges evaluated. The simulation results show that TNT and DNT would not leach beyond a depth of 30cm soil profile whereas a significant amount of HMX and RDX would pass the 30cm depth. It seems that the risk for contamination of groundwater is much higher for both HMX and RDX than for DNT and TNT as the substratum in this area consists of highly permeable lavas. Copyright © 2010 Elsevier B.V. All rights reserved.

Investigation of Pu(IV)-acetohydroxamic acid complex by solvent extraction with di(2-ethylhexyl) phosphoric acid

NASA Astrophysics Data System (ADS)

Brown, M. Alex; Paulenova, Alena; Tkac, Peter

2010-03-01

The stability constant of the Pu(IV)-acetohydroxamic acid complex Pu(AHA)3+ at 1 M ionic strength (pH = 0) has been investigated by method of solvent extraction. Di(2-ethylhexyl) phosphoric acid (HDEHP) was used to extract Pu(IV) from perchloric and nitric acid media at various AHA concentrations. Distribution ratios over a range of ligand concentrations were used in conjunction with graphical methods to obtain logβ1 = 14.3 ± 0.03 in perchloric acid. The stability constant determined from solutions in nitric acid was excluded because of the uncertainty in plutonium speciation.

Carbonate species as OH- carriers for decreasing the pH gradient between cathode and anode in biological fuel cells.

PubMed

Torres, César I; Lee, Hyung-Sool; Rittmann, Bruce E

2008-12-01

Anodes of biological fuel cells (BFCs) normally must operate at a near-neutral pH in the presence of various ionic species required for the function of the biological catalyst (e.g., substrate, nutrients, and buffers). These ionic species are in higher concentration than protons (H+) and hydroxides (OH-); slow transport of H+ and OH- equivalents between anode and cathode compartments can lead to a large pH gradient that can inhibit the function of biological components, decrease voltage efficiency in BFCs, or both. We evaluate the use of carbonate species as OH- carriers from the cathode to the anode compartment. This is achieved by adding CO2 to the influent air in the cathode. CO2 is an acid that combines with OH- in the cathode to produce bicarbonate and carbonate. These species can migrate to the anode compartment as OH- carriers at a rate much greater than can OH- itself when the pH is not extremely high in the cathode compartment We demonstrate this concept by feeding different air/CO2 mixtures to the cathode of a dual-chamber microbial fuel cell (MFC) fed with acetate as substrate. Our results show a 45% increase in power density (from 1.9 to 2.8 W/m2) by feeding air augmented with 2-10% CO2. The cell voltage increased by as much as 120 mV, indicating that the pH gradient decreased by as much as 2 pH units. Analysis of the anode effluent showed an average increase of 4.9 mM in total carbonate, indicating that mostly carbonate was transferred from the cathode compartment This process provides a simple way to minimize potential losses in BFCs due to pH gradients between anode and cathode compartments.

[Analyze nanofiltration separation rule of chlorogenic acid from low concentration ethanol by Donnan effect and solution-diffusion effect].

PubMed

Li, Cun-Yu; Liu, Li-Cheng; Jin, Li-Yang; Li, Hong-Yang; Peng, Guo-Ping

2017-07-01

To separate chlorogenic acid from low concentration ethanol and explore the influence of Donnan effect and solution-diffusion effect on the nanofiltration separation rule. The experiment showed that solution pH and ethanol volume percent had influences on the separation of chlorogenic acid. Within the pH values from 3 to 7 for chlorogenic acid in 30% ethanol, the rejection rate of chlorogenic acid was changed by 70.27%. Through the response surface method for quadratic regression model, an interaction had been found in molecule weight cut-off, pH and ethanol volume percent. In fixed nanofiltration apparatus, the existence states of chlorogenic acid determinedits separation rules. With the increase of ethanol concentration, the free form chlorogenic acid was easily adsorbed, dissolved on membrane surface and then caused high transmittance due to the solution-diffusion effect. However, at the same time, due to the double effects of Donnan effect and solution-diffusion effect, the ionic state of chlorogenic acid was hard to be adsorbed in membrane surface and thus caused high rejection rate. The combination of Box-Behnken design and response surface analysis can well optimize the concentrate process by nanofiltration, and the results showed that nanofiltration had several big advantages over the traditional vacuum concentrate technology, meanwhile, and solved the problems of low efficiency and serious component lossesin the Chinese medicines separation process for low concentration organic solvent-water solution. Copyright© by the Chinese Pharmaceutical Association.

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

PubMed

Bui, Tung Xuan; Choi, Heechul

2010-08-01

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

Stimuli-Responsive Polymer Brushes for Flow Control through Nanopores

PubMed Central

Adiga, Shashishekar P.; Brenner, Donald W.

2012-01-01

Responsive polymers attached to the inside of nano/micro-pores have attracted great interest owing to the prospect of designing flow-control devices and signal responsive delivery systems. An intriguing possibility involves functionalizing nanoporous materials with smart polymers to modulate biomolecular transport in response to pH, temperature, ionic concentration, light or electric field. These efforts open up avenues to develop smart medical devices that respond to specific physiological conditions. In this work, an overview of nanoporous materials functionalized with responsive polymers is given. Various examples of pH, temperature and solvent responsive polymers are discussed. A theoretical treatment that accounts for polymer conformational change in response to a stimulus and the associated flow-control effect is presented. PMID:24955529

Combined use of chiral ionic liquid and cyclodextrin for MEKC: Part I. Simultaneous enantioseparation of anionic profens.

PubMed

Wang, Bin; He, Jun; Bianchi, Victoria; Shamsi, Shahab A

2009-08-01

The enantiomers of five profen drugs were simultaneously separated by MEKC with the combined use of 2,3,6-tri-O-methyl-beta-cyclodextrin and chiral cationic ionic liquid, N-undecenoxy-carbonyl-L-leucinol bromide, which formed micelles in aqueous buffers. Enantioseparations of these profen drugs were optimized by varying the chain length and concentration of the IL surfactant using a standard recipe containing 35 mM 2,3,6-tri-O-methyl-beta-cyclodextrin, 5 mM sodium acetate at pH 5.0. The batch-to-batch reproducibility of N-undecenoxy-carbonyl-L-leucinol bromide was tested and found to have no significant impact in terms of enantiomeric resolution, efficiency, and migration time. Finally, this method was successfully applied for the quantitative determination of ibuprofen in pharmaceutical tablets.

Combined use of chiral ionic liquid and cyclodextrin for MEKC: Part I. Simultaneous enantioseparation of anionic profens

PubMed Central

Wang, Bin; He, Jun; Bianchi, Victoria; Shamsi, Shahab A.

2009-01-01

The enantiomers of five profen (PROF) drugs were simultaneously separated by MEKC with the combined use of 2, 3, 6-tri-O-methyl-β-cyclodextrin (TM-β-CD) and chiral cationic ionic liquid (IL), N-undecenoxy-carbonyl-L-leucinol bromide (L-UCLB), which formed micelles in aqueous buffers. Enantioseparations of these PROF drugs were optimized by varying the chain length and concentration of the IL surfactant using a standard recipe containing 35 mM TM-β-CD, 5 mM sodium acetate at pH 5.0. The batch-to-batch reproducibility of L-UCLB was tested and found to have no significant impact in terms of enantiomeric resolution, efficiency and migration time. Finally, this method was successfully applied for the quantitative determination of ibuprofen in pharmaceutical tablets. PMID:19650046

Electrostatics-driven assembly of uni-lamellar catanionic facetted vesicles

NASA Astrophysics Data System (ADS)

Leung, Cheuk-Yui; Palmer, Liam; Kewalramani, Sumit; Sknepnek, Rastko; Vernizzi, Graziano; Greenfield, Megan; Stupp, Samuel; Bedzyk, Michael; Olvera de La Cruz, Monica

2012-02-01

Nature utilizes shape to generate function. Organelle and halophilic bacteria wall envelopes, for example, adopt various polyhedral shapes to compartmentalize matter. The origin of these shapes is unknown. A large variety of shell geometries, either fully faceted polyhedra or mixed Janus-like vesicles with faceted and curved domains that resemble cellular shells can be generated by coassembling water-insoluble anionic (--1) amphiphiles with high valence cationic (+2 and +3) amphiphiles. Electron microscopy, X-ray scattering, theory and simulations demonstrate that the resulting faceted ionic shells are crystalline, and stable at high salt concentrations. The crystallization of the co-assembled single tail amphiphiles is induced by ionic correlations, and modified by the solution pH. This work promotes the design of faceted shapes for various applications and improves our understanding of the origin of polyhedral shells in nature.

Microsphere morphology tuning and photo-luminescence properties of monoclinic Y2WO6

NASA Astrophysics Data System (ADS)

Gao, Hong; Bai, Yulong; Zhang, Junying; Tang, Zilong

2015-04-01

Effects of the solution pH value and reaction time on the precursor morphology and photoluminescence properties are investigated for hydrothermally prepared monoclinic Y2WO6 phosphors. In the near-neutral environment, sodium dodecyl benzene sulfonate (SDBS) surfactant forms small microspheres micelles as template to synthesize microspherical precursor. H+ ions concentration affects the arrangement of negative ionic surfactant SDBS. As a result, jujube-liked and popcorn-like loose microspheres formed at low pH value. When the pH value is 5.2 and the hydrothermal reaction time reaches 24 h, respectively, the strongest luminescent intensity can be obtained. Under this condition, the precursor presented regular microsphere with diameter of 4.0 μm. After high-temperature heat treatment, the obtained phosphor particles still exhibit microsphere-like shape. Therefore, we provide an effective method to tune the morphology of Y2WO6 phosphors and study the relationship between morphology and luminescent performance.

Destabilization and Treatment of Emulsified Oils in Wastewaters by Electrocoagulation.

PubMed

Genc, Ayten; Bakirci, Busra

2016-11-01

  In this study, the optimum operating conditions for the treatment of emulsified oils by electrocoagulation were determined depending on droplet stability analysis. Zeta potential measurements were used as the indication of oil droplet charges. In addition, the effects of pH and ionic conductivity on the droplet sizes and surface charges were investigated. The studied emulsified oil droplet sizes were more sensitive to changes in pH rather than salt concentration. The droplets became larger and unstable in alkaline conditions. As the initial pH of wastewaters increased, the oil removal efficiency increased during the electrocoagulation experiments as well. The use of iron or aluminum electrodes resulted in higher removal efficiencies in comparison to stainless steel electrodes. In addition, the energy consumption for aluminum electrodes was much lower than iron electrodes. To obtain 98% oil removal efficiency, distance between the electrodes was recommended to be less than or equal to 1 cm.

pH controlled gating of toxic protein pores by dendrimers

NASA Astrophysics Data System (ADS)

Mandal, Taraknath; Kanchi, Subbarao; Ayappa, K. G.; Maiti, Prabal K.

2016-06-01

Designing effective nanoscale blockers for membrane inserted pores formed by pore forming toxins, which are expressed by several virulent bacterial strains, on a target cell membrane is a challenging and active area of research. Here we demonstrate that PAMAM dendrimers can act as effective pH controlled gating devices once the pore has been formed. We have used fully atomistic molecular dynamics (MD) simulations to characterize the cytolysin A (ClyA) protein pores modified with fifth generation (G5) PAMAM dendrimers. Our results show that the PAMAM dendrimer, in either its protonated (P) or non-protonated (NP) states can spontaneously enter the protein lumen. Protonated dendrimers interact strongly with the negatively charged protein pore lumen. As a consequence, P dendrimers assume a more expanded configuration efficiently blocking the pore when compared with the more compact configuration adopted by the neutral NP dendrimers creating a greater void space for the passage of water and ions. To quantify the effective blockage of the protein pore, we have calculated the pore conductance as well as the residence times by applying a weak force on the ions/water. Ionic currents are reduced by 91% for the P dendrimers and 31% for the NP dendrimers. The preferential binding of Cl- counter ions to the P dendrimer creates a zone of high Cl- concentration in the vicinity of the internalized dendrimer and a high concentration of K+ ions in the transmembrane region of the pore lumen. In addition to steric effects, this induced charge segregation for the P dendrimer effectively blocks ionic transport through the pore. Our investigation shows that the bio-compatible PAMAM dendrimers can potentially be used to develop therapeutic protocols based on the pH sensitive gating of pores formed by pore forming toxins to mitigate bacterial infections.Designing effective nanoscale blockers for membrane inserted pores formed by pore forming toxins, which are expressed by several virulent bacterial strains, on a target cell membrane is a challenging and active area of research. Here we demonstrate that PAMAM dendrimers can act as effective pH controlled gating devices once the pore has been formed. We have used fully atomistic molecular dynamics (MD) simulations to characterize the cytolysin A (ClyA) protein pores modified with fifth generation (G5) PAMAM dendrimers. Our results show that the PAMAM dendrimer, in either its protonated (P) or non-protonated (NP) states can spontaneously enter the protein lumen. Protonated dendrimers interact strongly with the negatively charged protein pore lumen. As a consequence, P dendrimers assume a more expanded configuration efficiently blocking the pore when compared with the more compact configuration adopted by the neutral NP dendrimers creating a greater void space for the passage of water and ions. To quantify the effective blockage of the protein pore, we have calculated the pore conductance as well as the residence times by applying a weak force on the ions/water. Ionic currents are reduced by 91% for the P dendrimers and 31% for the NP dendrimers. The preferential binding of Cl- counter ions to the P dendrimer creates a zone of high Cl- concentration in the vicinity of the internalized dendrimer and a high concentration of K+ ions in the transmembrane region of the pore lumen. In addition to steric effects, this induced charge segregation for the P dendrimer effectively blocks ionic transport through the pore. Our investigation shows that the bio-compatible PAMAM dendrimers can potentially be used to develop therapeutic protocols based on the pH sensitive gating of pores formed by pore forming toxins to mitigate bacterial infections. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02963a

Liquid-liquid separation in solutions of normal and sickle cell hemoglobin

NASA Astrophysics Data System (ADS)

Galkin, Oleg; Chen, Kai; Nagel, Ronald L.; Elison Hirsch, Rhoda; Vekilov, Peter G.

2002-06-01

We show that in solutions of human hemoglobin (Hb)oxy- and deoxy-Hb A or Sof near-physiological pH, ionic strength, and Hb concentration, liquid-liquid phase separation occurs reversibly and reproducibly at temperatures between 35 and 40°C. In solutions of deoxy-HbS, we demonstrate that the dense liquid droplets facilitate the nucleation of HbS polymers, whose formation is the primary pathogenic event for sickle cell anemia. In view of recent results that shifts of the liquid-liquid separation phase boundary can be achieved by nontoxic additives at molar concentrations up to 30 times lower than the protein concentrations, these findings open new avenues for the inhibition of the HbS polymerization.

Stabilization of model beverage cloud emulsions using protein-polysaccharide electrostatic complexes formed at the oil-water interface.

PubMed

Harnsilawat, Thepkunya; Pongsawatmanit, Rungnaphar; McClements, David J

2006-07-26

The potential of utilizing interfacial complexes, formed through the electrostatic interactions of proteins and polysaccharides at oil-water interfaces, to stabilize model beverage cloud emulsions has been examined. These interfacial complexes were formed by mixing charged polysaccharides with oil-in-water emulsions containing oppositely charged protein-coated oil droplets. Model beverage emulsions were prepared that consisted of 0.1 wt % corn oil droplets coated by beta-lactoglobulin (beta-Lg), beta-Lg/alginate, beta-Lg/iota-carrageenan, or beta-Lg/gum arabic interfacial layers (pH 3 or 4). Stable emulsions were formed when the polysaccharide concentration was sufficient to saturate the protein-coated droplets. The emulsions were subjected to variations in pH (from 3 to 7), ionic strength (from 0 to 250 mM NaCl), and thermal processing (from 30 or 90 degrees C), and the influence on their stability was determined. The emulsions containing alginate and carrageenan had the best stability to ionic strength and thermal processing. This study shows that the controlled formation of protein-polysaccharide complexes at droplet surfaces may be used to produce stable beverage emulsions, which may have important implications for industrial applications.

Natural organic matter (NOM) adsorption to multi-walled carbon nanotubes: effect of NOM characteristics and water quality parameters.

PubMed

Hyung, Hoon; Kim, Jae-Hong

2008-06-15

The effect of natural organic matter (NOM) characteristics and water quality parameters on NOM adsorption to multiwalled carbon nanotubes (MWNT) was investigated. Isotherm experiment results were fitted well with a modified Freundlich isotherm model that took into account the heterogeneous nature of NOM. The preferential adsorption of the higher molecular weight fraction of NOM was observed by size exclusion chromatographic analysis. Experiments performed with various NOM samples suggested that the degree of NOM adsorption varied greatly depending on the type of NOM and was proportional to the aromatic carbon content of NOM. The NOM adsorption to MWNT was also dependent on water quality parameters: adsorption increased as pH decreased and ionic strength increased. As a result of NOM adsorption to MWNT, a fraction of MWNT formed a stable suspension in water and the concentration of MWNT suspension depended on the amount of NOM adsorbed per unit mass of MWNT. The amount of MWNT suspended in water was also affected by ionic strength and pH. The findings in this study suggested that the fate and transport of MWNT in natural systems would be largely influenced by NOM characteristics and water quality parameters.

Removal of lindane from an aqueous solution by using aminopropyl silica gel-immobilized calix[6]arene.

PubMed

Tor, Ali; Aydin, Mehmet Emin; Aydin, Senar; Tabakci, Mustafa; Beduk, Fatma

2013-11-15

An aminopropyl silica gel-immobilized calix[6]arene (C[6]APS) has been used for the removal of lindane from an aqueous solution in batch sorption technique. The C[6]APS was synthesized with p-tert-butylcalix[6]arene hexacarboxylate derivative and aminopropyl silica gel in the presence of N,N'-diisopropyl carbodiimide coupling reagent. The sorption study was carried out as functions of solution pH, contact time, initial lindane concentration, C[6]APS dosage and ionic strength of solution. The matrix effect of natural water samples on the sorption efficiency of C[6]APS was also investigated. Maximum lindane removal was obtained at a wide pH range of 2-8 and sorption equilibrium was achieved in 2h. The isotherm analysis indicated that the sorption data can be represented by both Langmuir and Freundlich isotherm models. Increasing ionic strength of the solutions increased the sorption efficiency and matrix of natural water samples had no effect on the sorption of lindane. By using multilinear regression model, regression equation was also developed to explain the effects of the experimental variables. Copyright © 2013 Elsevier B.V. All rights reserved.

[Bromate reduction by granular activated carbon].

PubMed

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.

Separation of toxic rhodamine B from aqueous solution using an efficient low-cost material, Azolla pinnata, by adsorption method.

PubMed

Kooh, Muhammad Raziq Rahimi; Lim, Linda B L; Lim, Lee Hoon; Dahri, Muhammad Khairud

2016-02-01

This study investigated the potential of untreated Azolla pinnata (AP) to remove toxic rhodamine B (RB) dye. The effects of adsorbent dosage, pH, ionic strength, contact time, and concentration were studied. Experiments involving the effects of pH and ionic strength indicated that hydrophobic-hydrophobic interactions might be the dominant force of attraction for the RB-AP adsorption system. The kinetics modelling of the kinetics experiment showed that pseudo-second-order best represented the adsorption process. The Weber-Morris intraparticle diffusion model showed that intraparticle diffusion is not the rate-limiting step, while the Boyd model suggested that film diffusion might be rate-limiting. The adsorption isotherm model, Langmuir, best represented the adsorption process, and the maximum adsorption capacity was predicted to be 72.2 and 199.7 mg g(-1) at 25 and 65 °C, respectively. Thermodynamics study indicates spontaneity, endothermic and physisorption-dominant adsorption process. The adsorbents were regenerated to satisfactory level with distilled water, HNO3 and NaOH. Pre-treatment of adsorbent with oxalic acid, citric acid, NaOH, HCl and phosphoric acid was investigated but the adsorption capacity was less than the untreated AP.

Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid.

PubMed

Yan, Wei; Hu, Shan; Jing, Chuanyong

2012-04-15

Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Cs

Extensive structural change of the envelope protein of dengue virus induced by a tuned ionic strength: conformational and energetic analyses

NASA Astrophysics Data System (ADS)

Degrève, Léo; Fuzo, Carlos A.; Caliri, Antonio

2012-12-01

The Dengue has become a global public health threat, with over 100 million infections annually; to date there is no specific vaccine or any antiviral drug. The structures of the envelope (E) proteins of the four known serotype of the dengue virus (DENV) are already known, but there are insufficient molecular details of their structural behavior in solution in the distinct environmental conditions in which the DENVs are submitted, from the digestive tract of the mosquito up to its replication inside the host cell. Such detailed knowledge becomes important because of the multifunctional character of the E protein: it mediates the early events in cell entry, via receptor endocytosis and, as a class II protein, participates determinately in the process of membrane fusion. The proposed infection mechanism asserts that once in the endosome, at low pH, the E homodimers dissociate and insert into the endosomal lipid membrane, after an extensive conformational change, mainly on the relative arrangement of its three domains. In this work we employ all-atom explicit solvent Molecular Dynamics simulations to specify the thermodynamic conditions in that the E proteins are induced to experience extensive structural changes, such as during the process of reducing pH. We study the structural behavior of the E protein monomer at acid pH solution of distinct ionic strength. Extensive simulations are carried out with all the histidine residues in its full protonated form at four distinct ionic strengths. The results are analyzed in detail from structural and energetic perspectives, and the virtual protein movements are described by means of the principal component analyses. As the main result, we found that at acid pH and physiological ionic strength, the E protein suffers a major structural change; for lower or higher ionic strengths, the crystal structure is essentially maintained along of all extensive simulations. On the other hand, at basic pH, when all histidine residues are in the unprotonated form, the protein structure is very stable for ionic strengths ranging from 0 to 225 mM. Therefore, our findings support the hypothesis that the histidines constitute the hot points that induce configurational changes of E protein in acid pH, and give extra motivation to the development of new ideas for antivirus compound design.

The effect of soil properties on the toxicity and bioaccumulation of Ag nanoparticles and Ag ions in Enchytraeus crypticus.

PubMed

Topuz, Emel; van Gestel, Cornelis A M

2017-10-01

Standard natural Lufa soils (2.2, 2.3 and 5M) with different organic carbon contents (0.67-1.61%) and pH CaCl2 (5.5-7.3) were spiked with ionic Ag (AgNO 3 ) and polyvinyl pyrrolidone (AgNP-PVP) and citrate (AgNP-Cit) coated Ag nanoparticles (NPs). Enchytraeus crypticus were exposed for 21 days to assess effects on survival and reproduction. Soil, pore water and animals were analyzed for Ag. AgNP-Cit had a strong increasing effect on soil pH, leading to high enchytraeid mortality at concentrations higher than 60-100mg Ag/kg dry soil which made it impossible to determine the influence of soil properties on its toxicity. LC50s were lower for AgNO 3 than for AgNP-PVP (92-112 and 335-425mg Ag/kg dry soil, respectively) and were not affected by soil properties. AgNO 3 and AgNP-PVP had comparable reproductive toxicity with EC50s of 26.9-75.2 and 28.2-92.3mg Ag/kg dry soil, respectively; toxicity linearly increased with decreasing organic carbon content of the soils but did not show a clear effect of soil pH. Ag uptake in the enchytraeids was higher at higher organic carbon content, but could not explain differences in toxicity between soils. This study indicates that the bioavailability of both ionic and nanoparticulate Ag is mainly affected by soil organic carbon, with little effect of soil pH. Copyright © 2017. Published by Elsevier Inc.

The effect of intact talin and talin tail fragment on actin filament dynamics and structure depends on pH and ionic strength.

PubMed

Goldmann, W H; Hess, D; Isenberg, G

1999-03-01

We employed quasi-elastic light scattering and electron microscopy to investigate the influence of intact talin and talin tail fragment on actin filament dynamics and network structure. Using these methods, we confirm previous reports that intact talin induces cross-linking as well as filament shortening on actin networks. We now show that the effect of intact talin as well as talin tail fragment on actin networks is controlled by pH and ionic strength. At pH 7.5, actin filament dynamics in the presence of intact talin and talin tail fragment are characterized by a rapid decay of the dynamic structure factor and by a square root power law for the stretched exponential decay which is in contrast with the theory for pure actin solutions. At pH 6 and low ionic strength, intact talin cross-links actin filaments more tightly than talin tail fragment. Talin head fragment showed no effect on actin networks, indicating that the actin binding sites reside probably exclusively within the tail domain.

Sorption and complexation of Eu(III) on alumina: effects of pH, ionic strength, humic acid and chelating resin on kinetic dissociation study.

PubMed

Wang, X; Xu, D; Chen, L; Tan, X; Zhou, X; Ren, A; Chen, Ch

2006-04-01

The effects of pH (pH=2-12), ionic strength (0.01-2 mol/l NaNO(3)) and humic acid on the sorption and complexation of Eu(III) on alumina were investigated by using batch techniques. The experiments were carried out at room temperature and under ambient conditions. The results indicate that the sorption of Eu(III) on alumina is strongly influenced by humic acid. The sorption of Eu(III) on alumina is significantly dependent on pH values and independent of ionic strength. The sorption of Eu(III) on alumina may be attributed to surface complexation. The species of Eu(III) on HA-alumina colloids is dominated by both HA and alumina, and the addition sequences of HA or Eu(III) to the ternary system do not influence the sorption of Eu(III) to HA-coated alumina. Kinetic dissociation of Eu(III) from bare and HA-coated alumina was also studied by using the chelating resin. The result was discussed by a pseudo-first-order kinetics model.

Study of Np(V) Sorption by Ionic Exchange on Na, K, Ca and Mg-Montmorillonite

NASA Astrophysics Data System (ADS)

Benedicto, A.; Begg, J.; Zhao, P.; Kersting, A. B.; Zavarin, M.

2012-12-01

The transport behavior of actinides in soil and ground water are highly influenced by clay minerals due to their ubiquity in the environment, reactivity and colloidal properties. Neptunium(V) has been introduced in the environment as a result of nuclear weapons testing [e.g. 1, 2] and is a radionuclide of potential interest for safety assessment of high level radioactive waste disposal because its long half-life and high toxicity [3]. Surface complexation and ionic exchange have been identified as Np(V) sorption mechanisms onto montmorillonite. At pH below 5, Np(V) sorption is mainly attributed to ionic exchange. This study examines Np(V) ion exchange on Na, K, Ca and Mg forms of montmorillonite. Experiments were carried out using 237Np concentrations between 2 x 10-8 M and 5 x 10-6 M at three different ionic strengths 0.1, 0.01 and 0.001M. The pH was maintained at 4.5. Np(V) sorption to montmorillonite homoionized with monovalent cations (Na and K) demonstrated a markedly different behavior to that observed for montmorillonite homoionized with divalent cations (Ca and Mg). Np sorption to Na and K-montmorillonite was greater than Np sorption to Ca and Mg-montmorillonite. Isotherms with Na and K-montmorillonite showed a strong dependence on ionic strength: the percentage of Np adsorbed was near zero at 0.1M ionic strength, but increased to 30% at 0.001 M ionic strength. This suggests ionic exchange is the main Np adsorption mechanism under the experimental conditions investigated. Dependence on ionic strength was not observed in the Np sorption isotherms for Ca and Mg-montmorillonite indicating a low exchange capacity between Np and divalent cations. Modeling of the sorption experimental data will allow determination of the Na+↔NpO2+ and K+↔NpO2+ ionic exchange constants on montmorillonite. References: [1] A. R. Felmy; K. J. Cantrell; S. D. Conradson, Phys. Chem. Earth 2010, 35, 292-297 [2] D. K. Smith; D. L. Finnegan; S. M. Bowen, J. Environ. Radioact. 2003, 67, (1), 35-51 [3] N. Kozai; T. Ohnuki; S. Muraoka, J. Nucl. Sci. Technol. 1993, 30, (11), 1153-1159 This work was funded by U. S. DOE Office of Biological & Environmental Sciences, Subsurface Biogeochemistry Research Program, and performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344. A. Benedicto was supported by a Spanish Ministry of Science and Innovation 'FPI' pre-doctoral contract in CIEMAT (Spain). LLNL-ABS-570160

Conformational stability of apoflavodoxin.

PubMed Central

Genzor, C. G.; Beldarraín, A.; Gómez-Moreno, C.; López-Lacomba, J. L.; Cortijo, M.; Sancho, J.

1996-01-01

Flavodoxins are alpha/beta proteins that mediate electron transfer reactions. The conformational stability of apoflavodoxin from Anaboena PCC 7119 has been studied by calorimetry and urea denaturation as a function of pH and ionic strength. At pH > 12, the protein is unfolded. Between pH 11 and pH 6, the apoprotein is folded properly as judged from near-ultraviolet (UV) circular dichroism (CD) and high-field 1H NMR spectra. In this pH interval, apoflavodoxin is a monomer and its unfolding by urea or temperature follows a simple two-state mechanism. The specific heat capacity of unfolding for this native conformation is unusually low. Near its isoelectric point (3.9), the protein is highly insoluble. At lower pH values (pH 3.5-2.0), apoflavodoxin adopts a conformation with the properties of a molten globule. Although apoflavodoxin at pH 2 unfolds cooperatively with urea in a reversible fashion and the fluorescence and far-UV CD unfolding curves coincide, the transition midpoint depends on the concentration of protein, ruling out a simple two-state process at acidic pH. Apoflavodoxin constitutes a promising system for the analysis of the stability and folding of alpha/beta proteins and for the study of the interaction between apoflavoproteins and their corresponding redox cofactors. PMID:8819170

Dissolution behaviour of ferric pyrophosphate and its mixtures with soluble pyrophosphates: Potential strategy for increasing iron bioavailability.

PubMed

Tian, Tian; Blanco, Elena; Smoukov, Stoyan K; Velev, Orlin D; Velikov, Krassimir P

2016-10-01

Ferric pyrophosphate (FePP) is a widely used iron source in food fortification and in nutritional supplements, due to its white colour, that is very uncommon for insoluble Fe salts. Although its dissolution is an important determinant of Fe adsorption in human body, the solubility characteristics of FePP are complex and not well understood. This report is a study on the solubility of FePP as a function of pH and excess of pyrophosphate ions. FePP powder is sparingly soluble in the pH range of 3-6 but slightly soluble at pH<2 and pH>8. In the presence of pyrophosphate ions the solubility of FePP strongly increases at pH 5-8.5 due to formation a soluble complex between Fe(III) and pyrophosphate ions, which leads to an 8-10-fold increase in the total ionic iron concentration. This finding is beneficial for enhancing iron bioavailability, which important for the design of fortified food, beverages, and nutraceutical products. Copyright © 2016 Elsevier Ltd. All rights reserved.

Transformation of CuO Nanoparticles in the Aquatic Environment: Influence of pH, Electrolytes and Natural Organic Matter

PubMed Central

Peng, Cheng; Shen, Chensi; Zheng, Siyuan; Yang, Weiling; Hu, Hang; Liu, Jianshe; Shi, Jiyan

2017-01-01

Many studies have shown the effect of solution chemistry on the environmental behavior of metal-based nanoparticles (NPs), except CuO NPs. Here, we investigated the agglomeration, sedimentation, dissolution, and speciation of CuO NPs by varying pH, ionic strength, ionic valence, and natural organic matter (NOM). The results showed that as the pH moved away from 6, the size of CuO agglomerates decreased, along with the enhanced NP suspension stabilization, due to the increase of electrostatic repulsive force. Increasing ionic strength and valence intensified the agglomeration and sedimentation of CuO NPs because of the compression of electrical double layers. The presence of humic acid and citric acid enhanced the dispersion and stabilization of CuO NP suspension, but l-cysteine showed a different impact. Decreasing pH, increasing ionic strength and all NOM improved the dissolution of CuO NPs, but the divalent electrolyte (CaCl2) inhibited the Cu2+ release from CuO NPs compared to the monovalent electrolyte (NaCl). In addition, X-ray absorption near edge structure (XANES) analysis demonstrated that the presence of l-cysteine transformed more than 30% of CuO NPs to Cu(I)-cysteine by coordinating with thiol group. This study can give us an in-depth understanding on the environmental behavior and fate of CuO NPs in the aquatic environment. PMID:29036921

Interaction of two diclofenac acid salts with copolymers of ammoniomethacrylate: effect of additives and release profiles.

PubMed

Khalil, E; Sallam, A

1999-04-01

The copolymer of ammoniomethacrylate Eudragit RL (ERL) interacted with diclofenac acid salts (sodium and diethylamine salts) in aqueous solutions, forming a complex. Sorption experiments were done in aqueous solutions of either sodium lauryl sulfate (SLS), Tween 20, or Tween 80. The SLS competed strongly with the drug, even at low concentrations, and reduced significantly the amount of drug sorbed by ERL. Tweens at high concentrations exhibited two phase profiles: the sorption phase, which was short and during which drug concentration dropped sharply, and the release phase, during which the drug was released slowly over 24 hr and which was accompanied by dispersion of ERL particles into the colloidal dispersion. The interaction was dependent on temperature, ionic strength, and nature of the additives. The extent of interaction in water and phosphate buffer solutions was in the following order: water > pH 6 > pH 7-8. In-vitro dissolution studies of the dried complex were done over 24 hr. In water, the drug remained bound to the polymer. In aqueous surfactant solutions (SLS, Tween 20, and Tween 80) and phosphate buffer at pH 6.8, a linear relationship between drug concentration and the square root of time was obtained, indicating a matrix diffusion-controlled mechanism. However, 100% release was not reached, and resorption was observed in the phosphate buffer solution.

The Effect of Solution Conditions on the Nucleation Kinetics of Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Judge, Russell A.; Baird, James K.; Pusey, Marc L.

1998-01-01

An understanding of protein crystal nucleation rates and the effect of solution conditions upon them, is fundamental to the preparation of protein crystals of the desired size and shape for X-ray diffraction analysis. The ability to predict the effect of supersaturation, temperature, pH and precipitant concentration on the number and size of crystals formed is of great benefit in the pursuit of protein structure analysis. In this study we experimentally examine the effect of supersaturation, temperature, pH and sodium chloride concentration on the nucleation rate of tetragonal chicken egg white lysozyme crystals. In order to do this batch crystallization plates were prepared at given solution concentrations and incubated at three different temperatures over the period of one week. The number of crystals per well with their size and dimensions were recorded and correlated against solution conditions. Duplicate experiments indicate the reproducibility of the technique. Although it is well known that crystal numbers increase with increasing supersaturation, large changes in crystal number were also correlated against solution conditions of temperature, pH and salt concentration over the same supersaturation ranges. Analysis of these results enhance our understanding of the effect of solution conditions such as the dramatic effect that small changes in charge and ionic strength can have on the number of tetragonal lysozyme crystals that form and grow in solution.

Diffusion of Eu(III) in compacted bentonite-effect of pH, solution concentration and humic acid.

PubMed

Wang, Xiangke; Chen, Yixue; Wu, Yican

2004-06-01

The effect of pH, Eu(III) solution concentration and humic acid on the diffusion of Eu(III) in compacted bentonite (rho(b) = 1000 +/- 30 kg/m(3)) was studied with "in-diffusion" method at an ionic strength of 0.1M NaClO(4). The results (K(d) values from the first slice and theoretical calculation, apparent and effective diffusion coefficients) derived from the new capillary method are in good agreement with the literature data under similar conditions, and fit the Fick's second law very well. The results suggest that the diffusion of Eu(III) is dependent on pH values and independent on solution concentration in our experimental conditions. Humic acid forms precipitation/complexation with Eu(III) at the surface of compacted bentonite and thus deduces the diffusion/transport of Eu(III) in compacted bentonite. The K(d) values in compacted bentonite are in most cases lower than those in powdered bentonite obtained from batch experiments. The difference between the K(d) values from powdered and compacted bentonite is a strong function of the bulk density of the bentonite. The results suggest that the content of interlaminary space plays a very important role to the diffusion, sorption and migration of Eu(III) in compacted bentonite.

Extraction of trace tilmicosin in real water samples using ionic liquid-based aqueous two-phase systems.

PubMed

Pan, Ru; Shao, Dejia; Qi, Xueyong; Wu, Yun; Fu, Wenyan; Ge, Yanru; Fu, Haizhen

2013-01-01

The effective method of ionic liquid-based aqueous two-phase extraction, which involves ionic liquid (IL) (1-butyl-3-methyllimidazolium chloride, [C4mim]Cl) and inorganic salt (K2HPO4) coupled with high-performance liquid chromatography (HPLC), has been used to extract trace tilmicosin in real water samples which were passed through a 0.45 μm filter. The effects of the different types of salts, the concentration of K2HPO4 and of ILs, the pH value and temperature of the systems on the extraction efficiencies have all been investigated. Under the optimum conditions, the average extraction efficiency is up to 95.8%. This method was feasible when applied to the analysis of tilmicosin in real water samples within the range 0.5-40 μg mL(-1). The limit of detection was found to be 0.05 μg mL(-1). The recovery rate of tilmicosin was 92.0-99.0% from the real water samples by the proposed method. This process is suggested to have important applications for the extraction of tilmicosin.

A comparative evaluation of different ionic liquids for arsenic species separation and determination in wine varietals by liquid chromatography - hydride generation atomic fluorescence spectrometry.

PubMed

Castro Grijalba, Alexander; Fiorentini, Emiliano F; Martinez, Luis D; Wuilloud, Rodolfo G

2016-09-02

The application of different ionic liquids (ILs) as modifiers for chromatographic separation and determination of arsenite [As(III)], arsenate [As(V)], dimethylarsonic acid (DMA) and monomethylarsonic acid (MMA) species in wine samples, by reversed-phase high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry detection (RP-HPLC-HG-AFS) was studied in this work. Several factors influencing the chromatographic separation of the As species, such as pH of the mobile phase, buffer solution concentration, buffer type, IL concentration and length of alkyl groups in ILs were evaluated. The complete separation of As species was achieved using a C18 column in isocratic mode with a mobile phase composed of 0.5% (v/v) 1-octyl-3-methylimidazolium chloride ([C8mim]Cl) and 5% (v/v) methanol at pH 8.5. A multivariate methodology was used to optimize the variables involved in AFS detection of As species after they were separated by HPLC. The ILs showed remarkable performance for the separation of As species, which was obtained within 18min with a resolution higher than 0.83. The limits of detection for As(III), As(V), MMA and DMA were 0.81, 0.89, 0.62 and 1.00μg As L(-1). The proposed method was applied for As speciation analysis in white and red wine samples originated from different grape varieties. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of a tannase from Emericella nidulans immobilized on ionic and covalent supports for propyl gallate synthesis.

PubMed

Gonçalves, Heloísa Bressan; Jorge, João Atílio; Pessela, Benevides Costa; Lorente, Glória Fernandez; Guisán, José Manuel; Guimarães, Luis Henrique Souza

2013-04-01

The extracellular tannase from Emericela nidulans was immobilized on different ionic and covalent supports. The derivatives obtained using DEAE-Sepharose and Q-Sepharose were thermally stable from 60 to 75 °C, with a half life (t50) >24 h at 80 °C at pH 5.0. The glyoxyl-agarose and amino-glyoxyl derivatives showed a thermal stability which was lower than that observed for ionic supports. However, when the stability to pH was considered, the derivatives obtained from covalent supports were more stable than those obtained from ionic supports. DEAE-Sepharose and Q-Sepharose derivatives as well as the free enzyme were stable in 30 and 50 % (v/v) 1-propanol. The CNBr-agarose derivative catalyzed complete tannic acid hydrolysis, whereas the Q-Sepharose derivative catalyzed the transesterification reaction to produce propyl gallate (88 % recovery), which is an important antioxidant.

Multilaboratory study of the shifts in the IEP of anatase at high ionic strengths.

PubMed

Kosmulski, Marek; Dukhin, Andrei S; Priester, Torsten; Rosenholm, Jarl B

2003-07-01

The zeta-potentials of anatase at pH 2-11 in 0.1, 0.3, 0.5, and 1 moldm(-3) NaI were studied using the DT 1200 in three laboratories. At [NaI]=1 moldm(-3) the zeta-potentials were positive over the entire pH range. The previously observed tendency of the isoelectric point of anatase to shift to high pH at high ionic strength (M. Kosmulski, J.B. Rosenholm, J. Phys. Chem. 100 (1996) 11681) and the salt specificity of this effect were confirmed. The zeta-potentials obtained in different laboratories using DT 1200 are consistent within 3 mV.

Quantitative and qualitative optimization of allergen extraction from peanut and selected tree nuts. Part 2. Optimization of buffer and ionic strength using a full factorial experimental design.

PubMed

L'Hocine, Lamia; Pitre, Mélanie

2016-03-01

A full factorial design was used to assess the single and interactive effects of three non-denaturing aqueous (phosphate, borate, and carbonate) buffers at various ionic strengths (I) on allergen extractability from and immunoglobulin E (IgE) immunoreactivity of peanut, almond, hazelnut, and pistachio. The results indicated that the type and ionic strength of the buffer had different effects on protein recovery from the nuts under study. Substantial differences in protein profiles, abundance, and IgE-binding intensity with different combinations of pH and ionic strength were found. A significant interaction between pH and ionic strength was observed for pistachio and almond. The optimal buffer system conditions, which maximized the IgE-binding efficiency of allergens and provided satisfactory to superior protein recovery yield and profiles, were carbonate buffer at an ionic strength of I=0.075 for peanut, carbonate buffer at I=0.15 for almond, phosphate buffer at I=0.5 for hazelnut, and borate at I=0.15 for pistachio. The buffer type and its ionic strength could be manipulated to achieve the selective solubility of desired allergens. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Cocrystal solubility product analysis - Dual concentration-pH mass action model not dependent on explicit solubility equations.

PubMed

Avdeef, Alex

2017-12-15

A novel general computational approach is described to address many aspects of cocrystal (CC) solubility product (K sp ) determination of drug substances. The CC analysis program, pDISOL-X, was developed and validated with published model systems of various acid-base combinations of active pharmaceutical ingredients (APIs) and coformers: (i) carbamazepine cocrystal systems with 4-aminobenzoic acid, cinnamic acid, saccharin, and salicylic acid, (ii) for indomethacin with saccharin, (iii) for nevirapine with maleic acid, saccharin, and salicylic acid, and (iv) for gabapentin with 3-hydroxybenzoic acid. In all systems but gabapentin, the coformer is much more soluble than the API. The model systems selected are those with available published dual concentration-pH data, one set for the API and one set for the coformer, generally measured at eutectic points (thermodynamically-stable three phases: solution, cocrystal, and crystalline API or coformer). The carbamazepine-cinnamic acid CC showed a substantial elevation in the API equilibrium concentration above pH5, consistent with the formation of a complex between carbamazepine and cinnamate anion. The analysis of the gabapentin:3-hydroxybenzoic acid 1:1 CC system indicated four zones of solid suspensions: coformer (pH<3.25), coformer and cocrystal eutectic (pH3.25-4.44), cocrystal (pH4.44-5.62), and API (pH>5.62). The general approach allows for testing of many possible equilibrium models, including those comprising drug-coformer complexation. The program calculates the ionic strength at each pH. From this, the equilibrium constants are adjusted for activity effects, based on the Stokes-Robinson hydration theory. The complete speciation analysis of the CC systems may provide useful insights into pH-sensitive dissolution effects that could potentially influence bioavailability. Copyright © 2017 Elsevier B.V. All rights reserved.

Aminopyridine modified Spirulina platensis biomass for chromium(VI) adsorption in aqueous solution.

PubMed

Bayramoglu, Gulay; Akbulut, Aydin; Arica, M Yakup

Chemical modification of Spirulina platensis biomass was realized by sequential treatment of algal surface with epichlorohydrin and aminopyridine. Adsorptive properties of Cr(VI) ions on native and aminopyridine modified algal biomass were investigated by varying pH, contact time, ionic strength, initial Cr(VI) concentration, and temperature. FTIR and analytical analysis indicated that carboxyl and amino groups were the major functional groups for Cr(VI) ions adsorption. The optimum adsorption was observed at pH 3.0 for native and modified algal biomasses. The adsorption capacity was found to be 79.6 and 158.7 mg g(-1), for native and modified algal biomasses, respectively. For continuous system studies, the experiments were conducted to study the effect of important design parameters such as flow rate and initial concentration of metal ions, and the maximum sorption capacity was observed at a flow rate of 50 mL h(-1), and Cr(VI) ions concentration 200 mg L(-1) with modified biomass. Experimental data fitted a pseudo-second-order equation. The regeneration performance was observed to be 89.6% and 94.3% for native and modified algal biomass, respectively.

[Study on the micellar electrokinetic capillary chromatography (MECC) for several water soluble vitamins].

PubMed

Li, X; He, J

1997-03-01

In the paper, the influences of the concentration of sodium dodecyl sulphate (SDS) and borax (Na2B4O7), pH value and applied voltage on the MECC of water soluble vitamins--VB1, VB2, VB6, VB12 and VC in fused silica capillary were studied. In the system of SDS-Na2B4O7, the retention times of the vitamins mentioned above increase with the increase of concentration of SDS and Na2B4O7. But if SDS concentration is too high the separation will become worse, and if Na2B4O7 concentration is too high the peak will be broad because the increase of retention time will lead to the increase of diffusion of molecules. With the pH increasing, the separation efficiency is always increasing. The change of the applied voltage has little effect on the separation efficiency. However, at higher pH and applied voltage, the high ionic strength and large current will produce more Joule heat and cause higher background noise. The optimum run buffer for this separation contains 18mmol/L Na2B4O7 and 25mmol/L SDS, with pH at 8.5 by adjusted with hydrochloric acid. The separation was completed within 4min at an applied voltage of 14.0kV. The separation efficiencies ranged from 1.1 x 10(5) to 2.4 x 10(5) theoretical plates/meter. The application of this method to drug analysis is demonstrated.

Changes in the Molar Ellipticities of HEWL Observed by Circular Dichroism and Quantitated by Time Resolved Fluorescence Anisotropy Under Crystallizing Conditions

NASA Technical Reports Server (NTRS)

Sumida, John

2002-01-01

Fluid models for simple colloids predict that as the protein concentration is increased, crystallization should occur at some sufficiently high concentration regardless of the strength of attraction. However, empirical measurements do not fully support this assertion. Measurements of the second virial coefficient (B22) indicate that protein crystallization occurs only over a discrete range of solution parameters. Furthermore, observations of a strong correlation between protein solubility and B22, has led to an ongoing debate regarding the relationship between the two. Experimental work in our lab, using Hen Egg White Lysozyme (HEWL), previously revealed that the rotational anisotropy of the protein under crystallizing conditions changes systematically with pH, ionic strength and temperature. These observations are now supported by recent work revealing that small changes in the molar ellipticity also occur systematically with changes in ionic strength and temperature. This work demonstrates that under crystallization conditions, the protein native state is characterized by a conformational heterogeneity that may prove fundamental to the relationship between protein crystallization and protein solubility.

Forces of interactions between bare and polymer-coated iron and silica: effect of pH, ionic strength, and humic acids.

PubMed

Pensini, Erica; Sleep, Brent E; Yip, Christopher M; O'Carroll, Denis

2012-12-18

The interactions between a silica substrate and iron particles were investigated using atomic force microscopy-based force spectroscopy (AFM). The micrometer- and nanosized iron particles employed were either bare or coated with carboxymethyl cellulose (CMC), a polymer utilized to stabilize iron particle suspensions. The effect of water chemistry on the forces of interaction was probed by varying ionic strength (with 100 mM NaCl and 100 mM CaCl₂) or pH (4, 5.5, and 8) or by introducing 10 mg/L of humic acids (HA). When particles were uncoated, the forces upon approach between silica and iron were attractive at pH 4 and 5.5 and in 100 mM CaCl₂ at pH 8, but they were negligible in 100 mM NaCl buffered to pH 8 and repulsive in water buffered to pH 8 and in HA solutions. HA produced electrosteric repulsion between iron particles and silica, likely due to its sorption to iron particles. HA sorption to silica was excluded on the basis of experiments conducted with a quartz-crystal microbalance with dissipation monitoring. Repulsion with CMC-coated iron was attributed to electrosteric forces, which were damped at high ionic strength. An extended DLVO model and a modified version of Ohshima's theory were successfully utilized to model AFM data.

The effect of pH, buffer capacity and ionic strength on quetiapine fumarate release from matrix tablets prepared using two different polymeric blends.

PubMed

Hamed, Rania; AlJanabi, Reem; Sunoqrot, Suhair; Abbas, Aiman

2017-08-01

The objective of this study was to investigate the effect of the different physiological parameters of the gastrointestinal (GI) fluid (pH, buffer capacity, and ionic strength) on the in vitro release of the weakly basic BCS class II drug quetiapine fumarate (QF) from two once-a-day matrix tablet formulations (F1 and F2) developed as potential generic equivalents to Seroquel ® XR. F1 tablets were prepared using blends of high and low viscosity grades of hydroxypropyl methylcellulose (HPMC K4M and K100LV, respectively), while F2 tablets were prepared from HPMC K4M and PEGylated glyceryl behenate (Compritol ® HD5 ATO). The two formulations attained release profiles of QF over 24 h similar to that of Seroquel ® XR using the dissolution medium published by the Food and Drug Administration (FDA). A series of solubility and in vitro dissolution studies was then carried out using media that simulate the gastric and intestinal fluids and cover the physiological pH, buffer capacity and ionic strength range of the GIT. Solubility studies revealed that QF exhibits a typical weak base pH-dependent solubility profile and that the solubility of QF increases with increasing the buffer capacity and ionic strength of the media. The release profiles of QF from F1, F2 and Seroquel ® XR tablets were found to be influenced by the pH, buffer capacity and ionic strength of the dissolution media to varying degrees. Results highlight the importance of studying the physiological variables along the GIT in designing controlled release formulations for more predictive in vitro-in vivo correlations.

Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.

1992-01-01

A critical review of thermodynamic data for aqueous and solid V species is presented to evaluate dissolution, transport, and precipitation of V under natural conditions. Emphasis is given to results of experimental studies of V chemistry, especially those for which the experimental conditions are near those found in nature. Where possible, data are obtained for or corrected to the reference conditions of 298.15K, 1 atm (1.01325 bar) and zero ionic strength. Vanadium [IV] (VIV) and vanadium[V] (VV) are the most soluble forms of V in nature, and their complexes with fluoride, sulfate, and oxalate may act to increase V solubility under oxidizing conditions. Because redox behavior is of fundamental importance to understanding natural V chemistry, the kinetics of reduction of VIV to VIII H2S were studied. Although H2S is predicted from thermodynamic data to be capable of reducing VIV to VIII, this reaction has not been demonstrated experimentally. Experiments were carried out under conditions of temperature (45??C), pH (3.6-6.8), ionic strength (0.05-0.1 m), and V concentrations (9.8-240 ??molar) likely to be found in nature. Because the reaction is very slow, H2S concentrations in excess of natural conditions were used (8.1 ?? 10-4 to 0.41 atm). The results show that VIV is reduced to VIII under a variety of conditions. The rate increases with increasing pH, but is not appreciably affected by ionic strength (as represented by the concentration of KCl, which was used as the supporting electrolyte in all cases). Prior to initiation of the reaction, there is an induction period, the length of which increases with increasing KCl concentration or decreasing pH. Attempts to model the reaction mechanism by numerical methods have failed to produce a satisfying fit of the results, indicating partial reaction orders, a complex mechanism, or involvement of a variety of intermediate species. The results of the thermodynamic and kinetic studies were applied to understanding the genesis of V deposits such as those commonly found on the Colorado Plateau. Vanadium in these sandstone-hosted deposits is present mostly in the reduced oxidation state, VIII. Because of the insolubility of VIII oxyhydroxides, it is likely that a more oxidized form of V (either [IV] or [V]) was transported to the site of mineralization, and that the V was reduced in situ and subsequently precipitated. A probable reductant is hydrogen sulfide; the presence of pyrite cogenetic with the V minerals documents the presence of H2S during mineralization. The experiments described here show that H2S could have reduced VIV to V III, and thus led to the formation of these deposits. ?? 1992.

Dolomite surface speciation and reactivity in aquatic systems

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques; Thomas, Fabien

1999-10-01

The surface charge of dolomite (CaMg(CO3)2) was measured as a function of pH (6.5-11.5), pCO2 (10-3.5, 0.01, and 0.96 atm) and ionic strength (0.01, 0.1, and 0.5 M NaCl) using potentiometric titrations in a limited residence time reactor. Dolomite zeta potential (ζ) was determined using streaming potential and electrophoresis techniques at pH 2 to 12 in solutions having ionic strengths from 0.001 to 0.1 M NaCl as a function of aqueous Ca2+, Mg2+, and CO32- concentrations. The point of zero charge (PZC) and isoelectric point (IEP) of dolomite are the same (pH ∼8 at pCO2 ∼10-3.5 atm) and very close to those of calcite and magnesite. On the basis of these results, a surface complexation model (SCM) is proposed that postulates the presence of three distinct primary hydration sites: >CO3H°, >CaOH°, and >MgOH°. The intrinsic stability constants of dolomite surface reactions were determined by fitting the pH dependence of the surface charge and taking into account the isoelectric points and ζ-potential values for a wide range of solution compositions. In most natural aquatic environments, dolomite surface speciation can be modeled using the following species: >CO3-, >CO3Me+, >MeOH2+, >MeHCO3o, and >MeCO3-, where Me = Ca, Mg. The speciation model presented in this study allows description of metal and ligand adsorption onto dolomite surface and provides new insights on the mechanisms that control dolomite dissolution/crystallization in aqueous solutions. In particular, it is shown that dolomite dissolution is controlled by the protonation of >CO3H° surface complexes at pH < 6 and by hydrolysis of >MeOH2+ groups at higher pH.

Characterization of metal binding sites onto biochar using rare earth elements as a fingerprint.

PubMed

Pourret, Olivier; Houben, David

2018-02-01

The ability of biochar to immobilize metals relies on the amount of functional groups at its surface but the contribution of each functional groups (e.g. carboxylic, phenolic) to metal bonding is poorly known. Using a new approach based on previous works on rare earth element (REE) interactions with humic substances, we aim at elucidating the relative contribution of these binding sites to metal sorption under various conditions (i.e. pH and ionic strengths, IS). Using batch experiments, REE sorption onto biochar was analyzed from pH 3 to 9 and IS 10 -1 mol/L to 10 -3 mol/L. Rare earth element patterns show a Middle REE (MREE) downward concavity at acidic pH and low ionic strength. These patterns are in good agreement with existing datasets quantifying REE binding with humic substances. Indeed, the MREE downward concavity displayed by REE-biochar complexation pattern compares well with REE patterns with various organic compounds. This similarity in the REE complexation pattern shapes suggests that carboxylic groups are the main binding sites of REE in biochar. Overall, our results indicate that the strength of the metal bonding with biochar increases when pH and IS increase, suggesting that biochar is more efficient for long-term metal immobilization at near neutral pH and high ionic strength.

Determination of the second virial coefficient of bovine serum albumin under varying pH and ionic strength by composition-gradient multi-angle static light scattering.

PubMed

Ma, Yingfang; Acosta, Diana M; Whitney, Jon R; Podgornik, Rudolf; Steinmetz, Nicole F; French, Roger H; Parsegian, V Adrian

2015-01-01

Composition-gradient multi-angle static light scattering (CG-MALS) is an emerging technique for the determination of intermolecular interactions via the second virial coefficient B22. With CG-MALS, detailed studies of the second virial coefficient can be carried out more accurately and effectively than with traditional methods. In addition, automated mixing, delivery and measurement enable high speed, continuous, fluctuation-free sample delivery and accurate results. Using CG-MALS we measure the second virial coefficient of bovine serum albumin (BSA) in aqueous solutions at various values of pH and ionic strength of a univalent salt (NaCl). The systematic variation of the second virial coefficient as a function of pH and NaCl strength reveals the net charge change and the isoelectric point of BSA under different solution conditions. The magnitude of the second virial coefficient decreases to 1.13 x 10(-5) ml*mol/g(2) near the isoelectric point of pH 4.6 and 25 mM NaCl. These results illuminate the role of fundamental long-range electrostatic and van der Waals forces in protein-protein interactions, specifically their dependence on pH and ionic strength.

Blood acid-base changes during experimental emersion and reimmersion of the intertidal crab Carcinus maenas (L.).

PubMed

Truchot, J P

1975-04-01

The time course of blood acid-base changes was studied in Carcinus maenas during experimental emersion and reimmersion at 15 degrees C by measuring pH and PCO2 and calculating bicarbonate concentration. During the first 4 hr of the emersion period, a marked rise of PCO2 entails a respiratory acidosis which is progressively compensated by a slow increase of the bicarbonate concentration; this compensation is completed after about 100 hr and the steady state mean pH value approximates that found for the immersed controls. Return to aquatic conditions is characterized by a rapid decrease of both PCO2 and blood bicarbonate concentration. During the first 2 hr of the reimmersion period, the decrease of blood bicarbonate concentration is accompanied by excretion of a significant amount of base in water, thus suggesting that readjustments of acid-base balance take place at least in part by ionic exchanges between the blood and the external milieu. Initial status was restored after 9 hr. These finding agree with the general views concerning the blood acid-base changes which must occur at transition from water-to air-breathing.

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

USGS Publications Warehouse

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

1999-01-01

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

Effect of fertilizer application on ammonia emission and concentration levels of ammonium, nitrate, and nitrite ions in a rice field.

PubMed

Das, Piw; Sa, Jae-Hwan; Kim, Ki-Hyun; Jeon, Eui-Chan

2009-07-01

The concentrations of ammonium NH4+, nitrate NO3-, and nitrite NO2- ions were recorded along with ammonia (NH(3)) emission from a fertilized rice field located in the Kwangju province in South Korea over a period of 4 months (June to October 2006). The highest magnitude of NH(3) flux was 20,754 microg m(-2) h(-1), while the average flux value over the entire sampling period was 2,395 microg m(-2) h(-1). The highest ionic concentrations were 1.67, 0.44, and 0.71 ppm for NH4+, NO3-, and NO2- ions, respectively. Possible effects of soil pH on NH(3) fluxes were detected, as they concurrently exhibited a gradual and periodic change during the sampling period. Positive correlations existed between concentrations of NH4+ and NO2- ions and the soil pH. Positive correlations also existed between NH(3) emission flux and ambient (and water) temperatures. Results indicated that fertilizer application to rice can lead to significant emission of NH(3) along with NH4+ and NO3- ions.

Tension in Skinned Frog Muscle Fibers in Solutions of Varying Ionic Strength and Neutral Salt Composition

PubMed Central

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

Influence of daylight on the fate of silver and zinc oxide nanoparticles in natural aquatic environments.

PubMed

Odzak, Niksa; Kistler, David; Sigg, Laura

2017-07-01

Nanoparticles, such as silver (Ag-NP) and zinc oxide (ZnO-NP), are increasingly used in many consumer products. These nanoparticles (NPs) will likely be exposed to the aquatic environment (rain, river, lake water) and to light (visible and UV) in the products where they are applied, or after those products are discharged. Dissolution of Ag-NP and ZnO-NP is an important process because the dissolved Ag + and Zn 2+ are readily available and toxic for aquatic organisms. The objective of this study was to investigate the role of daylight (UV and visible) for the fate of engineered Ag-NP and ZnO-NPs in different types of natural waters. Ag-NP and ZnO-NP were exposed to rainwater, river Rhine, and lake waters (Greifen, Lucerne, Cristallina, Gruère) under different light conditions (no light, UV 300-400 nm and visible light 400-700 nm) for up to 8 days. Stronger agglomeration of Ag-NP was observed in the waters with higher ionic strength in comparison to those with lower ionic strength. Visible light tended to increase the dissolution of Ag-NP under most natural water conditions in comparison to dark conditions, whereas UV-light led to decreased dissolved Ag + after longer exposure time. These effects illustrate the dynamic interactions of Ag-NP with light, which may lead both to increased oxidation and to increased reduction of Ag + by organic compounds under UV-light. In the case of ZnO-NP, agglomeration occurred at higher ionic strength, but the effects of pH were predominant for dissolution, which occurred up to concentrations close to the solubility limit of ZnO(s) at pH around 8.2 and to nearly complete dissolution of ZnO-NP at lower pH (pH 4.8-6.5), with both visible and UV-light facilitating dissolution. This study thus shows that light conditions play an important role in the dissolution processes of nanoparticles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dissolution chemistry and biocompatibility of single-crystalline silicon nanomembranes and associated materials for transient electronics.

PubMed

Hwang, Suk-Won; Park, Gayoung; Edwards, Chris; Corbin, Elise A; Kang, Seung-Kyun; Cheng, Huanyu; Song, Jun-Kyul; Kim, Jae-Hwan; Yu, Sooyoun; Ng, Joanne; Lee, Jung Eun; Kim, Jiyoung; Yee, Cassian; Bhaduri, Basanta; Su, Yewang; Omennetto, Fiorenzo G; Huang, Yonggang; Bashir, Rashid; Goddard, Lynford; Popescu, Gabriel; Lee, Kyung-Mi; Rogers, John A

2014-06-24

Single-crystalline silicon nanomembranes (Si NMs) represent a critically important class of material for high-performance forms of electronics that are capable of complete, controlled dissolution when immersed in water and/or biofluids, sometimes referred to as a type of "transient" electronics. The results reported here include the kinetics of hydrolysis of Si NMs in biofluids and various aqueous solutions through a range of relevant pH values, ionic concentrations and temperatures, and dependence on dopant types and concentrations. In vitro and in vivo investigations of Si NMs and other transient electronic materials demonstrate biocompatibility and bioresorption, thereby suggesting potential for envisioned applications in active, biodegradable electronic implants.

Immobilization of an L-aminoacylase-producing strain of Aspergillus oryzae into gelatin pellets and its application in the resolution of D,L-methionine.

PubMed

Yuan Yj, Ying-jin; Wang Sh, Shu-hao; Song Zx, Zheng-xiao; Gao Rc, Rui-chang

2002-04-01

The conditions for immobilization of an l-aminoacylase-producing strain of Aspergillus oryzae in gelatin and the enzymic characteristics of the immobilized pellets were studied. The optimal concentrations of gelatin, glutaraldehyde and ethyldiamine and time of immobilization were determined. Scanning electron micrographs reveal the cross-linked structure differences between the native and immobilized pellets. Optimum pH and temperature of the native and immobilized pellets were determined. Effects of ionic strength and substrate concentration on relative activity of the native and immobilized pellets were investigated in detail. The immobilized pellets were more stable over broader temperature and pH ranges. In addition, the immobilized pellets showed stable activity under operational and storage conditions. The immobilized pellets lost about 20% of their initial activity after five cycles of reuse. The results reported in this paper show the potential for using the immobilized A. oryzae pellets to resolve d,l-methionine.

Improvement of chemical monitoring of water-chemistry conditions at thermal power stations based on electric conductivity and pH measurements

NASA Astrophysics Data System (ADS)

Larin, A. B.; Larin, B. M.

2016-05-01

The increased requirements to the quality of the water heat conductor for working superhigh (SHP) and supercritical (SCP) pressure power plants and promising units, including combined-cycle gas turbine (CCGT) units and power plants with ultrasupercritical parameters (USCPs), can largely be satisfied through specific electric conductivity and pH measurements for cooled heat conductor samples combined with calculations of ionic equilibria and indirect measurements of several specified and diagnostic parameters. The possibility of calculating the ammonia and chloride concentrations and the total concentration of hardness and sodium cations in the feed water of drum-type boilers and the phosphate and salt contents in boiler water was demonstrated. An equation for evaluating the content of potentially acid substances in the feed water of monotube boilers was suggested. The potential of the developed procedure for evaluating the state of waterchemistry conditions (WCCs) in power plants with CCGT units was shown.

Acid rain monitoring in East-Central Florida from 1977 to present

NASA Technical Reports Server (NTRS)

Madsen, B. C.; Kheoh, T.; Hinkle, C. R.; Dreschel, T. W.

1990-01-01

Rainfall has been collected on the University of Central Florida campus and at the Kennedy Space Center over a 12 year period. The chemical composition has been determined and summarized by monthly, annual periods, and for the entire 12 year period at both locations. The weighted average pH at each site is 4.58; however, annual weighted average pH has been equal to or above the 12 year average during six of the past eight years. Nitrate concentrations have increased slightly during recent years while excess sulfate concentrations have remained below the 12 year weighted average during six of the past seven years. Stepwise regression suggests that sulfate, nitrate, ammonium ion and calcium play major roles in the description of rainwater acidity. Annual acid deposition and annual rainfall have varied from 20 to 50 meg/(m(exp 2) year) and 100 to 180 cm/year, respectively. Sea salt comprises at least 25 percent of the total ionic composition.

Potentiation of TRPM7 Inward Currents by Protons

PubMed Central

Jiang, Jianmin; Li, Mingjiang; Yue, Lixia

2005-01-01

TRPM7 is unique in being both an ion channel and a protein kinase. It conducts a large outward current at +100 mV but a small inward current at voltages ranging from −100 to −40 mV under physiological ionic conditions. Here we show that the small inward current of TRPM7 was dramatically enhanced by a decrease in extracellular pH, with an ∼10-fold increase at pH 4.0 and 1–2-fold increase at pH 6.0. Several lines of evidence suggest that protons enhance TRPM7 inward currents by competing with Ca2+ and Mg2+ for binding sites, thereby releasing blockade of divalent cations on inward monovalent currents. First, extracellular protons significantly increased monovalent cation permeability. Second, higher proton concentrations were required to induce 50% of maximal increase in TRPM7 currents when the external Ca2+ and Mg2+ concentrations were increased. Third, the apparent affinity for Ca2+ and Mg2+ was significantly diminished at elevated external H+ concentrations. Fourth, the anomalous-mole fraction behavior of H+ permeation further suggests that protons compete with divalent cations for binding sites in the TRPM7 pore. Taken together, it appears that at physiological pH (7.4), Ca2+ and Mg2+ bind to TRPM7 and inhibit the monovalent cationic currents; whereas at high H+ concentrations, the affinity of TRPM7 for Ca2+ and Mg2+ is decreased, thereby allowing monovalent cations to pass through TRPM7. Furthermore, we showed that the endogenous TRPM7-like current, which is known as Mg2+-inhibitable cation current (MIC) or Mg nucleotide–regulated metal ion current (MagNuM) in rat basophilic leukemia (RBL) cells was also significantly potentiated by acidic pH, suggesting that MIC/MagNuM is encoded by TRPM7. The pH sensitivity represents a novel feature of TRPM7 and implies that TRPM7 may play a role under acidic pathological conditions. PMID:16009728

Effect of pH on the rheological and structural properties of gels of water-washed chicken-breast muscle at physiological ionic strength.

PubMed

Feng, Y; Hultin, H O

2001-08-01

Adjustment of pH from 6.4 to neutrality improved gelling ability and water-holding capacity of twice water-washed, minced chicken-breast muscle significantly at physiological ionic strength, at which the majority of the myofibrillar proteins, including myosin, are not soluble. A strain value of 2.2 was obtained at neutral pH. Myofibrils were the main components of the gel network at both pH 6.4 and 7.0; however, the myofibrillar distribution varied with the pH value. At pH 6.4, myofibrils formed a network of localized aggregates leaving large voids between, whereas at neutral pH, an evenly distributed network of myofibrils was formed. In addition, at neutral pH, a network of fine strands was found within the network of myofibrils. The network was much less developed at pH 6.4. The thin and thick filaments within each myofibrillar structure were disorganized at both pH values. The intramyofibrillar spaces were larger at neutral pH than at pH 6.4. It was proposed that adjustment of pH to neutrality increased electrostatic repulsion leading to a more even distribution of the myofibrillar proteins, a key factor responsible for the improved gel strength and water-holding capacity.

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

PubMed

Tsonev, Latchezar I; Hirsh, Allen G

2008-07-25

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

Adsorption of nucleotides onto Fe-Mg-Al rich swelling clays

NASA Astrophysics Data System (ADS)

Feuillie, Cécile; Daniel, Isabelle; Michot, Laurent J.; Pedreira-Segade, Ulysse

2013-11-01

Mineral surfaces may have played a role in the origin of the first biopolymers, by concentrating organic monomers from a dilute ocean. Swelling clays provide a high surface area for the concentration of prebiotic monomers, and have therefore been the subject of numerous investigations. In that context, montmorillonite, the most abundant swelling clay in modern environments, has been extensively studied with regard to adsorption and polymerization of nucleic acids. However, montmorillonite was probably rather marginal on the primitive ocean floor compared to iron-magnesium rich phyllosilicates such as nontronite that results from the hydrothermal alteration of a mafic or ultramafic oceanic crust. In the present paper, we study the adsorption of nucleotides on montmorillonite and nontronite, at various pH and ionic strength conditions plausible for Archean sea-water. A thorough characterization of the mineral surfaces shows that nucleotide adsorb mainly on the edge faces of the smectites by ligand exchange between the phosphate groups of the nucleotides and the -OH groups from the edge sites over a wide pH range (4-10). Nontronite is more reactive than montmorillonite. At low pH, additional ion exchange may play a role as the nucleotides become positively charged.

Simultaneous determination of Magnolol and Honokiol by amino acid ionic liquid synchronous fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Liu, Wei; Zhu, Xiashi

2018-05-01

A novel method based on amino acid ionic liquids (AAILs) as an additive synchronous fluorescence spectrometry is proposed for simultaneous determination of magnolol (MN) and honokiol (HN) in traditional Chinese medicine Houpu. The overlapping fluorescence spectrum of MN and HN could be completely separated in the AAILs medium. Experiment parameters (the type and concentration of AAILs, pH values and temperature) were discussed. The detection limits of MN and HN reached 1.46 ng/mL, 0.92 ng/mL and the recovery rates ranged from 98.6%-100.7%, 99.7%-100.6%, respectively. This methods was successfully employed for simultaneously determination of MN and HN in real samples. No significant differences could be found in the results of this method and the pharmacopoeia of People's Republic of China 2015 (Ch.P.2015). The experiment mechanisms were discussed by the Gaussian simulation and fluorescence quantum yield.

Comparison effects and dielectric properties of different dose methylene-blue-doped hydrogels.

PubMed

Yalçın, O; Coşkun, R; Okutan, M; Öztürk, M

2013-08-01

The dielectric properties of methylene blue (MB)-doped hydrogels were investigated by impedance spectroscopy. The real part (ε') and the imaginary part (ε") of the complex dielectric constant and the energy loss tangent/dissipation factor (tan δ) were measured in the frequency range of 10 Hz to 100 MHz at room temperature for pH 5.5 value. Frequency variations of the resistance, the reactance, and the impedance of the samples have also been investigated. The dielectric permittivity of the MB-doped hydrogels is sensitive to ionic conduction and electrode polarization in low frequency. Furthermore, the dielectric behavior in high-frequency parts was attributed to the Brownian motion of the hydrogen bonds. The ionic conduction for MB-doped samples was prevented for Cole-Cole plots, while the Cole-Cole plots for pure sample show equivalent electrical circuit. The alternative current (ac) conductivity increases with the increasing MB concentration and the frequency.

Production of Isolated Giant Unilamellar Vesicles under High Salt Concentrations

PubMed Central

Stein, Hannah; Spindler, Susann; Bonakdar, Navid; Wang, Chun; Sandoghdar, Vahid

2017-01-01

The cell membrane forms a dynamic and complex barrier between the living cell and its environment. However, its in vivo studies are difficult because it consists of a high variety of lipids and proteins and is continuously reorganized by the cell. Therefore, membrane model systems with precisely controlled composition are used to investigate fundamental interactions of membrane components under well-defined conditions. Giant unilamellar vesicles (GUVs) offer a powerful model system for the cell membrane, but many previous studies have been performed in unphysiologically low ionic strength solutions which might lead to altered membrane properties, protein stability and lipid-protein interaction. In the present work, we give an overview of the existing methods for GUV production and present our efforts on forming single, free floating vesicles up to several tens of μm in diameter and at high yield in various buffer solutions with physiological ionic strength and pH. PMID:28243205

Separation of carbohydrates using hydrophilic interaction liquid chromatography.

PubMed

Fu, Qing; Liang, Tu; Li, Zhenyu; Xu, Xiaoyong; Ke, Yanxiong; Jin, Yu; Liang, Xinmiao

2013-09-20

A strategy was developed to rapidly evaluate chromatographic properties of hydrophilic interaction chromatography (HILIC) columns for separating carbohydrates. Seven HILIC columns (Silica, Diol, TSK Amide-80, XAmide, Click Maltose, Click β-CD, and Click TE-Cys columns) were evaluated by using three monosaccharide and seven disaccharides as probes. The influence of column temperature on the peak shape and tautomerization of carbohydrates, as well as column selectivity were investigated. The influence of surface charge property on the retention was also studied by using glucose, glucuronic acid, and glucosamine, which indicated that buffer salt concentration and pH value in mobile phase was necessary to control the ionic interactions between ionic carbohydrates and HILIC columns. According to evaluation results, the XAmide column was selected as an example to establish experimental schemes for separation of complex mixtures of oligosaccharide. Copyright © 2013 Elsevier Ltd. All rights reserved.

Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines

NASA Astrophysics Data System (ADS)

Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee

2017-01-01

The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic brine lakes and acid mine drainage locations that contain precipitated iron oxyhydroxides.

Studies on improvement of pharmaceutical preparations prescribed in hospitals. IV. Dibekacin sulfate viscous solution for treatment of mouth and throat wounds.

PubMed

Namiki, N; Yokoyama, H; Moriya, K; Fukuda, M; Takashima, T; Uchida, Y; Yuasa, H; Kanaya, Y

1986-11-01

For the purpose of preventing suppuration of wounds of the oral cavity and throat, we attempted to develop a viscous solution of dibekacin sulfate (DKB) as a suitable medication. Solutions of different viscosity and antibacterial potency were prepared by mixing DKB, sodium carboxymethyl cellulose (CMC-Na), and water in varying proportions. Studies were then performed to ascertain relationships between the concentration of CMC-Na pH and viscosity, and between the viscosity and diffusion of DKB. The concentration of CMC-Na giving rise to optimal clinical efficacy was determined, and the concentration of DKB necessary for clinical treatment was estimated on the basis of the ionic binding constant between DKB and CMC-Na. As a result, the optimum CMC-Na concentration was found to be 2%, while the optimum DKB concentration was estimated to be 100 micrograms/ml.

The Purification and Concentration of Hog Cholera Virus*

PubMed Central

Cunliffe, H. R.; Rebers, P. A.

1968-01-01

Partial purification of hog cholera virus (HCV) using a simple batch-type chromatographic procedure with magnetic ferric oxide (MFO) is described. Infectious HCV was adsorbed from isotonic solutions to MFO and was eluted under conditions of low ionic strength and high pH. Aqueous solutions of 0.01 M sodium cyanide or 0.0003 M ammonium hydroxide effectively dissociated MFO-HCV complexes. The data indicate that 50 to 100% of the original HCV infectivity was recovered concomitant with a 90 to 95% reduction of extraneous organic nitrogen. MFO-purified HCV was concentrated by density gradient type centrifugations in buffered solutions of cesium chloride and sucrose. Prolonged isodensity centrifugations of concentrated MFO-purified HCV indicated a buoyant density of 1.14 to 1.15 gm/ml for the strain of virus used. PMID:15846899

Influence of ethanol content in the precipitation medium on the composition, structure and reactivity of magnesium-calcium phosphate.

PubMed

Babaie, Elham; Zhou, Huan; Lin, Boren; Bhaduri, Sarit B

2015-08-01

Biocompatible amorphous magnesium calcium phosphate (AMCP) particles were synthesized using ethanol in precipitation medium from moderately supersaturated solution at pH10. Some synthesis parameters such as, (Mg+Ca):P, Mg:Ca ratio and different drying methods on the structure and stability of as-produced powder was studied and characterized using SEM, XRD and cell cytocompatibility. The results showed that depending on the Mg(2+) concentration, nano crystalline Struvite (MgNH4PO4·6H2O) can also be alternatively formed. However, the as-formed AMCP preserved its amorphous structure after 7 days of incubation in SBF for tested phosphate concentration, and equally ionic concentration of magnesium and calcium. Copyright © 2015 Elsevier B.V. All rights reserved.

PROTOPLASMIC POTENTIALS IN HALICYSTIS

PubMed Central

Blinks, L. R.

1933-01-01

The nature and origin of the large "protoplasmic" potential in Halicystis must be studied by altering conditions, not only in external solutions, but in the sap and the protoplasm itself. Such interior alteration caused by the penetration of ammonia is described. Concentrations of NH4Cl in the sea water were varied from 0.00001 M to above 0.01 M. At pH 8.1 there is little effect below 0.0005 M NH4Cl. At about 0.001 M a sudden reversal of the potential difference across the protoplasm occurs, from about 68 mv. outside positive to 30 to 40 mv. outside negative. At this threshold value the time curve is characteristically S-shaped, with a slow beginning, a rapid reversal, and then an irregularly wavering negative value. There are characteristic cusps at the first application of the NH4Cl, also immediately after the reversal. The application of higher NH4Cl concentrations causes a more rapid reversal, and also a somewhat higher negative value. Conversely the reduction of NH4Cl concentrations causes recovery of the normal positive potential, but the threshold for recovery is at a lower concentration than for the original reversal. A temporary overshooting or increase of the positive potential usually occurs on recovery. The reversals may be repeated many times on the same cell without injury. The plot of P.D. against the log of ammonium ion concentration is not the straight line characteristic of ionic concentration effects, but has a break of 100 mv. or more at the threshold value. Further evidence that the potential is not greatly influenced by ammonium ions is obtained by altering the pH of the sea water. At pH 5, no reversal occurs with 0.1 M NH4Cl, while at pH 10.3, the NH4Cl threshold is 0.0001 M or less. This indicates that the reversal is due to undissociated ammonia. The penetration of NH3 into the cells increases both the internal ammonia and the pH. The actual concentration of ammonium salt in the sap is again shown to have little effect on the P.D. The pH is therefore the governing factor. But assuming that NH3 enters the cells until it is in equilibrium between sap and sea water, no sudden break of pH should occur, pH being instead directly proportional to log NH3 for any constant (NH4) concentration. Experimentally, a linear relation is found between the pH of the sap and the log NH3 in sea water. The sudden change of P.D. must therefore be ascribed to some system in the cell upon which the pH change operates. The pH value of the sap at the NH3 threshold is between 6.0 and 6.5 which corresponds well with the pH value found to cause reversal of P.D. by direct perfusion of solutions in the vacuole. PMID:19872757

Interactions between natural organic matter and gold nanoparticles stabilized with different organic capping agents.

PubMed

Stankus, Dylan P; Lohse, Samuel E; Hutchison, James E; Nason, Jeffrey A

2011-04-15

The adsorption of natural organic matter (NOM) to the surfaces of natural colloids and engineered nanoparticles is known to strongly influence, and in some cases control, their surface properties and aggregation behavior. As a result, the understanding of nanoparticle fate, transport, and toxicity in natural systems must include a fundamental framework for predicting such behavior. Using a suite of gold nanoparticles (AuNPs) with different capping agents, the impact of surface functionality, presence of natural organic matter, and aqueous chemical composition (pH, ionic strength, and background electrolytes) on the surface charge and colloidal stability of each AuNP type was investigated. Capping agents used in this study were as follows: anionic (citrate and tannic acid), neutral (2,2,2-[mercaptoethoxy(ethoxy)]ethanol and polyvinylpyrrolidone), and cationic (mercaptopentyl(trimethylammonium)). Each AuNP type appeared to adsorb Suwannee River Humic Acid (SRHA) as evidenced by measurable decreases in zeta potential in the presence of 5 mg C L(-1) SRHA. It was found that 5 mg C L(-1) SRHA provided a stabilizing effect at low ionic strength and in the presence of only monovalent ions while elevated concentrations of divalent cations lead to enhanced aggregation. The colloidal stability of the NPs in the absence of NOM is a function of capping agent, pH, ionic strength, and electrolyte valence. In the presence of NOM at the conditions examined in this study, the capping agent is a less important determinant of stability, and the adsorption of NOM is a controlling factor.

On the acid-base properties of humic acid in soil.

PubMed

Cooke, James D; Hamilton-Taylor, John; Tipping, Edward

2007-01-15

Humic acid was isolated from three contrasting organic-rich soils and acid-base titrations performed over a range of ionic strengths. Results obtained were unlike most humic acid data sets; they showed a greater ionic strength dependency at low pH than at high pH. Forward- and back-titrations with the base and acid revealed hysteresis, particularly at low pH. Previous authors attributed this type of hysteresis to humic acid aggregates-created during the isolation procedure-being redissolved during titration as the pH increased and regarded the results as artificial. However, forward- and back-titrations with organic-rich soils also demonstrated a similar hysteretic behavior. These observations indicate (i) that titrations of humic acid in aggregated form (as opposed to the more usual dissolved form) are more representative of the acid-base properties of humic acid in soil and (ii) that the ionic strength dependency of proton binding in humic acid is related to its degree of aggregation. Thus, the current use of models based on data from dissolved humic substances to predictthe acid-base properties of humic acid in soil under environmental conditions may be flawed and could substantially overestimate their acid buffering capacity.

Stability and activity of lysozyme in stoichiometric and non-stoichiometric protic ionic liquid (PIL)-water systems

NASA Astrophysics Data System (ADS)

Wijaya, Emmy C.; Separovic, Frances; Drummond, Calum J.; Greaves, Tamar L.

2018-05-01

There has been a substantial increase in enzyme applications within the biochemical and pharmaceutical industries, for example, as industrial biocatalysts. However, enzymes have narrow marginal stability which makes them prone to become inactive and/or denature with a slight change in the solvent environment. Typically industrial applications require harsher solvent environments than enzyme native environments, and hence there is a need to understand solvent-protein interactions in order to develop strategies to maintain, or enhance, the enzymatic activity under industrially relevant solvent conditions. Previously we have shown that protic ionic liquids (PILs) with water can have a stabilising effect on lysozyme, with a large variation dependent on which PIL ions are present, and the water concentration [E. C. Wijaya et al., Phys. Chem. Chem. Phys. 18(37), 25926-25936 (2016)]. Here we extend on this work using non-stoichiometric aqueous PIL solvents to investigate, and isolate, the role of pH and ionicity on enzymes. We have used the PILs ethylammonium nitrate (EAN) and ethanolammonium formate (EOAF) since our previous work has identified these as good solvents for lysozyme. Solvent libraries were made from these two PILs with an additional precursor acid or base to modify the acidity/basicity of the neutral stoichiometric PIL, and with water added, to have solutions with 4-17 mol. % of the PIL ions in water. Molar ratios of base:acid were varied between 1:1.05 and 2:1 for EAN and 1:1.25 and 2:1 for EOAF, which enabled from highly basic to highly acidic solutions to be obtained. This was to modify the acidity/basicity of the neutral stoichiometric PILs, without the addition of buffers. The structure and stability of hen egg white lysozyme (HEWL) were explored under these solvent conditions using synchrotron small angle X-ray scattering (SAXS), Fourier transform infrared (FTIR), and activity assays. The radius of gyration and Kratky plots obtained from the SAXS data showed little change with varying ionicity or acid:base ratio. FTIR showed that α-helix was maintained in all, except for the most acidic solvent conditions. The activity data show that HEWL was active between pH 0 and 11 for the EA:N-water system and pH 4.4 and 11 for the EOA:F-water system. This work indicates that ionic liquids have the potential to enable enzymes to maintain activity across a broader range of solvent conditions.

The reaction of selenium (IV) with ascorbic acid: its relevance in aqueous and soil systems.

PubMed

Pettine, Maurizio; Gennari, Francesca; Campanella, Luigi

2013-01-01

Abiotic processes able to reduce oxidized Se species may have a strong influence on the environmental behavior of selenium since Se toxicity, bioavailability and mobility follow the order Se(-II)0.3), while does not affect significantly the reduction of Se(IV) by H(2)A at low ratios (<0.1). Fe(III) also catalyzes the oxidation of H(2)A but in this case the possible diminution of the reduction rates of Se(IV) by H(2)A are masked by additional processes of adsorption on and coprecipitation by ferric oxyhydroxides, which lower the concentrations of Se(IV). Copyright © 2012 Elsevier Ltd. All rights reserved.

Effects of High-pH and High-Ionic-Strength Groundwater on Iodide, Pertechnetate, and Selenate Sorption to Hanford Sediments: Final Report for Subtask 3a

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

DI Kaplan; KE Parker; RD Orr

1998-10-14

As part of the Immobilized Low-Activity Waste-Performance Assessment three experiments were conducted to evaluate the effect of the expected near-field chemistry on the sorption of iodide, selenate, and pertechnetate onto a sediment obtained from the Hanford Site. These experiments were performed in fiscal year 1998 at the Pacific Northwest National Laboratory.' During these experiments, attention was directed at the identification of the chemical mechanisms controlling the sorption processes to provide technical defensibility for the selection of the distribution coefficients (IQ to be used in the remainder of the performance assessment. It was found, during the conduct of the experiments, thatmore » selenium and technetium I&s increased as ionic strength increased. The cause for this is most likely to be that the higher ionic strength caused the double layer around the particles to decrease, thereby permitting greater interaction with the mineral surfaces. Further, the pH level had an effect on the sorption of these anions. These are the first-ever experiments conducted with Hanford Site sediment in which the IQ were measured as a function of ionic strength and pH. Overall, the observed trends were consistent with more generalized geochemical principles. One of the most important contributions of these experiments was that they quantified the & changes induced by variations in ionic strength and pH that are expected to exist in the near field.« less

Affinity of hemoglobin for the cytoplasmic fragment of human erythrocyte membrane band 3. Equilibrium measurements at physiological pH using matrix-bound proteins: the effects of ionic strength, deoxygenation and of 2,3-diphosphoglycerate.

PubMed

Chétrite, G; Cassoly, R

1985-10-05

The cytoplasmic fragment of band 3 protein isolated from the human erythrocyte membrane was linked to a CNBr-activated Sepharose matrix in an attempt to measure, in batch experiments, its equilibrium binding constant with oxy- and deoxyhemoglobin at physiological pH and ionic strength values and in the presence or the absence of 2,3-diphosphoglycerate. All the experiments were done at pH 7.2, and equilibrium constants were computed on the basis of one hemoglobin tetramer bound per monomer of fragment. In 10 mM-phosphate buffer, a dissociation constant KD = 2 X 10(-4)M was measured for oxyhemoglobin and was shown to increase to 8 X 10(-4)M in the presence of 50 mM-NaCl. Association could not be demonstrated at higher salt concentrations. Diphosphoglycerate-stripped deoxyhemoglobin was shown to associate more strongly with the cytoplasmic fragment of band 3. In 10 mM-bis-Tris (pH 7.2) and in the presence of 120 mM-NaCl, a dissociation constant KD = 4 X 10(-4)M was measured. Upon addition of increasing amounts of 2,3-diphosphoglycerate, the complex formed between deoxyhemoglobin and the cytoplasmic fragment of band 3 was dissociated. On the reasonable assumption that the hemoglobin binding site present on band 3 fragment was not modified upon linking the protein to the Sepharose matrix, the results indicated that diphosphoglycerate-stripped deoxyhemoglobin or partially liganded hemoglobin tetramers in the T state could bind band 3 inside the intact human red blood cell.

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

PubMed

Zhou, Marilyn X; Foley, Joe P

2006-03-15

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

Acid-base behavior of the gaspeite (NiCO3(s)) surface in NaCl solutions.

PubMed

Villegas-Jiménez, Adrián; Mucci, Alfonso; Pokrovsky, Oleg S; Schott, Jacques

2010-08-03

Gaspeite is a low reactivity, rhombohedral carbonate mineral and a suitable surrogate to investigate the surface properties of other more ubiquitous carbonate minerals, such as calcite, in aqueous solutions. In this study, the acid-base properties of the gaspeite surface were investigated over a pH range of 5 to 10 in NaCl solutions (0.001, 0.01, and 0.1 M) at near ambient conditions (25 +/- 3 degrees C and 1 atm) by means of conventional acidimetric and alkalimetric titration techniques and microelectrophoresis. Over the entire experimental pH range, surface protonation and electrokinetic mobility are strongly affected by the background electrolyte, leading to a significant decrease of the pH of zero net proton charge (PZNPC) and the pH of isoelectric point (pH(iep)) at increasing NaCl concentrations. This challenges the conventional idea that carbonate mineral surfaces are chemically inert to background electrolyte ions. Multiple sets of surface complexation reactions (i.e., ionization and ion adsorption) were formulated within the framework of three electrostatic models (CCM, BSM, and TLM) and their ability to simulate proton adsorption and electrokinetic data was evaluated. A one-site, 3-pK, constant capacitance surface complexation model (SCM) reproduces the proton adsorption data at all ionic strengths and qualitatively predicts the electrokinetic behavior of gaspeite suspensions. Nevertheless, the strong ionic strength dependence exhibited by the optimized SCM parameters reveals that the influence of the background electrolyte on the surface reactivity of gaspeite is not fully accounted for by conventional electrostatic and surface complexation models and suggests that future refinements to the underlying theories are warranted.

Sorption of Lincomycin by Manure-Derived Biochars from Water

PubMed Central

Liu, Cheng-Hua; Chuang, Ya-Hui; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.; Gonzalez, Javier M.; Johnston, Cliff T.; Lehmann, Johannes; Zhang, Wei

2018-01-01

The presence of antibiotics in agroecosystems raises concerns about the proliferation of antibiotic-resistant bacteria and adverse effects to human health. Soil amendment with biochars pyrolized from manures may be a win-win strategy for novel manure management and antibiotics abatement. In this study, lincomycin sorption by manure-derived biochars was examined using batch sorption experiments. Lincomycin sorption was characterized by two-stage kinetics with fast sorption reaching quasi-equilibrium in the first 2 d, followed by slow sorption over 180 d. The fast sorption was primarily attributed to surface adsorption, whereas the long-term slow sorption was controlled by slow diffusion of lincomycin into biochar pore structures. Two-day sorption experiments were performed to explore effects of biochar particle size, solid/water ratio, solution pH, and ionic strength. Lincomycin sorption to biochars was greater at solution pH 6.0 to 7.5 below the dissociation constant of lincomycin (7.6) than at pH 9.9 to 10.4 above its dissociation constant. The enhanced lincomycin sorption at lower pH likely resulted from electrostatic attraction between the positively charged lincomycin and the negatively charged biochar surfaces. This was corroborated by the observation that lincomycin sorption decreased with increasing ionic strength at lower pH (6.7) but remained constant at higher pH (10). The long-term lincomycin sequestration by biochars was largely due to pore diffusion plausibly independent of solution pH and ionic composition. Therefore, manure-derived biochars had lasting lincomycin sequestration capacity, implying that biochar soil amendment could significantly affect the distribution, transport, and bioavailability of lincomycin in agroecosystems. PMID:27065399

A new approach combining different MRI methods to provide detailed view on swelling dynamics of xanthan tablets influencing drug release at different pH and ionic strength.

PubMed

Mikac, Ursa; Sepe, Ana; Kristl, Julijana; Baumgartner, Sasa

2010-08-03

The key element in drug release from hydrophilic matrix tablets is the gel layer that regulates the penetration of water and controls drug dissolution and diffusion. We have selected magnetic resonance imaging (MRI) as the method of choice for visualizing the dynamic processes occurring during the swelling of xanthan tablets in a variety of media. The aims were (i) to develop a new method using MRI for accurate determination of penetration, swelling and erosion fronts, (ii) to investigate the effects of pH and ionic strength on swelling, and (iii) to study the influence of structural changes in xanthan gel on drug release. Two dimensional (2D) MRI and one dimensional single point imaging (SPI) of swollen xanthan tablets were recorded, together with T(2) mapping. The border between dry and hydrated glassy xanthan-the penetration front-was determined from 1D SPI signal intensity profiles. The erosion front was obtained from signal intensity profiles of 2D MR images. The swelling front, where xanthan is transformed from a glassy to a rubbery state (gel formation), was determined from T(2) profiles. Further, the new combination of MRI methods for swelling front determination enables to explain the appearance of the unusual "bright front" observed on 2D MR images in tablets swollen in HCl pH 1.2 media, which represents the position of swelling front. All six media studied, differing in pH and ionic strength, penetrate through the whole tablet in 4h+/-0.3h, but formation of the gel layer is significantly delayed. Unexpectedly, the position of the swelling front was the same, independently of the different xanthan gel structures formed under different conditions of pH and ionic strength. The position of the erosion front, on the other hand, is strongly dependent on pH and ionic strength, as reflected in different thicknesses of the gel layers. The latter are seen to be the consequence of the different hydrodynamic radii of the xanthan molecules, which affect the drug release kinetics. The slowest release of pentoxifylline was observed in water where the thickest gel was formed, whereas the fastest release was observed in HCl pH 1.2, in which the gel layer was thinnest. Moreover, experiments simulating physiological conditions showed that changes of pH and ionic strength influence the xanthan gel structure relatively quickly, and consequently the drug release kinetics. It is therefore concluded that drug release is greatly influenced by changes in the xanthan molecular conformation, as reflected in changed thickness of the gel layer. A new method utilizing combination of SPI, multi-echo MRI and T(2) mapping eliminates the limitations of standard methods used in previous studies for determining moving fronts and improves current understanding of the dynamic processes involved in polymer swelling. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Adsorption of sulfamethoxazole by magnetic biochar: Effects of pH, ionic strength, natural organic matter and 17α-ethinylestradiol.

PubMed

Reguyal, Febelyn; Sarmah, Ajit K

2018-07-01

Recent studies have shown the widespread occurrence of pharmaceuticals in the aquatic environment leading to increasing global concern on their potential adverse effects in the environment and public health. In this study, we evaluated the use of magnetic biochar derived from pine sawdust, one of New Zealand's major wood wastes, to remove an emerging contaminant, sulfamethoxazole (SMX), at different pH, ionic strength, natural organic matter (NOM) and a competing compound, 17α-ethinylestradiol (EE2). In single-solute system, the sorption of SMX onto magnetic biochar was found to be highly pH-dependent and slightly increased with increase in ionic strength. However, the effects of pH, ionic strength and NOM were relatively insignificant compared to the sorption inhibition caused by EE2 in binary-solute system. Both SMX and EE2 sorption onto the highly carbonised biochar in magnetic biochar were postulated to be due to the π-π electron donor acceptor and hydrophobic interaction. EE2 is more hydrophobic than SMX. Hence, strong competition between these compounds was identified where EE2 markedly inhibited the sorption of SMX onto magnetic biochar in all artificial environmental conditions studied. Copyright © 2018 Elsevier B.V. All rights reserved.

Assessing the influence of media composition and ionic strength on drug release from commercial immediate-release and enteric-coated aspirin tablets.

PubMed

Karkossa, Frank; Klein, Sandra

2017-10-01

The objective of this test series was to elucidate the importance of selecting the right media composition for a biopredictive in-vitro dissolution screening of enteric-coated dosage forms. Drug release from immediate-release (IR) and enteric-coated (EC) aspirin formulations was assessed in phosphate-based and bicarbonate-based media with different pH, electrolyte composition and ionic strength. Drug release from aspirin IR tablets was unaffected by media composition. In contrast, drug release from EC aspirin formulations was affected by buffer species and ionic strength. In all media, drug release increased with increasing ionic strength, but in bicarbonate-based buffers was delayed when compared with that in phosphate-based buffers. Interestingly, the cation species in the dissolution medium had also a clear impact on drug release. Drug release profiles obtained in Blank CarbSIF, a new medium simulating pH and average ionic composition of small intestinal fluid, were different from those obtained in all other buffer compositions studied. Results from this study in which the impact of various media parameters on drug release of EC aspirin formulations was systematically screened clearly show that when developing predictive dissolution tests, it is important to simulate the ionic composition of intraluminal fluids as closely as possible. © 2017 Royal Pharmaceutical Society.

Extraction of ranitidine and nizatidine with using imidazolium ionic liquids prior spectrophotometric and chromatographic detection.

PubMed

Kiszkiel, Ilona; Starczewska, Barbara; Leśniewska, Barbara; Późniak, Patrycja

2015-03-15

A new extraction medium was proposed for liquid-liquid extraction of the histamine H2 receptor antagonists ranitidine (RNT) and nizatidine (NZT). The ionic liquids with low vapor pressure and favorable solvating properties for a range of compounds such as 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4mim][Tf2N] were tested for isolation of analytes. The extraction parameters of RNT and NZT, namely, amount of ionic liquid, pH of sample solution, shaking and centrifugation time were optimized. The isolation processes were performed with 1 mL of the ionic liquids. The extracted samples (pH values near 4) were shaken at 1750 rpm. The influence of interfering substances on the efficiency of extraction process was also studied. Methods for the histamine H2 receptor antagonists (ranitidine and nizatidine) determination after their separation using imidazolium ionic liquids by high performance liquid chromatography (HPLC) combined with UV spectrophotometry were developed. The application of ionic liquids in extraction step allows for selective isolation of analytes from aqueous matrices and their preconcentration. The above methods were applied to the determination of RNT and NZT in environmental samples (river water and wastewater after treatment). Copyright © 2014 Elsevier B.V. All rights reserved.

The novel acidophilic structure of the killer toxin from halotolerant yeast demonstrates remarkable folding similarity with a fungal killer toxin.

PubMed

Kashiwagi, T; Kunishima, N; Suzuki, C; Tsuchiya, F; Nikkuni, S; Arata, Y; Morikawa, K

1997-01-15

Several strains of yeasts and fungi produce proteinous substances, termed killer toxins, which kill sensitive strains. The SMK toxin, secreted by the halotolerant yeast Pichia farinosa KK1 strain, uniquely exhibits its maximum killer activity under conditions of acidic pH and high salt concentration. The toxin is composed of two distinct subunits, alpha and beta, which tightly interact with each other under acidic conditions. However, they are easily dissociated under neutral conditions and lose the killer activity. The three-dimensional structure of the SMK toxin will provide a better understanding of the mechanism of toxicity of this protein and the cause of its unique pH-dependent stability. Two crystal structures of the SMK toxin have been determined at 1.8 A resolution in different ionic strength conditions. The two subunits, alpha and beta, are jointly folded into an ellipsoidal, single domain structure belonging to the alpha/beta-sandwich family. The folding topology of the SMK toxin is essentially the same as that of the fungal killer toxin, KP4. This shared topology contains two left-handed split betaalphabeta motifs, which are rare in the other proteins. Many acidic residues are clustered at the bottom of the SMK toxin molecule. Some of the carboxyl sidechains interact with each other through hydrogen bonds. The ionic strength difference induces no evident structural change of the SMK toxin except that, in the high ionic strength crystal, a number of sulfate ions are electrostatically bound near the basic residues which are also locally distributed at the bottom of the toxin molecule. The two killer toxins, SMK and KP4, share a unique folding topology which contains a rare structural motif. This observation may suggest that these toxins are evolutionally and/or functionally related. The pH-dependent stability of the SMK toxin is a result of the intensive interactions between the carboxyl groups. This finding is important for protein engineering, for instance, towards stabilization of the toxin molecule in a broader pH range. The present crystallographic study revealed that the structure of the SMK toxin itself is hardly affected by the ionic strength, implying that a high salt concentration affects the sensitivity of the cell against the toxin.

SEPARATION OF PLUTONIUM FROM FISSION PRODUCTS BY A COLLOID REMOVAL PROCESS

DOEpatents

Schubert, J.

1960-05-24

A method is given for separating plutonium from uranium fission products. An acidic aqueous solution containing plutonium and uranium fission products is subjected to a process for separating ionic values from colloidal matter suspended therein while the pH of the solution is maintained between 0 and 4. Certain of the fission products, and in particular, zirconium, niobium, lanthanum, and barium are in a colloidal state within this pH range, while plutonium remains in an ionic form, Dialysis, ultracontrifugation, and ultrafiltration are suitable methods of separating plutonium ions from the colloids.

Effects of ionic strength and ion pairing on (plant-wide) modelling of anaerobic digestion.

PubMed

Solon, Kimberly; Flores-Alsina, Xavier; Mbamba, Christian Kazadi; Volcke, Eveline I P; Tait, Stephan; Batstone, Damien; Gernaey, Krist V; Jeppsson, Ulf

2015-03-01

Plant-wide models of wastewater treatment (such as the Benchmark Simulation Model No. 2 or BSM2) are gaining popularity for use in holistic virtual studies of treatment plant control and operations. The objective of this study is to show the influence of ionic strength (as activity corrections) and ion pairing on modelling of anaerobic digestion processes in such plant-wide models of wastewater treatment. Using the BSM2 as a case study with a number of model variants and cationic load scenarios, this paper presents the effects of an improved physico-chemical description on model predictions and overall plant performance indicators, namely effluent quality index (EQI) and operational cost index (OCI). The acid-base equilibria implemented in the Anaerobic Digestion Model No. 1 (ADM1) are modified to account for non-ideal aqueous-phase chemistry. The model corrects for ionic strength via the Davies approach to consider chemical activities instead of molar concentrations. A speciation sub-routine based on a multi-dimensional Newton-Raphson (NR) iteration method is developed to address algebraic interdependencies. The model also includes ion pairs that play an important role in wastewater treatment. The paper describes: 1) how the anaerobic digester performance is affected by physico-chemical corrections; 2) the effect on pH and the anaerobic digestion products (CO2, CH4 and H2); and, 3) how these variations are propagated from the sludge treatment to the water line. Results at high ionic strength demonstrate that corrections to account for non-ideal conditions lead to significant differences in predicted process performance (up to 18% for effluent quality and 7% for operational cost) but that for pH prediction, activity corrections are more important than ion pairing effects. Both are likely to be required when precipitation is to be modelled. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of preparation conditions on properties and permeability of chitosan-sodium hexametaphosphate capsules.

PubMed

Angelova, N; Hunkeler, D

2001-01-01

Capsules were obtained by interpolymer complexation between chitosan (polycation) and sodium hexametaphosphate (SMP, oligoanion). The effect of the preparation conditions on the capsule characteristics was evaluated. Specifically, the influence of variables such as pH, ionic strength, reagent concentration, and additives on the capsule permeability properties was investigated using dextran as a model permeant. The capsule membrane permeability was found to increase by decreasing the chitosan/SMP ratio as well as adding mannitol to the oligoanion recipient bath. Increasing the ionic strength or the pH of the initial chitosan solution was also found to enhance the membrane permeability, moving the membrane exclusion limit to higher values. Generally, the capsules prepared tinder all tested conditions had a relatively low permeability which rarely exceeded a molecular cut-off of 40 kD based on dextran standards. Furthermore, the diffusion rate showed a strong temporal dependence, indicating that the capsules prepared under various conditions exhibit different apparent pore size densities on the surface. The results indicated that, in order to obtain the desired capsule mass-transfer properties, the preparation conditions should be carefully considered and adjusted. Adding a polyol as well as low salt amount (less than 0.15%) is preferable as a means of modulating the diffusion characteristics, without disturbing the capsule mechanical stability.

Adsorption of transgenic insecticidal Cry1Ab protein to SiO2. 2. Patch-controlled electrostatic attraction.

PubMed

Madliger, Michael; Sander, Michael; Schwarzenbach, René P

2010-12-01

Adsorption governs the fate of Cry proteins from genetically modified Bt crops in soils. The effect of ionic strength (I) on the adsorption of Cry1Ab (isoelectric point IEP(Cry1Ab) ≈ 6) to negatively charged quartz (SiO(2)) and positively charged poly-L-lysine (PLL) was investigated at pH 5 to 8, using quartz crystal microbalance with dissipation monitoring and optical waveguide lightmode spectroscopy. Cry1Ab adsorbed via positively and negatively charged surface patches to SiO(2) and PLL, respectively. This patch controlled electrostatic attraction (PCEA) explains the observed increase in Cry1Ab adsorption to sorbents that carried the same net charge as the protein (SiO(2) at pH > IEP(Cry1Ab) and PLL at pH < IEP(Cry1Ab)) with decreasing I. In contrast, the adsorption of two reference proteins, BSA and HEWL, with different adsorption mechanism, were little affected by similar changes of I. Consistent with PCEA, Cry1Ab desorption from SiO(2) at pH > IEP(Cry1Ab) increased with increasing I and pH. Weak Cry1Ab-SiO(2) PCEA above pH 7 resulted in reversible, concentration dependent adsorption. Solution depletion experiments showed that PCEA also governed Cry1Ab adsorption to SiO(2) particles at environmentally relevant concentrations (a few ng mL(-1)). These results imply that models describing Cry1Ab adsorption to charged surfaces in soils need to account for the nonuniform surface charge distribution of the protein.

Chemical composition of rainwater in a tropical urban area of northern India

NASA Astrophysics Data System (ADS)

Jawad Al Obaidy, Abdul Hameed M.; Joshi, Himanshu

Rainwater samples during the monsoon of 2001 and 2002 were collected from Roorkee urban area, a medium sized "town group" situated on the right bank of Solani River, a tributary of the Ganga River, near the Himalayan foothills and analyzed for EC, pH, TSS, TDS and major ions. The median value of pH was 7.05, well above 5.6, which is the reference pH. The ratios of SO 42-+NO 3- and Ca 2++Mg 2+ (TA/TC) have been considered for acidity. In this study, ratio of TA/TC is quite below 1.0, indicating alkaline nature of rainwater. The concentration of ions in rain water have been observed to follow the pattern Ca 2+>HCO 3->Cl ->NO 3->Na +>Mg 2+>SO 42->K +. In order to estimate the marine and non-marine contribution, sea salt fraction has been calculated taking Na + as reference. All ionic ratios have been found to be higher than the recommended sea water ratios in all three types of land use, viz. residential, commercial and industrial, suggesting a significant contribution of non-marine origin for these components. A comparison with the data of the other Indian sites validates the inverse relation of Cl - and Na + with distance from the sea and highlights higher Ca 2+ concentration and lower SO 42- concentration.

Calculating the Ionization Constant of Functional Groups of Carboxyl Ion Exchangers

NASA Astrophysics Data System (ADS)

Meychik, N. R.; Stepanov, S. I.; Nikolaeva, Yu. I.

2018-02-01

The potentiometric titration of a weakly basic carboxyl cation exchanger, obtained via alkaline hydrolysis of an acrylonitrile copolymer with divinyl benzene (degree of crosslinking, 12%) in a wide range of variation in a solution of pH (2-12) and NaCl (concentration 0.01, 0.1, 0.5, 1 M), is considered. The maximum ion-exchange capacity of the ion exchanger for Na+ is determined (10.10 ± 0.088 mmol/g of the dry mass) and found to be independent of the solution's ionic strength. It is established that in the investigated range of NaCl concentrations and pH, the acid-base balance is adequately described by Gregor's equation. The parameters of this equation are calculated as a function of the NaCl concentration: p K a = 8.13 ± 0.04, n = 1.50 ± 0.02 for 0.01 M; p K a = 6.56 ± 0.04, n = 2.60 ± 0.07 for 0.1 M; and p K a = 5.66 ± 0.6, n = 2.62 ± 0.06 for 0.5 and 1 M. It is shown that to describe the acid-base balance correctly within the proposed model we must estimate the adequacy of the experimental and calculated values of the ion exchanger's capacity at each pH value according to the calculated parameters of Gregor's equation.

Reactive transport of metal contaminants in alluvium - Model comparison and column simulation

USGS Publications Warehouse

Brown, J.G.; Bassett, R.L.; Glynn, P.D.

2000-01-01

A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.

An integrated open framework for thermodynamics of reactions that combines accuracy and coverage.

PubMed

Noor, Elad; Bar-Even, Arren; Flamholz, Avi; Lubling, Yaniv; Davidi, Dan; Milo, Ron

2012-08-01

The laws of thermodynamics describe a direct, quantitative relationship between metabolite concentrations and reaction directionality. Despite great efforts, thermodynamic data suffer from limited coverage, scattered accessibility and non-standard annotations. We present a framework for unifying thermodynamic data from multiple sources and demonstrate two new techniques for extrapolating the Gibbs energies of unmeasured reactions and conditions. Both methods account for changes in cellular conditions (pH, ionic strength, etc.) by using linear regression over the ΔG(○) of pseudoisomers and reactions. The Pseudoisomeric Reactant Contribution method systematically infers compound formation energies using measured K' and pK(a) data. The Pseudoisomeric Group Contribution method extends the group contribution method and achieves a high coverage of unmeasured reactions. We define a continuous index that predicts the reversibility of a reaction under a given physiological concentration range. In the characteristic physiological range 3μM-3mM, we find that roughly half of the reactions in Escherichia coli's metabolism are reversible. These new tools can increase the accuracy of thermodynamic-based models, especially in non-standard pH and ionic strengths. The reversibility index can help modelers decide which reactions are reversible in physiological conditions. Freely available on the web at: http://equilibrator.weizmann.ac.il. Website implemented in Python, MySQL, Apache and Django, with all major browsers supported. The framework is open-source (code.google.com/p/milo-lab), implemented in pure Python and tested mainly on Linux. ron.milo@weizmann.ac.il Supplementary data are available at Bioinformatics online.

An integrated open framework for thermodynamics of reactions that combines accuracy and coverage

PubMed Central

Noor, Elad; Bar-Even, Arren; Flamholz, Avi; Lubling, Yaniv; Davidi, Dan; Milo, Ron

2012-01-01

Motivation: The laws of thermodynamics describe a direct, quantitative relationship between metabolite concentrations and reaction directionality. Despite great efforts, thermodynamic data suffer from limited coverage, scattered accessibility and non-standard annotations. We present a framework for unifying thermodynamic data from multiple sources and demonstrate two new techniques for extrapolating the Gibbs energies of unmeasured reactions and conditions. Results: Both methods account for changes in cellular conditions (pH, ionic strength, etc.) by using linear regression over the ΔG○ of pseudoisomers and reactions. The Pseudoisomeric Reactant Contribution method systematically infers compound formation energies using measured K′ and pKa data. The Pseudoisomeric Group Contribution method extends the group contribution method and achieves a high coverage of unmeasured reactions. We define a continuous index that predicts the reversibility of a reaction under a given physiological concentration range. In the characteristic physiological range 3μM–3mM, we find that roughly half of the reactions in Escherichia coli's metabolism are reversible. These new tools can increase the accuracy of thermodynamic-based models, especially in non-standard pH and ionic strengths. The reversibility index can help modelers decide which reactions are reversible in physiological conditions. Availability: Freely available on the web at: http://equilibrator.weizmann.ac.il. Website implemented in Python, MySQL, Apache and Django, with all major browsers supported. The framework is open-source (code.google.com/p/milo-lab), implemented in pure Python and tested mainly on Linux. Contact: ron.milo@weizmann.ac.il Supplementary Information: Supplementary data are available at Bioinformatics online. PMID:22645166

Biosorption of copper ions from dilute aqueous solutions on base treated rubber (Hevea brasiliensis) leaves powder: kinetics, isotherm, and biosorption mechanisms.

PubMed

Wan Ngah, W S; Hanafiah, M A K M

2008-01-01

The efficiency of sodium hydroxide treated rubber (Hevea brasiliensis) leaves powder (NHBL) for removing copper ions from aqueous solutions has been investigated. The effects of physicochemical parameters on biosorption capacities such as stirring speed, pH, biosorbent dose, initial concentrations of copper, and ionic strength were studied. The biosorption capacities of NHBL increased with increase in pH, stirring speed and copper concentration but decreased with increase in biosorbent dose and ionic strength. The isotherm study indicated that NHBL fitted well with Langmuir model compared to Freundlich and Dubinin-Radushkevich models. The maximum biosorption capacity determined from Langmuir isotherm was 14.97 mg/g at 27 degrees C. The kinetic study revealed that pseudosecond order model fitted well the kinetic data, while Boyd kinetic model indicated that film diffusion was the main rate determining step in biosorption process. Based on surface area analysis, NHBL has low surface area and categorized as macroporous. Fourier transform infrared (FT-IR) analyses revealed that hydroxyl, carboxyl, and amino are the main functional groups involved in the binding of copper ions. Complexation was one of the main mechanisms for the removal of copper ions as indicated by FT-IR spectra. Ion exchange was another possible mechanism since the ratio of adsorbed cations (Cu2+ and H+) to the released cations (Na+, Ca2+, and Mg2+) from NHBL was almost unity. Copper ions bound on NHBL were able to be desorbed at > 99% using 0.05 mol/L HCl, 0.01 mol/L HNO3, and 0.01 mol/L EDTA solutions.

Metal Complexation in Xylem Fluid 1

PubMed Central

White, Michael C.; Decker, A. Morris; Chaney, Rufus L.

1981-01-01

Xylem fluid was analyzed for numerous solutes to characterize chemically the sap as a medium for forming and transporting metal complexes. The stem exudate was collected hourly for 8 hours from topped 31-day-old soybean (Glycine max L. Merr.) and 46-day-old tomato (Lycopersicon esculentum Mill.) plants grown in normal (0.5 micromolar) and Za-phytotoxic nutrient solutions. Soybean plants were grown in the normal and high-Zn solutions for 24 days; tomato plants were grown for 32 days. The exudate was analyzed for seven organic acids, 22 amino acids, eight inorganic solutes, apparent ionic strength, and pH. Significant changes in many solutes occurred over the 8-hour sampling period. These fluctuations depended on plant species, individual solute, and Zn treatment, and demonstrated that extrapolation of xylem-fluid analyses to whole-plant xylem sap is valid only for sap samples collected shortly after topping a plant. Exudate pH decreased over the 8-hour period for both species; exudate ionic strength increased for tomato and decreased for soybean. At the normal-Zn treatment (0 to 1 hour), the highest acid micromolar concentrations in soybean exudate were: asparagine, 2,583; citric, 1,706; malic, 890; and malonic, 264. Under the same conditions, the highest acid micromolar concentrations in tomato exudate were: maleic, 1,206; malic, 628; glutamine, 522; citric, 301; and asparagine, 242. Cysteine and methionine were above detection limits only in soybean exudate. Zinc phytotoxicity caused significant changes in many solutes. The analyses reported here provide a comprehensive data base for further studies on metal-complex equilibria in xylem fluid. PMID:16661664

Sodium alginate/graphene oxide hydrogel beads as permeable reactive barrier material for the remediation of ciprofloxacin-contaminated groundwater.

PubMed

Zhao, Pingping; Yu, Fei; Wang, Ruoyu; Ma, Yao; Wu, Yanqing

2018-06-01

The wide occurrence of antibiotics in groundwater has raised serious concerns due to their impacts on humans and the ecosystem. Most of the research in groundwater remediation focuses on the exploitation of nano-materials. However, nano-materials have several disadvantages such as high production cost, rapid reduction in permeability, disposal problems, and high sensitivity to environmental conditions. To solve these issues, novel sodium alginate/graphene oxide hydrogel beads (GSA) were synthesised and their effectiveness as permeable reactive barrier (PRB) backfill material in the remediation of ciprofloxacin (CPX)-contaminated groundwater was tested. The adsorption of CPX onto GSA followed the pseudo-second-order kinetic model. The isotherm data followed the Freundlich model. The maximum adsorption capacity was 100 mg g -1 at pH 7.0. The adsorption process was sensitive to contact time, initial CPX concentration and ionic strength. However, it was not pH sensitive. Hydrophobic interaction, electrostatic interaction, ion exchange, H-bonding, and pore filling were proposed to be the main adsorption mechanisms. The effects of flow rate, influent CPX concentration, and ionic strength on the performance of PRB were confirmed through flow-through column experiments and by using a chemical non-equilibrium two-site model. Accordingly, a proper PRB was designed based on hydrogeological conditions. Finally, the lifetime and cost of the PRBs were calculated. The results obtained provided concrete evidence that GSA is a promising adsorbent material for PRBs applications in the remediation of CPX-contaminated groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Marcellos da Rosa, M.; Zetzsch, C.

2003-04-01

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

Direct Measurement of pH in Individual Particles via Raman Microspectroscopy and Variation in Acidity with Relative Humidity.

PubMed

Rindelaub, Joel D; Craig, Rebecca L; Nandy, Lucy; Bondy, Amy L; Dutcher, Cari S; Shepson, Paul B; Ault, Andrew P

2016-02-18

Atmospheric aerosol acidity is an important characteristic of aqueous particles, which has been linked to the formation of secondary organic aerosol by catalyzing reactions of oxidized organic compounds that have partitioned to the particle phase. However, aerosol acidity is difficult to measure and traditionally estimated using indirect methods or assumptions based on composition. Ongoing disagreements between experiments and thermodynamic models of particle acidity necessitate improved fundamental understanding of pH and ion behavior in high ionic strength atmospheric particles. Herein, Raman microspectroscopy was used to determine the pH of individual particles (H2SO4+MgSO4) based on sulfate and bisulfate concentrations determined from νs(SO4(2-)) and νs(HSO4(-)), the acid dissociation constant, and activity coefficients from extended Debye-Hückel calculations. Shifts in pH and peak positions of νs(SO4(2-)) and νs(HSO4(-)) were observed as a function of relative humidity. These results indicate the potential for direct spectroscopic determination of pH in individual particles and the need to improve fundamental understanding of ion behavior in atmospheric particles.

Influence Of Zwitterions on Properties and Morphology of Ionomers: Implications for Electro-Active Applications

DTIC Science & Technology

2010-08-01

membranes in EMIm ES ionic liquid at 10 wt% IL concentration resulted in composites with similar mechanical performance, but 1. REPORT DATE (DD-MM...TERMS zwitterionomer, thermal mechanical property, morphology, ionic liquid , ionic conductivity, transducer Tianyu Wu, Rebecca H. Brown, Andrew J. Duncan...expected entanglement concentration. Swelling of the zwitterionomer membranes in EMIm ES ionic liquid at 10 wt% IL concentration resulted in

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength.

PubMed

Flury, Markus; Czigány, Szabolcs; Chen, Gang; Harsh, James B

2004-07-01

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments. Copyright 2003 Elsevier B.V.

Silver Dissolution and Release from Ceramic Water Filters.

PubMed

Mittelman, Anjuliee M; Lantagne, Daniele S; Rayner, Justine; Pennell, Kurt D

2015-07-21

Application of silver nanoparticles (nAg) or silver nitrate (AgNO3) has been shown to improve the microbiological efficacy of ceramic water filters used for household water treatment. Silver release, however, can lead to undesirable health effects and reduced filter effectiveness over time. The objectives of this study were to evaluate the contribution of nanoparticle detachment, dissolution, and cation exchange to silver elution, and to estimate silver retention under different influent water chemistries. Dissolved silver (Ag(+)) and nAg release from filter disks painted with 0.03 mg/g casein-coated nAg or AgNO3 were measured as a function of pH (5-9), ionic strength (1-50 mM), and cation species (Na(+), Ca(2+), Mg(2+)). Silver elution was controlled by dissolution as Ag(+) and subsequent cation exchange reactions regardless of the applied silver form. Effluent silver levels fell below the drinking water standard (0.1 mg/L) after flushing with 30-42 pore volumes of pH 7, 10 mM NaNO3 at pH 7. When the influent water was at pH 5, contained divalent cations or 50 mM NaNO3, silver concentrations were 5-10 times above the standard. Our findings support regular filter replacement and indicate that saline, hard, or acidic waters should be avoided to minimize effluent silver concentrations and preserve silver treatment integrity.

Measuring the isoelectric point of the edges of clay mineral particles: the case of montmorillonite.

PubMed

Pecini, Eliana M; Avena, Marcelo J

2013-12-03

The isoelectric point (IEP) of the edge surface of a montmorillonite sample was determined by using electrophoretic mobility measurements. This parameter, which is fundamental for the understanding of the charging behavior of clay mineral surfaces, was never measured so far because of the presence of permanent negative charges within the montmorillonite structure, charges that mask the electrokinetic behavior of the edges. The strategy was to block or neutralize the structural charges with two different cations, methylene blue (MB(+)) and tetraethylenepentaminecopper(II) ([Cu(tetren)](2+)), so that the charging behavior of the particles becomes that of the edge surfaces. Adsorption isotherms of MB(+) and [Cu(tetren)](2+) at different ionic strengths (NaCl) were performed to establish the uptakes that neutralize the cation exchange capacity (CEC, 0.96 meq g(-1)) of the sample. At high adsorptive concentrations, there was a superequivalent adsorption of MB(+) (adsorption exceeding the CEC) and an equivalent adsorption of [Cu(tetren)](2+) (adsorption reaching the CEC). In both cases, structural charges were neutralized at uptakes very close to the CEC. Zeta potential (ζ) vs pH data at different ionic strengths of montmorillonite with adsorbed MB(+) allowed to estimate an upper limit of the edge's IEP, 5.3 ± 0.2. The same kind of data obtained with adsorbed [Cu(tetren)](2+) provided a lower limit of the IEP, 4.0 ± 0.2. These values are in agreement with previously informed IEP and point of zero charge of pyrophyllite, which is structurally analogous to montmorillonite but carries no permanent charges. The importance of knowing the IEP of the edge surface of clay minerals is discussed. This value characterizes the intrinsic reactivity of edges, that is, the protonating capacity of edge groups in absence of any electric field generated by structural charges. It also allows us to correct relative edge charge vs pH curves obtained by potentiometric titrations and to obtain the true edge charge vs pH curves at different electrolyte concentrations.

Development of device producing electrolyzed water for home care

NASA Astrophysics Data System (ADS)

Umimoto, K.; Nagata, S.; Yanagida, J.

2013-06-01

When water containing ionic substances is electrolyzed, electrolyzed water with strong bactericidal ability due to the available chlorine(AC) is generated on the anode side. Slightly acidic to neutral electrolyzed water (pH 6.5 to 7.5) is physiological pH and is suitable for biological applications. For producing slightly acidic to neutral electrolyzed water simply, a vertical-type electrolytic tank with an asymmetric structure was made. As a result, a small amount of strongly alkaline water was generated in the upper cathodic small chamber, and a large amount of weakly acidic water generated in the lower anodic large chamber. The pH and AC concentration in solutin mixed with both electrolyzed water were 6.3 and 39.5 ppm, respectively, This solution was slightly acidic to neutral electrolyzed water and had strong bactericidal activity. This device is useful for producing slightly acidic to neutral electrolyzed water as a disinfectant to employ at home care, when considering economic and environmental factors, since it returns to ordinary water after use.

The suitability of monopolar and bipolar ion exchange membranes as separators for biological fuel cells.

PubMed

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.

Metal-ion retention properties of water-soluble amphiphilic block copolymer in double emulsion systems (w/o/w) stabilized by non-ionic surfactants.

PubMed

Palencia, Manuel; Rivas, Bernabé L

2011-11-15

Metal-ion retention properties of water-soluble amphiphilic polymers in presence of double emulsion were studied by diafiltration. Double emulsion systems, water-in-oil-in-water, with a pH gradient between external and internal aqueous phases were prepared. A poly(styrene-co-maleic anhydride) (PSAM) solution at pH 6.0 was added to the external aqueous phase of double emulsion and by application of pressure a divalent metal-ion stream was continuously added. Metal-ions used were Cu(2+) and Cd(2+) at the same pH of polymer solution. According to our results, metal-ion retention is mainly the result of polymer-metal interaction. Interaction between PSMA and reverse emulsion globules is strongly controlled by amount of metal-ions added in the external aqueous phase. In addition, as metal-ion concentration was increased, a negative effect on polymer retention capacity and promotion of flocculation phenomena were produced. Copyright © 2011 Elsevier Inc. All rights reserved.

Reformation of casein particles from alkaline-disrupted casein micelles.

PubMed

Huppertz, Thom; Vaia, Betsy; Smiddy, Mary A

2008-02-01

In this study, the properties of casein particles reformed from alkaline disrupted casein micelles were studied. For this purpose, micelles were disrupted completely by increasing milk pH to 10.0, and subsequently reformed by decreasing milk pH to 6.6. Reformed casein particles were smaller than native micelles and had a slightly lower zeta-potential. Levels of ionic and serum calcium, as well as rennet coagulation time did not differ between milk containing native micelles or reformed casein particles. Ethanol stability and heat stability, >pH 7.0, were lower for reformed casein particles than native micelles. Differences in heat stability, ethanol stability and zeta-potential can be explained in terms of the influence of increased concentrations of sodium and chloride ions in milk containing reformed casein particles. Hence, these results indicate that, if performed in a controlled manner, casein particles with properties closely similar to those of native micelles can be reformed from alkaline disrupted casein micelles.

A mathematical model of the influence of salivary urea on the pH of fasted dental plaque and on the changes occurring during a cariogenic challenge.

PubMed

Dibdin, G H; Dawes, C

1998-01-01

Urea diffusing from saliva into dental plaque is converted to ammonia and carbon dioxide by bacterial ureases. The influence of normal salivary urea levels on the pH of fasted plaque and on the depth and duration of a Stephan curve is uncertain. A numerical model which simulates a cariogenic challenge (a 10% sucrose rinse alone or one followed by use of chewing-gum with or without sugar) was modified to include salivary urea levels from 0 to 30 mmol/l. It incorporated: site-dependent exchange between bulk saliva and plaque surfaces via a salivary film; sugar and urea diffusion into plaque; pH-dependent rates of acid formation and urea breakdown; diffusion and dissociation of end-products and other buffers (acetate, lactate, phosphate, ammonia and carbonate); diffusion of protons and other ions; equilibration with fixed and mobile buffers; and charge-coupling between ionic flows. The Km (2.12 mmol/l) and Vmax (0.11 micromol urea/min/mg dry weight) values for urease activity and the pH dependence of Vmax were taken from the literature. From the results, it is predicted that urea concentrations normally present in saliva (3-5 mmol/l) will increase the pH at the base of a 0.5-mm-thick fasted plaque by up to 1 pH unit, and raise the pH minimum after a sucrose rinse or sugar-containing chewing-gum by at least half a pH unit. The results suggest that plaque cariogenicity may be inversely related to salivary urea concentrations, not only when the latter are elevated because of disease, but even when they are in the normal range.

Analysis of the statistical thermodynamic model for nonlinear binary protein adsorption equilibria.

PubMed

Zhou, Xiao-Peng; Su, Xue-Li; Sun, Yan

2007-01-01

The statistical thermodynamic (ST) model was used to study nonlinear binary protein adsorption equilibria on an anion exchanger. Single-component and binary protein adsorption isotherms of bovine hemoglobin (Hb) and bovine serum albumin (BSA) on DEAE Spherodex M were determined by batch adsorption experiments in 10 mM Tris-HCl buffer containing a specific NaCl concentration (0.05, 0.10, and 0.15 M) at pH 7.40. The ST model was found to depict the effect of ionic strength on the single-component equilibria well, with model parameters depending on ionic strength. Moreover, the ST model gave acceptable fitting to the binary adsorption data with the fitted single-component model parameters, leading to the estimation of the binary ST model parameter. The effects of ionic strength on the model parameters are reasonably interpreted by the electrostatic and thermodynamic theories. The effective charge of protein in adsorption phase can be separately calculated from the two categories of the model parameters, and the values obtained from the two methods are consistent. The results demonstrate the utility of the ST model for describing nonlinear binary protein adsorption equilibria.

Ionic Liquid Dispersive Liquid-Liquid Microextraction Method for the Determination of Irinotecan, an Anticancer Drug, in Water and Urine Samples Using UV-Vis Spectrophotometry.

PubMed

Uysal, Deniz; Karadaş, Cennet; Kara, Derya

2017-05-01

A new, simple, efficient, and environmentally friendly ionic liquid dispersive liquid-liquid microextraction method was developed for the determination of irinotecan, an anticancer drug, in water and urine samples using UV-Vis spectrophotometry. The ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate was used as the extraction solvent, and ethanol was used as the disperser solvent. The main parameters affecting the extraction efficiency, including sample pH, volume of the ionic liquid, choice of the dispersive solvent and its volume, concentration of NaCl, and extraction and centrifugation times, were investigated and optimized. The effect of interfering species on the recovery of irinotecan was also examined. Under optimal conditions, the LOD (3σ) was 48.7 μg/L without any preconcentration. Because the urine sample was diluted 10-fold, the LOD for urine would be 487 μg/L. However, this could be improved 16-fold if preconcentration using a 40 mL aliquot of the sample is used. The proposed method was successfully applied to the determination of irinotecan in tap water, river water, and urine samples spiked with 10.20 mg/L for the water samples and 8.32 mg/L for the urine sample. The average recovery values of irinotecan determined were 99.1% for tap water, 109.4% for river water, and 96.1% for urine.

Optimization of oligomeric enzyme activity in ionic liquids using Rhodotorula glutinis yeast phenylalanine ammonia lyase.

PubMed

Barron, Christiaan C; Sponagle, Brandon J D; Arivalagan, Pugazhendhi; D'Cunha, Godwin B

2017-01-01

Phenylalanine ammonia lyase (E.C.4.3.1.24, PAL) activity of Rhodotorula glutinis yeast has been demonstrated in four commonly used ionic liquids. PAL forward reaction was carried out in 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO 4 ]), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF 6 ]) and 1-butyl-3-methylimidazolium lactate ([BMIM][lactate]). Our experiments have revealed that PAL is catalytically active in ionic liquids and the enzyme activity in ([BMIM][PF 6 ]) is comparable to that obtained in aqueous buffer medium. Different conditions were optimized for maximal PAL forward activity including time of incubation (30.0min) L -phenylalanine substrate concentration (30.0mM), nature of buffer (50.0mM Tris-HCl), pH (9.0), temperature (37°C), and speed of agitation (100 rev min -1 ). Under these optimized conditions, about 83% conversion of substrate to product was obtained for the PAL forward reaction that was determined using UV spectroscopy at 290nm. PAL reverse reaction in ([BMIM][PF 6 ]) was determined spectrophotometrically at 520nm; and about 59% substrate conversion was obtained. This data provides further knowledge in enzyme biocatalysis in non-aqueous media, and may be of importance when studying the function of other oligomeric/multimeric proteins and enzymes in ionic liquids. Copyright © 2016 Elsevier Inc. All rights reserved.

pH-Driven Ordering Transitions in Liquid Crystal Induced by Conformational Changes of Cardiolipin.

PubMed

Sidiq, Sumyra; Verma, Indu; Pal, Santanu Kumar

2015-04-28

We report an investigation of interfacial phenomena occurring at aqueous-liquid crystal (LC) interfaces that triggers an orientational ordering transition of the LC in the presence of cardiolipin (CL) by varying pH, salt concentration and valence. In particular, the effects of three different conformational isomeric forms of the CL are observed to cause the response of the LC ordering to vary significantly from one to another at those interfaces. An ordering transition of the LC was observed when the CL is mostly in undissociated (at pH 2) and/or in bicyclic (at pH 4) conformation in which LC shows changes in the optical appearance from bright to dark. By contrast, no change in the optical appearance of the LC was observed when the pH of the system increases to 8 or higher in which the CL mostly exists in the open conformation. Fluorescence microscopy measurements further suggest that pH-dependent conformational forms of the CL have different ability to self-assemble (thus different packing efficiency) at aqueous-LC interfaces leading to dissimilar orientational behavior of the LC. Specifically, we found that change in headgroup-headgroup repulsion of the central phosphatidyl groups of the CL plays a key role in tuning the lipid packing efficiency and thus responses to interfacial phenomena. Orientational ordering transition of the LC was also observed as a function of increasing the ionic strength (buffer capacity) and strongly influenced in the presence of mono and divalent cations. Langmuir-Blodgett (LB) and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) measurements provide further insight in modulation of the lipid packing efficiency and alkyl chain conformation of the CL at different pH and ionic conditions. Overall, the results presented in this paper establish that LCs offer a promising approach to differentiate different conformations (label free detection) of the CL through ordering transition of the LC at aqueous-LC interfaces.

Supramolecular Assembly of a Biomineralizing Antimicrobial Peptide in Coarse-Grained Monte Carlo Simulations (Postprint)

DTIC Science & Technology

2010-07-05

aqueous solutions at a wide pH range.7 Silica forms rapidly at room temperature in the absence of other ionic catalysts or cofactors (buffers, salts...and other ionic species) that are normally required with in vitro biosilica synthesis. The silaffins are uniquely functionalized; serine residues are...alkaline conditions mimic the properties of the poly- ionic modifications on native silaffins.13,14 The zwitterionic properties facilitate intermolecular

Iron species determination by task-specific ionic liquid-based in situ solvent formation dispersive liquid-liquid microextraction combined with flame atomic absorption spectrometry.

PubMed

Sadeghi, Susan; Ashoori, Vahid

2017-10-01

The task-specific ionic liquid (TSIL) of 1-ethyl-3-methylimidazolium bromide functionalized with 8-hydroxyquinoline was used as a chelating agent and extracting solvent for dispersive liquid-liquid microextraction and subsequent determination of Fe(III) by flame atomic absorption spectrometry. The in situ solvent formation of TSIL using KPF 6 provided the desired water-immiscible ionic liquid. The total Fe concentration could be determined after pre-oxidation of Fe(II) to Fe(III). Various factors affecting the proposed extraction procedure were optimized. The proposed analytical conditions were: sample pH 5, TSIL amount 0.3% (w/v), KPF 6 amount 0.15% (w/v), anti-sticking 0.1% (w/v) and salt concentration 5% (w/v). Under optimal conditions, the linear dynamic ranges for Fe(III) and total Fe were 20-80 and 20-110 ng mL -1 , respectively, with a detection limit of 6.9 ng mL -1 for Fe(III) and relative standard deviation of 2.2%. The proposed method was successfully applied to the determination of trace Fe(III) in water (underground, tap, refined water and artificial sea water) and beverage (apple, tomato, and tea) samples. The developed method offers advantages such as simplicity, ease of operation, and extraction of Fe(III) from aqueous solutions without the use of organic solvent. It was successfully applied for iron speciation in different real samples. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

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

PubMed

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

2006-10-01

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

Single-molecule spectroscopy of the unexpected collapse of an unfolded protein at low pH

NASA Astrophysics Data System (ADS)

Hofmann, Hagen; Nettels, Daniel; Schuler, Benjamin

2013-09-01

The dimensions of intrinsically disordered and unfolded proteins critically depend on the solution conditions, such as temperature, pH, ionic strength, and osmolyte or denarurant concentration. However, a quantitative understanding of how the complex combination of chain-chain and chain-solvent interactions is affected by the solvent is still missing. Here, we take a step towards this goal by investigating the combined effect of pH and denaturants on the dimensions of an unfolded protein. We use single-molecule fluorescence spectroscopy to extract the dimensions of unfolded cold shock protein (CspTm) in mixtures of the denaturants urea and guanidinium chloride (GdmCl) at neutral and acidic pH. Surprisingly, even though a change in pH from 7 to 2.9 increases the net charge of CspTm from -3.8 to +10.2, the radius of gyration of the chain is very similar under both conditions, indicating that protonation of acidic side chains at low pH results in additional hydrophobic interactions. We use a simple shared binding site model that describes the joint effect of urea and GdmCl, together with polyampholyte theory and an ion cloud model that includes the chemical free energy of counterion interactions and side chain protonation, to quantify this effect.

Peroxidase-mediated polymerization of 1-naphthol: impact of solution pH and ionic strength.

PubMed

Bhandari, Alok; Xu, Fangxiang; Koch, David E; Hunter, Robert P

2009-01-01

Peroxidase-mediated oxidation has been proposed as a treatment method for naphthol-contaminated water. However, the impact of solution chemistry on naphthol polymerization and removal has not been documented. This research investigated the impact of pH and ionic strength on peroxidase-mediated removal of 1-naphthol in completely mixed batch reactors. The impact of hydrogen peroxide to 1-naphthol ratio and activity of horseradish peroxidase was also studied. Size exclusion chromatography was used to estimate the molecular weight distribution of oligomeric products, and liquid chromatography/mass spectrometry was used to estimate product structure. Naphthol transformation decreased with ionic strength, and substrate removal was lowest at neutral pHs. Solution pH influenced the size and the composition of the oligomeric products. An equimolar ratio of H(2)O(2):naphthol was sufficient for optimal naphthol removal. Polymerization products included naphthoquinones and oligomers derived from two, three, and four naphthol molecules. Our results illustrate the importance of water chemistry when considering a peroxidase-based approach for treatment of naphthol-contaminated waters.

Biocompatible Stimuli-Responsive W/O/W Multiple Emulsions Prepared by One-Step Mixing with a Single Diblock Copolymer Emulsifier.

PubMed

Protat, Marine; Bodin, Noémie; Gobeaux, Frédéric; Malloggi, Florent; Daillant, Jean; Pantoustier, Nadège; Guenoun, Patrick; Perrin, Patrick

2016-09-22

Multiple water-in-oil-in-water (W/O/W) emulsions are promising materials in designing carriers of hydrophilic molecules or drug delivery systems, provided stability issues are solved and biocompatible chemicals can be used. In this work, we designed a biocompatible amphiphilic copolymer, poly(dimethylsiloxane)-b-poly(2-(dimethylamino)ethyl methacrylate) (PDMS-b-PDMAEMA), that can stabilize emulsions made with various biocompatible oils. The hydrophilic/hydrophobic properties of the copolymer can be adjusted using both pH and ionic strength stimuli. Consequently, the making of O/W (oil in water), W/O (water in oil), and W/O/W emulsions can be achieved by sweeping the pH and ionic strength. Of importance, W/O/W emulsions are formulated over a large pH and ionic strength domain in a one-step emulsification process via transitional phase inversion and are stable for several months. Cryo-TEM and interfacial tension studies show that the formation of these W/O/W emulsions is likely to be correlated to the interfacial film curvature and microemulsion morphology.

Study on the inclusion behavior of p-sulfonatocalix[6]arene with propranolol by spectrofluorometry

NASA Astrophysics Data System (ADS)

Li, Hui; Song, Jin-Ping; Chao, Jian-Bin; Shuang, Shao-Min; Dong, Chuan

2012-11-01

The inclusion interaction between propranolol (PPL) and p-sulfonatocalix[6]arene (SCX6) was investigated by fluorescence and 1H NMR spectroscopy. Influences of pH, temperature, ionic strength and the concentration of SCX6 were examined in detail. In phosphate buffer solution with pH 7.5, the fluorescence of PPL dramatically quenched upon addition of SCX6 revealing the formation of inclusion complexes between PPL and SCX6. The stoichiometric ratio was verified to be 1:1 by the continuous variation method. The inclusion constant of PPL-SCX6 complexes was calculated as 2.2 × 104 L/mol by the nonlinear curve fitting method. 1H NMR titration spectra testified that the aliphatic chain of PPL may be partially penetrated into the hydrophobic cavity of SCX6. This was confirmed by molecular dynamics calculations.

Extraction, isolation and characterisation of oil bodies from pumpkin seeds for therapeutic use.

PubMed

Adams, Gary G; Imran, Shahwar; Wang, Sheng; Mohammad, Abubaker; Kok, M Samil; Gray, David A; Channell, Guy A; Harding, Stephen E

2012-10-15

Pumpkin, a member of the Cucurbitaceae family has been used frequently as functional medicines for therapeutic use. Several phytochemicals such as polysaccharides, phenolic glycosides, 13-hydroxy-9Z, 11E-octadecatrienoic acid from the leaves of pumpkin, proteins from germinated seeds, have been isolated. Here the influence of pH, ionic strength, and temperature on the properties and stability of oil bodies from pumpkin (Cucurbita) were determined with a view to patterning oil body size and structure for future therapeutic intervention. Oil bodies from pumpkin seeds were extracted, isolated, characterised using optical microscopy, zeta potential and particle size distribution obtained. During microscopic analysis, the oil bodies were more intact and in an integrated form at the time of extraction but were ruptured with time. Water extracted oil bodies were spherical for all four layers where cream had larger oil bodies then upper curd. Lower curd and supernatant had considerably smaller size with lower curd densely packed and seemed to be rich in oil bodies than any of the four layers. At pH 3, in the absence of salt, the zeta potential is approximately +30 mV, but as the salt concentration increases, the ζ potential rises at 10 mM but then decreases over the salt range. This trend continues for the upper curd, lower curd and the supernatant and the degree of the reduction (mV) in zeta potential is of the order cream

Determining equilibrium osmolarity in poly(ethylene glycol)/chondrotin sulfate gels mimicking articular cartilage.

PubMed

Sircar, S; Aisenbrey, E; Bryant, S J; Bortz, D M

2015-01-07

We present an experimentally guided, multi-phase, multi-species polyelectrolyte gel model to make qualitative predictions on the equilibrium electro-chemical properties of articular cartilage. The mixture theory consists of two different types of polymers: poly(ethylene gylcol) (PEG), chondrotin sulfate (ChS), water (acting as solvent) and several different ions: H(+), Na(+), Cl(-). The polymer chains have covalent cross-links whose effect on the swelling kinetics is modeled via Doi rubber elasticity theory. Numerical studies on equilibrium polymer volume fraction and net osmolarity (difference in the solute concentration across the gel) show a complex interplay between ionic bath concentrations, pH, cross-link fraction and the average charge per monomer. Generally speaking, swelling is aided due to a higher average charge per monomer (or a higher particle fraction of ChS, the charged component of the polymer), low solute concentration in the bath, a high pH or a low cross-link fraction. A peculiar case arises at higher values of cross-link fraction, where it is observed that increasing the average charge per monomer leads to gel deswelling. Copyright © 2014 Elsevier Ltd. All rights reserved.

Exchangeable Ions Are Responsible for the In Vitro Antibacterial Properties of Natural Clay Mixtures

PubMed Central

Otto, Caitlin C.; Haydel, Shelley E.

2013-01-01

We have identified a natural clay mixture that exhibits in vitro antibacterial activity against a broad spectrum of bacterial pathogens. We collected four samples from the same source and demonstrated through antibacterial susceptibility testing that these clay mixtures have markedly different antibacterial activity against Escherichia coli and methicillin-resistant Staphylococcus aureus (MRSA). Here, we used X-ray diffraction (XRD) and inductively coupled plasma – optical emission spectroscopy (ICP-OES) and – mass spectrometry (ICP-MS) to characterize the mineralogical and chemical features of the four clay mixture samples. XRD analyses of the clay mixtures revealed minor mineralogical differences between the four samples. However, ICP analyses demonstrated that the concentrations of many elements, Fe, Co, Cu, Ni, and Zn, in particular, vary greatly across the four clay mixture leachates. Supplementation of a non-antibacterial leachate containing lower concentrations of Fe, Co, Ni, Cu, and Zn to final ion concentrations and a pH equivalent to that of the antibacterial leachate generated antibacterial activity against E. coli and MRSA, confirming the role of these ions in the antibacterial clay mixture leachates. Speciation modeling revealed increased concentrations of soluble Cu2+ and Fe2+ in the antibacterial leachates, compared to the non-antibacterial leachates, suggesting these ionic species specifically are modulating the antibacterial activity of the leachates. Finally, linear regression analyses comparing the log10 reduction in bacterial viability to the concentration of individual ion species revealed positive correlations with Zn2+ and Cu2+ and antibacterial activity, a negative correlation with Fe3+, and no correlation with pH. Together, these analyses further indicate that the ion concentration of specific species (Fe2+, Cu2+, and Zn2+) are responsible for antibacterial activity and that killing activity is not solely attributed to pH. PMID:23691149

Aerosols in polluted versus nonpolluted air masses Long-range transport and effects on clouds

NASA Technical Reports Server (NTRS)

Pueschel, R. F.; Van Valin, C. C.; Castillo, R. C.; Kadlecek, J. A.; Ganor, E.

1986-01-01

To assess the influence of anthropogenic aerosols on the physics and chemistry of clouds in the northeastern United States, aerosol and cloud-drop size distributions, elemental composition of aerosols as a function of size, and ionic content of cloud water were measured on Whiteface Mountain, NY, during the summers of 1981 and 1982. In several case studies, the data were cross-correlated with different air mass types - background continental, polluted continental, and maritime - that were advected to the sampling site. The results are the following: (1) Anthropogenic sources hundreds of kilometers upwind cause the small-particle (accumulation) mode number to increase from hundreds of thousands per cubic centimeter and the mass loading to increase from a few to several tens of micrograms per cubic meter, mostly in the form of sulfur aerosols. (2) A significant fraction of anthropogenic sulfur appears to act as cloud condensation nuclei (CCN) to affect the cloud drop concentration. (3) Clouds in Atlantic maritime air masses have cloud drop spectra that are markedly different from those measured in continental clouds. The drop concentration is significantly lower, and the drop size spectra are heavily skewed toward large drops. (4) Effects of anthropogenic pollutants on cloud water ionic composition are an increase of nitrate by a factor of 50, an increase of sulfate by more than one order of magnitude, and an increase of ammonium ion by a factor of 7. The net effect of the changes in ionic concentrations is an increase in cloud water acidity. An anion deficit even in maritime clouds suggests an unknown, possibly biogenic, source that could be responsible for a pH below neutral, which is frequently observed in nonpolluted clouds.

Effects of pH and Carbon Source on Synechococcus PCC 7002 Cultivation: Biomass and Carbohydrate Production with Different Strategies for pH Control.

PubMed

De Farias Silva, Carlos Eduardo; Sforza, Eleonora; Bertucco, Alberto

2017-02-01

Synechococcus PCC 7002 is an interesting species in view of industrial production of carbohydrates. The cultivation performances of this species are strongly affected by the pH of the medium, which also influences the carbohydrate accumulation. In this work, different methods of pH control were analyzed, in order to obtain a higher production of both Synechococcus biomass and carbohydrates. To better understand the influence of pH on growth and carbohydrate productivity, manual and automatic pH regulation in CO 2 and bicarbonate system were applied. The pH value of 8.5 resulted the best to achieve both of these goals. From an industrial point of view, an alternative way to maintain the pH practically constant during the entire period of cultivation is the exploitation of the bicarbonate-CO 2 buffer system, with the double aim to maintain the pH in the viability range and also to provide the amount of carbon required by growth. In this condition, a high concentration of biomass (6 g L -1 ) and carbohydrate content (around 60 %) were obtained, which are promising in view of a potential use for bioethanol production. The chemical equilibrium of C-N-P species was also evaluated by applying the ionic balance equations, and a relation between the sodium bicarbonate added in the medium and the equilibrium value of pH was discussed.

[Influence of Different Type of Surfactant on Bacteriolytic Activity of Lysozyme].

PubMed

Ivanov, R A; Soboleva, O A; Smirnov, S A; Levashov, P A

2015-01-01

The influence ofvarious surfactants (anionic sodium dodecyl sulfate, SDS, cationic dodecyltrimethylarnmonium bromide, DTAB, and zwitterionic cocoamidopropylbetaine, CAPB) on the activity of the chicken egg lysozyme is investigated. Lysis of Gram-positive bacteria by the enzyme was carried out at pH 7.2 and ionic strength of 0.15 M. It was found that at low SDS and DTAB concentrations (less than 1 x 10(-5) M) the bacteriolytic activity increases by 30-140%. At higher concentrations (1 x 10(-5) - 1 x 10(4) M) the activity returns to the level observed in the absence of the surfactants. The elevated activity correlated with the formation of hydrophobic lysozyme-surfactant complexes. Introduction of CAPB at concentrations above 1 x 10(-5) M sig, nificantly diminished the bacteriolytic activity due to CAPB induced aggregation of lysozyme.

Effects of temperature, pH, and ionic strength on the Henry's law constant of triethylamine

NASA Astrophysics Data System (ADS)

Leng, Chun-Bo; Roberts, Jason E.; Zeng, Guang; Zhang, Yun-Hong; Liu, Yong

2015-05-01

The Henry's law constants (KH) of triethylamine (TEA) in pure water and in 1-octanol were measured for the temperatures pertinent to the lower troposphere (278-298 K) using a bubble column system coupled to a Fourier transform infrared spectrometer. The KH values of TEA in water and 1-octanol at 298 K are 5.75 ± 0.86 mol L-1 atm-1 and 115.62 ± 5.78 mol L-1 atm-1. The KH values display strong dependence on temperature, pH, and ionic strength. The characteristic times for TEA to establish an equilibrium between gas and droplet with a size of 5.6 µm are ~33 s (298 K, pH = 5.6); ~8.9 × 102 s (278 K, pH = 5.6); ~1.3 × 103 s (298 K, pH = 4.0); and 3.6 × 104 s (278 K, pH = 4.0). The evaluation of TEA partitioning between gas phase and condensed phase implies that TEA predominantly resides in rainwater, and TEA loss to organic aerosol is negligible.

Facilitated strontium transport by remobilization of strontium-containing secondary precipitates in Hanford Site subsurface.

PubMed

Wang, Guohui; Um, Wooyong

2013-03-15

Significantly enhanced immobilization of radionuclides (such as (90)Sr and (137)Cs) due to adsorption and coprecipitation with neo-formed colloid-sized secondary precipitates has been reported at the U.S. Department of Energy's Hanford Site. However, the stability of these secondary precipitates containing radionuclides in the subsurface under changeable field conditions is not clear. Here, the authors tested the remobilization possibility of Sr-containing secondary precipitates (nitrate-cancrinite) in the subsurface using saturated column experiments under different geochemical and flow conditions. The columns were packed with quartz sand that contained secondary precipitates (nitrate-cancrinite containing Sr), and leached using colloid-free solutions under different flow rates, varying pH, and ionic strength conditions. The results indicate remobilization of the neo-formed secondary precipitates could be possible given a change of pH of ionic strength and flow rate conditions. The remobility of the neo-formed precipitates increased with the rise in the leaching solution flow rate and pH (in a range of pH 4-11), as well as with decreasing solution ionic strength. The increased mobility of Sr-containing secondary precipitates with changing background conditions can be a potential source for additional radionuclide transport in Hanford Site subsurface environments. Published by Elsevier B.V.

Ultrasound-assisted ionic liquid-based micellar extraction combined with microcrystalline cellulose as sorbent in dispersive microextraction for the determination of phenolic compounds in propolis.

PubMed

Cao, Jun; Peng, Li-Qing; Du, Li-Jing; Zhang, Qi-Dong; Xu, Jing-Jing

2017-04-22

An ionic liquid-(IL) based micellar extraction combined with microcrystalline cellulose- (MCC) assisted dispersive micro solid-phase extraction method was developed to extract phenolic compounds from propolis. A total of 20 target compounds were identified by ultra-high- performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry. The main extraction parameters were optimized and included the ultrasonic power, ultrasonic time, sample pH, type of IL, the concentration of [C12mim]Br, extraction time, concentration of MCC, type of sorbent and type of elution solvents. Under the optimum conditions, the proposed method exhibited good linearities (r 2  ≥ 0.999) for all plant phenolic compounds with the lower limits of detection in the range of 0.21-0.41 ng/mL. The recoveries ranged from 82.74% to 97.88% for pinocembrin, chrysin and galangin. Compared with conventional solvent extraction, the present method was simpler and more efficient and required less organic solvent and a shorter extraction time. Finally, the methodology was successfully used for the extraction and enrichment of phenolic compounds in propolis. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of ultra-trace aluminum in human albumin by cloud point extraction and graphite furnace atomic absorption spectrometry.

PubMed

Sun, Mei; Wu, Qianghua

2010-04-15

A cloud point extraction (CPE) method for the preconcentration of ultra-trace aluminum in human albumin prior to its determination by graphite furnace atomic absorption spectrometry (GFAAS) had been developed in this paper. The CPE method was based on the complex of Al(III) with 1-(2-pyridylazo)-2-naphthol (PAN) and Triton X-114 was used as non-ionic surfactant. The main factors affecting cloud point extraction efficiency, such as pH of solution, concentration and kind of complexing agent, concentration of non-ionic surfactant, equilibration temperature and time, were investigated in detail. An enrichment factor of 34.8 was obtained for the preconcentration of Al(III) with 10 mL solution. Under the optimal conditions, the detection limit of Al(III) was 0.06 ng mL(-1). The relative standard deviation (n=7) of sample was 3.6%, values of recovery of aluminum were changed from 92.3% to 94.7% for three samples. This method is simple, accurate, sensitive and can be applied to the determination of ultra-trace aluminum in human albumin. 2009 Elsevier B.V. All rights reserved.

Impact of Surface Active Ionic Liquids on the Cloud Points of Nonionic Surfactants and the Formation of Aqueous Micellar Two-Phase Systems.

PubMed

Vicente, Filipa A; Cardoso, Inês S; Sintra, Tânia E; Lemus, Jesus; Marques, Eduardo F; Ventura, Sónia P M; Coutinho, João A P

2017-09-21

Aqueous micellar two-phase systems (AMTPS) hold a large potential for cloud point extraction of biomolecules but are yet poorly studied and characterized, with few phase diagrams reported for these systems, hence limiting their use in extraction processes. This work reports a systematic investigation of the effect of different surface-active ionic liquids (SAILs)-covering a wide range of molecular properties-upon the clouding behavior of three nonionic Tergitol surfactants. Two different effects of the SAILs on the cloud points and mixed micelle size have been observed: ILs with a more hydrophilic character and lower critical packing parameter (CPP < 1 / 2 ) lead to the formation of smaller micelles and concomitantly increase the cloud points; in contrast, ILs with a more hydrophobic character and higher CPP (CPP ≥ 1) induce significant micellar growth and a decrease in the cloud points. The latter effect is particularly interesting and unusual for it was accepted that cloud point reduction is only induced by inorganic salts. The effects of nonionic surfactant concentration, SAIL concentration, pH, and micelle ζ potential are also studied and rationalized.

The role of groundwater chemistry in the transport of bacteria to water-supply wells

USGS Publications Warehouse

Harvey, R.W.; Metge, D.W.

1999-01-01

Static mini-columns and in situ injection and recovery tests were used to assess the effects of modest changes in groundwater chemistry upon the pH-dependence of bacterial attachment, a primary determinant of bacterial mobility in drinking water aquifers. In uncontaminated groundwater (<1 mg l-1 dissolved organic carbon, DOC), bacterial attachment to aquifer grain surfaces declined steadily from 93 to 20% in response to an increase in pH from 5.8 to 7.8. However, bacterial attachment in modestly-contaminated groundwater (4 mg l-1 DOC) was relatively insensitive to pH change from pH 3.5 to pH 8, as was bacterial attachment in uncontaminated groundwater amended with only ~3 mg l-1 of purified humic acid. Destruction by UV-oxidation of the DOC in contaminated groundwater partially restored the pH-dependence of bacterial attachment. Results from static column tests and from a small-scale (3.6 m) natural-gradient injection and recovery study suggest that low concentrations of surfactants can also substantively alter the attraction of groundwater bacteria for grain surfaces and, therefore can alter the transport of bacteria to water-supply wells. This phenomenon was pH-sensitive and dependent upon the nature of the surfactant. At pH 7.6, 200 mg l-1 of the non-ionic surfactant, Imbentin, caused a doubling of fractional bacterial attachment in aquifer-sediment columns, but had little effect under slightly acidic conditions (e.g. at pH 5.8). In contrast, 1 mg l-1 of linear alkylbenzene sulphonate (LAS) surfactant, a common sewage-derived contaminant, decreased the fractional bacterial attachment by more than 30% at pH 5.8, but had little effect at pH 7.3.Static mini-columns and in situ injection and recovery tests were used to assess the effects of modest changes in groundwater chemistry upon the pH-dependence of bacterial attachment, a primary determinant of bacterial mobility in drinking water aquifers. In uncontaminated groundwater (<1 mg l-1 dissolved organic carbon, DOC), bacterial attachment to aquifer grain surfaces declined steadily from 93 to 20% in response to an increase in pH from 5.8 to 7.8. However, bacterial attachment in modestly-contaminated groundwater (4 mg l-1 DOC) was relatively insensitive to pH change from pH 3.5 to pH 8, as was bacterial attachment in uncontaminated groundwater amended with only approx. 3 mg l-1 of purified humic acid. Destruction of UV-oxidation of the DOC in contaminated groundwater partially restored the pH-dependence of bacterial attachment. Results from the static column tests and from a small-scale (3.6 m) natural-gradient injection and recovery study suggest that low concentrations of surfactants can also substantively alter the attraction of groundwater bacteria for grain surfaces and, therefore can alter the transport of bacteria to water-supply wells. This phenomenon was pH-sensitive and dependent upon the nature of the surfactant. At pH 7.6, 200 mg l-1 of the non-ionic surfactant, Imbentin, caused a doubling of fractional bacterial attachment in aquifer-sediment columns, but had little effect under slightly acidic conditions (e.g. at pH 5.8). In contrast, 1 mg l-1 of linear alkylbenzene sulphonate (LAS) surfactant, a common sewage-derived contaminant, decreased the fractional bacterial attachment by more than 30% at pH 5.8, but had little effect at pH 7.3.

Effects of molecular composition of natural organic matter on ferric iron complexation at circumneutral pH.

PubMed

Fujii, Manabu; Imaoka, Akira; Yoshimura, Chihiro; Waite, T D

2014-04-15

Thermodynamic and kinetic parameters for ferric iron (Fe[III]) complexation by well-characterized humic substances (HS) from various origins were determined by a competitive ligand method with 5-sulfosalicylic acid at circumneutral pH (6.0-8.0) and an ionic strength of ∼0.06 M. The measured Fe binding properties including conditional stability constants and complexation capacities ranged over more than 2 orders of magnitude, depending on the origin and the particular operationally defined fraction of HS examined. Statistical comparison of the complexation parameters to a range of chemical properties of the HS indicated a strong positive correlation between Fe(III) complexation capacity and aromatic carbon content in the HS at all pHs examined. In contrast, the complexation capacity was determined to be up to a few orders of magnitude smaller than the concentration of carboxylic and phenolic groups present. Therefore, specific functional groups including those resident in the proximity of aromatic structures within the HS are likely preferable for Fe(III) coordination under the conditions examined. Overall, our results suggest that the concentration of dissolved Fe(III) complexes in natural waters is substantially influenced by variation in HS characteristics in addition to other well-known factors such as HS concentration and nature and concentration of competing cations present.

Micellar liquid chromatography

NASA Astrophysics Data System (ADS)

Basova, Elena M.; Ivanov, Vadim M.; Shpigun, Oleg A.

1999-12-01

Background and possibilities of practical applications of micellar liquid chromatography (MLC) are considered. Various retention models in MLC, the effects of the nature and concentration of surfactants and organic modifiers, pH, temperature and ionic strength on the MLC efficiency and selectivity are discussed. The advantages and limitations of MLC are demonstrated. The performance of MLC is critically evaluated in relationship to the reversed-phase HPLC and ion-pair chromatography. The potential of application of MLC for the analysis of pharmaceuticals including that in biological fluids and separation of inorganic anions, transition metal cations, metal chelates and heteropoly compounds is described. The bibliography includes 146 references.

Purification and characterization of halophilic lipase of Chromohalobacter sp. from ancient salt well.

PubMed

Ai, Li; Huang, Yaping; Wang, Chuan

2018-06-04

A halophilic lipase (LipS2) was produced by Chromohalobacter canadensis strain which was isolated from ancient salt well of Zigong, China. LipS2 was purified to homogeneity and showed a single band with molecular mass of 58 kDa by SDS-PAGE. LipS2 preferred middle-to-long acyl chain esters with C14 triglycerides as optimum substrate. It was noteworthy that LipS2 displayed efficient hydrolysis activity to some vegetable oils which were composed of polyunsaturated fatty acid. LipS2 showed high activity in range of 2.5-3.5 M NaCl, no activity without salt. Optimum temperature and pH were 55 °C and pH 8.5, respectively. Notably, the thermostability and pH stability of LipS2, varying with salt concentration, reached optimum in the presence of 3.0 M NaCl. LipS2 was stimulated by Ca 2+ and Mg 2+ , inhibited by Zn 2+ , Cu 2+ , Mn 2+ , Fe 2+ , and Hg 2+ . Moreover, LipS2 displayed significant tolerance to organic solvents including methanol, ethanol, ethyl acetate and acetone, especially, LipS2 activity was enhanced markedly by the hexane and benzene. Non-ionic surfactants increased LipS2 activity, while ionic surfactants decreased activity. This was the first report on halophilic lipase of Chromohalobacter from ancient salt well. The results suggested that LipS2 may have considerable potential for biotechnological applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Brain microdialysis as a tool to explore the ionic profile of the brain extracellular space in neurocritical patients: a methodological approach and feasibility study.

PubMed

Martínez-Valverde, Tamara; Vidal-Jorge, Marian; Montoya, Noelia; Sánchez-Guerrero, Angela; Manrique, Susana; Munar, Francisca; Pellegri, Maria-Dolors; Poca, Maria-Antonia; Sahuquillo, Juan

2015-01-01

Our aim is to determine whether the ionic concentration in brain microdialysate enables calculations of the actual Na(+), K(+), and Cl(-) concentrations in vitro and whether this method can be applied to determine the ionic concentrations in the brain extracellular fluid. We designed an experiment using CMA-71 probes (M Dialysis, Stockholm, Sweden) and the standard conditions used in a clinical setting. Nine CMA-71 probes were inserted in different matrices and perfused with mock cerebrospinal fluid containing 3% albumin at the standard infusion rate used in the clinical setting (0.3 μL/min). Microvials were replaced every 12 h, and the ionic concentrations, both in the dialysate and the matrix, were analyzed. For each ion, scatter plots were built, with [Na(+)], [K(+)], and [Cl(-)] in the dialysate as the predictor variables and the matrix concentrations as the outcome variables. A linear regression model allowed us to calculate the true ionic concentrations in the matrix. To demonstrate the feasibility of the method, we present the calculated ionic profile of one patient with a malignant infarction and a second with a severe traumatic brain injury. Our results confirm that the ionic concentration in microdialysate can be used to calculate the true concentrations of ions in a matrix and the actual concentrations in the extracellular fluid. Microdialysis offers the unique possibility of monitoring the dynamic changes of ions in the brain over time and opens a new avenue to explore the brain's ionic profile, its changes in brain edema, and how this profile can be modified with different therapies.

The unexpected mechanism underlying the high-valent mono-oxo-rhenium(V) hydride catalyzed hydrosilylation of C=N functionalities: insights from a DFT study.

PubMed

Wang, Jiandi; Wang, Wenmin; Huang, Liangfang; Yang, Xiaodi; Wei, Haiyan

2015-04-07

In this study, we theoretically investigated the mechanism underlying the high-valent mono-oxo-rhenium(V) hydride Re(O)HCl2(PPh3)2 (1) catalyzed hydrosilylation of C=N functionalities. Our results suggest that an ionic S(N)2-Si outer-sphere pathway involving the heterolytic cleavage of the Si-H bond competes with the hydride pathway involving the C=N bond inserted into the Re-H bond for the rhenium hydride (1) catalyzed hydrosilylation of the less steric C=N functionalities (phenylmethanimine, PhCH=NH, and N-phenylbenzylideneimine, PhCH=NPh). The rate-determining free-energy barriers for the ionic outer-sphere pathway are calculated to be ∼28.1 and 27.6 kcal mol(-1), respectively. These values are slightly more favorable than those obtained for the hydride pathway (by ∼1-3 kcal mol(-1)), whereas for the large steric C=N functionality of N,1,1-tri(phenyl)methanimine (PhCPh=NPh), the ionic outer-sphere pathway (33.1 kcal mol(-1)) is more favorable than the hydride pathway by as much as 11.5 kcal mol(-1). Along the ionic outer-sphere pathway, neither the multiply bonded oxo ligand nor the inherent hydride moiety participate in the activation of the Si-H bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diffusion of neutral and ionic species in charged membranes: boric acid, arsenite, and water.

PubMed

Goli, Esmaiel; Hiemstra, Tjisse; Van Riemsdijk, Willem H; Rahnemaie, Rasoul; Malakouti, Mohammad Jafar

2010-10-15

Dynamic ion speciation using DMT (Donnan membrane technique) requires insight into the physicochemical characteristics of diffusion in charged membranes (tortuosity, local diffusion coefficients) as well as ion accumulation. The latter can be precluded by studying the diffusion of neutral species, such as boric acid, B(OH)₃⁰(aq), arsenite, As(OH)₃⁰(aq), or water. In this study, the diffusion rate of B(OH)₃⁰ has been evaluated as a function of the concentration, pH, and ionic strength. The rate is linearly dependent on the concentration of solely the neutral species, without a significant contribution of negatively charged species such as B(OH)₄⁻, present at high pH. A striking finding is the very strong effect (factor of ~10) of the type of cation (K(+), Na(+), Ca(2+), Mg(2+), Al(3+), and H(+)) on the diffusion coefficient of B(OH)₃⁰ and also As(OH)₃⁰. The decrease of the diffusion coefficient can be rationalized as an enhancement of the mean viscosity of the confined solution in the membrane. The diffusion coefficients can be described by a semiempirical relationship, linking the mean viscosity of the confined solute of the membrane to the viscosity of the free solution. In proton-saturated membranes, as used in fuel cells, viscosity is relatively more enhanced; i.e., a stronger water network is formed. Extraordinarily, our B(OH)₃-calibrated model (in HNO₃) correctly predicts the reported diffusion coefficient of water (D(H₂O)), measured with ¹H NMR and quasi-elastic neutron scattering in H(+)-Nafion membranes. Upon drying these membranes, the local hydronium, H(H₂O)(n)(+), concentration and corresponding viscosity increase, resulting in a severe reduction of the diffusion coefficient (D(H₂O) ≈ 5-50 times), in agreement with the model. The present study has a second goal, i.e., development of the methodology for measuring the free concentration of neutral species in solution. Our data suggest that the free concentration can be measured with DMT in natural systems if one accounts for the variation in the cation composition of the membrane and corresponding viscosity/diffusion coefficient.

Charge tunable thin-film composite membranes by gamma-ray triggered surface polymerization.

PubMed

Reis, Rackel; Duke, Mikel C; Tardy, Blaise L; Oldfield, Daniel; Dagastine, Raymond R; Orbell, John D; Dumée, Ludovic F

2017-06-30

Thin-film composite poly(amide) (PA) membranes have greatly diversified water supplies and food products. However, users would benefit from a control of the electrostatic interactions between the liquid and the net surface charge interface in order to benefit wider application. The ionic selectivity of the 100 nm PA semi-permeable layer is significantly affected by the pH of the solution. In this work, for the first time, a convenient route is presented to configure the surface charge of PA membranes by gamma ray induced surface grafting. This rapid and up-scalable method offers a versatile route for surface grafting by adjusting the irradiation total dose and the monomer concentration. Specifically, thin coatings obtained at low irradiation doses between 1 and 10 kGy and at low monomer concentration of 1 v/v% in methanol/water (1:1) solutions, dramatically altered the net surface charge of the pristine membranes from -25 mV to +45 mV, whilst the isoelectric point of the materials shifted from pH 3 to pH 7. This modification resulted in an improved water flux by over 55%, from 45.9 to up 70 L.m -2 .h -1 , whilst NaCl rejection was found to drop by only 1% compared to pristine membranes.

Retention and release of oil-in-water emulsions from filled hydrogel beads composed of calcium alginate: impact of emulsifier type and pH.

PubMed

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.

Equilibrium partitioning of organic compounds to OASIS HLB® as a function of compound concentration, pH, temperature and salinity.

PubMed

Jeong, Yoonah; Schäffer, Andreas; Smith, Kilian

2017-05-01

Oasis hydrophilic lipophilic balance ® (Oasis HLB) is commonly employed in solid phase extraction (SPE) of environmental contaminants and within polar organic chemical integrative passive samplers (POCIS). In this study batch experiments were carried out to evaluate the relative affinity of a range of relevant organic pollutants to Oasis HLB in aqueous systems. The influence of sorbate concentration, temperature, pH, and salinity on the equilibrium sorption was investigated. Equilibrium partition ratios (K D ) of 28 compounds were determined, ranging over three orders of magnitude from 1.16 × 10 3  L/kg (atenolol) to 1.07 × 10 6  L/kg (isoproturon). The Freundlich model was able to describe the equilibrium partitioning to Oasis HLB, and an analysis of the thermodynamic parameters revealed the spontaneous and exothermic nature of the partitioning process. Ionic strength had only a minor effect on the partitioning, whereas pH had a considerable effect but only for ionizable compounds. The results show that apolar interactions between the Oasis HLB and analyte mainly determine the equilibrium partitioning. These research findings can be used to optimize the application of SPE and POCIS for analyses of environmental contaminants even in complex mixtures. Copyright © 2017 Elsevier Ltd. All rights reserved.

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

The strong affinity of carbon nanotubes (CNTs) to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength) and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB) from multi-walled carbon nanotubes (MWNTs). The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH < 7 vs. pH > 7). In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs. PMID:28348336

Effects of pH on transport properties of articular cartilages.

PubMed

Loret, Benjamin; Simões, Fernando M F

2010-02-01

Articular cartilages swell and shrink depending on the ionic strength of the electrolyte they are in contact with. This electro-chemo-mechanical coupling is due to the presence of fixed electrical charges on proteoglycans (PGs). In addition, at nonphysiological pH, collagen fibers become charged. Therefore, variation of the pH of the electrolyte has strong implications on the electrical charge of cartilages and, by the same token, on their transport and mechanical properties. Articular cartilages are viewed as three-phase multi-species porous media. The constitutive framework is phrased in the theory of thermodynamics of porous media. Acid-base reactions, as well as calcium binding, are embedded in this framework. Although macroscopic in nature, the model accounts for a number of biochemical details defining collagen and PGs. The change of the electrical charge is due to the binding of hydrogen ions on specific sites of PGs and collagen. Simulations are performed mimicking laboratory experiments where either the ionic strength or the pH of the bath, the cartilage piece is in contact with, is varied. They provide the evolutions of the chemical compositions of mobile ions, of the sites of acid-base reactions and calcium binding, and of the charges of collagen and glycosaminoglycans, at constant volume fraction of water. Emphasis is laid on the effects of pH, ionic strength and calcium binding on the transport properties of cartilages, and, in particular, on the electrical conductivity and electro-osmotic coefficient.

A dynamic system for the simulation of fasting luminal pH-gradients using hydrogen carbonate buffers for dissolution testing of ionisable compounds.

PubMed

Garbacz, Grzegorz; Kołodziej, Bartosz; Koziolek, Mirko; Weitschies, Werner; Klein, Sandra

2014-01-23

The hydrogen carbonate buffer is considered as the most biorelevant buffer system for the simulation of intestinal conditions and covers the physiological pH range of the luminal fluids from pH 5.5 to about pH 8.4. The pH value of a hydrogen carbonate buffer is the result of a complex and dynamic interplay of the concentration of hydrogen carbonate ions, carbonic acid, the concentration of dissolved and solvated carbon dioxide and its partial pressure above the solution. The complex equilibrium between the different ions results in a thermodynamic instability of hydrogen carbonate solutions. In order to use hydrogen carbonate buffers with pH gradients in the physiological range and with the dynamics observed in vivo without changing the ionic strength of the solution, we developed a device (pHysio-grad®) that provides both acidification of the dissolution medium by microcomputer controlled carbon dioxide influx and alkalisation by degassing. This enables a continuous pH control and adjustment during dissolution of ionisable compounds. The results of the pH adjustment indicate that the system can compensate even rapid pH changes after addition of a basic or acidic moiety in amounts corresponding up to 90% of the overall buffer capacity. The results of the dissolution tests performed for a model formulation containing ionizable compounds (Nexium 20mg mups) indicate that both the simulated fasting intraluminal pH-profiles and the buffer species can significantly affect the dissolution process by changing the lag time prior to initial drug release and the release rate of the model compound. A prediction of the in vivo release behaviour of this formulation is thus most likely strongly related to the test conditions such as pH and buffer species. Copyright © 2013 Elsevier B.V. All rights reserved.

Physicochemical degradation studies of calcium phosphate glass ceramic in the CaO-P2O5-MgO-TiO2 system.

PubMed

Dias, A G; Gibson, I R; Santos, J D; Lopes, M A

2007-03-01

The aim of this work was to evaluate the in vitro degradation behaviour of a 45CaO-37P(2)O(5)-5MgO-13TiO(2) (mol.%) glass ceramic, under two different simulated physiological conditions: normal physiological pH 7.4, and pH 3.0, which was designed to simulate the acidic conditions produced by osteoclast cells. The in vitro testing was carried out at 37 degrees C for up to 42 days for the pH 7.4 solution and for up to 1 day for the pH 3.0 solution. The incorporation of TiO(2) into the glass structure leads to the precipitation of specific crystalline phases in the glass matrix, namely alpha- and beta-Ca(2)P(2)O(7), TiP(2)O(7) and CaTi(4)(PO(4))(6). The degradation testing at pH 3.0 showed a higher weight loss compared with degradation testing at pH 7.4; the weight loss under the acidic condition after 1 day (24 h) was about 10 times higher than the weight loss after 42 days of immersion at pH 7.4. The ionic release profile of Ca(2+), PO(4)(3-), Mg(2+) and Ti(4+) showed a continuous increase in concentration over all immersion times for both testing solutions. After 1 day of immersion at pH 3.0, the concentration levels of Mg(2+), Ca(2+), PO(4)(3-) were about six times higher than the levels achieved after 42 days of immersion at pH 7.4. The glass ceramic showed similar degradation to hydroxyapatite, and therefore has potential to be used in certain clinical applications where relatively slow resorption of the implant and replacement by bone is required, e.g. cranioplasty.

Impact of multicomponent ionic transport on pH fronts propagation in saturated porous media

NASA Astrophysics Data System (ADS)

Muniruzzaman, Muhammad; Rolle, Massimo

2016-04-01

Multicomponent ionic interactions have been increasingly recognized as important factors for the displacement of charged species in porous media under both diffusion- [1,2] and advection-dominated flow regimes [3,4]. In this study we investigate the propagation of pH fronts during multicomponent ionic transport in saturated porous media under flow-through conditions. By performing laboratory bench-scale experiments combined with numerical modeling we show the important influence of Coulombic effects on proton transport in the presence of ionic admixtures. The experiments were performed in a quasi two-dimensional flow-through setup under steady-state flow and transport conditions. Dilute solutions of hydrochloric acid with MgCl2 (1:2 strong electrolyte) were used as tracer solutions to experimentally test the effect of electrochemical cross-coupling on the migration of diffusive/dispersive pH fronts. We focus on two experimental scenarios, with different composition of tracer solutions, causing remarkably different effects on the propagation of the acidic fronts with relative differences in the penetration depth of pH fronts of 36% between the two scenarios and of 25% and 15% for each scenario with respect to the transport of ions at liberated state (i.e., without considering the charge effects). Also significant differences in the dilution of the distinct ionic plumes, quantified using the flux-related dilution index at the laboratory bench scale [5], were measured at the outflow of the flow-through system. The dilution of the pH plumes also changed considerably (26% relative difference) in the two flow-through experiments only due to the different composition of the pore water solution and to the electrostatic coupling of the ions in the flow-through setups. Numerical transport simulations were performed to interpret the laboratory experiments. The simulations were based on a multicomponent ionic formulation accurately capturing the Coulombic interactions between the transported ions in the flow-through system. The results of purely forward simulations show a very good agreement with the high-resolution measurements performed at the outlet of the flow-through setup and illustrate the importance of charge effects on pH fronts propagation in porous media. [1] Giambalvo, E. R., C. I. Steefel, A. T. Fisher, N. D. Rosenberg, and C. G. Wheat (2002), Effect of fluid-sediment reaction on hydrothermal fluxes of major elements, eastern flank of the Juan de Fuca Ridge, Geochim. Cosmochim. Acta, 66, 1739-1757. [2] Appelo, C. A. J., and P. Wersin (2007), Multicomponent diffusion modeling in clay systems with application to the diffusion of tritium, iodide, and sodium in opalinus clay, Environ. Sci. Technol., 41, 5002-5007. [3] Rolle, M., M. Muniruzzaman, C. M. Haberer, and P. Grathwohl (2013), Coulombic effects in advection-dominated transport of electrolytes in porous media: Multicomponent ionic dispersion, Geochim. Cosmochim. Acta, 120, 195-205. [4] Muniruzzaman, M., C. M. Haberer, P. Grathwohl, and M. Rolle (2014), Multicomponent ionic dispersion during transport of electrolytes in heterogeneous porous media: Experiments and model-based interpretation, Geochim. Cosmochim. Acta, 141, 656-669. [5] Rolle, M., G. Chiogna, D. L. Hochstetler, and P. K. Kitanidis (2013), On the importance of diffusion and compound-specific mixing for groundwater transport: An investigation from pore to field scale, J. Contam. Hydrol., 153, 51-68.

Characteristics and gelling property of phosphorylated gelatin from the skin of unicorn leatherjacket.

PubMed

Kaewruang, Phanngam; Benjakul, Soottawat; Prodpran, Thummanoon

2014-03-01

The characteristics and gelling property of gelatin from the skin of unicorn leatherjacket, phosphorylated with sodium tripolyphosphate (STPP) at various concentrations (0.25%, 0.50%, 0.75% and 1.00% w/w), for different times (1 and 3h) at 65°C, were studied. With the increase of STPP concentration and time, no increase in bound phosphate was observed. The highest gel strength was obtained for gelatin phosphorylated using 0.25% STPP for 1h (P<0.05). When the effect of pH (5, 7, 9 and 11) on phosphorylation and gel property of gelatin was investigated, gelatin phosphorylated at pH 9 had the highest gel strength (204.3g) (P<0.05) and exhibited a finer and more compact network structure with smaller pores. Gelatin became negatively charged (-3.89mV) and might undergo an ionic interaction to a higher extent, thereby strengthening the gel network. Thus, the phosphorylation, under the appropriate condition, could improve the gelling property of gelatin from the skin of unicorn leatherjacket. Copyright © 2013 Elsevier Ltd. All rights reserved.

Power generation by a pH-regulated conical nanopore through reverse electrodialysis

NASA Astrophysics Data System (ADS)

Hsu, Jyh-Ping; Lin, Sheng-Chang; Lin, Chih-Yuan; Tseng, Shiojenn

2017-10-01

To assess the possibility of energy harvesting through reverse electrodialysis (RED), we consider the electrokinetic behavior of the ion transport in a pH-regulated conical nanopore connecting two large reservoirs having different bulk salt concentrations, taking account of the effect of osmotic flow. In particular, we examine the influence of the ion diffusion direction, the solution pH, and the bulk concentration ratio on that behavior in detail, and discuss the underlying mechanisms. We show that the geometrically asymmetric nature of the nanopore yields profound and interesting phenomena arising mainly from the distribution of ions in its interior. Assuming a single polymeric nanopore, a power density of 18.2 W/m2 can be generated. We show that the present system has the potential of serving as an ion-selective and a salinity gradient power generation device. The maximum power efficiency which is based on assuming a linear ionic distribution in nanopore can yield appreciable deviation, especially if pH deviates significantly from 7, where the presence of H+ and OH- needs be considered.

Characterization and evaluation of acid rain in East Central Florida from 1978 to 1987: Ten year summary report

NASA Technical Reports Server (NTRS)

Madsen, Brooks C.; Dreschel, Thomas W.; Hinkle, C. Ross

1989-01-01

Rainfall was collected on the University of Central Florida (UCF) campus near Orlando since July 1977 and at the Kennedy Space Center (KSC), Florida since August 1977. Since November 1983, the KSC site has been affiliated with the National Atmospheric Deposition Network. Annual volume weighted pH was slightly above the 10 year mean of 4.58 during four of the past five years. Nitrate concentrations have risen somewhat during recent years while excess sulfate concentrations have remained below the 10 year mean during four of the past years. These observations hold for both the UCF and KSC data. The distribution of individual sample pH was nearly identical at UCF and KSC. Stepwise regression suggests that sulfate, nitrate, ammonium ion, and calcium play major roles in the description of rainwater acidity. Annual acid deposition and annual rainfall have varied from 30 to 50 meq/m2-yr and 100 to 180 cm/yr, respectively. Sea salt comprises about 25 percent (UCF) and greater than 50 percent (KSC) of total ionic composition.

Gate modulation of proton transport in a nanopore.

PubMed

Mei, Lanju; Yeh, Li-Hsien; Qian, Shizhi

2016-03-14

Proton transport in confined spaces plays a crucial role in many biological processes as well as in modern technological applications, such as fuel cells. To achieve active control of proton conductance, we investigate for the first time the gate modulation of proton transport in a pH-regulated nanopore by a multi-ion model. The model takes into account surface protonation/deprotonation reactions, surface curvature, electroosmotic flow, Stern layer, and electric double layer overlap. The proposed model is validated by good agreement with the existing experimental data on nanopore conductance with and without a gate voltage. The results show that the modulation of proton transport in a nanopore depends on the concentration of the background salt and solution pH. Without background salt, the gated nanopore exhibits an interesting ambipolar conductance behavior when pH is close to the isoelectric point of the dielectric pore material, and the net ionic and proton conductance can be actively regulated with a gate voltage as low as 1 V. The higher the background salt concentration, the lower is the performance of the gate control on the proton transport.

Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

PubMed

Yang, Jin; Bitter, Julie L; Smith, Billy A; Fairbrother, D Howard; Ball, William P

2013-12-17

This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (<4 mg/L of dissolved organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

Effect of chelators on functionality of milk protein concentrates obtained by ultrafiltration at a constant pH and temperature.

PubMed

Ramchandran, Lata; Luo, XiaoXia; Vasiljevic, Todor

2017-11-01

Modulating conditions during ultrafiltration of skim milk appears to be a feasible strategy to obtain milk protein concentrates (MPC) with tailored functionalities. Adjustment of pH and process temperature attenuated properties of casein micelle resulting in enhanced emulsification capacity. Additional pre-treatment options such as addition of calcium chelators can further impact on the functionality of MPC by modifying the calcium distribution and casein micelle integrity. The objective of the project was to establish effects of pre-treating skim milk with calcium chelators (EDTA or citrate) in concentrations between 10 to 30 mm prior to UF on the physical properties of the feed, corresponding retentates and dried MPC, including particle size, zeta potential and calcium distribution in skim milk and the corresponding retentates, as well as the physical functionalities such as solubility, heat stability and emulsifying properties. Addition of calcium chelators (EDTA or citrate), at levels 20-30 mm concentrations reduced casein micelle size as well as total, soluble and ionic calcium contents that resulted in MPC with enhanced solubility and heat stability. The emulsion capacity was, however, improved only with EDTA at 10 mm concentration. The enhanced functionality is attributed to the reduced particle size resulting from the removal of calcium from the retentate that could modify micellar casein to an extent sufficient to cause such improvements.

Metal bioavailability and toxicity to fish in low-alkalinity lakes: A critical review

USGS Publications Warehouse

Spry, D.J.; Wiener, James G.

1991-01-01

Fish in low-alkalinity lakes having pH of 6·0–6·5 or less often have higher body or tissue burdens of mercury, cadmium, and lead than do fish in nearby lakes with higher pH. The greater bioaccumulation of these metals in such waters seems to result partly from the greater aqueous abundances of biologically available forms (CH3 Hg+, Cd2+, and Pb2+) at low pH. In addition, the low concentrations of aqueous calcium in low-alkalinity lakes increase the permeability of biological membranes to these metals, which in fish may cause greater uptake from both water and food. Fish exposed to aqueous inorganic aluminum in the laboratory and field accumulate the metal in and on the epithelial cells of the gills; however, there is little accumulation of aluminum in the blood or internal organs. In low-pH water, both sublethal and lethal toxicity of aluminum has been clearly demonstrated in both laboratory and field studies at environmental concentrations. In contrast, recently measured aqueous concentrations of total mercury, methylmercury, cadmium, and lead in low-alkalinity lakes are much lower than the aqueous concentrations known to cause acute or chronic toxicity in fish, although the vast majority of toxicological research has involved waters with much higher ionic strength than that in low-alkalinity lakes. Additional work with fish is needed to better assess (1) the toxicity of aqueous metals in low-alkalinity waters, and (2) the toxicological significance of dietary methylmercury and cadmium.

Effects of Ionic Dependence of DNA Persistence Length on the DNA Condensation at Room Temperature

NASA Astrophysics Data System (ADS)

Mao, Wei; Liu, Yan-Hui; Hu, Lin; Xu, Hou-Qiang

2016-05-01

DNA persistence length is a key parameter for quantitative interpretation of the conformational properties of DNA and related to the bending rigidity of DNA. A series of experiments pointed out that, in the DNA condensation process by multivalent cations, the condensed DNA takes elongated coil or compact globule states and the population of the compact globule states increases with an increase in ionic concentration. At the same time, single molecule experiments carried out in solution with multivalent cations (such as spermidine, spermine) indicated that DNA persistence length strongly depends on the ionic concentration. In order to revolve the effects of ionic concentration dependence of persistence length on DNA condensation, a model including the ionic concentration dependence of persistence length and strong correlation of multivalent cation on DNA is provided. The autocorrelation function of the tangent vectors is found as an effective way to detect the ionic concentration dependence of toroidal conformations. With an increase in ion concentration, the first periodic oscillation contained in the autocorrelation function shifts, the number of segment contained in the first periodic oscillation decreases gradually. According to the experiments, the average long-axis length is defined to estimate the ionic concentration dependence of condensation process further. The relation between long-axis length and ionic concentration matches the experimental results qualitatively. Supported by National Natural Science Foundation of China under Grant Nos. 11047022, 11204045, 11464004 and 31360215; The Research Foundation from Ministry of Education of China (212152), Guizhou Provincial Tracking Key Program of Social Development (SY20123089, SZ20113069); The General Financial Grant from the China Postdoctoral Science Foundation (2014M562341); The Research Foundation for Young University Teachers from Guizhou University (201311); The West Light Foundation (2015) and College Innovation Talent Team of Guizhou Province, (2014) 32

Product development studies of amino acid conjugate of Aceclofenac.

PubMed

Singh, Ajay Pal; Ramadan, Wafa Mossa; Dahiya, Rajiv; Sarpal, A S; Pathak, Kamla

2009-04-01

The prodrugs designed by classical approach increase lipophilicity of the drug, which decreases the water solubility thus decreasing the concentration gradient, which controls drug absorption. To overcome the limitations of traditional prodrug approach, water soluble prodrugs can be designed by adding selected amino acid to the drug moiety that are the substrates for the enzyme located at the intestinal brush border thus overcoming pharmaceutical problem without compromising bioavailability. ACaa (Amino acid conjugate of Aceclofenac) was synthesized by conjugation with l-phenylalanine by conventional coupling method using N, N-dicyclohexylcarbodiimide and ACaa was characterized by melting point, TLC, photomicrograph, UV, FT-IR, FT-NMR, MS-FAB, XRD and DSC. As a part of product development study ACaa was subjected to studies like In-vivo in albino rats and in-vitro like ACaa reversion to AC (Aceclofenac) in aqueous buffers of pH 1.21, 2.38. 3.10, 6.22 and 7.41, at a constant concentration (0.05M), ionic strength (micro = 0.5) and at a temperature of 37 degrees C +/- 0.5 degrees C, ACaa showed negligible reversion (2.15 %) up to 24 hrs study at acidic pH thus suggesting stability in acidic environment of stomach, the rate of reversion increased as pH of medium increased. pH- partition profile, pH- solubility profile and micromeritic studies were also carried out in comparison to pure drug. The solubility and lipophilicity of ACaa exhibited higher values at all pH range when compared to AC. The micromeritic properties also evaluated in terms of particle shape and size, IQCS and kurtosis. Resulting IQCS value approached zero thus suggesting reducing in the degree of skewness.

Mobile colloid generation induced by a cementitious plume: mineral surface-charge controls on mobilization.

PubMed

Li, Dien; Kaplan, Daniel I; Roberts, Kimberly A; Seaman, John C

2012-03-06

Cementitious materials are increasingly used as engineered barriers and waste forms for radiological waste disposal. Yet their potential effect on mobile colloid generation is not well-known, especially as it may influence colloid-facilitated contaminant transport. Whereas previous papers have studied the introduction of cement colloids into sediments, this study examined the influence of cement leachate chemistry on the mobilization of colloids from a subsurface sediment collected from the Savannah River Site, USA. A sharp mobile colloid plume formed with the introduction of a cement leachate simulant. Colloid concentrations decreased to background concentrations even though the aqueous chemical conditions (pH and ionic strength) remained unchanged. Mobile colloids were mainly goethite and to a lesser extent kaolinite. The released colloids had negative surface charges and the mean particle sizes ranged primarily from 200 to 470 nm. Inherent mineralogical electrostatic forces appeared to be the controlling colloid removal mechanism in this system. In the background pH of ~6.0, goethite had a positive surface charge, whereas quartz (the dominant mineral in the immobile sediment) and kaolinite had negative surface charges. Goethite acted as a cementing agent, holding kaolinite and itself onto the quartz surfaces due to the electrostatic attraction. Once the pH of the system was elevated, as in the cementitious high pH plume front, the goethite reversed to a negative charge, along with quartz and kaolinite, then goethite and kaolinite colloids were mobilized and a sharp spike in turbidity was observed. Simulating conditions away from the cementitious source, essentially no colloids were mobilized at 1:1000 dilution of the cement leachate or when the leachate pH was ≤ 8. Extreme alkaline pH environments of cementitious leachate may change mineral surface charges, temporarily promoting the formation of mobile colloids.

Specialist gelator for ionic liquids.

PubMed

Hanabusa, Kenji; Fukui, Hiroaki; Suzuki, Masahiro; Shirai, Hirofusa

2005-11-08

Cyclo(l-beta-3,7-dimethyloctylasparaginyl-L-phenylalanyl) (1) and cyclo(L-beta-2-ethylhexylasparaginyl-L-phenylalanyl) (2), prepared from L-asparaginyl-L-phenylalanine methyl ester, have been found to be specialist gelators for ionic liquids. They can gel a wide variety of ionic liquids, including imizazolium, pyridinium, pyrazolidinium, piperidinium, morpholinium, and ammonium salts. The mean minimum gel concentrations (MGCs) necessary to make gels at 25 degrees C were determined for ionic liquids. The gel strength increased at a rate nearly proportional to the concentration of added gelator. The strength of the transparent gel of 1-butylpyridinium tetrafluoroborate ([C(4)py]BF(4)), prepared at a concentration of 60 g L(-1) (gelator 1/[C(4)py]BF(4)), was ca. 1500 g cm(-2). FT-IR spectroscopy indicated that a driving force for gelation was intermolecular hydrogen bonding between amides and that the phase transition from gel to liquid upon heating was brought about by the collapse of hydrogen bonding. The gels formed from ionic liquids were very thermally stable; no melting occurs up to 140 degrees C when the gels were prepared at a concentration of 70 g L(-1) (gelator/ionic liquid). The ionic conductivities of the gels were nearly the same as those of pure ionic liquids. The gelator had electrochemical stability and a wide electrochemical window. When the gels were prepared from ionic liquids containing propylene carbonate, the ionic conductivities of the resulting gels increased to levels rather higher than those of pure ionic liquids. The gelators also gelled ionic liquids containing supporting electrolytes.

Ionic Size Effects: Generalized Boltzmann Distributions, Counterion Stratification, and Modified Debye Length.

PubMed

Liu, Bo; Liu, Pei; Xu, Zhenli; Zhou, Shenggao

2013-10-01

Near a charged surface, counterions of different valences and sizes cluster; and their concentration profiles stratify. At a distance from such a surface larger than the Debye length, the electric field is screened by counterions. Recent studies by a variational mean-field approach that includes ionic size effects and by Monte Carlo simulations both suggest that the counterion stratification is determined by the ionic valence-to-volume ratios. Central in the mean-field approach is a free-energy functional of ionic concentrations in which the ionic size effects are included through the entropic effect of solvent molecules. The corresponding equilibrium conditions define the generalized Boltzmann distributions relating the ionic concentrations to the electrostatic potential. This paper presents a detailed analysis and numerical calculations of such a free-energy functional to understand the dependence of the ionic charge density on the electrostatic potential through the generalized Boltzmann distributions, the role of ionic valence-to-volume ratios in the counterion stratification, and the modification of Debye length due to the effect of ionic sizes.

Ionic Size Effects: Generalized Boltzmann Distributions, Counterion Stratification, and Modified Debye Length

PubMed Central

Liu, Bo; Liu, Pei; Xu, Zhenli; Zhou, Shenggao

2013-01-01

Near a charged surface, counterions of different valences and sizes cluster; and their concentration profiles stratify. At a distance from such a surface larger than the Debye length, the electric field is screened by counterions. Recent studies by a variational mean-field approach that includes ionic size effects and by Monte Carlo simulations both suggest that the counterion stratification is determined by the ionic valence-to-volume ratios. Central in the mean-field approach is a free-energy functional of ionic concentrations in which the ionic size effects are included through the entropic effect of solvent molecules. The corresponding equilibrium conditions define the generalized Boltzmann distributions relating the ionic concentrations to the electrostatic potential. This paper presents a detailed analysis and numerical calculations of such a free-energy functional to understand the dependence of the ionic charge density on the electrostatic potential through the generalized Boltzmann distributions, the role of ionic valence-to-volume ratios in the counterion stratification, and the modification of Debye length due to the effect of ionic sizes. PMID:24465094

Pyridinium ionic liquid-based liquid-solid extraction of inorganic and organic iodine from Laminaria.

PubMed

Peng, Li-Qing; Yu, Wen-Yan; Xu, Jing-Jing; Cao, Jun

2018-01-15

A simple, green and effective extraction method, namely, pyridinium ionic liquid- (IL) based liquid-solid extraction (LSE), was first designed to extract the main inorganic and organic iodine compounds (I - , monoiodo-tyrosine (MIT) and diiodo-tyrosine (DIT)). The optimal extraction conditions were as follows: ultrasonic intensity 100W, IL ([EPy]Br) concentration 200mM, extraction time 30min, liquid/solid ratio 10mL/g, and pH value 6.5. The morphologies of Laminaria were studied by scanning electron microscopy and transmission electron microscopy. The recovery values of I - , MIT and DIT from Laminaria were in the range of 88% to 94%, and limits of detection were in the range of 59.40 to 283.6ng/g. The proposed method was applied to the extraction and determination of iodine compounds in three Laminaria. The results showed that IL-based LSE could be a promising method for rapid extraction of bioactive iodine from complex food matrices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory

NASA Astrophysics Data System (ADS)

Elzbieciak-Wodka, Magdalena; Popescu, Mihail N.; Ruiz-Cabello, F. Javier Montes; Trefalt, Gregor; Maroni, Plinio; Borkovec, Michal

2014-03-01

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10-21 J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

Measurements of dispersion forces between colloidal latex particles with the atomic force microscope and comparison with Lifshitz theory.

PubMed

Elzbieciak-Wodka, Magdalena; Popescu, Mihail N; Montes Ruiz-Cabello, F Javier; Trefalt, Gregor; Maroni, Plinio; Borkovec, Michal

2014-03-14

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10(-21) J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces.

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.

Transfer Behavior of the Weakly Acidic BCS Class II Drug Valsartan from the Stomach to the Small Intestine During Fasted and Fed States.

PubMed

Hamed, Rania; Alnadi, Sabreen Hasan

2018-05-07

The objective of this study was to investigate the transfer behavior of the weakly acidic BCS class II drug valsartan from the stomach to the small intestine during fasted and fed states. An in vitro transfer model previously introduced by Kostewicz et al. (J Pharm Pharmacol 56(1):43-51, 2004) based on a syringe pump and a USP paddle apparatus was used to determine the concentration profiles of valsartan in the small intestine. Donor phases of simulated gastric fluid during fasted (FaSSGF) and fed (FeSSGF) states were used to predisperse Diovan® tablets (160 mg valsartan). The initial concentrations of valsartan in FaSSGF and FeSSGF were 6.2 and 91.8%, respectively. Valsartan dispersions were then transferred to acceptor phases that simulate intestinal fluid and cover the physiological properties (pH, buffer capacity, and ionic strength) of the gastrointestinal fluid at a flow rate of 2 mL/min. The pH measurements were reported at time intervals corresponded to those of the transfer experiments to investigate the effect of percent dissolved of valsartan in the donor phase on lowering the pH of the acceptor phases. The f2 similarity test was used to compare the concentration profiles in the acceptor phases. In fasted state, the concentration of valsartan in the acceptor phases ranged between 33.1 and 89.4% after 240 min. Whereas in fed state, valsartan was fully dissolved in all acceptor phases within a range of 94.5-104.9% after 240 min. Therefore, the transfer model provides a useful screen for the concentrations of valsartan in the small intestine during fasted and fed states.

Effects of ionic strength, temperature, and pH on degradation of selected antibiotics

USGS Publications Warehouse

Loftin, K.A.; Adams, C.D.; Meyer, M.T.; Surampalli, R.

2008-01-01

Aqueous degradation rates, which include hydrolysis and epimerization, for chlorretracycline (CTC), oxytetracycline (OTC), tetracycline (TET), lincomycin (LNC), sulfachlorpyridazine (SCP), sulfadimethoxine (SDM), sulfathiazole (STZ), trimethoprim (TRM), and tylosin A (TYL) were studied as a function of ionic strength (0.0015, 0.050, or 0.084 mg/L as Na2HPO4), temperature (7, 22, and 35??C), and pH (2, 5, 7, 9, and 11). Multiple linear regression revealed that ionic strength did not significantly affect (?? = 0.05) degradation rates for all compounds, but temperature and pH affected rates for CTC, OTC, and TET significandy (?? = 0.05). Degradation also was observed for TYL at pH 2 and 11. No significant degradation was observed for LNC, SCR SDM, STZ, TRM, and TYL (pH 5, 7, and 9) under study conditions. Pseudo first-order rate constants, half-lives, and Arrhenius coefficients were calculated where appropriate. In general, hydrolysis rates for CTC, OTC, and TET increased as pH and temperature increased following Arrhenius relationships. Known degradation products were used to confirm that degradation had occurred, but these products were not quantified. Half-lives ranged from less than 6 h up to 9.7 wk for the tetracyclines and for TYL (pH 2 and 11), but no degradation of LIN, the sulfonamides, or TRM was observed during the study period. These results indicate that tetracyclines and TYL at pH 2 and 11 are prone to pH-mediated transformation and hydrolysis in some cases, but not the sulfonamides, LIN nor TRM are inclined to degrade under study conditions. This indicates that with the exception of CTC OTC, and TET, pH-mediated reactions such as hydrolysis and epimerization are not likely removal mechanisms in surface water, anaerobic swine lagoons, wastewater, and ground water. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Fermentation pH influences the physiological-state dynamics of Lactobacillus bulgaricus CFL1 during pH-controlled culture.

PubMed

Rault, Aline; Bouix, Marielle; Béal, Catherine

2009-07-01

This study aims at better understanding the effects of fermentation pH and harvesting time on Lactobacillus bulgaricus CFL1 cellular state in order to improve knowledge of the dynamics of the physiological state and to better manage starter production. The Cinac system and multiparametric flow cytometry were used to characterize and compare the progress of the physiological events that occurred during pH 6 and pH 5 controlled cultures. Acidification activity, membrane damage, enzymatic activity, cellular depolarization, intracellular pH, and pH gradient were determined and compared during growing conditions. Strong differences in the time course of viability, membrane integrity, and acidification activity were displayed between pH 6 and pH 5 cultures. As a main result, the pH 5 control during fermentation allowed the cells to maintain a more robust physiological state, with high viability and stable acidification activity throughout growth, in opposition to a viability decrease and fluctuation of activity at pH 6. This result was mainly explained by differences in lactate concentration in the culture medium and in pH gradient value. The elevated content of the ionic lactate form at high pH values damaged membrane integrity that led to a viability decrease. In contrast, the high pH gradient observed throughout pH 5 cultures was associated with an increased energetic level that helped the cells maintain their physiological state. Such results may benefit industrial starter producers and fermented-product manufacturers by allowing them to better control the quality of their starters, before freezing or before using them for food fermentation.

Sorption and desorption studies of a reactive azo dye on effective disposal of redundant material.

PubMed

Çelekli, Abuzer; Bozkurt, Hüseyin

2013-07-01

The effective disposal of redundant elephant dung (ED) is important for environmental protection and utilization of resource. The aim of this study was to remove a toxic-azo dye, Reactive Red (RR) 120, using this relatively cheap material as a new adsorbent. The FTIR-ATR spectra of ED powders before and after the sorption of RR 120 and zero point charge (pHzpc) of ED were determined. The sorption capacity of ED for removing of RR 120 were carried out as functions of particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. Sorption isotherm, kinetic, activation energy, thermodynamic, and desorption parameters of RR 120 on ED were studied. The sorption process was found to be dependent on particle size, adsorbent dose, pH, temperature, ionic strength, initial dye concentration, and contact time. FTIR-ATR spectroscopy indicated that amine and amide groups have significant role on the sorption of RR 120 on ED. The pHzpc of ED was found to be 7.3. Sorption kinetic of RR 120 on ED was well described by sigmoidal Logistic model. The Langmuir isotherm was well fitted to the equilibrium data. The maximum sorption capacity was 95.71 mg g(-1). The sorption of RR 120 on ED was mainly physical and exothermic according to results of D-R isotherm, Arrhenius equation, thermodynamic, and desorption studies. The thermodynamic parameters showed that this process was feasible and spontaneous. This study showed that ED as a low-cost adsorbent had a great potential for the removal of RR 120 as an alternative eco-friendly process.

New perspective on glycoside hydrolase binding to lignin from pretreated corn stover

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

Yarbrough, John M.; Mittal, Ashutosh; Mansfield, Elisabeth

Background: Non-specific binding of cellulases to lignin has been implicated as a major factor in the loss of cellulase activity during biomass conversion to sugars. It is believed that this binding may strongly impact process economics through loss of enzyme activities during hydrolysis and enzyme recycling scenarios. The current model suggests glycoside hydrolase activities are lost though non-specific/non-productive binding of carbohydrate-binding domains to lignin, limiting catalytic site access to the carbohydrate components of the cell wall. Results: In this study, we compared component enzyme affinities of a commercial Trichoderma reesei cellulase formulation, Cellic CTec2, towards extracted corn stover lignin usingmore » sodium dodecyl sulfate-polyacrylamide gel electrophoresis and p-nitrophenyl substrate activities to monitor component binding, activity loss, and total protein binding. Protein binding was strongly affected by pH and ionic strength. β-D-glucosidases and xylanases, which do not have carbohydrate-binding modules (CBMs) and are basic proteins, demonstrated the strongest binding at low ionic strength, suggesting that CBMs are not the dominant factor in enzyme adsorption to lignin. Despite strong adsorption to insoluble lignin, β-D-glucosidase and xylanase activities remained high, with process yields decreasing only 4–15 % depending on lignin concentration. Conclusion: We propose that specific enzyme adsorption to lignin from a mixture of biomass-hydrolyzing enzymes is a competitive affinity where β-D-glucosidases and xylanases can displace CBM interactions with lignin. Process parameters, such as temperature, pH, and salt concentration influence the individual enzymes’ affinity for lignin, and both hydrophobic and electrostatic interactions are responsible for this binding phenomenon. Moreover, our results suggest that concern regarding loss of critical cell wall degrading enzymes to lignin adsorption may be unwarranted when complex enzyme mixtures are used to digest biomass.« less

The copper complexation ability of a synthetic humic-like acid formed by an abiotic humification process and the effect of experimental factors on its copper complexation ability.

PubMed

Yang, Ting; Hodson, Mark E

2018-03-26

Humic acids have an important impact on the distribution, toxicity, and bioavailability of hazardous metals in the environment. In this study, a synthetic humic-like acid (SHLA) was prepared by an abiotic humification process using catechol and glycine as humic precursors and a MnO 2 catalyst. The effect of physico-chemical conditions (ionic strength from 0.01 to 0.5 M NaNO 3 , pH from 4 to 8, temperature from 25 to 45 °C, and humic acid concentration from 5 to 100 mg/L) on the complexation ability of SHLA for Cu 2+ were investigated. A commercial humic acid (CHA, CAS: 1415-93-6) from Sigma-Aldrich was also studied for comparison. The results showed that for pH 4 to 8, the conditional stability constants (log K) of SHLA and CHA were in the range 5.63-8.62 and 4.87-6.23, respectively, and complexation capacities (CC) were 1.34-2.61 and 1.42-2.31 mmol/g, respectively. The Cu complexation ability of SHLA was higher than that of the CHA due to its higher number of acidic functional groups (SHLA 19.19 mmol/g; CHA 3.87 mmol/g), extent of humification and aromaticity (AL/AR: 0.333 (SHLA); 1.554 (CHA)), and O-alkyl functional groups (SHLA 15.56%; CHA 3.45%). The log K and complexation efficiency (fraction of metal bound to SHLA) of SHLA were higher at higher pH, lower ionic strength, higher temperature, and higher SHLA concentration. Overall, SHLA was a good and promising complexation agent for copper in both soil washing of copper contaminated soil and the treatment of copper-containing wastewater.

New perspective on glycoside hydrolase binding to lignin from pretreated corn stover

DOE PAGES

Yarbrough, John M.; Mittal, Ashutosh; Mansfield, Elisabeth; ...

2015-12-18

Background: Non-specific binding of cellulases to lignin has been implicated as a major factor in the loss of cellulase activity during biomass conversion to sugars. It is believed that this binding may strongly impact process economics through loss of enzyme activities during hydrolysis and enzyme recycling scenarios. The current model suggests glycoside hydrolase activities are lost though non-specific/non-productive binding of carbohydrate-binding domains to lignin, limiting catalytic site access to the carbohydrate components of the cell wall. Results: In this study, we compared component enzyme affinities of a commercial Trichoderma reesei cellulase formulation, Cellic CTec2, towards extracted corn stover lignin usingmore » sodium dodecyl sulfate-polyacrylamide gel electrophoresis and p-nitrophenyl substrate activities to monitor component binding, activity loss, and total protein binding. Protein binding was strongly affected by pH and ionic strength. β-D-glucosidases and xylanases, which do not have carbohydrate-binding modules (CBMs) and are basic proteins, demonstrated the strongest binding at low ionic strength, suggesting that CBMs are not the dominant factor in enzyme adsorption to lignin. Despite strong adsorption to insoluble lignin, β-D-glucosidase and xylanase activities remained high, with process yields decreasing only 4–15 % depending on lignin concentration. Conclusion: We propose that specific enzyme adsorption to lignin from a mixture of biomass-hydrolyzing enzymes is a competitive affinity where β-D-glucosidases and xylanases can displace CBM interactions with lignin. Process parameters, such as temperature, pH, and salt concentration influence the individual enzymes’ affinity for lignin, and both hydrophobic and electrostatic interactions are responsible for this binding phenomenon. Moreover, our results suggest that concern regarding loss of critical cell wall degrading enzymes to lignin adsorption may be unwarranted when complex enzyme mixtures are used to digest biomass.« less

Aggregation work at polydisperse micellization: ideal solution and "dressed micelle" models comparing to molecular dynamics simulations.

PubMed

Burov, S V; Shchekin, A K

2010-12-28

General thermodynamic relations for the work of polydisperse micelle formation in the model of ideal solution of molecular aggregates in nonionic surfactant solution and the model of "dressed micelles" in ionic solution have been considered. In particular, the dependence of the aggregation work on the total concentration of nonionic surfactant has been analyzed. The analogous dependence for the work of formation of ionic aggregates has been examined with regard to existence of two variables of a state of an ionic aggregate, the aggregation numbers of surface active ions and counterions. To verify the thermodynamic models, the molecular dynamics simulations of micellization in nonionic and ionic surfactant solutions at two total surfactant concentrations have been performed. It was shown that for nonionic surfactants, even at relatively high total surfactant concentrations, the shape and behavior of the work of polydisperse micelle formation found within the model of the ideal solution at different total surfactant concentrations agrees fairly well with the numerical experiment. For ionic surfactant solutions, the numerical results indicate a strong screening of ionic aggregates by the bound counterions. This fact as well as independence of the coefficient in the law of mass action for ionic aggregates on total surfactant concentration and predictable behavior of the "waterfall" lines of surfaces of the aggregation work upholds the model of "dressed" ionic aggregates.

Characterization of Nano-scale Aluminum Oxide Transport through Porous Media

NASA Astrophysics Data System (ADS)

Norwood, S.; Reynolds, M.; Miao, Z.; Brusseau, M. L.; Johnson, G. R.

2011-12-01

Colloidal material (including that in the nanoparticle size range) is naturally present in most subsurface environments. Mobilization of these colloidal materials via particle disaggregation may occur through abrupt changes in flow rate and/or via chemical perturbations, such as rapid changes in ionic strength or solution pH. While concentrations of natural colloidal materials in the subsurface are typically small, those concentrations may be greatly increased at contaminated sites such as following the application of metal oxides for groundwater remediation efforts. Additionally, while land application of biosolids has become common practice in the United States as an alternative to industrial fertilizers, biosolids have been shown to contain a significant fraction of organic and inorganic nano-scale colloidal materials such as oxides of iron, titanium, and aluminum. Given their reactivity and small size, there are many questions concerning the potential migration of nano-scale colloidal materials through the soil column and their potential participation in the facilitated transport of contaminants, such as heavy metals and emerging pollutants. The purpose of this study was to investigate the transport behavior of aluminum oxide (Al2O3) nanoparticles through porous media. The impacts of pH, ionic strength, pore-water velocity (i.e., residence time), and aqueous-phase concentration on transport was investigated. All experiments were conducted with large injection pulses to fully characterize the impact of long-term retention and transport behavior relevant for natural systems wherein multiple retention processes may be operative. The results indicate that the observed nonideal transport behavior of the nano-scale colloids is influenced by multiple retention mechanisms/processes. Given the ubiquitous nature of these nano-scale colloids in the environment, a clear understanding of their transport and fate is necessary in further resolving the potential for facilitated transport of toxins through the subsurface and into our surface and groundwater bodies.

Bone Marrow Stem Cells in Response to Intervertebral Disc-Like Matrix Acidity and Oxygen Concentration: Implications for Cell-based Regenerative Therapy.

PubMed

Naqvi, Syeda M; Buckley, Conor T

2016-05-01

In vitro culture of porcine bone marrow stem cells (BMSCs) in varying pH microenvironments in a three-dimensional hydrogel system. To characterize the response of BMSCs to varying pH environments (blood [pH 7.4], healthy intervertebral disc (IVD) (pH 7.1), mildly degenerated IVD (pH 6.8), and severely degenerated IVD (pH 6.5) in three-dimensional culture under normoxic (20%) and hypoxic (5%) conditions. The IVD is an avascular organ relying on diffusion of essential nutrients through the cartilaginous endplates (CEPs) thereby creating a challenging microenvironment. Within a degenerated IVD, oxygen and glucose concentrations decrease further (<5% oxygen, <5 mmol/L glucose) and matrix acidity (

Thermodynamics of aggregate formation between a non-ionic polymer and ionic surfactants: An isothermal titration calorimetric study.

PubMed

Patel, Salin Gupta; Bummer, Paul M

2017-01-10

This report examines the energetics of aggregate formation between hydroxypropyl methylcellulose (HPMC) and model ionic surfactants including sodium dodecyl sulfate (SDS) at pharmaceutically relevant concentrations using the isothermal titration calorimetry (ITC) technique and a novel treatment of calorimetric data that accounts for the various species formed. The influence of molecular weight of HPMC, temperature and ionic strength of solution on the aggregate formation process was explored. The interaction between SDS and HPMC was determined to be an endothermic process and initiated at a critical aggregation concentration (CAC). The SDS-HPMC interactions were observed to be cooperative in nature and dependent on temperature and ionic strength of the solution. Molecular weight of HPMC significantly shifted the interaction parameters between HPMC and SDS such that at the highest molecular weight (HPMC K-100M;>240kDa), although the general shape of the titration curve (enthalpogram) was observed to remain similar, the critical concentration parameters (CAC, polymer saturation concentration (C sat ) and critical micelle concentration (CMC)) were significantly altered and shifted to lower concentrations of SDS. Ionic strength was also observed to influence the critical concentration parameters for the SDS-HPMC aggregation and decreased to lower SDS concentrations with increasing ionic strength for both anionic and cationic surfactant-HPMC systems. From these data, other thermodynamic parameters of aggregation such as ΔH agg ° , ΔG agg ° , H agg ° , ΔS agg ° , and ΔC p were calculated and utilized to postulate the hydrophobic nature of SDS-HPMC aggregate formation. The type of ionic surfactant head group (anionic vs. cationic i.e., dodecyltrimethylammonium bromide (DTAB)) was found to influence the strength of HPMC-surfactant interactions wherein a distinct CAC signifying the strength of HPMC-DTAB interactions was not observed. The interpretation of the microcalorimetric data at different temperatures and ionic strengths while varying properties of polymer and surfactant was a very effective tool in investigating the nature and energetics of HPMC and ionic surfactant interactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Ionic liquid ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of the aqueous phase for preconcentration of heavy metals ions prior to determination by LC-UV.

PubMed

Werner, Justyna

2018-05-15

Ionic liquid ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of the aqueous phase was used for preconcentration of Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ , Pb 2+ in natural water samples prior to liquid chromatography with UV detection. In the proposed method, the ammonium pyrrolidinedithiocarbamate was used as a complexing agent and the phosphonium ionic liquid trihexyl(tetradecyl)phosphonium bis[(2,4,4-trimethyl)pentyl]phosphinate (Cyphos IL 104) was used as an extractant. Ultrasound energy was used to disperse the extractant in the aqueous phase. After microextraction, the ionic liquid and aqueous phases were separated by centrifugation. Then the aqueous phase was frozen and the lighter than water ionic liquid phase containing metal ions complexes with pyrrolidinedithiocarbamate was separated and dissolved in a small volume of methanol prior to injection into the liquid chromatograph. Several parameters including the volume of extractant, the pH of the sample, the concentration of complexing agent, the time of ultrasound energy treatment, the time and speed of centrifugation and the effect of ionic strength were optimized. Under the optimized conditions (10 µL of Cyphos IL 104, pH = 5, 0.3% w/v ammonium pyrrolidinedithiocarbamate, 60 s of ultrasound use, 5 min/5000 rpm (2516×g) of centrifugation, 2.0 mg of NaCl), preconcentration factors were 211, 210, 209, 207 and 211 for Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ and Pb 2+ respectively. Linearity was observed in the ranges 0.2-75.0 µg L -1 for Pb 2+ , Cd 2+ , Co 2+ and 0.5-100.0 µg L -1 for Cu 2+ , Ni 2+ . The limits of detection were 0.03 µg L -1 for Ni 2+ , 0.03 µg L -1 for Co 2+ , 0.03 µg L -1 for Cd 2+ , 0.02 µg L -1 for Cu 2+ , 0.02 µg L -1 for Pb 2+ , respectively. The accuracy of this method was evaluated by preconcentration and determination of Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ , Pb 2+ in certified reference materials (TMRAIN-04 and NIST 1643e) with the recovery values in the range of 97-102%. The presented method has been successfully applied for the determination of analytes in natural water samples (river and lake waters). Copyright © 2018 Elsevier B.V. All rights reserved.

Adsorption Properties of Low-Cost Biomaterial Derived from Prunus amygdalus L. for Dye Removal from Water

PubMed Central

Deniz, Fatih

2013-01-01

The capability of Prunus amygdalus L. (almond) shell for dye removal from aqueous solutions was investigated and methyl orange was used as a model compound. The effects of operational parameters including pH, ionic strength, adsorbent concentration and mesh size, dye concentration, contact time, and temperature on the removal of dye were evaluated. The adsorption kinetics conformed to the pseudo-second-order kinetic model. The equilibrium data pointed out excellent fit to the Langmuir isotherm model with maximum monolayer adsorption capacity of 41.34 mg g−1 at 293 K. Thermodynamic analysis proved a spontaneous, favorable, and exothermic process. It can be concluded that almond shell might be a potential low-cost adsorbent for methyl orange removal from aqueous media. PMID:23935442

eQuilibrator--the biochemical thermodynamics calculator.

PubMed

Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

2012-01-01

The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like 'how much Gibbs energy is released by ATP hydrolysis at pH 5?' are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use.

Removal of copper(II) from some environmental samples by sorptive-flotation using powdered marble wastes as sorbents and oleic acid as surfactant.

PubMed

Ghazy, S E; Samra, S E; Mahdy, A F M; El-Morsy, S M

2004-11-01

A simple and economic experimental sorptive -flotation procedure is presented for the removal of copper(II) species from aqueous solutions. It is based on using powdered marble wastes (PMW), which are widespread and inexpensive and may represent an environmental problem, as the effective inorganic sorbent and oleic (HOL) as the surfactant. The main parameters (i.e. initial solution pH, sorbent, surfactant and copper concentrations, stirring times, ionic strength, temperature and the presence of foreign ions) influencing the flotation of PMW and /or Cu(II) were examined. Nearly, 100% of PMW and Cu(II) were removed from aqueous solutions at pH7 after stirring for 10 min and at room temperature, (approximately 25 degrees C). The procedure was successfully applied to recover Cu(II) spiked to some natural water samples. A mechanism for sorption and flotation is suggested.

An Investigation of the Adsorption Characteristics of 5'ATP and 5'AMP onto the Surface of Caso4 x 2H2O

NASA Technical Reports Server (NTRS)

Calderon, J.; Sweeney, M. A.

1984-01-01

A model has been proposed in which solid surfaces can act as a site for cataletic activity of condensation reactions for certain biomolecules. From this model, the adsorption characteristics of 5'ATP and 5'AMP onto the surface of CaSO4.2H2O was chosen for study. It has been proven that 5'ATP and 5'AMP do adsorb onto the surface of CaSO4. Studies were then made to determine the dependence of absorption versus time, concentration, ionic strength and pH. It was found that the adsorption of the nucleotides is highly pH dependent, primarily determined by the phosphate acid groups of the nucleic acid molecule. From this investigation, the data obtained is discussed in relation to the model for the prebiotic earth.

An investigation of the adsorption characteristics of 5 prime ATP and 5 prime AMP onto the surface of CaSO sub 4 x 2H sub 2 O

NASA Technical Reports Server (NTRS)

Calderon, J.; Sweeney, M. A.

1986-01-01

A model has been proposed (Lahev and Chans, 1982) in which solid surfaces can act as a site for catalytic activity of condensation reactions for certain biomolecules. From this model, the adsorption characteristics of 5'ATP and 5'AMP onto the surface of CaSO4 2H2O was chosen for study. It has been proven that 5'ATP and 5'AMP do adsorb onto the surface of CaSO4. Studies were then made to determine the dependence of adsorption versus time, concentration, ionic strength and pH. It was found that the adsorption of the nucleotides is highly pH dependent, primarily determined by the phosphate acid groups of the nucleic acid molecule. From this investigation, the data obtained are discussed in relation to the model for the prebiotic earth.

eQuilibrator—the biochemical thermodynamics calculator

PubMed Central

Flamholz, Avi; Noor, Elad; Bar-Even, Arren; Milo, Ron

2012-01-01

The laws of thermodynamics constrain the action of biochemical systems. However, thermodynamic data on biochemical compounds can be difficult to find and is cumbersome to perform calculations with manually. Even simple thermodynamic questions like ‘how much Gibbs energy is released by ATP hydrolysis at pH 5?’ are complicated excessively by the search for accurate data. To address this problem, eQuilibrator couples a comprehensive and accurate database of thermodynamic properties of biochemical compounds and reactions with a simple and powerful online search and calculation interface. The web interface to eQuilibrator (http://equilibrator.weizmann.ac.il) enables easy calculation of Gibbs energies of compounds and reactions given arbitrary pH, ionic strength and metabolite concentrations. The eQuilibrator code is open-source and all thermodynamic source data are freely downloadable in standard formats. Here we describe the database characteristics and implementation and demonstrate its use. PMID:22064852

Investigation of Zn2+ and Cd2+ Adsorption Performanceby Different Weathering Basalts

NASA Astrophysics Data System (ADS)

Xue, Q.; Shuo, Q.; Chen, H.

2016-12-01

Geological barriers play an important role in preventing pollution of groundwater. Basalts are common geological media; however, there have not been any studies that report the effect of basalt type on the metal ion adsorption performance. In this study, we explored the metal ion (Zn2+ and Cd2+) adsorption ability of two kinds of weathering basalts: the origin weathering basalt (WB) and the eluvial deposit (ED), both of which were derived from same basaltic formation. Characteristics of the sediments were examined by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Barrett-Joyner-Halenda (BJH) measurement and the rapid potentiometric titration (RPT) method. Batch experiments were performed to evaluate the Zn2+ and Cd2+ adsorption performance of WB and ED and how adsorption was affected by contact time, initial metal ion concentration, pH and ionic strength. Despite WB and ED having similar chemical compositions, WB exhibited better adsorption than ED likely due to the fact that WB was rougher and had more small-sized spherical structures and stronger electrostatic forces. The adsorption process fit the Freundlich isotherm model well. The adsorption efficiency decreased with a decrease of pH (from 4 to 2) and with increasing ionic strength. These results suggest that a geological barrier composed of WB media might be able to effectively sequester metallic contaminants to prevent them from reaching groundwater.

Label-free specific detection of femtomolar cardiac troponin using an integrated nanoslit array fluidic diode.

PubMed

Liu, Yifan; Yobas, Levent

2014-12-10

We demonstrate here for the first time the utility of an integrated nanofluidic diode for detecting and quantifying physiologically relevant macromolecules. Troponin T, a key human cardiac protein biomarker, was selectively and rapidly detected free of labels for concentrations down to 10 fg/mL (∼ 0.3 fM) in buffer as well as 10 pg/mL (∼ 300 fM) in untreated human serum. This ultrasensitive detection arises from monolithic integration of a unique nanofluidic diode structure that is highly robust and amenable to site-specific surface modification. The structure features a planar nanoslit array where each nanoslit is defined at a nominal width of 70 nm over a micrometer-scale silicon trench without the use of high-resolution patterning techniques. Through vapor deposition, a glass layer is placed at a nonuniform thickness, tapering the trench profile upward and contributing to the triangular nanoslit structure. This asymmetric profile is essential for ionic current rectification noted here at various pH values, ionic strengths, and captured target species, which modulate the surface-charge density within the sensitive region of the nanoslit. The nanoslit, unlike nanopores, offers only 1D confinement, which appears to be adequate for reasonable rectification. The measurements are found in quantitative agreement with the diode simulations for the first time based on a pH- and salt-dependent surface-charge model.

Silica-gel Particles Loaded with an Ionic Liquid for Separation of Zr(IV) Prior to Its Determination by ICP-OES.

PubMed

Marwani, Hadi M; Alsafrani, Amjad E; Asiri, Abdullah M; Rahman, Mohammed M

2016-06-29

A new ionic liquid loaded silica gel amine (SG-APTMS-N,N-EPANTf₂) was developed, as an adsorptive material, for selective adsorption and determination of zirconium, Zr(IV), without the need for a chelating intermediate. Based on a selectivity study, the SG-APTMS-N,N-EPANTf₂ phase showed a perfect selectivity towards Zr(IV) at pH 4 as compared to other metallic ions, including gold [Au(III)], copper [Cu(II)], cobalt [Co(II)], chromium [Cr(III)], lead [Pb(II)], selenium [Se(IV)] and mercury [Hg(II)] ions. The influence of pH, Zr(IV) concentration, contact time and interfering ions on SG-APTMS-N,N-EPANTf₂ uptake for Zr(IV) was evaluated. The presence of incorporated donor atoms in newly synthesized SG-APTMS-N,N-EPANTf₂ phase played a significant role in enhancing its uptake capacity of Zr(IV) by 78.64% in contrast to silica gel (activated). The equilibrium and kinetic information of Zr(IV) adsorption onto SG-APTMS-N,N-EPANTf₂ were best expressed by Langmuir and pseudo second-order kinetic models, respectively. General co-existing cations did not interfere with the extraction and detection of Zr(IV). Finally, the analytical efficiency of the newly developed method was also confirmed by implementing it for the determination of Zr(IV) in several water samples.

Textile dye removal from aqueous solutions by malt bagasse: Isotherm, kinetic and thermodynamic studies.

PubMed

Fontana, Klaiani B; Chaves, Eduardo S; Sanchez, Jefferson D S; Watanabe, Erica R L R; Pietrobelli, Juliana M T A; Lenzi, Giane G

2016-02-01

The biosorption of orange solimax TGL 182% (OS-TGL) textile dye onto new and low cost biossorbent (malt bagasse) in aqueous solutions was investigated. The malt bagasse was characterized by Fourier transform infrared spectroscopy and specific surface area (BET method).Batch biosorption experiments were conducted in order to determine the following parameters: particles size, pH, agitation speed, temperature, contact time, biomass dosage, influence of the ionic strength and, finally, the influence of other textile dye on the OS-TGL biosorption. The optimum conditions for OS-TGL removal were obtained at pH 1.5, agitation speed of 150rpm, contact time of 180min and biomass dosage 2, 8gL(-1). The results show that the kinetics of biosorption followed a pseudo-second-order model and by increasing the temperature from 293 up to 313K, the biosorption capacity was improved. The Langmuir model showed better fit and the estimated biosorption capacity was 23.2mgg(-1). The negative values of Gibbs free energy, ΔG°, and positive value of enthalpy, ΔH°, confirm the spontaneous nature and endothermic character of the biosorption process. The results of the ionic strength effect indicated that the biosorption process under study had a strong tolerance in high salt concentrations. The removal capacity (>95%) was not affected with the presence of other textile dyes. Copyright © 2015 Elsevier Inc. All rights reserved.

The effects of environmental conditions on the enrichment of antibiotics on microplastics in simulated natural water column.

PubMed

Shen, Xian-Cheng; Li, De-Chang; Sima, Xiao-Feng; Cheng, Hui-Yuan; Jiang, Hong

2018-06-20

Concerns regarding the release of microplastics (MPs) into the environment led us to explore the relationship between the different environmental factors and physicochemical properties of MPs, as well as the change of interaction between MPs and organic pollutants. In this study, the effects of environmental factors (ageing conditions), such as pH, temperature, ionic strength, ageing time, and humic acid (HA) concentration, on the characteristics of MPs and their adsorption toward tetracycline (TC) were systematically investigated. The results showed that ageing factors such as pH, ionic strength, and temperature were found to have little impact on the adsorptive capacity of MPs for TC. However, MPs aged in HA solution exhibited a significant decreased adsorptive capacity for TC. HA, which has numerous functional groups, can cover the surface of MPs and change their hydrophobicity, thereby reducing the adsorption affinity to TC. The electrostatic repulsion between adsorbed HA and TC molecules may also decrease the adsorption of TC. In addition, the competing effect of HA for adsorption sites on the surface of MPs further reduces the adsorption of TC. The data presented in this work provide useful information for understanding the transfer of antibiotics by aged MPs, which is of fundamental importance to assess the environmental impact of MPs. Copyright © 2018 Elsevier Inc. All rights reserved.

Ammonium pyrrolidine dithiocarbamate anchored Symphoricarpus albus biomass for lead(II) removal: batch and column biosorption study.

PubMed

Akar, Sibel Tunali; Arslan, Derya; Alp, Tugba

2012-08-15

The biosorption properties of APDC modified S. albus were tested in batch and column conditions. Effective experimental parameters such as pH, biosorbent dosage, contact time, temperature, initial lead(II) ion concentration, flow rate and bed height were investigated. The biosorption capacity of modified biosorbent was at maximum when lead(II) solution pH and biosorbent dosage were 5.5 and 2.0 g L(-1), respectively. The biosorption equilibrium was established in 20 min. Langmuir isotherm fitted well to the equilibrium data and kinetics is found to fit pseudo-second-order model. Increase in ionic strength of lead(II) solutions caused a slight decrease in the biosorption yield of APDC-modified biosorbent. Co-ions affected the biosorption performance of modified biomass up to maximum 20.81% reduction. Column biosorption of lead(II) showed higher biosorption yields at lower flow rates. Required time of breakthrough point was found to be 200 min. The recommended mechanism was found to depend mainly on electrostatic interaction, ion-exchange and complex formation. The ion-exchange mechanism for lead(II) biosorption onto the modified biosorbent is verified from the ionic strength effect and EDX analysis. Carbonyl, phosphate and CN groups on the modified surface of S. albus were found to responsible for complexation with lead(II). Copyright © 2012 Elsevier B.V. All rights reserved.

Harnessing Poly(ionic liquid)s for Sensing Applications.

PubMed

Guterman, Ryan; Ambrogi, Martina; Yuan, Jiayin

2016-07-01

The interest in poly(ionic liquid)s for sensing applications is derived from their strong interactions to a variety of analytes. By combining the desirable mechanical properties of polymers with the physical and chemical properties of ILs, new materials can be created. The tunable nature of both ionic liquids and polymers allows for incredible diversity, which is exemplified in their broad applicability. In this article we examine the new field of poly(ionic liquid) sensors by providing a detailed look at the current state-of-the-art sensing devices for solvents, gases, biomolecules, pH, and anions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a P((MAA-co-NVP)-g-EG) Hydrogel Platform for Oral Protein Delivery: Effects of Hydrogel Composition on Environmental Response and Protein Partitioning.

PubMed

Steichen, Stephanie; O'Connor, Colleen; Peppas, Nicholas A

2017-01-01

Hydrogels based upon terpolymers of methacrylic acid, N-vinyl pyrrolidone, and poly(ethylene glycol) are developed and characterized for their ability to respond to changes in environmental pH and to partition protein therapeutics of varying molecular weights and isoelectric points. P((MAA-co-NVP)-g-EG) hydrogels are synthesized with PEG-based cross-linking agents of varying length and incorporation densities. The composition is confirmed using FT-IR spectroscopy and shows peak shifts indicating hydrogen bonding. Scanning electron microscopy reveals microparticles with an irregular, planar morphology. The pH-responsive behavior of the hydrogels is confirmed under equilibrium and dynamic conditions, with the hydrogel collapsed at acidic pH and swollen at neutral pH. The ability of the hydrogels to partition model protein therapeutics at varying pH and ionic strength is evaluated using three model proteins: insulin, porcine growth hormone, and ovalbumin. Finally, the microparticles are evaluated for adverse interactions with two model intestinal cell lines and show minimal cytotoxicity at concentrations below 5 mg mL -1 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of acidic deposition on in-lake phosphorus availability: a lesson from lakes recovering from acidification.

PubMed

Kopáček, Jiří; Hejzlar, Josef; Kaňa, Jiří; Norton, Stephen A; Stuchlík, Evžen

2015-03-03

Lake water concentrations of phosphorus (P) recently increased in some mountain areas due to elevated atmospheric input of P rich dust. We show that increasing P concentrations also occur during stable atmospheric P inputs in central European alpine lakes recovering from atmospheric acidification. The elevated P availability in the lakes results from (1) increasing terrestrial export of P accompanying elevated leaching of dissolved organic carbon and decreasing phosphate-adsorption ability of soils due to their increasing pH, and (2) decreasing in-lake P immobilization by aluminum (Al) hydroxide due to decreasing leaching of ionic Al from the recovering soils. The P availability in the recovering lakes is modified by the extent of soil acidification, soil composition, and proportion of till and meadow soils in the catchment. These mechanisms explain several conflicting observations of the acid rain effects on surface water P concentrations.

Ion transport in a pH-regulated nanopore.

PubMed

Yeh, Li-Hsien; Zhang, Mingkan; Qian, Shizhi

2013-08-06

Fundamental understanding of ion transport phenomena in nanopores is crucial for designing the next-generation nanofluidic devices. Due to surface reactions of dissociable functional groups on the nanopore wall, the surface charge density highly depends upon the proton concentration on the nanopore wall, which in turn affects the electrokinetic transport of ions, fluid, and particles within the nanopore. Electrokinetic ion transport in a pH-regulated nanopore, taking into account both multiple ionic species and charge regulation on the nanopore wall, is theoretically investigated for the first time. The model is verified by the experimental data of nanopore conductance available in the literature. The results demonstrate that the spatial distribution of the surface charge density at the nanopore wall and the resulting ion transport phenomena, such as ion concentration polarization (ICP), ion selectivity, and conductance, are significantly affected by the background solution properties, such as the pH and salt concentration.

Laser Raman spectra of mono-, oligo- and polysaccharides in solution

NASA Astrophysics Data System (ADS)

Barrett, T. W.

We examined the Raman spectra of thirteen sugars—seven monosaccharides, two disaccharides, one trisaccharide and three polysaccharides—in the wavelength range 200—1700 cm -1 and (i) varied the phosphate buffered solution from pH 6.0 to 8.5 at constant ionic strength of 0.1 and (ii) varied HCl solutions from pH 0.8 to 5.0. As is to be expected with molecules containing COH groupings, all the molecular spectra are distinct. Of the thirteen sugars examined, only D-fructose 1,6-diphosphate (FDP) demonstrated spectral changes for the pH range 6.0—8.5 in phosphate buffer; but all exhibited band intensity enhancement in HCl at the lower pHs, but not band wavenumber changes. The results indicate that: (i) changes in the pH of the major intracellular buffer, phosphate, toward acidity, are able to hydrolyze the 1-phosphate group of FDP and the relative concentration of fructose 1-phosphate to fructose 6-phosphate is indicated by the intensity ratio of the 982 and 1080 cm -1 bands; (ii) it appears that all phosphate groups of FDP are hydrolyzed at pH 0.8 in HCl; and (iii) although conditions of extreme acidity are able to hydrolyze other sugars examined, there is no major degradation.

An Electrochemistry Study of Cryoelectrolysis in Frozen Physiological Saline.

PubMed

Manuel, Thomas J; Munnangi, Pujita; Rubinsky, Boris

2017-07-01

Cryoelectrolysis is a new minimally invasive tissue ablation surgical technique that combines the processes of electrolysis and solid/liquid phase transformation (freezing). This study investigated this new technique by measuring the pH front propagation and the changes in resistance in a tissue simulant made of physiological saline gel with a pH dye as a function of the sample temperature in the high subzero range above the eutectic. Results demonstrated that effective electrolysis can occur in a high subzero freezing milieu and that the propagation of the pH front is only weakly dependent on temperature. These observations are consistent with a mechanism involving ionic movement through the concentrated saline solution channels between ice crystals at subfreezing temperatures above the eutectic. Moreover, results suggest that Joule heating in these microchannels may cause local microscopic melting, the observed weak dependence of pH front propagation on temperature, and the large changes in resistance with time. A final insight provided by the results is that the pH front propagation from the anode is more rapid than from the cathode, a feature indicative of the electro-osmotic flow from the cathode to the anode. The findings in this paper may be critical for designing future cryoelectrolytic ablation surgery protocols.

The history and character of acid precipitation in eastern North America

Treesearch

Charles V. Cogbill

1976-01-01

The history and present distribution of precipitation acidity in eastern North America is reviewed. Precipitation chemistry from the 1920's indicates heavy ionic deposition, but low acidity (calculated) in Tennessee (pH 7.4) and New York (pH 6.15). However, high acidity was apparently widespread over northeast North America by 1955-56 and measured pH's below...

A study on the interaction of horse heart cytochrome c with some conventional and ionic liquid surfactants probed by ultraviolet-visible and fluorescence spectroscopic techniques.

PubMed

Mondal, Satyajit; Das, Bijan

2018-06-05

The interactions of a protein cytochrome c with some selected conventional and ionic liquid surfactants have been investigated at pH7.4 using ultraviolet-visible and fluorescence spectroscopic techniques. We used four conventional surfactants - cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), sodium N-dodecanoylsarcosinate (SDDS), and N-decanoyl-N-methylglucamine (Mega 10), and a surface active ionic liquid 1-hexadecyl-3-methylimidazolium chloride (C 16 MeImCl). All the investigated surfactants were found to induce an unfolding of the protein cytochrome c. In presence of CTAB, SDDS and C 16 MeImCl, the heme iron atom was found to loose methionine from its axial position. Differential binding of the surfactant monomers and their micelles to the protein molecules was inferred. The ionic surfactants were found to be more effective than the nonionic one in unfolding the investigated protein. However, the extent of binding of CTAB/C 16 MeImCl to cytochrome c reaches a plateau past the critical micellization concentration (cmc) of the surfactant. For each of the cytochrome c-DTAB, cytochrome c-SDDS and cytochrome c-Mega 10 system, although there exists an inflection in the surfactant-binding, saturation point could not be detected. It has been demonstrated from the ultraviolet-visible spectral studies that the oxidation state of iron in cytochrome c does not change when the protein binds with the investigated surfactants. Copyright © 2018 Elsevier B.V. All rights reserved.

A study on the interaction of horse heart cytochrome c with some conventional and ionic liquid surfactants probed by ultraviolet-visible and fluorescence spectroscopic techniques

NASA Astrophysics Data System (ADS)

Mondal, Satyajit; Das, Bijan

2018-06-01

The interactions of a protein cytochrome c with some selected conventional and ionic liquid surfactants have been investigated at pH 7.4 using ultraviolet-visible and fluorescence spectroscopic techniques. We used four conventional surfactants - cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), sodium N-dodecanoylsarcosinate (SDDS), and N-decanoyl-N-methylglucamine (Mega 10), and a surface active ionic liquid 1-hexadecyl-3-methylimidazolium chloride (C16MeImCl). All the investigated surfactants were found to induce an unfolding of the protein cytochrome c. In presence of CTAB, SDDS and C16MeImCl, the heme iron atom was found to loose methionine from its axial position. Differential binding of the surfactant monomers and their micelles to the protein molecules was inferred. The ionic surfactants were found to be more effective than the nonionic one in unfolding the investigated protein. However, the extent of binding of CTAB/C16MeImCl to cytochrome c reaches a plateau past the critical micellization concentration (cmc) of the surfactant. For each of the cytochrome c-DTAB, cytochrome c-SDDS and cytochrome c-Mega 10 system, although there exists an inflection in the surfactant-binding, saturation point could not be detected. It has been demonstrated from the ultraviolet-visible spectral studies that the oxidation state of iron in cytochrome c does not change when the protein binds with the investigated surfactants.

The use of a combination of different MR methods to study swelling of hydrophilic xanthan matrix tablets at different pHs.

PubMed

Mikac, U; Sepe, A; Kristl, J; Baumgartner, I

2012-01-01

Modified-release matrix tablets have been extensively used by the pharmaceutical industry as one of the most successful oral drug-delivery systems. The key element in drug release from hydrophilic matrix tablets is the gel layer that regulates the penetration of water and controls drug dissolution and diffusion. Magnetic resonance imaging (MRI) is a powerful, non-invasive technique that can help improve our understanding of the gel layer formed on swellable, polymer-matrix tablets, as well as the layer's properties and its influence on the drug release. The aim was to investigate the effects of pH and ionic strength on swelling and to study the influence of structural changes in xanthan gel on drug release. For this purpose a combination of different MRI methods for accurate determination of penetration, swelling and erosion fronts was used. The position of the penetration and swelling fronts were the same, independently of the different xanthan gel structures formed under different conditions of pH and ionic strength. The position of the erosion front, on the other hand, is strongly dependent on pH and ionic strength, as reflected in different thicknesses of the gel layers.

Solvent-free direct reductive amination by catalytic use of an organotin reagent incorporated on an ionic liquid.

PubMed

Pham, Phuoc Dien; Bertus, Philippe; Legoupy, Stéphanie

2009-11-07

An organotin reagent supported on an ionic liquid was used as a highly effective catalyst (down to 0.1 mol%) for the direct reductive amination of aldehydes and ketones using PhSiH3; this solvent-free method facilitates purification of the products, thus minimizing the contamination by tin.

Conductivity-Relaxation Relations in Nanocomposite Polymer Electrolytes Containing Ionic Liquid.

PubMed

Shojaatalhosseini, Mansoureh; Elamin, Khalid; Swenson, Jan

2017-10-19

In this study, we have used nanocomposite polymer electrolytes, consisting of poly(ethylene oxide) (PEO), δ-Al 2 O 3 nanoparticles, and lithium bis(trifluoromethanesolfonyl)imide (LiTFSI) salt (with 4 wt % δ-Al 2 O 3 and PEO:Li ratios of 16:1 and 8:1), and added different amounts of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesolfonyl)imide (BMITFSI). The aim was to elucidate whether the ionic liquid is able to dissociate the Li-ions from the ether oxygens and thereby decouple the ionic conductivity from the segmental polymer dynamics. The results from DSC and dielectric spectroscopy show that the ionic liquid speeds up both the segmental polymer dynamics and the motion of the Li + ions. However, a close comparison between the structural (α) relaxation process, given by the segmental polymer dynamics, and the ionic conductivity shows that the motion of the Li + ions decouples from the segmental polymer dynamics at higher concentrations of the ionic liquid (≥20 wt %) and instead becomes more related to the viscosity of the ionic liquid. This decoupling increases with decreasing temperature. In addition to the structural α-relaxation, two more local relaxation processes, denoted β and γ, are observed. The β-relaxation becomes slightly faster at the highest concentration of the ionic liquid (at least for the lower salt concentration), whereas the γ-relaxation is unaffected by the ionic liquid, over the whole concentration range 0-40 wt %.

Porous media augmented with biochar for the retention of E. coli

NASA Astrophysics Data System (ADS)

Kolotouros, Christos A.; Manariotis, Ioannis D.; Karapanagioti, Hrissi K.

2016-04-01

A significant number of epidemic outbreaks has been attributed to waterborne fecal-borne pathogenic microorganisms from contaminated ground water. The transport of pathogenic microorganisms in groundwater is controlled by physical and chemical soil properties like soil structure, texture, percent water saturation, soil ionic strength, pore-size distribution, soil and solution pH, soil surface charge, and concentration of organic carbon in solution. Biochar can increase soil productivity by improving both chemical and physical soil properties. The mixing of biochar into soils may stimulate microbial population and activate dormant soil microorganisms. Furthermore, the application of biochar into soil affects the mobility of microorganisms by altering the physical and chemical properties of the soil, and by retaining the microorganisms on the biochar surface. The aim of this study was to investigate the effect of biochar mixing into soil on the transport of Escherichia coli in saturated porous media. Initially, batch experiments were conducted at two different ionic strengths (1 and 150 mM KCl) and at varying E. coli concentrations in order to evaluate the retention of E. coli on biochar in aqueous solutions. Kinetic analysis was conducted, and three isotherm models were employed to analyze the experimental data. Column experiments were also conducted in saturated sand columns augmented with different biochar contents, in order to examine the effect of biochar on the retention of E. coli. The Langmuir model fitted better the retention experimental data, compared to Freundlich and Tempkin models. The retention of E. coli was enhanced at lower ionic strength. Finally, biochar-augmented sand columns were more capable in retaining E. coli than pure sand columns.

Surface-active ionic liquids for palladium-catalysed cross coupling in water: effect of ionic liquid concentration on the catalytically active species† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7ra07757b

PubMed Central

Taskin, Meltem; Cognigni, Alice; Zirbs, Ronald; Reimhult, Erik

2017-01-01

We report the design and synthesis of surface-active ionic liquids for application in palladium-catalyzed cross coupling reactions. A series of dodecylimidazolium-based ionic liquids were applied as additives in the Heck reaction of ethyl acrylate and iodobenzene, and high yields of >90% could be obtained in water without the addition of further ligands. Our results indicate that the ionic liquid concentration in water is the key factor affecting the formation of the catalytically active species and hence the yield. Moreover, imidazolium-based ionic liquids that are able to form a carbene species differ significantly from conventional cationic surfactants, as a concentration dependent formation of the N-heterocyclic carbene complex was observed. PMID:29308189

Ionic pH and glucose sensors fabricated using hydrothermal ZnO nanostructures

NASA Astrophysics Data System (ADS)

Wang, Jyh-Liang; Yang, Po-Yu; Hsieh, Tsang-Yen; Juan, Pi-Chun

2016-01-01

Hydrothermally synthesized aluminum-doped ZnO (AZO) nanostructures have been adopted in extended-gate field-effect transistor (EGFET) sensors to demonstrate the sensitive and stable pH and glucose sensing characteristics of AZO-nanostructured EGFET sensors. The AZO-nanostructured EGFET sensors exhibited the following superior pH sensing characteristics: a high current sensitivity of 0.96 µA1/2/pH, a high linearity of 0.9999, less distortion of output waveforms, a small hysteresis width of 4.83 mV, good long-term repeatability, and a wide sensing range from pHs 1 to 13. The glucose sensing characteristics of AZO-nanostructured biosensors exhibited the desired sensitivity of 60.5 µA·cm-2·mM-1 and a linearity of 0.9996 up to 13.9 mM. The attractive characteristics of high sensitivity, high linearity, and repeatability of using ionic AZO-nanostructured EGFET sensors indicate their potential use as electrochemical and disposable biosensors.

Structure evolution of gelatin particles induced by pH and ionic strength.

PubMed

Xu, Jing; Li, Tianduo; Tao, Furong; Cui, Yuezhi; Xia, Yongmei

2013-03-01

Microstructure of gelatin particles played a key role in determining the physicochemical properties of gelatin. Ionic strength and pH as systematic manners were considered to affect gelatin particles structure on the micrometer scale. Scanning electron microscopy was used for depicting the morphologies of gelatin particles. Increasing pH to 10.0 or decreasing pH to 4.0, spherical, spindle, and irregular aggregates of gelatin particles at 2, 6, 10, and 14% solution (w/w) were all transformed to spindle aggregates. When NaCl was added to the system, the molecular chains of gelatin possibly rearranged themselves in a stretched state, and the ribbon aggregates was observed. The structural transitions of gelatin aggregates were strongly depended on the electrostatic repulsion. In the gelatin-sodium dodecyl sulfate (SDS) case, the micrometer scale of aggregates was larger and the different degrees of cross-links were induced through hydrophobic interaction and electrostatic repulsion. Copyright © 2012 Wiley Periodicals, Inc.

Sensitive voltammetric determination of chloramphenicol by using single-wall carbon nanotube-gold nanoparticle-ionic liquid composite film modified glassy carbon electrodes.

PubMed

Xiao, Fei; Zhao, Faqiong; Li, Jiangwen; Yan, Rui; Yu, Jingjing; Zeng, Baizhao

2007-07-16

A novel composite film modified glassy carbon electrode has been fabricated and characterized by scanning electron microscope (SEM) and voltammetry. The composite film comprises of single-wall carbon nanotube (SWNT), gold nanoparticle (GNP) and ionic liquid (i.e. 1-octyl-3-methylimidazolium hexafluorophosphate), thus has the characteristics of them. The resulting electrode shows good stability, high accumulation efficiency and strong promotion to electron transfer. On it, chloramphenicol can produce a sensitive cathodic peak at -0.66 V (versus SCE) in pH 7.0 phosphate buffer solutions. Parameters influencing the voltammetric response of chloramphenicol are optimized, which include the composition of the film and the operation conditions. Under the optimized conditions, the peak current is linear to chloramphenicol concentration in the range of 1.0x10(-8)-6.0x10(-6) M, and the detection limit is estimated to be 5.0x10(-9) M after an accumulation for 150 s on open circuit. The electrode is applied to the determination of chloramphenicol in milk samples, and the recoveries for the standards added are 97.0% and 100.3%. In addition, the electrochemical reaction of chloramphenicol and the effect of single-wall carbon nanotube, gold nanoparticle and ionic liquid are discussed.

Application of a thiourea-containing task-specific ionic liquid for the solid-phase extraction cleanup of lead ions from red lipstick, pine leaves, and water samples.

PubMed

Saljooqi, Asma; Shamspur, Tayebeh; Mohamadi, Maryam; Mostafavi, Ali

2014-07-01

Here, task-specific ionic liquid solid-phase extraction is proposed for the first time. In this approach, a thiourea-functionalized ionic liquid is immobilized on the solid sorbent, multiwalled carbon nanotubes. These modified nanotubes packed into a solid-phase extraction column are used for the selective extraction and preconcentration of ultra-trace amounts of lead(II) from aqueous samples prior to electrothermal atomic absorption spectroscopy determination. The thiourea functional groups act as chelating agents for lead ions retaining them and so, give the selectivity to the sorbent. Elution of the retained ions can be performed using an acidic thiourea solution. The effects of experimental parameters including pH of the aqueous solution, type and amount of eluent, and the flow rates of sample and eluent solutions on the separation efficiency are investigated. The linear dependence of absorbance of lead on its concentration in the initial solution is in the range of 0.5-40.0 ng/mL with the detection limit of 0.13 ng/mL (3(Sb)/m, n = 10). The proposed method is applicable to the analysis of red lipstick, pine leaves, and water samples for their lead contents. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biosorption of trivalent chromium on the brown seaweed biomass.

PubMed

Yun, Y S; Park, D; Park, J M; Volesky, B

2001-11-01

Biosorption has attracted attention as a cost-effective means for the treatment of metal-bearing wastewater. However, the mechanism of metal binding is not clearly understood, and consequently, modeling of the biosorption performance is still raising debates. In this study, the biosorption of trivalent chromium was investigated with protonated brown alga Ecklonia biomass as a model system. Titration of the biomass revealed that it contains at least three types of functional groups. The Fourier transform infrared spectrometry showed that the carboxyl group was the chromium-binding site within the pH range (pH 1-5) used in this study, where chromium does not precipitate. The pK value and the number of carboxyl groups were estimated to be 4.6 +/- 0.1 and 2.2 +/- 0.1 mmol/g, respectively. The equilibrium sorption isotherms determined at different solution pH indicated that the uptake of chromium increased significantly with increasing pH. A model for the description of chromium biosorption was developed incorporating the hydrolysis reactions that chromium undergoes in the aquatic phase. The model was able to predict the equilibrium sorption experimental data at different pH values and chromium concentrations. In addition, the speciation of the binding site as a function of the solution pH was predicted using the model in order to visualize the distribution of chromium ionic species on the binding site.

Influence of pH on the transport of silver nanoparticles in saturated porous media: laboratory experiments and modeling

NASA Astrophysics Data System (ADS)

Flory, Jason; Kanel, Sushil R.; Racz, LeeAnn; Impellitteri, Christopher A.; Silva, Rendahandi G.; Goltz, Mark N.

2013-03-01

Given the ubiquity of silver nanoparticles (AgNPs) and their potential for toxic effects on both humans and the environment, it is important to understand their environmental fate and transport. The purpose of this study is to gain information on the transport properties of commercial AgNP suspensions in a glass bead-packed column under saturated flow conditions at different solution pH levels. Commercial AgNPs were characterized using high-resolution transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, ultraviolet visible spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. Transport data were collected at different pH levels (4, 6.5, 9, and 11) at fixed ionic strength. Capture of AgNPs increased as the pH of the solution increased from 4 to 6.5. Further increase in pH to 9 and 11 decreased the attachment of AgNPs to the glass beads. AgNP concentration versus time breakthrough data were simulated using an advection-dispersion model incorporating both irreversible and reversible attachment. In particular, a reversible attachment model is required to simulate breakthrough curve tailing at near neutral pH, when attachment is most significant. The laboratory and modeling study reveals that for natural groundwaters, AgNP transport in porous media may be retarded due to capture; but ultimately, most of the mass may be slowly released over time.

Surface complexation modeling of zinc sorption onto ferrihydrite.

PubMed

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

2004-02-01

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

Single-molecule-sensitive fluorescence resonance energy transfer in freely-diffusing attoliter droplets

NASA Astrophysics Data System (ADS)

Rahmanseresht, Sheema; Milas, Peker; Ramos, Kieran P.; Gamari, Ben D.; Goldner, Lori S.

2015-05-01

Fluorescence resonance energy transfer (FRET) from individual, dye-labeled RNA molecules confined in freely-diffusing attoliter-volume aqueous droplets is carefully compared to FRET from unconfined RNA in solution. The use of freely-diffusing droplets is a remarkably simple and high-throughput technique that facilitates a substantial increase in signal-to-noise for single-molecular-pair FRET measurements. We show that there can be dramatic differences between FRET in solution and in droplets, which we attribute primarily to an altered pH in the confining environment. We also demonstrate that a sufficient concentration of a non-ionic surfactant mitigates this effect and restores FRET to its neutral-pH solution value. At low surfactant levels, even accounting for pH, we observe differences between the distribution of FRET values in solution and in droplets which remain unexplained. Our results will facilitate the use of nanoemulsion droplets as attoliter volume reactors for use in biophysical and biochemical assays, and also in applications such as protein crystallization or nanoparticle synthesis, where careful attention to the pH of the confined phase is required.

Properties of purified cytosolic isoenzyme I of Cu,Zn-superoxide dismutase from Nicotiana plumbaginifolia leaves.

PubMed

Ragusa, S; Cambria, M T; Scarpa, M; Di Paolo, M L; Falconi, M; Rigo, A; Cambria, A

2001-11-01

The isoenzyme I of cytosolic Cu,Zn-superoxide dismutase (SOD) from Nicotiana plumbaginifolia (tobacco) leaves has been purified to apparent homogeneity. The relative molecular mass of the native isoenzyme, determined by gel filtration chromatography, is about 33.2 kDa. SDS-polyacrylamide gel electrophoresis shows that the enzyme is composed of two equal subunits of 16.6 kDa The isolectric point, assayed by isoelectric focusing, in the pH range of 3.5-6.5, is 4.3. The enzyme stability was tested at different temperatures, pH, and concentration of inhibitors (KCN and H(2)O(2)). The catalytic constant (k(cat)) was 1.17 +/- 0.14 x 10(9) M(-1) s(-1) at pH 9.9 and 0.1 M ionic strength. The activation energy of the thermal denaturation process is 263 kJ mol(-1). The electrostatic surface potential of the modeled tobacco Cu,Zn-SOD I was calculated showing that the functional spatial network of charges on the protein surface has been maintained, independently of the amino acid substitution around the active sites. Copyright 2001 Academic Press.

Highly efficient and selective adsorption of In{sup 3+} on pristine Zn/Al layered double hydroxide (Zn/Al-LDH) from aqueous solutions

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

Barnabas, Mary Jenisha; Parambadath, Surendran; Mathew, Aneesh

2016-01-15

A pristine Zn/Al-layered double hydroxide (Zn/Al-LDH) showed excellent adsorption ability and selectivity towards In{sup 3+} ions from aqueous solutions. The adsorption behaviour as a function of the contact time, solution pH, ionic strength, and amount of adsorbent under ambient conditions revealed a strong dependency on the pH and ionic strength over In{sup 3+} intake. The structure and properties of Zn/Al-LDH and In{sup 3+} adsorbed Zn/Al-LDH (In–Zn/Al-LDH) were examined carefully by X-ray diffraction, Fourier transform infrared spectroscopy, N{sub 2}-sorption/desorption, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent had a sufficient number of active sites that were responsible for the In{sup 3+}more » adsorption and quite stable even after the adsorption process. The selective adsorption of In{sup 3+} on Zn/Al-LDH was also observed even from a mixture containing competing ions, such as Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+}. The adsorption experiments showed that Zn/Al-LDH is a promising material for the pre-concentration and selective removal of In{sup 3+} from large volumes of aqueous solutions. - Highlights: • A pristine Zn/Al-layered double hydroxide showed good selectivity for In{sup 3+} ions. • The material exhibited a maximum In{sup 3+} intake of 205 mg g{sup −1} at pH 6. • The materials showed good affinity of In{sup 3+} over Cu{sup 2+} and Pb{sup 2+} from ion mixtures.« less

Modified granulation of red mud by weak gelling and its application to stabilization of Pb.

PubMed

Luo, Hui-li; Huang, Sheng-sheng; Luo, Lin; Wu, Gen-yi; Liu, Yan

2012-08-15

This study presents a novel modification of red mud (RM) with cementitious materials by rotary drum granulation under partial hydration. Admixtures and surfactants were applied to improve the microspore structure of red mud-based granules in order to stabilize Pb steadily. Through XRD and SEM-EDS analyses, it was demonstrated that calcite, the main alkali in RM, was partially concreted and coated. Compared to pH 12.47 for RM, the lowest pH of the granules was 10.66 implying that the release of OH(-) from hydrolysis and decomposition was decreased. Based on stabilization of Pb, influence on soil properties and forming qualities, composition of the optimum granule PSP was determined as 5% cement, 5% gypsum, 1% rice straw, and 0.1% emulsifier OP-10. Within a 90 d remediation, immobilization of ionic Pb in a 500 mg kg(-1) Pb-contaminated artificial soil was 9.85 mg kg(-1) at day 30 with 5% PSP2 as substitute. Furthermore, the reverse increase diminished as the final concentration was 11.13 mg kg(-1) while it was 14.25 mg kg(-1) by RM. The increase of residual Pb was 122.61%, which was better than the 83.92% of RM. Particularly, the highest pH in mine soil was 11.09 at day 1 with RM, but the decrease of ionic Pb was 46.26%. Meanwhile, a significant deviation from the control soil zeta-potential lasted longer and the recovery was more difficult, as compared to the granules. Therefore, a granulated modification of RM is shown to be very important when aiming at steady release of OH(-) to improve the later stabilization of Pb. Copyright © 2012 Elsevier B.V. All rights reserved.

Formulation and characterization of nanoencapsulated curcumin using sodium caseinate and its incorporation in ice cream.

PubMed

Kumar, Deep Diyuti; Mann, Bimlesh; Pothuraju, Ramesh; Sharma, Rajan; Bajaj, Rajesh; Minaxi

2016-01-01

In the present investigation, the preparation and characterization of a curcumin nanoemulsion with milk protein (sodium caseinate) and its incorporation into ice cream were undertaken. Among the different combinations, the most stable formulation was observed using milk fat (8%), medium chain triglycerides (2%), curcumin (0.24%) and sodium caseinate (6%) with a mean particle size of 333.8 ± 7.18 nm, a zeta potential of -44.1 ± 0.72 mV and an encapsulation efficiency of 96.9 ± 0.28%. The effect of different processing conditions (heating, pH and ionic strength) on the particle size distribution and zeta potential of the nanoemulsion was evaluated. During heat treatment, the particle size of the nanoemulsion was increased from 333.8 ± 7.18 to 351.1 ± 4.04 nm. The nanoemulsion was destabilized at pH 4.6 and the particle size increased above and below pH 5.0. However, there was a slight increase in the particle size with a change in the ionic concentration. The release kinetics data suggested that in simulated gastro-intestinal digestion, the nanoemulsion was stable against pepsin digestion (a 5.25% release of curcumin), while pancreatic action led to a 16.12% release of curcumin from the nanoemulsion. Finally, our formulation was successfully incorporated into ice cream and the sensory attributes were evaluated. No significant difference was observed in the scores of the sensory attributes between the control and ice cream prepared with a curcumin nanoemulsion. Moreover, the encapsulation efficiency of the curcumin incorporated into the ice cream was 93.7%, which indicates that it can withstand the processing conditions. The findings suggest that ice cream is a suitable dairy product for the delivery of lipophilic bioactive components (curcumin) which can be used for therapeutic purposes.

Development of ochratoxin a in cereal by chemiluminescence enzyme immunoassay

NASA Astrophysics Data System (ADS)

Li, Min; Liu, Renrong; Zhu, Lixin; Chen, Zhenzhen

2017-11-01

A rapid, simple and sensitive chemiluminescence enzyme immunoassay method (CLEIA) was established to detect ochratoxin A (OTA) in cereal. Optimal conditions including antibody dilution ratio and enzyme conjugate, ionic strength, pH value and organic solvent. Established indirect competition inhibition curve to determine the linear working range, detection limit and recovery rate. Results: The 50% inhibitory concentration and the detection limit of the CLEIA were78.8pg/mL and 14.86 pg/mL, respectively, with a linear range of 0.015-0.4ng/mL. At 1∼4μpg/kg fortified levels in wheat, mean recoveries ranged from 67.47% to100.35%.

Production of xanthan gum from a chemically defined medium introduction

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

Weisrock, W.P.; Klein, H.S.

1983-02-22

Heteropolysaccharides produced by the action of Xanthomonas bacteria on carbohydrate media have a potential application as film forming agents, as thickeners in oil field drilling fluids and fracturing liquids and as emulsifying, stabilizing, and sizing agents. Heteropolysaccharides, particularly, xanthan gum, have a significant potential as mobility control agents in micellar polymer flooding. Xanthan gum has excellent viscosifying properties at low concentration, is resistant to shear degradation and exhibits only minimal losses in viscosity as a function of temperature, pH, and ionic strength. For these reasons, xanthan gum is an attractive alternative to synthetic polyacrylamides for enhanced oil recovery operations. 15more » claims.« less