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.

A model study of factors involved in adhesion of Pseudomonas fluorescens to meat.

PubMed Central

Piette, J P; Idziak, E S

1992-01-01

A study was undertaken to investigate the factors involved in the adhesion of Pseudomonas fluorescens to model meat surfaces (tendon slices). Adhesion was fast (less than 2.5 min) and was not suppressed by killing the cells with UV, gamma rays, or heat, indicating that physiological activity was not required. In various salt solutions (NaCl, KCl, CaCl2, MgCl2), adhesion increased with increasing ionic strength up to 10 to 100 mM, suggesting that, at low ionic strengths, electrostatic interactions were involved in the adhesion process. At higher ionic strengths (greater than 10 to 100 mM) or in the presence of Al3+ ions, adhesion was sharply reduced. Selectively blocking of carboxyl or amino groups at the cell surface by chemical means did not affect adhesion. These groups are therefore not directly involved in an adhesive bond with tendon. Given a sufficient cell concentration (10(10) CFU.ml-1) in the adhesion medium, the surface of tendon was almost entirely covered with adherent bacteria. This suggests that if the adhesion is specific, the attachment sites on the tendon surface must be located within collagen or proteoglycan molecules. Images PMID:1444387

Polycation induced actin bundles.

PubMed

Muhlrad, Andras; Grintsevich, Elena E; Reisler, Emil

2011-04-01

Three polycations, polylysine, the polyamine spermine and the polycationic protein lysozyme were used to study the formation, structure, ionic strength sensitivity and dissociation of polycation-induced actin bundles. Bundles form fast, simultaneously with the polymerization of MgATP-G-actins, upon the addition of polycations to solutions of actins at low ionic strength conditions. This indicates that nuclei and/or nascent filaments bundle due to attractive, electrostatic effect of polycations and the neutralization of repulsive interactions of negative charges on actin. The attractive forces between the filaments are strong, as shown by the low (in nanomolar range) critical concentration of their bundling at low ionic strength. These bundles are sensitive to ionic strength and disassemble partially in 100 mM NaCl, but both the dissociation and ionic strength sensitivity can be countered by higher polycation concentrations. Cys374 residues of actin monomers residing on neighboring filaments in the bundles can be cross-linked by the short span (5.4Å) MTS-1 (1,1-methanedyl bismethanethiosulfonate) cross-linker, which indicates a tight packing of filaments in the bundles. The interfilament cross-links, which connect monomers located on oppositely oriented filaments, prevent disassembly of bundles at high ionic strength. Cofilin and the polysaccharide polyanion heparin disassemble lysozyme induced actin bundles more effectively than the polylysine-induced bundles. The actin-lysozyme bundles are pathologically significant as both proteins are found in the pulmonary airways of cystic fibrosis patients. Their bundles contribute to the formation of viscous mucus, which is the main cause of breathing difficulties and eventual death in this disorder. Copyright © 2011 Elsevier B.V. All rights reserved.

Colloidal Mechanisms of Gold Nanoparticle Loss in Asymmetric Flow Field-Flow Fractionation.

PubMed

Jochem, Aljosha-Rakim; Ankah, Genesis Ngwa; Meyer, Lars-Arne; Elsenberg, Stephan; Johann, Christoph; Kraus, Tobias

2016-10-07

Flow field-flow fractionation is a powerful method for the analysis of nanoparticle size distributions, but its widespread use has been hampered by large analyte losses, especially of metal nanoparticles. Here, we report on the colloidal mechanisms underlying the losses. We systematically studied gold nanoparticles (AuNPs) during asymmetrical flow field-flow fractionation (AF4) by systematic variation of the particle properties and the eluent composition. Recoveries of AuNPs (core diameter 12 nm) stabilized by citrate or polyethylene glycol (PEG) at different ionic strengths were determined. We used online UV-vis detection and off-line elementary analysis to follow particle losses during full analysis runs, runs without cross-flow, and runs with parts of the instrument bypassed. The combination allowed us to calculate relative and absolute analyte losses at different stages of the analytic protocol. We found different loss mechanisms depending on the ligand. Citrate-stabilized particles degraded during analysis and suffered large losses (up to 74%). PEG-stabilized particles had smaller relative losses at moderate ionic strengths (1-20%) that depended on PEG length. Long PEGs at higher ionic strengths (≥5 mM) caused particle loss due to bridging adsorption at the membrane. Bulk agglomeration was not a relevant loss mechanism at low ionic strengths ≤5 mM for any of the studied particles. An unexpectedly large fraction of particles was lost at tubing and other internal surfaces. We propose that the colloidal mechanisms observed here are relevant loss mechanisms in many particle analysis protocols and discuss strategies to avoid them.

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

General strategy for biodetection in high ionic strength solutions using transistor-based nanoelectronic sensors.

PubMed

Gao, Ning; Zhou, Wei; Jiang, Xiaocheng; Hong, Guosong; Fu, Tian-Ming; Lieber, Charles M

2015-03-11

Transistor-based nanoelectronic sensors are capable of label-free real-time chemical and biological detection with high sensitivity and spatial resolution, although the short Debye screening length in high ionic strength solutions has made difficult applications relevant to physiological conditions. Here, we describe a new and general strategy to overcome this challenge for field-effect transistor (FET) sensors that involves incorporating a porous and biomolecule permeable polymer layer on the FET sensor. This polymer layer increases the effective screening length in the region immediately adjacent to the device surface and thereby enables detection of biomolecules in high ionic strength solutions in real-time. Studies of silicon nanowire field-effect transistors with additional polyethylene glycol (PEG) modification show that prostate specific antigen (PSA) can be readily detected in solutions with phosphate buffer (PB) concentrations as high as 150 mM, while similar devices without PEG modification only exhibit detectable signals for concentrations ≤10 mM. Concentration-dependent measurements exhibited real-time detection of PSA with a sensitivity of at least 10 nM in 100 mM PB with linear response up to the highest (1000 nM) PSA concentrations tested. The current work represents an important step toward general application of transistor-based nanoelectronic detectors for biochemical sensing in physiological environments and is expected to open up exciting opportunities for in vitro and in vivo biological sensing relevant to basic biology research through medicine.

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.

TiO₂ nanoparticle transport and retention through saturated limestone porous media under various ionic strength conditions.

PubMed

Esfandyari Bayat, Ali; Junin, Radzuan; Derahman, Mohd Nawi; Samad, Adlina Abdul

2015-09-01

The impact of ionic strength (from 0.003 to 500mM) and salt type (NaCl vs MgCl2) on transport and retention of titanium dioxide (TiO2) nanoparticles (NPs) in saturated limestone porous media was systematically studied. Vertical columns were packed with limestone grains. The NPs were introduced as a pulse suspended in aqueous solutions and breakthrough curves in the column outlet were generated using an ultraviolent-visible spectrometry. Presence of NaCl and MgCl2 in the suspensions were found to have a significant influence on the electrokinetic properties of the NP aggregates and limestone grains. In NaCl and MgCl2 solutions, the deposition rates of the TiO2-NP aggregates were enhanced with the increase in ionic strength, a trend consistent with traditional Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Furthermore, the NP aggregates retention increased in the porous media with ionic strength. The presence of salts also caused a considerable delay in the NPs breakthrough time. MgCl2 as compared to NaCl was found to be more effective agent for the deposition and retention of TiO2-NPs. The experimental results followed closely the general trends predicted by the filtration and DLVO calculations. Overall, it was found that TiO2-NP mobility in the limestone porous media depends on ionic strength and salt type. Copyright © 2015 Elsevier Ltd. All rights reserved.

Structural instability of shell-like assemblies of a keplerate-type polyoxometalate induced by ionic strength.

PubMed

Veen, Sandra J; Kegel, Willem K

2009-11-19

We demonstrate a new structural instability of shell-like assemblies of polyoxometalates. Besides the colloidal instability, that is, the formation of aggregates that consist of many single layered POM-shells, these systems also display an instability on a structural scale within the shell-like assemblies. This instability occurs at significantly lower ionic strength than the colloidal stability limit and only becomes evident after a relatively long time. For the polyoxometalate, abbreviated as {Mo(72)Fe(30)}, it is shown that the structural stability limit of POM-shells lies between a NaCl concentration of 1.00 and 5.00 mM in aqueous solution.

Facilitated transport of Cu with hydroxyapatite nanoparticles in saturated sand: Effects of solution ionic strength and composition

USDA-ARS?s Scientific Manuscript database

Column experiments were conducted to investigate the facilitated transport of Cu in association with hydroxyapatite nanoparticles (nHAP) in water-saturated quartz sand at different solution concentrations of NaCl (0 to 100 mM) or CaCl2 (0.1 to 1.0 mM). The experimental breakthrough curves and retent...

Ionic Strength-Controlled Mn (Hydr)oxide Nanoparticle Nucleation on Quartz: Effect of Aqueous Mn(OH)2.

PubMed

Jung, Haesung; Jun, Young-Shin

2016-01-05

The early formation of manganese (hydr)oxide nanoparticles at mineral-water interfaces is crucial in understanding how Mn oxides control the fate and transport of heavy metals and the cycling of nutrients. Using atomic force microscopy, we investigated the heterogeneous nucleation and growth of Mn (hydr)oxide under varied ionic strengths (IS; 1-100 mM NaNO3). Experimental conditions (i.e., 0.1 mM Mn(2+) (aq) concentration and pH 10.1) were chosen to be relevant to Mn remediation sites. We found that IS controls Mn(OH)2 (aq) formation, and that the controlled Mn(OH)2 (aq) formation can affect the system's saturation and subsequent Mn(OH)2 (s) and further Mn3O4 (s) nanoparticle formation. In 100 mM IS system, nucleated Mn (hydr)oxide particles had more coverage on the quartz substrate than those in 1 mM and 10 mM IS systems. This high IS also resulted in low supersaturation ratio and thus favor heterogeneous nucleation, having better structural matching between nucleating Mn (hydr)oxides and quartz. The unique information obtained in this work improves our understanding of Mn (hydr)oxide formation in natural as well as engineered aqueous environments, such as groundwater contaminated by natural leachate and acid mine drainage remediation.

Contribution of capillary electrophoresis to an integrated vision of humic substances size and charge characterizations

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

D'Orlye, Fanny; Reiller, Pascal E.

2014-02-15

The physicochemical properties of three different humic substances (HS) are probed using capillary zone electrophoresis in alkaline carbonate buffers, pH 10. Special attention is drawn to the impact of the electrolyte ionic strength and counter-ion nature, chosen within the alkali-metal series, on HS electrophoretic mobility. Taylor-Aris dispersion analysis provides insights into the hydrodynamic radius (R-H) distributions of HS. The smallest characterized entities are of nano-metric dimensions, showing neither ionic strength- nor alkali-metal-induced aggregation. These results are compared with the entities evidenced in dynamic light scattering measurements, the size of which is two order of magnitude higher, ca. 100 nm. Themore » extended Onsager model provides a reasonable description of measured electrophoretic mobilities in the ionic strength range 1-50 mM, thus allowing the estimation of limiting mobilities and ionic charge numbers for the different HS samples. An unexpected HS electrophoretic mobility increase (in absolute value) is observed in the order Li{sup +} ≤ Na{sup +} ≤ K{sup +} ≤ Cs{sup +} and discussed either in terms of retarding forces or in terms of ion-ion interactions. (authors)« less

CADDIS Volume 2. Sources, Stressors and Responses: Ionic Strength

EPA Pesticide Factsheets

Introduction to the ionic strength module, when to list ionic strength as a candidate cause, ways to measure ionic strength, simple and detailed conceptual diagrams for ionic strength, ionic strength module references and literature reviews.

CADDIS Volume 2. Sources, Stressors and Responses: Ionic Strength - Simple Conceptual Diagram

EPA Pesticide Factsheets

Introduction to the ionic strength module, when to list ionic strength as a candidate cause, ways to measure ionic strength, simple and detailed conceptual diagrams for ionic strength, ionic strength module references and literature reviews.

CADDIS Volume 2. Sources, Stressors and Responses: Ionic Strength - Detailed Conceptual Diagram

EPA Pesticide Factsheets

Introduction to the ionic strength module, when to list ionic strength as a candidate cause, ways to measure ionic strength, simple and detailed conceptual diagrams for ionic strength, ionic strength module references and literature reviews.

Donnan membrane technique (DMT) for anion measurement.

PubMed

Vega, Flora Alonso; Weng, Liping; Temminghoff, Erwin J M; Van Riemsdijk, Willem H

2010-04-01

Donnan membrane technique (DMT) is developed and tested for determination of free anion concentrations. Time needed to reach the Donnan membrane equilibrium depends on type of ions and the background. The Donnan membrane equilibrium is reached in 1 day for Cl(-), 1-2 days for NO(3)(-), 1-4 days for SO(4)(2-) and SeO(4)(2-), and 1-14 days for H(2)PO(4)(-) in a background of 2-200 mM KCl or K(2)SO(4). The strongest effect of ionic strength on equilibrium time is found for H(2)PO(4)(-), followed by SO(4)(2-) and SeO(4)(2-), and then by Cl(-) and NO(3)(-). The negatively charged organic particles of fulvic and humic acids do not pass the membrane. Two approaches for the measurement of different anion species of the same element, such as SeO(4)(2-) and HSeO(3)(-), using DMT are proposed and tested. These two approaches are based on transport kinetics or response to ionic strength difference. A transport model that was developed previously for cation DMT is applied in this work to analyze the rate-limiting step in the anion DMT. In the absence of mobile/labile complexes, transport tends to be controlled by diffusion in solution at a low ionic strength, whereas at a higher ionic strength, diffusion in the membrane starts to control the transport.

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.

Cytochrome c oxidase inhibition by calcium at physiological ionic composition of the medium: Implications for physiological significance of the effect.

PubMed

Vygodina, Tatiana V; Mukhaleva, Elizaveta; Azarkina, Natalia V; Konstantinov, Alexander A

2017-12-01

Cytochrome c oxidase (CcO) from mammalian mitochondria binds Ca 2+ and Na + in a special cation binding site. Binding of Ca 2+ brings about partial inhibition of the enzyme while Na + competes with Ca 2+ for the binding site and protects the enzyme from the inhibition [Vygodina, T., Kirichenko, A. and Konstantinov, A.A. (2013). Direct Regulation of Cytochrome c oxidase by Calcium Ions. PLoS One 8(9): e74436]. In the original studies, the inhibition was found to depend significantly on the ionic composition of the buffer. Here we describe inhibition of CcO by Ca 2+ in media containing the main ionic components of cytoplasm (150mM KCl, 12mM NaCl and 1mM MgCl 2 ). Under these conditions, Ca 2+ inhibits CcO with effective K i of 20-26μM, that is an order of magnitude higher than determined earlier in the absence of Na + . At physiological value of ionic strength, the inhibition can be observed at any turnover number of CcO, rather than only at low TN (<10s -1 ) as found previously. The inhibition requires partially oxidized state of cytochrome c and is favored by high ionic strength with a sharp transition at 0.1-0.2M. The high K i =20-26μM found for CcO inhibition by calcium matches closely the known value of "K m " for Ca 2+ -induced activation of the mitochondrial calcium uniporter. The inhibition of CcO by Ca 2+ is proposed to modulate mitochondrial Ca 2+ -uptake via the mitochondrial calcium uniporter, promote permeability transition pore opening and induce reduction of Mia40 in the mitochondrial intermembrane space. Copyright © 2017 Elsevier B.V. All rights reserved.

High Ionic Strength Depresses Muscle Contractility by Decreasing both Force per Cross-bridge and the Number of Strongly Attached Cross-bridges

PubMed Central

Wang, Li; Bahadir, Anzel; Kawai, Masataka

2015-01-01

An increase in ionic strength (IS) lowers Ca2+ activated tension in muscle fibres, however, its molecular mechanism is not well understood. In this study, we used single rabbit psoas fibres to perform sinusoidal analyses. During Ca2+ activation, the effects of ligands (ATP, Pi, and ADP) at IS ranging 150 mM – 300 mM were studied on three rate constants to characterize elementary steps of the cross-bridge cycle. The IS effects were studied because a change in IS modifies the inter- and intra-molecular interactions, hence they may shed light on the molecular mechanisms of force generation. Both the ATP binding affinity (K1) and the ADP binding affinity (K0) increased to 2-3x, and the Pi binding affinity (K5) decreased to 1/2, when IS was raised from 150 mM to 300 mM. The effect on ATP/ADP can be explained by stereospecific and hydrophobic interaction, and the effect on Pi can be explained by the electrostatic interaction with myosin. The increase in IS increased cross-bridge detachment steps (k2 and k−4), indicating that electrostatic repulsion promotes these steps. However, IS did not affect attachment steps (k−2 and k4). Consequently, the equilibrium constant of the detachment step (K2) increased by ~100%, and the force generation step (K4) decreased by ~30%. These effects together diminished the number of force-generating cross-bridges by 11%. Force/cross-bridge (T56) decreased by 26%, which correlates well with a decrease in the Debye length that limits the ionic atmosphere where ionic interactions take place. We conclude that the major effect of IS is a decrease in force/cross-bridge, but a decrease in the number of force generating cross-bridge also takes place. The stiffness during rigor induction did not change with IS, demonstrating that in-series compliance is not much affected by IS. PMID:25836331

Role of Heavy Meromyosin in Heat-Induced Gelation in Low Ionic Strength Solution Containing L-Histidine.

PubMed

Hayakawa, Toru; Yoshida, Yuri; Yasui, Masanori; Ito, Toshiaki; Wakamatsu, Jun-ichi; Hattori, Akihito; Nishimura, Takanori

2015-08-01

The gelation of myosin has a very important role in meat products. We have already shown that myosin in low ionic strength solution containing L-histidine forms a transparent gel after heating. To clarify the mechanism of this unique gelation, we investigated the changes in the nature of myosin subfragments during heating in solutions with low and high ionic strengths with and without L-histidine. The hydrophobicity of myosin and heavy meromyosin (HMM) in low ionic strength solution containing L-histidine was lower than in high ionic strength solution. The SH contents of myosin and HMM in low ionic strength solution containing l-histidine did not change during the heating process, whereas in high ionic strength solution they decreased slightly. The heat-induced globular masses of HMM in low ionic strength solution containing L-histidine were smaller than those in high ionic strength solution. These findings suggested that the polymerization of HMM molecules by heating was suppressed in low ionic strength solution containing L-histidine, resulting in formation of the unique gel. © 2015 Institute of Food Technologists®

Heat-induced gelation of myosin in a low ionic strength solution containing L-histidine.

PubMed

Hayakawa, T; Yoshida, Y; Yasui, M; Ito, T; Iwasaki, T; Wakamatsu, J; Hattori, A; Nishimura, T

2012-01-01

Binding properties are important for meat products and are substantially derived from the heat-induced gelation of myosin. We have shown that myosin is solubilized in a low ionic strength solution containing L-histidine. To clarify its processing characteristics, we investigated properties and structures of heat-induced gels of myosin solubilized in a low ionic strength solution containing L-histidine. Myosin in a low ionic strength solution formed transparent gels at 40-50°C, while myosin in a high ionic strength solution formed opaque gels at 60-70°C. The gel of myosin in a low ionic strength solution with L-histidine showed a fine network consisting of thin strands and its viscosity was lower than that of myosin in a high ionic strength solution at 40-50°C. The rheological properties of heat-induced gels of myosin at low ionic strength are different from those at high ionic strength. This difference might be caused by structural changes in the rod region of myosin in a low ionic strength solution containing L-histidine. Copyright © 2011 Elsevier Ltd. All rights reserved.

Excessive Counterion Condensation on Immobilized ssDNA in Solutions of High Ionic Strength

PubMed Central

Rant, Ulrich; Arinaga, Kenji; Fujiwara, Tsuyoshi; Fujita, Shozo; Tornow, Marc; Yokoyama, Naoki; Abstreiter, Gerhard

2003-01-01

We present experiments on the bias-induced release of immobilized, single-stranded (ss) 24-mer oligonucleotides from Au-surfaces into electrolyte solutions of varying ionic strength. Desorption is evidenced by fluorescence measurements of dye-labeled ssDNA. Electrostatic interactions between adsorbed ssDNA and the Au-surface are investigated with respect to 1), a variation of the bias potential applied to the Au-electrode; and 2), the screening effect of the electrolyte solution. For the latter, the concentration of monovalent salt in solution is varied from 3 to 1600 mM. We find that the strength of electric interaction is predominantly determined by the effective charge of the ssDNA itself and that the release of DNA mainly occurs before the electrochemical double layer has been established at the electrolyte/Au interface. In agreement with Manning's condensation theory, the measured desorption efficiency (ηrel) stays constant over a wide range of salt concentrations; however, as the Debye length is reduced below a value comparable to the axial charge spacing of the DNA, ηrel decreases substantially. We assign this effect to excessive counterion condensation on the DNA in solutions of high ionic strength. In addition, the relative translational diffusion coefficient of ssDNA in solution is evaluated for different salt concentrations. PMID:14645075

Excessive counterion condensation on immobilized ssDNA in solutions of high ionic strength.

PubMed

Rant, Ulrich; Arinaga, Kenji; Fujiwara, Tsuyoshi; Fujita, Shozo; Tornow, Marc; Yokoyama, Naoki; Abstreiter, Gerhard

2003-12-01

We present experiments on the bias-induced release of immobilized, single-stranded (ss) 24-mer oligonucleotides from Au-surfaces into electrolyte solutions of varying ionic strength. Desorption is evidenced by fluorescence measurements of dye-labeled ssDNA. Electrostatic interactions between adsorbed ssDNA and the Au-surface are investigated with respect to 1), a variation of the bias potential applied to the Au-electrode; and 2), the screening effect of the electrolyte solution. For the latter, the concentration of monovalent salt in solution is varied from 3 to 1600 mM. We find that the strength of electric interaction is predominantly determined by the effective charge of the ssDNA itself and that the release of DNA mainly occurs before the electrochemical double layer has been established at the electrolyte/Au interface. In agreement with Manning's condensation theory, the measured desorption efficiency (etarel) stays constant over a wide range of salt concentrations; however, as the Debye length is reduced below a value comparable to the axial charge spacing of the DNA, etarel decreases substantially. We assign this effect to excessive counterion condensation on the DNA in solutions of high ionic strength. In addition, the relative translational diffusion coefficient of ssDNA in solution is evaluated for different salt concentrations.

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.

Transport of selected bacterial pathogens in agricultural soil and quartz sand.

PubMed

Schinner, Tim; Letzner, Adrian; Liedtke, Stefan; Castro, Felipe D; Eydelnant, Irwin A; Tufenkji, Nathalie

2010-02-01

The protection of groundwater supplies from microbial contamination necessitates a solid understanding of the key factors controlling the migration and retention of pathogenic organisms through the subsurface environment. The transport behavior of five waterborne pathogens was examined using laboratory-scale columns packed with clean quartz at two solution ionic strengths (10 mM and 30 mM). Escherichia coli O157:H7 and Yersinia enterocolitica were selected as representative Gram-negative pathogens, Enterococcus faecalis was selected as a representative Gram-positive organism, and two cyanobacteria (Microcystis aeruginosa and Anabaena flos-aquae) were also studied. The five organisms exhibit differing attachment efficiencies to the quartz sand. The surface (zeta) potential of the microorganisms was characterized over a broad range of pH values (2-8) at two ionic strengths (10 mM and 30 mM). These measurements are used to evaluate the observed attachment behavior within the context of the DLVO theory of colloidal stability. To better understand the possible link between bacterial transport in model quartz sand systems and natural soil matrices, additional experiments were conducted with two of the selected organisms using columns packed with loamy sand obtained from an agricultural field. This investigation highlights the need for further characterization of waterborne pathogen surface properties and transport behavior over a broader range of environmentally relevant conditions. Copyright 2008 Elsevier Ltd. All rights reserved.

Linker DNA accessibility in chromatin fibers of different conformations: a reevaluation.

PubMed Central

Zlatanova, J; Leuba, S H; Yang, G; Bustamante, C; van Holde, K

1994-01-01

New studies on chromatin fiber morphology, using the technique of scanning force microscopy (SFM), have caused us to reexamine recent analysis of nuclease digestion of chromatin. Chicken erythrocyte chromatin fibers, glutaraldehyde-fixed at 0, 10, and 80 mM NaCl, were imaged with the help of SFM. The chromatin fibers possessed a loose three-dimensional 30-nm structure even in the absence of added salt. This structure slightly condensed upon addition of 10 mM NaCl, and highly compacted, irregularly segmented fibers were observed at 80 mM NaCl. This sheds new light upon our previously reported analysis of the kinetics of digestion by soluble and membrane-immobilized micrococcal nuclease [Leuba, S. H., Zlatanova, J. & van Holde, K. (1994) J. Mol. Biol. 235, 871-880]. While the low-ionic-strength fibers were readily digested, the highly compacted structure formed at 80 mM NaCl was refractory to nuclease attack, implying that the linkers were fully accessible in the low-ionic-strength conformation but not in the condensed fibers. We now find that cleavage of the linker DNA by a small molecule, methidiumpropyl-EDTA-Fe(II), proceeds for all types of conformations at similar rates. Thus, steric hindrance is responsible for the lack of accessibility to micrococcal nuclease in the condensed fiber. Taken in total the data suggest that reexamination of existing models of chromatin conformation is warranted. Images PMID:8202481

Electrical and Electrorheological Properties of Alumina/Natural Rubber (STR XL) Composites

PubMed Central

Tangboriboon, Nuchnapa; Uttanawanit, Nuttapot; Longtong, Mean; Wongpinthong, Piraya; Sirivat, Anuvat; Kunanuruksapong, Ruksapong

2010-01-01

The electrorheological properties (ER) of natural rubber (XL)/alumina (Al2O3) composites were investigated in oscillatory shear mode under DC electrical field strengths between 0 to 2 kV/mm. SEM micrographs indicate a mean particle size of 9.873 ± 0.034 µm and particles that are moderately dispersed in the matrix. The XRD patterns indicate Al2O3 is of the β-phase polytype which possesses high ionic conductivity. The storage modulus (G′) of the composites, or the rigidity, increases by nearly two orders of magnitude, with variations in particle volume fraction and electrical field strength. The increase in the storage modulus is caused the ionic polarization of the alumina particles and the induced dipole moments set up in the natural rubber matrix.

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.

Transport of Cryptosporidium oocysts in porous media: Role of straining and physicochemical filtration

USGS Publications Warehouse

Tufenkji, N.; Miller, G.F.; Ryan, J.N.; Harvey, R.W.; Elimelech, M.

2004-01-01

The transport and filtration behavior of Cryptosporidium parvum oocysts in columns packed with quartz sand was systematically examined under repulsive electrostatic conditions. An increase in solution ionic strength resulted in greater oocyst deposition rates despite theoretical predictions of a significant electrostatic energy barrier to deposition. Relatively high deposition rates obtained with both oocysts and polystyrene latex particles of comparable size at low ionic strength (1 mM) suggest that a physical mechanism may play a key role in oocyst removal. Supporting experiments conducted with latex particles of varying sizes, under very low ionic strength conditions where physicochemical filtration is negligible, clearly indicated that physical straining is an important capture mechanism. The results of this study indicate that irregularity of sand grain shape (verified by SEM imaging) contributes considerably to the straining potential of the porous medium. Hence, both straining and physicochemical filtration are expected to control the removal of C. parvum oocysts in settings typical of riverbank filtration, soil infiltration, and slow sand filtration. Because classic colloid filtration theory does not account for removal by straining, these observations have important implications with respect to predictions of oocyst transport.

The initial single yeast cell adhesion on glass via optical trapping and Derjaguin-Landau-Verwey-Overbeek predictions

NASA Astrophysics Data System (ADS)

Castelain, Mickaël; Pignon, Frédéric; Piau, Jean-Michel; Magnin, Albert

2008-04-01

We used an optical tweezer to investigate the adhesion of yeast Saccharomyces cerevisiae onto a glass substrate at the initial contact. Micromanipulation of free-living objects with single-beam gradient optical trap enabled to highlight mechanisms involved in this initial contact. As a function of the ionic strength and with a displacement parallel to the glass surface, the yeast adheres following different successive ways: (i) Slipping and rolling at 1.5mM NaCl, (ii) slipping, rolling, and sticking at 15mM NaCl, and (iii) only sticking at 150mM. These observations were numerous and reproducible. A kinetic evolution of these adhesion phenomena during yeast movement was clearly established. The nature, range, and relative intensity of forces involved in these different adhesion mechanisms have been worked out as a quantitative analysis from Derjaguin-Landau-Verwey-Overbeek (DLVO) and extended DLVO theories. Calculations show that the adhesion mechanisms observed and their affinity with ionic strength were mainly governed by the Lifshitz-van der Waals interaction forces and the electrical double-layer repulsion to which are added specific contact forces linked to "sticky" glycoprotein secretion, considered to be the main forces capable of overcoming the short-range Lewis acid-base repulsions.

FY04 LDRD Final Report: Interaction of Viruses with Membranes and Soil Materials

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

Schaldach, C M

2005-02-08

The influence of ionic strength on the electrostatic interaction of viruses with environmentally relevant surfaces was determined for three viruses, MS2, Q{beta} and Norwalk. The environmental surface is modeled as charged Gouy-Chapman plane with and without a finite atomistic region (patch) of opposite charge. The virus is modeled as a particle comprised of ionizable amino acid residues in a shell surrounding a spherical RNA core of negative charge, these charges being compensated for by a Coulomb screening due to intercalated ions. Surface potential calculations for each of the viruses show excellent agreement with electrophoretic mobility and zeta potential measurements asmore » a function of pH. The results indicate that the electrostatic interaction between the virus and the planar surface, mitigated by the ionic strength of the solute, is dependent upon the spatial distribution of the amino acid residues in the different viruses. Specifically, the order of interaction energies with the patch (MS2 greatest at 5 mM; Norwalk greatest at 20 mM) is dependent upon the ionic strength of the fluid as a direct result of the viral coat amino acid distributions. We have developed an atomistic-scale method of calculation of the binding energy of viruses to surfaces including electrostatic, van der Waals, electron-overlap repulsion, surface charge polarization (images), and hydrophobic effects. The surface is treated as a Gouy-Chapman plane allowing inclusion of pH and ionic strength effects on the electrostatic potential at each amino acid charge. Van der Waals parameters are obtained from the DREIDING force field and from Hamaker constant measurements. We applied this method to the calculation of the Cowpea Mosaic Virus (CPMV), a negatively charged virus at a pH of 7.0, and find that the viral-gold surface interaction is very long range for both signs of surface potential, a result due to the electrostatic forces. For a negative (Au) surface potential of -0.05 volts, a nearly 4 eV barrier must be overcome to reach 1 nm from the surface.« less

Solution chemistry effects on orthophosphate adsorption by cationized solid wood residues

Treesearch

K.G. Karthikeyan; Mandla A. Tshabalala; D. Wang; M. Kalbasi

2004-01-01

Adsorption of orthophosphate anions in aqueous solution by cationized milled solid wood residues was characterized as a function of sorbate-to- sorbent ratio (=0.001-2.58 mmol of P/g substrate), pH (3-9), ionic strength, I (no I control; 0.001 and 0.01 M NaCl), reaction time (4 min to 24 h), and in the presence of other competing anions (0.08-50 mM SO4 2-; 0.08-250 mM...

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

Hydrogel based sensor arrays (2 × 2) with perforated piezoresistive diaphragms for metabolic monitoring (in vitro)

PubMed Central

Orthner, M.P.; Lin, G.; Avula, M.; Buetefisch, S.; Magda, J.; Rieth, L.W.; Solzbacher, F.

2010-01-01

This report details the first experimental results from novel hydrogel sensor array (2 × 2) which incorporates analyte diffusion pores into a piezoresistive diaphragm for the detection of hydrogel swelling pressures and hence chemical concentrations. The sensor assembly was comprised of three components, the active four sensors, HPMA/DMA/TEGDMA (hydroxypropyl methacrylate (HPMA), N,N-dimethylaminoethyl methacrylate (DMA) and crosslinker tetra-ethyleneglycol dimethacrylate (TEGDMA)) hydrogel, and backing plate. Each of the individual sensors of the array can be used with various hydrogels used to measure the presence of a number of stimuli including pH, ionic strength, and glucose concentrations. Ideally, in the future, these sensors will be used for continuous metabolic monitoring applications and implanted subcutaneously. In this paper and to properly characterize the sensor assembly, hydrogels sensitive to changes ionic strength were synthesized using hydroxypropyl methacrylate (HPMA), N,N-dimethylaminoethyl methacrylate (DMA) and crosslinker tetra-ethyleneglycol dimethacrylate (TEGDMA) and inserted into the sensor assembly. This hydrogel quickly and reversibly swells when placed environments of physiological buffer solutions (PBS) with ionic strengths ranging from 0.025 to 0.15 M, making it ideal for proof-of-concept testing and initial characterization. The assembly was wire bonded to a printed circuit board and coated with 3 ± 0.5 μm of Parylene-C using chemical vapor deposition (CVD) to protect the sensor and electrical connections during ionic strength wet testing. Two versions of sensors were fabricated for comparison, the first incorporated diffusion pores into the diaphragm, and the second used a solid diaphragm with perforated backing plate. This new design (perforated diaphragm) was shown to have slightly higher sensitivity than solid diaphragm sensors with separate diffuse backing plates when coupled with the hydrogel. The sensitivities for the 1 mm × 1 mm, 1.25 mm × 1.25 mm, 1.5 mm × 1.5 mm perforated diaphragm sensors were 53.3 ± 6.5, 171.7 ± 8.8, and 271.47 ± 27.53 mV/V-M, respectively. These results show that perforations in the diaphragm can be used not only to allow the diffusion of analyte into the cavity but to increase mechanical stress in the piezoresistive diaphragm, thereby increasing sensor output signal. The time constants for swelling (τswelling) and contracting (τcontracting) were calculated by fitting the sensor output half cycles to an exponential growth function. We found that the sensors' response was initially retarded during the preliminary hydrogel conditioning period then improved after 3–5 cycles with values of approximately 9 and 7 min for τswelling and τcontracting. For all sensors tested τswelling > τcontracting. This may be due to the increased loading on the hydrogel from the diaphragm during the swelling process. During contraction the diaphragm aids the hydrogel by reversibly applying mechanical pressure and therefore reducing τcontracting. Long term stability testing showed the sensors remained functional for upwards of 2 weeks in the test phosphate buffer solution (PBS). PMID:23750073

Hydrogel based sensor arrays (2 × 2) with perforated piezoresistive diaphragms for metabolic monitoring (in vitro).

PubMed

Orthner, M P; Lin, G; Avula, M; Buetefisch, S; Magda, J; Rieth, L W; Solzbacher, F

2010-03-19

This report details the first experimental results from novel hydrogel sensor array (2 × 2) which incorporates analyte diffusion pores into a piezoresistive diaphragm for the detection of hydrogel swelling pressures and hence chemical concentrations. The sensor assembly was comprised of three components, the active four sensors, HPMA/DMA/TEGDMA (hydroxypropyl methacrylate (HPMA), N,N-dimethylaminoethyl methacrylate (DMA) and crosslinker tetra-ethyleneglycol dimethacrylate (TEGDMA)) hydrogel, and backing plate. Each of the individual sensors of the array can be used with various hydrogels used to measure the presence of a number of stimuli including pH, ionic strength, and glucose concentrations. Ideally, in the future, these sensors will be used for continuous metabolic monitoring applications and implanted subcutaneously. In this paper and to properly characterize the sensor assembly, hydrogels sensitive to changes ionic strength were synthesized using hydroxypropyl methacrylate (HPMA), N,N-dimethylaminoethyl methacrylate (DMA) and crosslinker tetra-ethyleneglycol dimethacrylate (TEGDMA) and inserted into the sensor assembly. This hydrogel quickly and reversibly swells when placed environments of physiological buffer solutions (PBS) with ionic strengths ranging from 0.025 to 0.15 M, making it ideal for proof-of-concept testing and initial characterization. The assembly was wire bonded to a printed circuit board and coated with 3 ± 0.5 μm of Parylene-C using chemical vapor deposition (CVD) to protect the sensor and electrical connections during ionic strength wet testing. Two versions of sensors were fabricated for comparison, the first incorporated diffusion pores into the diaphragm, and the second used a solid diaphragm with perforated backing plate. This new design (perforated diaphragm) was shown to have slightly higher sensitivity than solid diaphragm sensors with separate diffuse backing plates when coupled with the hydrogel. The sensitivities for the 1 mm × 1 mm, 1.25 mm × 1.25 mm, 1.5 mm × 1.5 mm perforated diaphragm sensors were 53.3 ± 6.5, 171.7 ± 8.8, and 271.47 ± 27.53 mV/V-M, respectively. These results show that perforations in the diaphragm can be used not only to allow the diffusion of analyte into the cavity but to increase mechanical stress in the piezoresistive diaphragm, thereby increasing sensor output signal. The time constants for swelling ( τ swelling ) and contracting ( τ contracting ) were calculated by fitting the sensor output half cycles to an exponential growth function. We found that the sensors' response was initially retarded during the preliminary hydrogel conditioning period then improved after 3-5 cycles with values of approximately 9 and 7 min for τ swelling and τ contracting . For all sensors tested τ swelling > τ contracting . This may be due to the increased loading on the hydrogel from the diaphragm during the swelling process. During contraction the diaphragm aids the hydrogel by reversibly applying mechanical pressure and therefore reducing τ contracting . Long term stability testing showed the sensors remained functional for upwards of 2 weeks in the test phosphate buffer solution (PBS).

The Effect of Ionic Strength on the Haemolytic Activity of Complement

PubMed Central

Wardlaw, A. C.; Walker, H. G.

1963-01-01

The haemolytic activity of guinea-pig complement has been measured in isotonic solutions of various ionic strengths in the range 0.034–0.28 and shown to be maximum at an ionic strength close to 0.08. Haemolytic activity was virtually abolished at ionic strength 0.034, while at 0.28, the complement titre was only about 20 per cent of the value found at the physiological ionic strength 0.155. NaCl, KCl, LiBr and K2SO4 were the electrolytes used to provide ionic strength, and sucrose, mannitol and inositol the non-electrolytes used to maintain isotonicity. Nine permutations of the four electrolytes with the three non-electrolytes were tested and gave similar results. Human and rabbit complements also showed optimum haemolytic activity at ionic strength 0.08–0.10. PMID:13998876

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.

Thermophilic Ferritin 24mer Assembly and Nanoparticle Encapsulation Modulated by Interdimer Electrostatic Repulsion.

PubMed

Pulsipher, Katherine W; Villegas, Jose A; Roose, Benjamin W; Hicks, Tacey L; Yoon, Jennifer; Saven, Jeffery G; Dmochowski, Ivan J

2017-07-18

Protein cage self-assembly enables encapsulation and sequestration of small molecules, macromolecules, and nanomaterials for many applications in bionanotechnology. Notably, wild-type thermophilic ferritin from Archaeoglobus fulgidus (AfFtn) exists as a stable dimer of four-helix bundle proteins at a low ionic strength, and the protein forms a hollow assembly of 24 protomers at a high ionic strength (∼800 mM NaCl). This assembly process can also be initiated by highly charged gold nanoparticles (AuNPs) in solution, leading to encapsulation. These data suggest that salt solutions or charged AuNPs can shield unfavorable electrostatic interactions at AfFtn dimer-dimer interfaces, but specific "hot-spot" residues controlling assembly have not been identified. To investigate this further, we computationally designed three AfFtn mutants (E65R, D138K, and A127R) that introduce a single positive charge at sites along the dimer-dimer interface. These proteins exhibited different assembly kinetics and thermodynamics, which were ranked in order of increasing 24mer propensity: A127R < wild type < D138K ≪ E65R. E65R assembled into the 24mer across a wide range of ionic strengths (0-800 mM NaCl), and the dissociation temperature for the 24mer was 98 °C. X-ray crystal structure analysis of the E65R mutant identified a more compact, closed-pore cage geometry. A127R and D138K mutants exhibited wild-type ability to encapsulate and stabilize 5 nm AuNPs, whereas E65R did not encapsulate AuNPs at the same high yields. This work illustrates designed protein cages with distinct assembly and encapsulation properties.

Influence of solution chemistry on the inactivation of particle-associated viruses by UV irradiation.

PubMed

Feng, Zhe; Lu, Ruiqing; Yuan, Baoling; Zhou, Zhenming; Wu, Qingqing; Nguyen, Thanh H

2016-12-01

MS2 inactivation by UV irradiance was investigated with the focus on how the disinfection efficacy is influenced by bacteriophage MS2 aggregation and adsorption to particles in solutions with different compositions. Kaolinite and Microcystis aeruginosa were used as model inorganic and organic particles, respectively. In the absence of model particles, MS2 aggregates formed in either 1mM NaCl at pH=3 or 50-200mM ionic strength CaCl 2 solutions at pH=7 led to a decrease in the MS2 inactivation efficacy because the virions located inside the aggregate were protected from the UV irradiation. In the presence of kaolinite and Microcystis aeruginosa, MS2 adsorbed onto the particles in either 1mM NaCl at pH=3 or 50-200mM CaCl 2 solutions at pH=7. In contrast to MS2 aggregates formed without the presence of particles, more MS2 virions adsorbed on these particles were exposed to UV irradiation to allow an increase in MS2 inactivation. In either 1mM NaCl at pH from 4 to 8 or 2-200mM NaCl solutions at pH=7, the absence of MS2 aggregation and adsorption onto the model particles explained why MS2 inactivation was not influenced by pH, ionic strength, and the presence of model particles in these conditions. The influence of virus adsorption and aggregation on the UV disinfection efficiency found in this research suggests the necessity of accounting for particles and cation composition in virus inactivation for drinking water. Copyright © 2016 Elsevier B.V. All rights reserved.

Ionic strength and DOC determinations from various freshwater sources to the San Francisco Bay

USGS Publications Warehouse

Hunter, Y.R.; Kuwabara, J.S.

1994-01-01

An exact estimation of dissolved organic carbon (DOC) within the salinity gradient of zinc and copper metals is significant in understanding the limit to which DOC could influence metal speciation. A low-temperature persulfate/oxygen/ultraviolet wet oxidation procedure was utilized for analyzing DOC samples adapted for ionic strength from major freshwater sources of the northern and southern regions of San Francisco Bay. The ionic strength of samples was modified with a chemically defined seawater medium up to 0.7M. Based on the results, a minimum effect of ionic strength on oxidation proficiency for DOC sources to the Bay over an ionic strength gradient of 0.0 to 0.7 M was observed. There was no major impacts of ionic strength on two Suwanee River fulvic acids. In general, the noted effects associated with ionic strength were smaller than the variances seen in the aquatic environment between high- and low-temperature methods.

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.

Determination of the Effects of Medium Composition on the Monochloramine Disinfection Kinetics of Nitrosomonas europaea by the Propidium Monoazide Quantitative PCR and Live/Dead BacLight Methods

EPA Science Inventory

Various media compositions (phosphate 1-50 mM; ionic strength 2.8-150 meq/L) significantly affected Nitrosomonas europaea monochloramine disinfection kinetics determined by Live/Dead BacLight (LD) and propidium monoazide quantitative PCR (PMA-qPCR) methods (lag coefficient 37-490...

Distinct Effects of Humic Acid on Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Sand Column

EPA Science Inventory

Distinct effects of humic acid (HA, 0 – 10 mg L-1) on the transport of titanium dioxide (rutile) nanoparticles (nTiO2) through saturated sand columns were observed under conditions of environmental relevance (ionic strength 3 – 200 mM NaCl, pH 5.7 and 9.0). Specifical...

Erythrocyte agglutination by wheat germ agglutinin: ionic strength dependence of the contact seam topology.

PubMed

Rolfe, M; Parmar, A; Hoy, T G; Coakley, W T

2001-01-01

The topology of the cell-cell contact seam formed when normal or pronase pre-treated (PPT) erythrocytes are exposed to wheat germ agglutinin (WGA) in isotonic media of different ionic strengths was examined here. Lectin uptake and cell agglutination were also quantified. Agglutination of normal cells was gradually and significantly inhibited as ionic strength (IS) was reduced from 0.15 (buffered 145 mm NaCl) to 0.105. Agglutination was less inhibited in PPT cells, even when IS was reduced to 0.09. Cell contact seams formed during agglutination showed patterns of localized contacts. The scale of the patterns, i.e. the average lateral separation distance of contact regions, was 0.62 microm for normal cells and was significantly shorter, at 0.44 microm, for PPT cells at an IS of 0.15. The scale increased significantly for both cell types when the IS was reduced to 0.09. Flow cytometry measurements showed that WGA uptake by normal cells increased slightly, whilst that for PPT cells was unchanged, as IS was decreased from 0.15 to 0.09. The results imply that, whilst ionic strength change does not exert a strong influence on intermolecular WGA-ligand binding, physico-chemical modification of the interaction between cells modulates not only the extent and progression of the biospecific lectin-induced cell-cell agglutination but also the topology of the contact seam. The IS dependence of contact separation in WGA-agglutinated cells is contrasted here with that reported for cells adhering in dextran solutions. The influence of IS change and pronase pre-treatment on contact pattern are consistent with predictions, from interfacial instability theory, of punctuate thinning of the aqueous layer separating bilayer membranes in close apposition.

Viscoelastic properties of cationic starch adsorbed on quartz studied by QCM-D.

PubMed

Tammelin, Tekla; Merta, Juha; Johansson, Leena-Sisko; Stenius, Per

2004-12-07

The adsorption and viscoelastic properties of layers of a cationic polyelectrolyte (cationic starch, CS, with 2-hydroxy-3-trimethylammoniumchloride as the substituent) adsorbed from aqueous solutions (pH 7.5, added NaCl 0, 1, 100, and 500 mM) on silica were studied with a quartz crystal microbalance with dissipation (QCM-D). Three different starches were investigated (weight-average molecular weights M(w) approximately 8.7 x 10(5) and 4.5 x 10(5) with degree of substitution DS = 0.75 and M(w) approximately 8.8 x 10(5) with DS = 0.2). At low ionic strength, the adsorbed layers are thin and rigid and the amount adsorbed can be calculated using the Sauerbrey equation. When the ionic strength is increased, significant changes take place in the amount of adsorbed CS and the viscoelasticity of the adsorbed layer. These changes were analyzed assuming that the layer can be described as a Voigt element on a rigid surface in contact with purely viscous solvent. It was found that CS with low charge density forms a thicker and more mobile layer with higher viscosity and elasticity than CS with high charge density. The polymers adsorbed on the silica even when the ionic strength was so high that electrostatic interactions were effectively screened. At this high ionic strength, it was possible to study the effect of molecular weight and molecular weight distribution of the CS on the properties of the adsorbed film. Increasing the molecular weight of CS resulted in a larger hydrodynamic thickness. CS with a narrow molecular weight distribution formed a more compact and rigid layer than broadly distributed CS, presumably due to the better packing of the molecules.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

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

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

Charge-based characterization of nanometric cationic bifunctional maghemite/silica core/shell particles by capillary zone electrophoresis.

PubMed

d'Orlyé, Fanny; Varenne, Anne; Georgelin, Thomas; Siaugue, Jean-Michel; Teste, Bruno; Descroix, Stéphanie; Gareil, Pierre

2009-07-01

In view of employing functionalized nanoparticles (NPs) in the context of an immunodiagnostic, aminated maghemite/silica core/shell particles were synthesized so as to be further coated with an antibody or an antigen via the amino groups at their surface. Different functionalization rates were obtained by coating these maghemite/silica core/shell particles with 3-(aminopropyl)triethoxysilane and 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane at different molar ratios. Adequate analytical performances with CE coupled with UV-visible detection were obtained through semi-permanent capillary coating with didodecyldimethyl-ammonium bromide, thus preventing particle adsorption. First, the influence of experimental conditions such as electric field strength, injected particle amount as well as electrolyte ionic strength and pH, was evaluated. A charge-dependent electrophoretic mobility was evidenced and the separation selectivity was tuned according to electrolyte ionic strength and pH. The best resolutions were obtained at pH 8.0, high ionic strength (ca. 100 mM), and low total particle volume fraction (ca. 0.055%), thus eliminating interference effects between different particle populations in mixtures. A protocol derived from Kaiser's original description was performed for quantitation of the primary amino groups attached onto the NP surface. Thereafter a correlation between particle electrophoretic mobility and the density of amino groups at their surface was established. Eventually, CE proved to be an easy, fast, and reliable method for the determination of NP effective surface charge density.

The flexible structure of the K24S28 region of Leucine-Rich Amelogenin Protein (LRAP) bound to apatites as a function of surface type, calcium, mutation, and ionic strength

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

Lu, Junxia; Burton, Sarah D.; Xu, Yimin

2014-07-11

Leucine-Rich Amelogenin Protein (LRAP) is a member of the amelogenin family of biomineralization proteins, proteins which play a critical role in enamel formation. Recent studies have revealed the structure and orientation of the N- and C-terminus of LRAP bound to hydroxyapatite (HAP), a surface used as an analog of enamel. The structure of one region, K24 to S28, was found to be sensitive to phosphorylation of S16, the only naturally observed site of serine phosphorylation in LRAP, suggesting that the residues from K24 to S28 may sit at a key region of structural flexibility and play a role in themore » protein’s function. In this work, we investigated the sensitivity of the structure and orientation of this region when bound to HAP as a function of several factors which may vary during enamel formation to influence structure: the ionic strength (0.05 M, 0.15 M, 0.2 M), the calcium concentration (0.07 mM and 0.4 mM), and the surface to which it is binding (HAP and carbonated apatite (CAP), a more direct mimic of enamel). A naturally occurring mutation found in amelogenin (T21I), was also investigated. The structure in the K24S28 region of the protein was found to be sensitive to these conditions, with the CAP surface and excess Ca2+ (8:1 [Ca2+]:[LRAP-K24S28(+P)]) resulting in a much tighter helix, while low ionic strength relaxed the helical structure. Higher ionic strength and the point mutation did not result in any structural change in this region. The distance of the backbone of K24 from the surface was most sensitive to excess Ca2+ and in the T21I-mutation. Collectively, these data suggest that the protein is able to accommodate structural changes while maintaining its interaction with the surface, and provides further evidence of the structural sensitivity of the K24 to S28 region, a sensitivity that may contribute to function in biomineralization. This research was supported by NIH-NIDCR Grant DE-015347. The research was performed at the Pacific Northwest National Laboratory (PNNL), a facility operated by Battelle for the U.S. Department of Energy.« less

Characterization of aggregates of surface modified fullerenes by asymmetrical flow field-flow fractionation with multi-angle light scattering detection.

PubMed

Astefanei, Alina; Kok, Wim Th; Bäuerlein, Patrick; Núñez, Oscar; Galceran, Maria Teresa; de Voogt, Pim; Schoenmakers, Peter J

2015-08-21

Fullerenes are carbon nanoparticles with widespread biomedical, commercial and industrial applications. Attributes such as their tendency to aggregate and aggregate size and shape impact their ability to be transported into and through the environment and living tissues. Knowledge of these properties is therefore valuable for their human and environmental risk assessment as well as to control their synthesis and manufacture. In this work, asymmetrical flow-field flow fractionation (AF4) coupled to multi-angle light scattering (MALS) was used for the first time to study the size distribution of surface modified fullerenes with both polyhydroxyl and carboxyl functional groups in aqueous solutions having different pH (6.5-11) and ionic strength values (0-200mM) of environmental relevance. Fractionation key parameters such as flow rates, flow programming, and membrane material were optimized for the selected fullerenes. The aggregation of the compounds studied appeared to be indifferent to changes in solution pH, but was affected by changes in the ionic strength. Polyhydroxy-fullerenes were found to be present mostly as 4nm aggregates in water without added salt, but showed more aggregation at high ionic strength, with an up to 10-fold increase in their mean hydrodynamic radii (200mM), due to a decrease in the electrostatic repulsion between the nanoparticles. Carboxy-fullerenes showed a much stronger aggregation degree in water (50-100nm). Their average size and recoveries decreased with the increase in the salt concentration. This behavior can be due to enhanced adsorption of the large particles to the membrane at high ionic strength, because of their higher hydrophobicity and much larger particle sizes compared to polyhydroxy-fullerenes. The method performance was evaluated by calculating the run-to-run precision of the retention time (hydrodynamic radii), and the obtained RSD values were lower than 1%. MALS measurements showed aggregate sizes that were in good agreement with the AF4 data. A comparison of the scattering radii from the MALS with the hydrodynamic radii obtained from the retention times in AF4 indicated that the aggregate shapes are far from spherical. TEM images of the fullerenes in the dry state also showed branched and irregular clusters. Copyright © 2015 Elsevier B.V. All rights reserved.

Distinct Effects of Humic Acid on Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Sand Columns

EPA Science Inventory

The distinct effects of humic acid (HA, 0−10 mg L−1) on the transport of titanium dioxide (rutile) nanoparticles (nTiO2) through saturated sand columns were observed under conditions of environmental relevance (ionic strength 3−200 mM NaCl, pH 5.7 and 9.0). Specifically, the tra...

Separation of alpha-lactalbumin grafted- and non-grafted maghemite core/silica shell nanoparticles by capillary zone electrophoresis.

PubMed

Petr, Jan; Teste, Bruno; Descroix, Stéphanie; Siaugue, Jean-Michel; Gareil, Pierre; Varenne, Anne

2010-08-01

The use of nanoparticles (NPs) in immunodiagnostics is a challenging task for many reasons, including the need for miniaturization. In view of the development of an assay dedicated to an original, miniaturized and fully automated immunodiagnostics which aims to mimic in vivo interactions, magnetic zwitterionic bifunctional amino/polyethyleneoxide maghemite core/silica shell NPs functionalized with allergenic alpha-lactalbumin were characterized by CE. Proper analytical performances were obtained through semi-permanent capillary coating with didodecyldimethylammonium bromide (DDAB) or permanent capillary wall modification by hydroxypropylcellulose. The influence of experimental conditions (e.g. buffer component nature, pH, ionic strength, and electric field strength) on sample stability, electrophoretic mobility, and dispersion was investigated using either DDAB- or hydroxypropylcellulose-coated capillaries. Adsorption to the capillary wall and aggregation phenomena were evaluated according to the CE conditions. The proper choice of experimental conditions, i.e. separation under -10 kV in a 25 mM ionic strength MES/NaOH (pH 6.0) with a DDAB-coated capillary, allowed the separation of the grafted and the non-grafted NPs.

Removal of natural organic matter by titanium tetrachloride: The effect of total hardness and ionic strength.

PubMed

Zhao, Y X; Shon, H K; Phuntsho, S; Gao, B Y

2014-02-15

This study is the first attempt to investigate the effect of total hardness and ionic strength on coagulation performance and the floc characteristics of titanium tetrachloride (TiCl4). Membrane fouling under different total hardness and ionic strength conditions was also evaluated during a coagulation-ultrafiltration (C-UF) hybrid process. Coagulation experiments were performed with two simulated waters, using humic acid (HA, high molecular weight) and fulvic acid (FA, relatively low molecular weight), respectively, as model natural organic matter (NOM). Results show that both particle and organic matter removal can be enhanced by increasing total hardness and ionic strength. Floc characteristics were significantly influenced by total hardness and ionic strength and were improved in terms of floc size, growth rate, strength, recoverability and compactness. The results of the UF tests show that the pre-coagulation with TiCl4 significantly improves the membrane permeate fluxes. Under different total hardness and ionic strength conditions, the membrane permeate flux varied according to both NOM and floc characteristics. The increase in total hardness and ionic strength improved the membrane permeate flux in the case of HA simulated water treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Concept of Ionic Strength Eighty Years after Its Introduction in Chemistry

ERIC Educational Resources Information Center

Manuel E. Sastre de Vicente

2004-01-01

Some comments on the relationship of ionic strength to macroscopic concepts such as thermodynamic quantities and microscopic ones such as molecule size are presented. The meaning of ionic strength is also reviewed.

Entropic and Electrostatic Effects on the Folding Free Energy of a Surface-Attached Biomolecule: An Experimental and Theoretical Study

PubMed Central

Watkins, Herschel M.; Vallée-Bélisle, Alexis; Ricci, Francesco; Makarov, Dmitrii E.; Plaxco, Kevin W.

2012-01-01

Surface-tethered biomolecules play key roles in many biological processes and biotechnologies. However, while the physical consequences of such surface attachment have seen significant theoretical study, to date this issue has seen relatively little experimental investigation. In response we present here a quantitative experimental and theoretical study of the extent to which attachment to a charged –but otherwise apparently inert– surface alters the folding free energy of a simple biomolecule. Specifically, we have measured the folding free energy of a DNA stem loop both in solution and when site-specifically attached to a negatively charged, hydroxyl-alkane-coated gold surface. We find that, whereas surface attachment is destabilizing at low ionic strength it becomes stabilizing at ionic strengths above ~130 mM. This behavior presumably reflects two competing mechanisms: excluded volume effects, which stabilize the folded conformation by reducing the entropy of the unfolded state, and electrostatics, which, at lower ionic strengths, destabilizes the more compact folded state via repulsion from the negatively charged surface. To test this hypothesis we have employed existing theories of the electrostatics of surface-bound polyelectrolytes and the entropy of surface-bound polymers to model both effects. Despite lacking any fitted parameters, these theoretical models quantitatively fit our experimental results, suggesting that, for this system, current knowledge of both surface electrostatics and excluded volume effects is reasonably complete and accurate. PMID:22239220

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.

Effects of anions and cations on the resting membrane potential of internally perfused barnacle muscle fibres

PubMed Central

Lakshminarayanaiah, N.; Rojas, E.

1973-01-01

1. Single barnacle muscle fibres from Megabalanus psittacus (Darwin) were internally perfused with a number of K salt solutions (200 mM) which were made isotonic to the barnacle saline with sucrose. 2. 200 mM-K acetate solution, in general, was found to be more effective than other solutions of K salts in generating and maintaining stable resting membrane potential of -56·0 ± 0·7 mV (all potentials are referred to the external solutions as ground). The various K salts, on the basis of the magnitude of the resting potential they generated in the muscle fibres, followed the sequence, acetate > isethionate > aspartate > glutamate > fluoride > monohydrogen phosphate > succinate > citrate > sulphate > oxalate > iodobenzoate > ferrocyanide > chlorate > nitrate > chloride > thiocyanate > iodide > bromide > cyanide. 3. The resting potential in muscle fibres perfused with solutions of acetate, aspartate and glutamate increased linearly with the logarithm of the K concentration (slope = 30·4 mV for K acetate and 27·4 for K aspartate and glutamate) when the ionic strength of the solutions was progressively increased from 50 to 650 mM. On the other hand, similar increase of ionic strength beyond 200 mM of solutions of K isethionate, fluoride, monohydrogen phosphate, succinate and citrate depolarized the muscle fibres. 4. Perfusion of acetate solutions of other alkali metal ions gave low values for the resting potential and followed the sequence K > Na > Rb > Li > Cs. Also NH4 and Tris ions gave low values for the resting potential which underwent oscillations associated with the twitching of the fibre and occasionally became positive in value (action potential). 5. Addition of tetraethyl ammonium chloride (TEA-Cl), 20-100 mM, to K acetate solutions (200 mM) depolarized the fibre membrane and the consequent reduction of resting potential varied linearly with the logarithm of TEA concentration. 6. Replacement of chloride ion by acetate or isethionate in the external solution did not change significantly the resting potential although the values were consistently lower by about 2 mV. 7. Complete elimination of K in the external solution and reduction of its ionic strength using sucrose depolarized the muscle fibres by about 27 mV when Na was changed from 475 to 1 mM. Under these conditions, external solutions completely in acetate form gave resting potentials which were more positive than those observed in completely chloride solutions by 6-8 mV. 8. Replacement of Na by Li, Tris, choline, tetramethyl or tetraethyl ammonium ion in the external solution made the values of the resting potential more positive (depolarization). Similarly increasing the concentration of K (or Cs or Rb in place of K) by correspondingly decreasing the concentration of Na in the outside solution depolarized the fibres and the resting potential became zero at a concentration of 280 mM (or 308 or 1500 mM for Rb or Cs, respectively) on extrapolation. PMID:4754874

Purification of foot-and-mouth disease virus by heparin as ligand for certain strains.

PubMed

Du, Ping; Sun, Shiqi; Dong, Jinjie; Zhi, Xiaoying; Chang, Yanyan; Teng, Zhidong; Guo, Huichen; Liu, Zaixin

2017-04-01

The goal of this project was to develop an easily operable and scalable process for the recovery and purification of foot-and-mouth disease virus (FMDV) from cell culture. Heparin resins HipTrap Heparin HP and AF-Heparin HC-650 were utilized to purify FMDV O/HN/CHA/93. Results showed that the purity of AF-Heparin HC-650 was ideal. Then, the O/HN/CHA/93, O/Tibet/CHA/99, Asia I/HN/06, and A/CHA/HB/2009 strains were purified by AF-Heparin HC-650. Their affinity/virus recoveries were approximately 51.2%/45.8%, 71.5%/70.9%, 96.4%/73.5, and 59.5%/42.1%, respectively. During a stepwise elution strategy, the viral particles were mainly eluted at 300mM ionic strength peaks. The heparin affinity chromatography process removed more than 94% of cellular and medium proteins. Anion exchange resin Capto Q captured four FMD virus particles; 40% of binding proteins and 80%-90% of viral particles were eluted at 450mM NaCl. Moreover, ionic strength varied from 30 to 450mM had no effect on the immunity to FMDV. The results revealed that heparin sulfate may be the main receptor for CHA/99 strain attachment-susceptible cells. Heparin affinity chromatography can reach perfect results, especially when used as a ligand of the virus. Anion exchange is useful only as previous step for further purification. Copyright © 2016. Published by Elsevier B.V.

The negative and positive electrorheological behavior and vibration damping characteristics of colemanite and polyindene/colemanite conducting composite

NASA Astrophysics Data System (ADS)

Cetin, B.; Unal, H. I.; Erol, O.

2012-12-01

In this study, the electrorheological (ER) properties of colemanite and polyindene (94.8% PIn)/colemanite (5.2%) conducting composite were investigated by dispersion in silicone oil (SO). The zeta (ζ)-potentials and antisedimentation ratios of the materials were determined. Some parameters which affect the ER properties of all the dispersions such as the volume fraction, electric field strength (E), shear rate, frequency and temperature were investigated. The rather unusual behavior known as the negative ER effect was observed for colemanite/SO above E = 1.5 kV mm-1 and for PIn/colemanite/SO under all values of the electric field strength even at high volume fraction. This negative ER response was converted to a positive one by the addition of non-ionic surfactant. Furthermore, glycerol was used as a polar promoter and observed to enhance the ER activity of the colemanite/SO system. Creep-recovery tests were applied to all the dispersions studied to investigate their behavior under sustained shear stress. Finally, 28% and 30% vibration damping capacities were achieved using an automobile shock absorber for the glycerol/colemanite/SO and non-ionic surfactant/PIn/colemanite/SO systems under the E = 0.17 kV mm-1 condition, respectively.

Retention of neodymium by dolomite at variable ionic strength as probed by batch and column experiments.

PubMed

Emerson, H P; Zengotita, F; Richmann, M; Katsenovich, Y; Reed, D T; Dittrich, T M

2018-10-01

The results presented in this paper highlight the complexity of adsorption and incorporation processes of Nd with dolomite and significantly improve upon previous work investigating trivalent actinide and lanthanide interactions with dolomite. Both batch and mini column experiments were conducted at variable ionic strength. These data highlight the strong chemisorption of Nd to the dolomite surface (equilibrium K d 's > 3000 mL/g) and suggest that equilibrium adsorption processes may not be affected by ionic strength based on similar results at 0.1 and 5.0 M ionic strength in column breakthrough and equilibrium batch (>5 days) results. Mini column experiments conducted over approximately one year also represent a significant development in measurement of sorption of Nd in the presence of flow as previous large-scale column experiments did not achieve breakthrough likely due to the high loading capacity of dolomite for Nd (up to 240 μg/g). Batch experiments in the absence of flow show that the rate of Nd removal increases with increasing ionic strength (up to 5.0 M) with greater removal at greater ionic strength for a 24 h sampling point. We suggest that the increasing ionic strength induces increased mineral dissolution and re-precipitation caused by changes in activity with ionic strength that lead to increased removal of Nd through co-precipitation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Method for printing functional protein microarrays

NASA Technical Reports Server (NTRS)

Delehanty, James B.; Ligler, Frances S.

2003-01-01

Piezoelectric dispensing of proteins from borosilicate glass capillaries is a popular method of protein biochip fabrication that offers the advantages of sample recovery and noncontact with the printing substrate. However, little regard has been given to the quantitative aspects of dispensing minute volumes (1 nL or less) at the low protein concentrations (20 micrograms/mL or less) typically used in microprinting. Specifically, loss of protein sample due to nonspecific adsorption to the glass surface of the dispensing capillaries can limit the amount of protein delivered to the substrate. We demonstrate the benefits of a low ionic strength buffer containing the carrier protein BSA that effectively minimizes the ionic strength-dependent phenomenon of nonspecific protein adsorption to borosilicate glass. Over the concentration range of 20-2.5 micrograms/mL, the dispensing of a reference IgG in 10 mM PBS including 0.1% BSA resulted in the deposition of 3.6- to 44-fold more IgG compared to the deposition of IgG in standard 150 mM PBS in the absence of BSA. Furthermore, when the IgG was dispensed with carrier protein, the resulting spots exhibited a more uniform morphology. In a direct immunoassay for cholera toxin, capture antibody spots dispensed in 10 mM PBS containing 0.1% BSA produced fluorescent signals that were 2.8- to 4.3-fold more intense than antibody spots that were dispensed in 150 mM PBS without BSA. Interestingly, no differences were observed in the specific activities of the capture antibodies as a result of printing in the different buffers. The implications of these results on the future development of protein biochips are discussed.

High ionic strength depresses muscle contractility by decreasing both force per cross-bridge and the number of strongly attached cross-bridges.

PubMed

Wang, Li; Bahadir, Anzel; Kawai, Masataka

2015-06-01

An increase in ionic strength (IS) lowers Ca(2+) activated tension in muscle fibres, however, its molecular mechanism is not well understood. In this study, we used single rabbit psoas fibres to perform sinusoidal analyses. During Ca(2+) activation, the effects of ligands (ATP, Pi, and ADP) at IS ranging 150-300 mM were studied on three rate constants to characterize elementary steps of the cross-bridge cycle. The IS effects were studied because a change in IS modifies the inter- and intra-molecular interactions, hence they may shed light on the molecular mechanisms of force generation. Both the ATP binding affinity (K1) and the ADP binding affinity (K 0) increased to 2-3x, and the Pi binding affinity (K5) decreased to 1/2, when IS was raised from 150 to 300 mM. The effect on ATP/ADP can be explained by stereospecific and hydrophobic interaction, and the effect on Pi can be explained by the electrostatic interaction with myosin. The increase in IS increased cross-bridge detachment steps (k2 and k-4), indicating that electrostatic repulsion promotes these steps. However, IS did not affect attachment steps (k-2 and k4). Consequently, the equilibrium constant of the detachment step (K2) increased by ~100%, and the force generation step (K4) decreased by ~30%. These effects together diminished the number of force-generating cross-bridges by 11%. Force/cross-bridge (T56) decreased by 26%, which correlates well with a decrease in the Debye length that limits the ionic atmosphere where ionic interactions take place. We conclude that the major effect of IS is a decrease in force/cross-bridge, but a decrease in the number of force generating cross-bridge also takes place. The stiffness during rigor induction did not change with IS, demonstrating that in-series compliance is not much affected by IS.

Determination of the Effects of Medium Composition on the Monochloramine Disinfection Kinetics of Nitrosomonas europaea by the Propidium Monoazide Quantitative PCR and Live/Dead BacLight Methods ▿

PubMed Central

Wahman, David G.; Schrantz, Karen A.; Pressman, Jonathan G.

2010-01-01

Various medium compositions (phosphate, 1 to 50 mM; ionic strength, 2.8 to 150 meq/liter) significantly affected Nitrosomonas europaea monochloramine disinfection kinetics, as determined by the Live/Dead BacLight (LD) and propidium monoazide quantitative PCR (PMA-qPCR) methods (lag coefficient, 37 to 490 [LD] and 91 to 490 [PMA-qPCR] mg·min/liter; Chick-Watson rate constant, 4.0 × 10−3 to 9.3 × 10−3 [LD] and 1.6 × 10−3 to 9.6 × 10−3 [PMA-qPCR] liter/mg·min). Two competing effects may account for the variation in disinfection kinetic parameters: (i) increasing kinetics (disinfection rate constant [k] increased, lag coefficient [b] decreased) with increasing phosphate concentration and (ii) decreasing kinetics (k decreased, b increased) with increasing ionic strength. The results support development of a standard medium for evaluating disinfection kinetics in drinking water. PMID:20952645

Through thick and thin: a microfluidic approach for continuous measurements of biofilm viscosity and the effect of ionic strength.

PubMed

Paquet-Mercier, F; Parvinzadeh Gashti, M; Bellavance, J; Taghavi, S M; Greener, J

2016-11-29

Continuous, non-intrusive measurements of time-varying viscosity of Pseudomonas sp. biofilms are made using a microfluidic method that combines video tracking with a semi-empirical viscous flow model. The approach uses measured velocity and height of tracked biofilm segments, which move under the constant laminar flow of a nutrient solution. Following a low viscosity growth stage, rapid thickening was observed. During this stage, viscosity increased by over an order of magnitude in less than ten hours. The technique was also demonstrated as a promising platform for parallel experiments by subjecting multiple biofilm-laden microchannels to nutrient solutions containing NaCl in the range of 0 to 34 mM. Preliminary data suggest a strong relationship between ionic strength and biofilm properties, such as average viscosity and rapid thickening onset time. The technique opens the way for a combinatorial approach to study the response of biofilm viscosity under well-controlled physical, chemical and biological growth conditions.

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.

Effects of ionic strength on passive and iontophoretic transport of cationic permeant across human nail.

PubMed

Smith, Kelly A; Hao, Jinsong; Li, S Kevin

2009-06-01

Transport across the human nail under hydration can be modeled as hindered transport across aqueous pore pathways. As such, nail permselectivity to charged species can be manipulated by changing the ionic strength of the system in transungual delivery to treat nail diseases. The present study investigated the effects of ionic strength upon transungual passive and iontophoretic transport. Transungual passive and anodal iontophoretic transport experiments of tetraethylammonium ion (TEA) were conducted under symmetric conditions in which the donor and receiver had the same ionic strength in vitro. Experiments under asymmetric conditions were performed to mimic the in vivo conditions. Prior to the transport studies, TEA uptake studies were performed to assess the partitioning of TEA into the nail. Permselectivity towards TEA was inversely related to ionic strength in both passive and iontophoretic transport. The permeability and transference number of TEA were higher at lower ionic strengths under the symmetric conditions due to increased partitioning of TEA into the nail. Transference numbers were smaller under the asymmetric conditions compared with their symmetric counterparts. The results demonstrate significant ionic strength effects upon the partitioning and transport of a cationic permeant in transungual transport, which may be instrumental in the development of transungual delivery systems.

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.

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.

Influence of Ionic Strength on the Deposition of Metal-Phenolic Networks.

PubMed

Guo, Junling; Richardson, Joseph J; Besford, Quinn A; Christofferson, Andrew J; Dai, Yunlu; Ong, Chien W; Tardy, Blaise L; Liang, Kang; Choi, Gwan H; Cui, Jiwei; Yoo, Pil J; Yarovsky, Irene; Caruso, Frank

2017-10-10

Metal-phenolic networks (MPNs) are a versatile class of self-assembled materials that are able to form functional thin films on various substrates with potential applications in areas including drug delivery and catalysis. Different metal ions (e.g., Fe III , Cu II ) and phenols (e.g., tannic acid, gallic acid) have been investigated for MPN film assembly; however, a mechanistic understanding of the thermodynamics governing MPN formation remains largely unexplored. To date, MPNs have been deposited at low ionic strengths (<5 mM), resulting in films with typical thicknesses of ∼10 nm, and it is still unclear how a bulk complexation reaction results in homogeneous thin films when a substrate is present. Herein we explore the influence of ionic strength (0-2 M NaCl) on the conformation of MPN precursors in solution and how this determines the final thickness and morphology of MPN films. Specifically, the film thickness increases from 10 nm in 0 M NaCl to 12 nm in 0.5 M NaCl and 15 nm in 1 M NaCl, after which the films grow rougher rather than thicker. For example, the root-mean-square roughness values of the films are constant below 1 M NaCl at 1.5 nm; in contrast, the roughness is 3 nm at 1 M NaCl and increases to 5 nm at 2 M NaCl. Small-angle X-ray scattering and molecular dynamics simulations allow for comparisons to be made with chelated metals and polyelectrolyte thin films. For example, at a higher ionic strength (2 M NaCl), sodium ions shield the galloyl groups of tannic acid, allowing them to extend away from the Fe III center and interact with other MPN complexes in solution to form thicker and rougher films. As the properties of films determine their final performance and application, the ability to tune both thickness and roughness using salts may allow for new applications of MPNs.

Controlling adsorption and passivation properties of bovine serum albumin on silica surfaces by ionic strength modulation and cross-linking.

PubMed

Park, Jae Hyeon; Sut, Tun Naw; Jackman, Joshua A; Ferhan, Abdul Rahim; Yoon, Bo Kyeong; Cho, Nam-Joon

2017-03-29

Understanding the physicochemical factors that influence protein adsorption onto solid supports holds wide relevance for fundamental insights into protein structure and function as well as for applications such as surface passivation. Ionic strength is a key parameter that influences protein adsorption, although how its modulation might be utilized to prepare well-coated protein adlayers remains to be explored. Herein, we investigated how ionic strength can be utilized to control the adsorption and passivation properties of bovine serum albumin (BSA) on silica surfaces. As protein stability in solution can influence adsorption kinetics, the size distribution and secondary structure of proteins in solution were first characterized by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and circular dichroism (CD) spectroscopy. A non-monotonic correlation between ionic strength and protein aggregation was observed and attributed to colloidal agglomeration, while the primarily α-helical character of the protein in solution was maintained in all cases. Quartz crystal microbalance-dissipation (QCM-D) experiments were then conducted in order to track protein adsorption onto silica surfaces as a function of ionic strength, and the measurement responses indicated that total protein uptake at saturation coverage is lower with increasing ionic strength. In turn, the QCM-D data and the corresponding Voigt-Voinova model analysis support that the surface area per bound protein molecule is greater with increasing ionic strength. While higher protein uptake under lower ionic strengths by itself did not result in greater surface passivation under subsequent physiologically relevant conditions, the treatment of adsorbed protein layers with a gluteraldehyde cross-linking agent stabilized the bound protein in this case and significantly improved surface passivation. Collectively, our findings demonstrate that ionic strength modulation influences BSA adsorption uptake on account of protein spreading and can be utilized in conjunction with covalent cross-linking strategies to prepare well-coated protein adlayers for improved surface passivation.

Reproduction of Venezulean Equine Encephalomyelitis Virus at Low Ionic Strength

DTIC Science & Technology

1975-02-28

AD/A-006 206 REPRODUCTION OF VENEZUELAN EQUINE ENCEPHALOMYELITIS VIRUS AT LOW IONIC STRENGTH T.M. Sokolova, et al Army Medical Research Institute of... Reproduction of Venezuelan equine encephalo- Translation myelitis virus at low ionic strength 6. PERFORM4ING ORG. REPORT NU14BER II!LTT, 0491 7. AUTHOR(a... REPRODUCTION OF VENEZUELAN EQUINE ENCEPHALOMYELITIS VIRUS AT LOW IONIC STRFNGTH Article by T. M. Sokolova, I. B. Tazulakhova, S. S. Grigoryan and F. I. e v

Ionic strength-induced formation of smectite quasicrystals enhances nitroaromatic compound sorption.

PubMed

Li, Hui; Pereira, Tanya R; Teppen, Brian J; Laird, David A; Johnston, Cliff T; Boyd, Stephen A

2007-02-15

Sorption of organic contaminants by soils is a determinant controlling their transport and fate in the environment. The influence of ionic strength on nitroaromatic compound sorption by K+- and Ca2+ -saturated smectite was examined. Sorption of 1,3-dinitrobenzene by K-smectite increased as KCl ionic strength increased from 0.01 to 0.30 M. In contrast, sorption by Ca-smectite at CaCl2 ionic strengths of 0.015 and 0.15 M remained essentially the same. The "salting-out" effect on the decrease of 1,3-dinitrobenzene aqueous solubility within this ionic strength range was <1.5% relative to the solubility in pure water. This decrease of solubility is insufficient to account for the observed increase of sorption by K-smectite with increasing KCl ionic strength. X-ray diffraction patterns and light absorbance of K-clay suspensions indicated the aggregation of clay particles and the formation of quasicrystal structures as KCI ionic strength increased. Sorption enhancement is attributed to the formation of better-ordered K-clay quasicrystals with reduced interlayer distances rather than to the salting-out effect. Dehydration of 1,3-dinitrobenzene is apparently a significant driving force for sorption, and we show for the first time that sorption of small, planar, neutral organic molecules, namely, 1,3-dinitrobenzene, causes previously expanded clay interlayers to dehydrate and collapse in aqueous suspension.

Translational recognition of the 5'-terminal 7-methylguanosine of globin messenger RNA as a function of ionic strength.

PubMed

Chu, L Y; Rhoads, R E

1978-06-13

The translation of rabbit globin mRNA in cell-free systems derived from either wheat germ or rabbit reticulocyte was studied in the presence of various analogues of the methylated 5' terminus (cap) as a function of ionic strength. Inhibition by these analogues was strongly enhanced by increasing concentrations of KCl, K(OAc), Na(OAc), or NH4(OAc). At appropriate concentrations of K(OAc), both cell-free systems were equally sensitive to inhibition by m7GTP. At 50 mM K(OAc), the reticulocyte system was not sensitive to m7GMP or m7GTP, but at higher concentrations up to 200 mM K(OAc), both nucleotides caused strong inhibition. The compound in m7G5'ppp5'Am was inhibitory at all concentrations of K(OAc) ranging from 50 to 200 mM, although more strongly so at the higher concentrations. Over the same range of nucleotide concentrations, the compounds GMP, GTP, and G5'ppp5'Am were not inhibitors. The mobility on sodium dodecyl sulfate-polyacrylamide electrophoresis of the translation product was that of globin at all K(OAc) concentrations in the presence of m7GTP. Globin mRNA from which the terminal m7GTP group had been removed by chemical treatment (periodate-cyclohexylamine-alkaline phosphatase) or enzymatic treatment (tobacco acid pyrophosphatase-alkaline phosphatase) was translated less efficiently than untreated globin mRNA at higher K(OAc) concentrations, but retained appreciable activity at low K(OAc) concentrations.

The Effect of Ionic Strength on the Solubility of an Electrolyte

ERIC Educational Resources Information Center

Willey, Joan D.

2004-01-01

A simple experiment was conducted for studying and demonstrating visually and dramatically the effect of ionic strength on the solubility of an electrolyte is described. It is seen that the experiment visually illustrates the effect of ionic strength on electrolyte solubility by the appearance of the two solutions and by the difference in the…

Evaluation of effects of pH and ionic strength on colloidal stability of IgG solutions by PEG-induced liquid-liquid phase separation.

PubMed

Thompson, Ronald W; Latypov, Ramil F; Wang, Ying; Lomakin, Aleksey; Meyer, Julie A; Vunnum, Suresh; Benedek, George B

2016-11-14

Colloidal stability of IgG antibody solutions is important for pharmaceutical and medicinal applications. Solution pH and ionic strength are two key factors that affect the colloidal stability of protein solutions. In this work, we use a method based on the PEG-induced liquid-liquid phase separation to examine the effects of pH and ionic strength on the colloidal stability of IgG solutions. We found that at high ionic strength (≥0.25M), the colloidal stability of most of our IgGs is insensitive to pH, and at low ionic strength (≤0.15M), all IgG solutions are much more stable at pH 5 than at pH 7. In addition, the PEG-induced depletion force is less efficient in causing phase separation at pH 5 than at pH 7. In contrast to the native inter-protein interaction of IgGs, the effect of depletion force on phase separation of the antibody solutions is insensitive to ionic strength. Our results suggest that the long-range electrostatic inter-protein repulsion at low ionic strength stabilizes the IgG solutions at low pH. At high ionic strength, the short-range electrostatic interactions do not make a significant contribution to the colloidal stability for most IgGs with a few exceptions. The weaker effect of depletion force at lower pH indicates a reduction of protein concentration in the condensed phase. This work advances our basic understanding of the colloidal stability of IgG solutions and also introduces a practical approach to measuring protein colloidal stability under various solution conditions.

Viscoelasticity of nano-alumina dispersions

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

Rand, B.; Fries, R.

1996-06-01

The flow and viscoelastic properties of electrostatically stabilized nano-alumina dispersions have been studied as a function of ionic strength and volume fraction of solids. At low ionic strength the suspensions were deflocculated and showed a transition from viscous to elastic behavior as the solid content increased associated with the onset of double layer interpenetration. The phase transition was progressively shifted to higher solids fractions with increasing ionic strength. At higher ionic strength, above the critical coagulation concentration, the suspensions formed attractive networks characterized by high elasticity. Two independent methods of estimating the effective radius of electrostatically stabilized {open_quotes}soft{close_quotes} particles, a{submore » eff}, are presented based on phase angle data and a modified Dougherty-Krieger equation. The results suggest that a{sub eff} is not constant for a given system but changes with both solids fraction and ionic strength.« less

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 effect of addition of primary positive salts, complex salt, on the ionic strength and rate constant at various temperatures by reaction kinetics

NASA Astrophysics Data System (ADS)

Kurade, S. S.; Ramteke, A. A.

2018-05-01

In this work, we have investigated the rate of reaction by using ionic strength at different temperatures. The main goal of this experiment is to determine the relation between ionic strength with reaction rate, reaction time and rate constant with temperature. It is observed that the addition of positive salt indicate the increasing ionic strength with increase in run time at various temperatures. Thus the temperature affects the speed of reaction and mechanism by which chemical reaction occurs and time variable plays vital role in the progress of reaction at different temperatures.

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.

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.

On the Formation of Lightweight Nanocrystalline Aluminum Alloys by Electrodeposition

DOE PAGES

Hilty, Robert D.; Masur, Lawrence J.

2017-08-08

New nanocrystalline aluminum alloys have been fabricated by electrodeposition. These are thermodynamically stable alloys of Al-Mn and Al-Zr with grain sizes < 100nm. Al-Mn and Al-Zr alloys are characterized here showing high strength (up to 1350 MPa) and hardness (up to 450 HVN) while maintaining the specific gravity of Al. Smooth and dense deposits plated from ionic liquids, such as EMIM:Cl (1-Ethyl-3-methylimidazolium chloride), can develop to thicknesses of 1mm or more.

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.

Polarographic determination of lead hydroxide formation constants at low ionic strength

USGS Publications Warehouse

Lind, Carol J.

1978-01-01

Values of formation constants for lead hydroxide at 25 ??C were calculated from normal pulse polarographic measurements of 10-6 M lead in 0.01 M sodium perchlorate. The low concentrations simulate those found in many freshwaters, permitting direct application of the values when considering distributions of lead species. The precise evaluation of species distribution in waters at other ionic strengths requires activity coefficient corrections. As opposed to much of the previously published work done at high ionic strength, the values reported here were obtained at low ionic strength, permitting use of smaller and better defined activity coefficient corrections. These values were further confirmed by differential-pulse polarography and differential-pulse anodic stripping voltammetry data. The logs of the values for ??1??? ??2???, and ??3??? were calculated to be 6.59, 10.80, and 13.63, respectively. When corrected to zero ionic strength these values were calculated to be 6.77, 11.07, and 13.89, respectively.

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.

Dispersion and stability of bare hematite nanoparticles: effect of dispersion tools, nanoparticle concentration, humic acid and ionic strength

PubMed Central

Dickson, Dionne; Liu, Guangliang; Li, Chenzhong; Tachiev, Georgio; Cai, Yong

2012-01-01

The aggregation and sedimentation of iron oxide nanoparticles (IONPs) can significantly affect the mobility and reactivity of IONPs and subsequently influence the interaction between IONPs and environmental contaminants. Dispersing bare IONPs into a stable suspension within nanoscale range is an important step for studying the interaction of IONPs with contaminants (e.g., toxic metals). In this study, different techniques to disperse bare IONPs (vortex, bath sonication and probe ultrasonication) and the effects of important environmental factors such as dissolved organic matter and ionic strength on the stability of IONPs dispersions were investigated. Vortex minimally dispersed IONPs with hydrodynamic diameter outside the “nanosize range” (698–2400nm). Similar to vortex, bath sonication could not disperse IONPs efficiently. Probe ultrasonication was more effective at dispersing IONPs (50% or more) with hydrodynamic diameters ranging from 120–140 nm with minimal changes in size and sedimentation of IONPs for a prolonged period of time. Over the course of 168 hours, considerable amounts of IONPs remained dispersed in the presence and absence of low ionic strength (0.1 mM of NaCl) and 100 mg/L of humic acid (HA). These results indicate that IONPs can be broken down efficiently into “nanosize range” by probe ultrasonication and a degree of stability can be achieved without the use of synthetic modifiers to enhance colloidal stability. This dispersion tool could be used to develop a laboratory method to study the adsorption mechanism between dispersed bare IONPs and toxic contaminants. PMID:22289174

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.

High Concentrations of Sodium Chloride Improve Microbicidal Activity of Ibuprofen against Common Cystic Fibrosis Pathogens.

PubMed

Muñoz, Adrián J; Alasino, Roxana V; Garro, Ariel G; Heredia, Valeria; García, Néstor H; Cremonezzi, David C; Beltramo, Dante M

2018-05-17

Ibuprofen (IBU-H), a widely used anti-inflammatory, also shows a marked antimicrobial effect against several bacterial species, including those involved in cystic fibrosis such as Pseudomona aeruginosa , methicillin resistant Staphylococcus aureus and Burkholderia cepacia complex. Additionally, our results show significant synergy between water soluble Na-ibuprofen (IBU-Na) and ionic strength. Salt concentrations above 0.5 M modify the zeta potential promoting the action of Na-IBU; thus, with 1 M sodium chloride, IBU-Na is ten times more efficient than in the absence of ionic strength, and the minimum effective contact time is reduced from hours to minutes. In short time periods, where neither IBU-Na nor controls with 1 M NaCl show activity, the combination of both leads to a reduction in the bacterial load. We also analyzed whether the changes caused by salt on the bacterial membrane also promoted the activity of other microbicide compounds used in cystic fibrosis like gentamicin, tobramycin and phosphomycin. The results show that the presence of ionic strength only enhanced the bactericidal activity of the amphipathic molecule of IBU-Na. In this respect, the effect of saline concentration was also reflected in the surface properties of IBU-Na, where, in addition to the clear differences observed between 145 mM and 1 M, singular behaviors were also found, different in each condition. The combination of anti-inflammatory activity and this improved bactericidal effect of Na-IBU in hypertonic solution provides a new alternative for the treatment of respiratory infections of fibrotic patients based on known and widely used compounds.

Tangeretin-loaded protein nanoparticles fabricated from zein/β-lactoglobulin: preparation, characterization, and functional performance.

PubMed

Chen, Jingjing; Zheng, Jinkai; McClements, David Julian; Xiao, Hang

2014-09-01

The aim of this study was to design a colloidal delivery system to encapsulate poor water-soluble bioactive flavonoid tangeretin so that it could be utilized in various food products as functional ingredient. Tangeretin-loaded protein nanoparticles were produced by mixing an organic phase containing zein and tangeretin with an aqueous phase containing β-lactoglobulin and then converted into powder by freeze-drying. This powder formed a colloidal suspension when dispersed in water that is relatively stable to particle aggregation and sedimentation. The influence of temperature, ionic strength, and pH on the stability of the protein nanoparticles was tested. Extensive particle aggregation occurred at high ionic strength (>100mM) and intermediate pH (4.5-5.5) due to reduced electrostatic repulsion. Extensive aggregation also occurred at temperatures exceeding 60 °C, which was presumably due to increased hydrophobic attraction. Overall, this study shows that protein-based nanoparticles can be used to encapsulate bioactive tangeretin so that it can be readily dispersed in compatible food products. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ionic strength independence of charge distributions in solvation of biomolecules

NASA Astrophysics Data System (ADS)

Virtanen, J. J.; Sosnick, T. R.; Freed, K. F.

2014-12-01

Electrostatic forces enormously impact the structure, interactions, and function of biomolecules. We perform all-atom molecular dynamics simulations for 5 proteins and 5 RNAs to determine the dependence on ionic strength of the ion and water charge distributions surrounding the biomolecules, as well as the contributions of ions to the electrostatic free energy of interaction between the biomolecule and the surrounding salt solution (for a total of 40 different biomolecule/solvent combinations). Although water provides the dominant contribution to the charge density distribution and to the electrostatic potential even in 1M NaCl solutions, the contributions of water molecules and of ions to the total electrostatic interaction free energy with the solvated biomolecule are comparable. The electrostatic biomolecule/solvent interaction energies and the total charge distribution exhibit a remarkable insensitivity to salt concentrations over a huge range of salt concentrations (20 mM to 1M NaCl). The electrostatic potentials near the biomolecule's surface obtained from the MD simulations differ markedly, as expected, from the potentials predicted by continuum dielectric models, even though the total electrostatic interaction free energies are within 11% of each other.

Crystallization of beef heart cytochrome c oxidase

NASA Astrophysics Data System (ADS)

Yoshikawa, Shinya; Shinzawa, Kyoko; Tsukihara, Tomitake; Abe, Toshio; Caughey, Winslow S.

1991-03-01

The three-dimensional structure of cytochrome c oxidase, a complex (multimetal, multisubunit) membrane protein is critical to elucidation of the mechanism of the enzymic reactions and their control. Our recent developments in the crystallization of the enzyme isolated from beef hearts are presented. The crystals appeared more readily at higher protein concentration, lower ionic strength, higher detergent concentration (Brij-35) and lower temperature. Large crystals were obtained by changing one of these parameters to the crystallization point as slowly as possible, keeping the other parameters constant. Increasing the detergent concentration was the most successful method, producing green crystals of the resting oxidized form as hexagonal bipyramids with typical dimensions of 0.6 mm. The usual procedures for crystallization of water soluble proteins, such as increasing ionic strength by vapor diffusion, were not applicable for this enzyme. Crystals of the resting oxidized enzyme belong to a space group of P6 2 or P6 4 with cell dimensions, a = b = 208.7 Å and c = 282.3 Å. The Patterson function shows that the crystal exhibited a non-crystallographic two-fold axis parallel to the c-axis in the asymmetric unit.

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.

Conformational dynamics of bacterial trigger factor in apo and ribosome-bound states.

PubMed

Can, Mehmet Tarik; Kurkcuoglu, Zeynep; Ezeroglu, Gokce; Uyar, Arzu; Kurkcuoglu, Ozge; Doruker, Pemra

2017-01-01

The chaperone trigger factor (TF) binds to the ribosome exit tunnel and helps cotranslational folding of nascent chains (NC) in bacterial cells and chloroplasts. In this study, we aim to investigate the functional dynamics of fully-atomistic apo TF and its complex with 50S. As TF accomodates a high percentage of charged residues on its surface, the effect of ionic strength on TF dynamics is assessed here by performing five independent molecular dynamics (MD) simulations (total of 1.3 micro-second duration) at 29 mM and 150 mM ionic strengths. At both concentrations, TF exhibits high inter- and intra-domain flexibility related to its binding (BD), core (CD), and head (HD) domains. Even though large oscillations in gyration radius exist during each run, we do not detect the so-called 'fully collapsed' state with both HD and BD collapsed upon the core. In fact, the extended conformers with relatively open HD and BD are highly populated at the physiological concentration of 150 mM. More importantly, extended TF snapshots stand out in terms of favorable docking onto the 50S subunit. Elastic network modeling (ENM) indicates significant changes in TF's functional dynamics and domain decomposition depending on its conformation and positioning on the 50S. The most dominant slow motions are the lateral sweeping and vertical opening/closing of HD relative to 50S. Finally, our ENM-based efficient technique -ClustENM- is used to sample atomistic conformers starting with an extended TF-50S complex. Specifically, BD and CD motions are restricted near the tunnel exit, while HD is highly mobile. The atomistic conformers generated without an NC are in agreement with the cryo-EM maps available for TF-ribosome-NC complex.

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.

Neptunium(V) Adsorption to Bacteria at Low and High Ionic Strength

NASA Astrophysics Data System (ADS)

Ams, D.; Swanson, J. S.; Reed, D. T.

2010-12-01

Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO2+ aquo and associated complexed species, is readily soluble, interacts weakly with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface containment. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO2+) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacteria/Np mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria used were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. The observed adsorption behavior may be linked to similarities and differences in the characteristics of the moieties between the cell walls of common gram-negative soil and halophilic bacteria. Moreover, differences in adsorption behavior may also reflect ionic strength effects as the electronic double layer is compressed with increasing ionic strength. These results further highlight the importance of electrostatic interactions in the adsorption process between dissolved metals and bacterial surfaces. This work expands the understanding of actinide-bacteria adsorption phenomena to high ionic strength environmental conditions that are relevant as an aid to predicting Np(V) fate and transport behavior in areas such as the vicinity of salt-based nuclear waste repositories and high ionic-strength groundwaters at DOE sites.

Specific binding of (/sup 3/H-Tyr8)physalaemin to rat submaxillary gland substance P receptor

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

Bahouth, S.W.; Lazaro, D.M.; Brundish, D.E.

1985-01-01

(/sup 3/H)Physalaemin ((/sup 3/H)PHY) binds to a single class of noninteracting sites on rat submaxillary gland membranes suspended in high ionic strength media with a KD of 2.7 nM, a Bmax of 240 fmol/mg of protein, and low nonspecific binding. The relative potencies of substance P (SP) and its fragments in competing with (/sup 3/H)PHY correlate with their relative salivation potencies. This indicates that (/sup 3/H)PHY interacts with a physiologically relevant SP receptor. In low ionic strength media, the KD of (/sup 3/H)PHY does not change, but SP and some of its fragments are more potent than PHY in competingmore » with (/sup 3/H) PHY. Computer-assisted analysis of (/sup 3/H)PHY and (/sup 3/H)SP binding in high and low ionic strength media demonstrated that both peptides are equipotent in high ionic strength but that the affinity of SP increases by 70-fold in low ionic strength. The SP fragments that contain a basic residue in positions 1 and/or 3 also display an increased affinity in low ionic strength. These findings document that (/sup 3/H)PHY binding in high ionic strength (mu . 0.6) accurately reflects the pharmacological potencies of agonists on the SP-P receptor. The binding of (/sup 3/H)PHY, like that of (/sup 3/H)SP, increases by the addition of divalent cations (Mg2+ greater than Ca2+ greater than Mn2+). Guanine nucleotides decrease (/sup 3/H)PHY binding by decreasing the Bmax to the same level (160 fmol/mg of protein), in the presence or absence of Mg2+.« less

Titin PEVK segment: charge-driven elasticity of the open and flexible polyampholyte

PubMed Central

FORBES, JEFFREY G.; JIN, ALBERT J.; MA, KAN; GUTIERREZ-CRUZ, GUSTAVO; TSAI, WANXIA L.; WANG, KUAN

2015-01-01

The giant protein titin spans half of the sarcomere length and anchors the myosin thick filament to the Z-line of skeletal and cardiac muscles. The passive elasticity of muscle at a physiological range of stretch arises primarily from the extension of the PEVK segment, which is a polyampholyte with dense and alternating-charged clusters. Force spectroscopy studies of a 51 kDa fragment of the human fetal titin PEVK domain (TP1) revealed that when charge interactions were reduced by raising the ionic strength from 35 to 560 mM, its mean persistence length increased from 0.30±0.04 nm to 0.60±0.07 nm. In contrast, when the secondary structure of TP1 was altered drastically by the presence of 40 and 80% (v/v) of trifluoroethanol, its force-extension behavior showed no significant shift in the mean persistence length of ~0.18±0.03 nm at the ionic strength of 15 mM. Additionally, the mean persistence length also increased from 0.29 to 0.41 nm with increasing calcium concentration from pCa 5–8 to pCa 3–4. We propose that PEVK is not a simple entropic spring as is commonly assumed, but a highly evolved, gel-like enthalpic spring with its elasticity dominated by the sequence-specific charge interactions. A single polyampholyte chain may be fine-tuned to generate a broad range of molecular elasticity by varying charge pairing schemes and chain configurations. PMID:16465472

Light scattering measurements supporting helical structures for chromatin in solution.

PubMed

Campbell, A M; Cotter, R I; Pardon, J F

1978-05-01

Laser light scattering measurements have been made on a series of polynucleosomes containing from 50 to 150 nucleosomes. Radii of gyration have been determined as a function of polynucleosome length for different ionic strength solutions. The results suggest that at low ionic strength the chromatin adopts a loosely helical structure rather than a random coil. The helix becomes more regular on increasing the ionic strength, the dimension resembling those proposed by Finch and Klug for their solenoid model.

Nanoparticle transport in water-unsaturated porous media: effects of solution ionic strength and flow rate

NASA Astrophysics Data System (ADS)

Prédélus, Dieuseul; Lassabatere, Laurent; Louis, Cédric; Gehan, Hélène; Brichart, Thomas; Winiarski, Thierry; Angulo-Jaramillo, Rafael

2017-03-01

This paper presents the influence of ionic strength and flow on nanoparticle (NP) retention rate in an unsaturated calcareous medium, originating from a heterogeneous glaciofluvial deposit of the region of Lyon (France). Laboratory columns 10 cm in diameter and 30 cm in length were used. Silica nanoparticles (Au-SiO2-FluoNPs), with hydrodynamic diameter ranging from 50 to 60 nm and labeled with fluorescein derivatives, were used to simulate particle transport, and bromide was used to characterize flow. Three flow rates and five different ionic strengths were tested. The transfer model based on fractionation of water into mobile and immobile fractions was coupled with the attachment/detachment model to fit NPs breakthrough curves. The results show that increasing flow velocity induces a decrease in nanoparticle retention, probably as the result of several physical but also geochemical factors. The results show that NPs retention increases with ionic strength. However, an inversion of retention occurs for ionic strength >5.10-2 M, which has been scarcely observed in previous studies. The measure of zeta potential and DLVO calculations show that NPs may sorb on both solid-water and air-water interfaces. NPs size distribution shows the potential for nanoparticle agglomeration mostly at low pH, leading to entrapment in the soil pores. These mechanisms are highly sensitive to both hydrodynamic and geochemical conditions, which explains their high sensitivity to flow rates and ionic strength.

ATPase activity and light scattering of acto-heavy meromyosin: dependence on ATP concentration and on ionic strength.

PubMed

Dancker, P

1975-01-01

1. The dependence on ATP concentration of ATPase activity and light scattering decrease of acto-HMM could be described at very low ionic strength by one hyperbolic adsorption isotherm with a dissociation constant of 3 X 10(-6)M. Hence the increase of ATP ase activity was paralleled by a decrease in light scattering. At higher values of ionic strength ATPase activity stopped rising before HMM was completely saturated with ATP. Higher ionic strength prevented ATPase activity from further increasing when the rigor links (links between actin and nucleotide-free myosin), which have formerly protected the ATPase against the suppressing action of higher ionic strength have fallen below a certain amount. This protecting influence of rigor links did not require tropomyosin-troponin. 2. For complete activation of ATPase activity by actin less actin was needed when HMM was incompletely saturated with ATP than when it was completely saturated with ATP. 3. The apparent affinity of ATP to regulated acto-HMM (which contained tropomyosin-troponin) was lower than to unregulated acto-HMM (which was devoid of tropomyosin-troponin). In the presence of rigor complexes (indicated by an incomplete decrease of light scattering) the ATPase activity of regulated acto-HMM was higher than that of unregulated acto-HMM. At increasing ATP concentrations the ATPase activity of regulated acto-HMM stopped rising at a similar degree of saturation with ATP as the ATPase activity of unregulated acto-HMM at the same ionic strength.

Two-site ionic labeling with pyranine: implications for structural dynamics studies of polymers and polypeptides by time-resolved fluorescence anisotropy.

PubMed

Sharma, Jai; Tleugabulova, Dina; Czardybon, Wojciech; Brennan, John D

2006-04-26

Time-resolved fluorescence anisotropy (TRFA) is widely used to study dynamic motions of biomolecules in a variety of environments. However, depolarization due to rapid side chain motions often complicates the interpretation of anisotropy decay data and interferes with the accurate observation of segmental motions. Here, we demonstrate a new method for two-point ionic labeling of polymers and biomolecules that have appropriately spaced amino groups using the fluorescent probe 8-hydroxyl-1,3,6-trisulfonated pyrene (pyranine). TRFA analysis shows that such labeling provides a more rigid attachment of the fluorophore to the macromolecule than the covalent or single-point ionic labeling of amino groups, leading to time-resolved anisotropy decays that better reflect the backbone motion of the labeled polymer segment. Optimal coupling of pyranine to biomolecule dynamics is shown to be obtained for appropriately spaced Arg groups, and in such cases the ionic binding is stable up to 150 mM ionic strength. TRFA was used to monitor the behavior of pyranine-labeled poly(allylamine) (PAM) and poly-d-lysine (PL) in sodium silicate derived sol-gel materials and revealed significant restriction of backbone motion upon entrapment for both polymers, an observation that was not readily apparent in a previous study with entrapped fluorescein-labeled PAM and PL. The implications of these findings for fluorescence studies of polymer and biomolecule dynamics are discussed.

Cystathionine β-Synthase (CBS) Domains 1 and 2 Fulfill Different Roles in Ionic Strength Sensing of the ATP-binding Cassette (ABC) Transporter OpuA*

PubMed Central

Karasawa, Akira; Erkens, Guus B.; Berntsson, Ronnie P.-A.; Otten, Renee; Schuurman-Wolters, Gea K.; Mulder, Frans A. A.; Poolman, Bert

2011-01-01

The cystathionine β-synthase module of OpuA in conjunction with an anionic membrane surface acts as a sensor of internal ionic strength, which allows the protein to respond to osmotic stress. We now show by chemical modification and cross-linking studies that CBS2-CBS2 interface residues are critical for transport activity and/or ionic regulation of transport, whereas CBS1 serves no functional role. We establish that Cys residues in CBS1, CBS2, and the nucleotide-binding domain are more accessible for cross-linking at high than low ionic strength, indicating that these domains undergo conformational changes when transiting between the active and inactive state. Structural analyses suggest that the cystathionine β-synthase module is largely unstructured. Moreover, we could substitute CBS1 by a linker and preserve ionic regulation of transport. These data suggest that CBS1 serves as a linker and the structured CBS2-CBS2 interface forms a hinge point for ionic strength-dependent rearrangements that are transmitted to the nucleotide-binding domain and thereby affect translocation activity. PMID:21878634

A novel conductance glucose biosensor in ultra-low ionic strength solution triggered by the oxidation of Ag nanoparticles.

PubMed

Song, Yonghai; Chen, Jingyi; Liu, Hongyu; Li, Ping; Li, Hongbo; Wang, Li

2015-09-03

A simple, sensitive and effective method to detect glucose in ultra-low ionic strength solution containing citrate-capped silver nanoparticles (CCAgNPs) was developed by monitoring the change of solution conductance. Glucose was catalyzed into gluconic acid firstly by glucose oxidase in an O2-saturated solution accompanied by the reduction of O2 into hydrogen peroxide (H2O2). Then, CCAgNPs was oxidized by H2O2 into Ag(+) and the capping regent of citrate was released at the same time. All these resulted Ag(+), gluconic acid and the released citrate would contribute to the increase of solution ionic strength together, leading to a detectable increase of solution conductance. And a novel conductance glucose biosensor was developed with a routine linear range of 0.06-4.0 mM and a suitable detection limit of 18.0 μM. The novel glucose biosensor was further applied in energy drink sample and proven to be suitable for practical system with low ionic strength. The proposed conductance biosensor achieved a significant breakthrough of glucose detection in ultra-low ionic strength media. Copyright © 2015 Elsevier B.V. All rights reserved.

Electrophoretic mobilities of erythrocytes in various buffers

NASA Technical Reports Server (NTRS)

Plank, L. D.; Kunze, M. E.; Todd, P. W.

1985-01-01

The calibration of space flight equipment depends on a source of standard test particles, this test particle of choice is the fixed erythrocyte. Erythrocytes from different species have different electrophoretic mobilities. Electrophoretic mobility depends upon zeta potential, which, in turn depends upon ionic strength. Zeta potential decreases with increasing ionic strength, so cells have high electrophoretic mobility in space electrophoresis buffers than in typical physiological buffers. The electrophoretic mobilities of fixed human, rat, and rabbit erythrocytes in 0.145 M salt and buffers of varying ionic strength, temperature, and composition, to assess the effects of some of the unique combinations used in space buffers were characterized. Several effects were assessed: glycerol or DMSO (dimethylsulfoxide) were considered for use as cryoprotectants. The effect of these substances on erythrocyte electrophoretic mobility was examined. The choice of buffer depended upon cell mobility. Primary experiments with kidney cells established the choice of buffer and cryoprotectant. A nonstandard temperature of EPM in the suitable buffer was determined. A loss of ionic strength control occurs in the course of preparing columns for flight, the effects of small increases in ionic strength over the expected low values need to be evaluated.

Coupled ion redistribution and electronic breakdown in low-alkali boroaluminosilicate glass

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

Choi, Doo Hyun, E-mail: cooldoo@add.re.kr; Randall, Clive, E-mail: car4@psu.edu; Furman, Eugene, E-mail: euf1@psu.edu

2015-08-28

Dielectrics with high electrostatic energy storage must have exceptionally high dielectric breakdown strength at elevated temperatures. Another important consideration in designing a high performance dielectric is understanding the thickness and temperature dependence of breakdown strengths. Here, we develop a numerical model which assumes a coupled ionic redistribution and electronic breakdown is applied to predict the breakdown strength of low-alkali glass. The ionic charge transport of three likely charge carriers (Na{sup +}, H{sup +}/H{sub 3}O{sup +}, Ba{sup 2+}) was used to calculate the ionic depletion width in low-alkali boroaluminosilicate which can further be used for the breakdown modeling. This model predictsmore » the breakdown strengths in the 10{sup 8}–10{sup 9 }V/m range and also accounts for the experimentally observed two distinct thickness dependent regions for breakdown. Moreover, the model successfully predicts the temperature dependent breakdown strength for low-alkali glass from room temperature up to 150 °C. This model showed that breakdown strengths were governed by minority charge carriers in the form of ionic transport (mostly sodium) in these glasses.« less

Gelatinization kinetic of waxy starches under pressure according to ionic strength

NASA Astrophysics Data System (ADS)

Simonin, Hélène; Guyon, Claire; de Lamballerie, Marie; Lebail, Alain

2010-12-01

High pressure is a potential technology for the texturization of food products at ambient temperature. In this area, waxy starches are particularly interesting because they gelatinize quickly under sufficient pressure. However, gelatinization may be influenced by other components in the food matrix. Here, we investigate the influence of increasing ionic strength on gelatinization rate and kinetics at 500 MPa for waxy corn and waxy rice starches. We show that increasing ionic strength strongly retards and inhibits starch gelatinization under pressure and leads to heterogeneous gels with remnant granules.

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.

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

High rate capacitive performance of single-walled carbon nanotube aerogels

DOE PAGES

Van Aken, Katherine L.; Pérez, Carlos R.; Oh, Youngseok; ...

2015-05-30

Single-walled carbon nanotube (SWCNT) aerogels produced by critical-point-drying of wet-gel precursors exhibit unique properties, such as high surface-area-to-volume and strength-to-weight ratios. They are free-standing, are binder-free, and can be scaled to thicknesses of more than 1 mm. In this paper, we examine the electric double layer capacitive behavior of these materials using a common room temperature ionic liquid electrolyte, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI). Electrochemical performance is assessed through galvanostatic cycling, cyclic voltammetry and impedance spectroscopy. Results indicate stable capacitive performance over 10,000 cycles as well as an impressive performance at high charge and discharge rates, due to accessible pore networks andmore » enhanced electronic and ionic conductivities of SWCNT aerogels. Finally, these materials can find applications in mechanically compressible and flexible supercapacitor devices with high power requirements.« less

Friction and wear behavior of glasses and ceramics

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Adhesion, friction, and wear behavior of glasses and ionic solids are reviewed. These materials are shown to behave in a manner similar to other solids with respect to adhesion. Their friction characteristics are shown to be sensitive to environmental constituents and surface films. This sensitivity can be related to a reduction in adhesive bonding and the changes in surficial mechanical behavior associated with Rehbinder and Joffe effects. Both friction and wear properties of ionic crystalline solids are highly anisotropic. With metals in contact with ionic solids the fracture strength of the ionic solid and the shear strength in the metal and those properties that determine these will dictate which of the materials undergoes adhesive wear. The chemical activity of the metal plays an important role in the nature and strength of the adhesive interfacial bond that develops between the metal and a glass or ionic solid.

Interaction between 2',4-dihydroxychalcone and the N, f, e conformers of bovine serum albumin: influence of temperature and ionic strength.

PubMed

Curvale, Rolando A; Debattista, Nora B; Pappano, Nora B

2012-04-01

UV-Vis spectroscopy was used to study the interaction between the 2',4- dihydroxychalcone, flavonoid which is known to have anti-tumor activity in vitro, and others biological properties, and the N, F and E conformers of bovine serum albumin at different ionic strengths and temperatures. The Klotz model was found to be adequate to determine the constants and number of binding sites. The reaction was found to be exothermic and spontaneous. The number of binding sites decreases and the reaction is more exergonic along with the increase in ionic strength and the conformational change of N to E. The reactions were necessarily hydrophobic and followed by a process of ionic character.

Agglomeration behavior of lipid-capped gold nanoparticles

NASA Astrophysics Data System (ADS)

Ranjan, Rajeev; Kirillova, Maria A.; Esimbekova, Elena N.; Zharkov, Sergey M.; Kratasyuk, Valentina A.

2018-04-01

The current investigation deciphers aggregation pattern of gold nanoparticles (AuNPs) and lipid-treated AuNPs when subjected to aqueous sodium chloride solution with increasing ionic strengths (100-400 nM). AuNPs were synthesized using 0.29 mM chloroauric acid and by varying the concentrations of trisodium citrate (AuNP1 1.55 mM, AuNP2 3.1 mM) and silver nitrate (AuNP3 5.3 μM, AuNP4 10.6 μM) with characteristic LSPR peaks in the range of 525-533 nm. TEM analysis revealed AuNPs to be predominantly faceted nanocrystals with the average size of AuNP1 to be 35 ± 5 nm, AuNP2 15 ± 5 nm, AuNP3 30 ± 5 nm, and AuNP4 30 ± 5 nm and the zeta-average for AuNPs were calculated to be 31.23, 63.80, 26.08, and 28 nm respectively. Induced aggregation was observed within 10 s in all synthesized AuNPs while lipid-treated AuNP2 (AuNP2-L) was found to withstand ionic interferences at all concentration levels. However, lipid-treated AuNPs synthesized using silver nitrate and 1.55 mM trisodium citrate (AuNP3, AuNP4) showed much lower stability. The zeta potential values of lipid-treated AuNPs (AuNP1-L-1 x/200, - 17.93 ± 1.02 mV; AuNP2-L-1 x/200, - 21.63 ± 0.70; AuNP3-L-1 x/200, - 14.54 ± 0.90; AuNP3-L-1 x/200 - 13.77 ± 0.83) justified these observations. To summarize, AuNP1 and AuNP2 treated with lipid mixture 1 equals or above 1 x/200 or 1 x/1000 respectively showed strong resistance against ionic interferences (up to 400 mM NaCl). Use of lipid mixture 1 for obtaining highly stable AuNPs also provided functional arms of various lengths which can be used for covalent coupling. [Figure not available: see fulltext.

Influence of Zwitterions on Thermomechanical Properties and Morphology of Acrylic Copolymers: Implications for Electroactive Applications

DTIC Science & Technology

2011-09-30

transducers from branched sulfonated polysulfones.7 The mechanical strength of the membranes drastically decreased upon introduction of ionic liquids to... liquids ,8 and zwitterionomers maintained mechanical strengths upon swelling with 10 wt % ionic liquid . Zwitterions are chargedmolecules that contain...water purification5 to biotechnology.6 A unique combination of physical properties of ionomeric membranes is the ionic con- ductivity of lowmolar mass

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.

A novel hydrogel based piezoresistive pressure sensor platform for chemical sensing

NASA Astrophysics Data System (ADS)

Orthner, Michael P.

New hydrogel-based micropressure sensor arrays for use in the fields of chemical sensing, physiological monitoring, and medical diagnostics are developed and demonstrated. This sensor technology provides reliable, linear, and accurate measurements of hydrogel swelling pressures, a function of ambient chemical concentrations. For the first time, perforations were implemented into the pressure sensors piezoresistive diaphragms, used to simultaneously increase sensor sensitivity and permit diffusion of analytes into the hydrogel cavity. It was shown through analytical and numerical (finite element) methods that pore shape, location, and size can be used to modify the diaphragm mechanics and concentrate stress within the piezoresistors, thus improving electrical output (sensitivity). An optimized pore pattern was chosen based on these numerical calculations. Fabrication was performed using a 14-step semiconductor fabrication process implementing a combination of potassium hydroxide (KOH) and deep reactive ion etching (DRIE) to create perforations. The sensor arrays (2x2) measure approximately 3 x 5 mm2 and used to measure full scale pressures of 50, 25, and 5 kPa, respectively. These specifications were defined by the various swelling pressures of ionic strength, pH and glucose specific hydrogels that were targeted in this work. Initial characterization of the sensor arrays was performed using a custom built bulge testing apparatus that simultaneously measured deflection (optical profilometry), pressure, and electrical output. The new perforated diaphragm sensors were found to be fully functional with sensitivities ranging from 23 to 252 muV/V-kPa with full scale output (FSO) ranging from 5 to 80 mV. To demonstrate proof of concept, hydrogels sensitive to changes in ionic strength were synthesized using hydroxypropyl-methacrylate (HPMA), N,N-dimethylaminoethyl-methacrylate (DMA) and a tetra-ethyleneglycol-dimethacrylate (TEGDMA) crosslinker. This hydrogel quickly and reversibly swells when placed environments of physiological buffer solutions (PBS) with ionic strengths ranging from 0.025 to 0.15 M. Chemical testing showed sensors with perforated diaphragms have higher sensitivity than those with solid diaphragms, and sensitivities ranging from 53.3+/-6.5 to 271.47+/-27.53 mV/V-M, depending on diaphragm size. Additionally, recent experiments show sensors utilizing Ultra Violet (UV) polymerized glucose sensitive hydrogels respond reversibly to physiologically relevant glucose concentrations from 0 to 20 mM.

Influence of droplet size, pH and ionic strength on endotoxin-triggered ordering transitions in liquid crystalline droplets

PubMed Central

Miller, Daniel S.; Abbott, Nicholas L.

2012-01-01

We report an investigation of ordering transitions that are induced in water-dispersed, micrometer-sized droplets of a thermotropic liquid crystal (LC) by the bacterial lipopolysaccharide endotoxin. We reveal that the ordering transitions induced by endotoxin – from a bipolar state of the droplets to a radial state – are strongly dependent on the size of the LC droplets. Specifically, as the diameters of the LC droplets increase from 2 μm to above 10 μm (in phosphate buffered saline with an ionic strength of 90 mM and a pH of 7.2), we measured the percentage of droplets exhibiting a radial configuration in the presence of 100 pg/mL endotoxin to decrease from 98 ± 1 % to 3 ± 2 %. In addition, we measured a decrease in either the ionic strength or pH of the aqueous phase to reduce the percentage of droplets exhibiting a radial configuration in the presence of endotoxin. These results, when interpreted within the context of a simple thermodynamic model that incorporates the contributions of elasticity and surface anchoring to the free energies of the LC droplets, lead us to conclude that (i) the elastic constant K24 plays a central role in determining the size-dependent response of the LC droplets to endotoxin, and (ii) endotoxin-triggered ordering transitions occur only under solution conditions (pH, ionic strength) where the combined contributions of elasticity and surface anchoring to the free energies of the bipolar and radial configurations of the LC droplets are similar in magnitude. Our analysis also suggests that the presence of endotoxin perturbs the free energies of the LC droplets by ~10−17 J/droplet, which is comparable to the standard free energy of self-association of ~103 endotoxin molecules. These results, when combined with prior reports of localization of endotoxin at the center of LC droplets, are consistent with the hypothesis that self-assembly of endotoxin within micrometer-sized LC droplets provides the driving force for the ordering transitions. Overall, these results advance our understanding of ordering transitions triggered by the interactions of analytes with LC droplets and, more broadly, provide guidance to the design of LC droplet systems as the basis of stimuli-responsive soft materials. PMID:23675387

Interaction of indole-papaverine with DNA in solutions of various ionic strength

NASA Astrophysics Data System (ADS)

Travkina, V. I.; Moroshkina, E. B.; Osinnikova, D. N.

2017-11-01

Interaction of synthetic alkaloid of isoquinoline series, which is an analogue of the biologically active compound papaverine, was studied by spectral, microcalorimetric, optical and hydrodynamic methods at different ionic strengths of medium. It was found that the investigated compound may interact with DNA in various ways depending on the ratio of ligand - DNA concentrations and ionic strength of solution (μ). When μ = 0.001, indole-papaverine intercalates into the double helix of DNA. The increase of μ resulted in a decrease of the affinity of the compound to DNA and a change its binding method.

Molecular simulation study of feruloyl esterase adsorption on charged surfaces: effects of surface charge density and ionic strength.

PubMed

Liu, Jie; Peng, Chunwang; Yu, Gaobo; Zhou, Jian

2015-10-06

The surrounding conditions, such as surface charge density and ionic strength, play an important role in enzyme adsorption. The adsorption of a nonmodular type-A feruloyl esterase from Aspergillus niger (AnFaeA) on charged surfaces was investigated by parallel tempering Monte Carlo (PTMC) and all-atom molecular dynamics (AAMD) simulations at different surface charge densities (±0.05 and ±0.16 C·m(-2)) and ionic strengths (0.007 and 0.154 M). The adsorption energy, orientation, and conformational changes were analyzed. Simulation results show that whether AnFaeA can adsorb onto a charged surface is mainly controlled by electrostatic interactions between AnFaeA and the charged surface. The electrostatic interactions between AnFaeA and charged surfaces are weakened when the ionic strength increases. The positively charged surface at low surface charge density and high ionic strength conditions can maximize the utilization of the immobilized AnFaeA. The counterion layer plays a key role in the adsorption of AnFaeA on the negatively charged COOH-SAM. The native conformation of AnFaeA is well preserved under all of these conditions. The results of this work can be used for the controlled immobilization of AnFaeA.

Novel sample preparation method for surfactant containing suppositories: effect of micelle formation on drug recovery.

PubMed

Kalmár, Éva; Ueno, Konomi; Forgó, Péter; Szakonyi, Gerda; Dombi, György

2013-09-01

Rectal drug delivery is currently at the focus of attention. Surfactants promote drug release from the suppository bases and enhance the formulation properties. The aim of our work was to develop a sample preparation method for HPLC analysis for a suppository base containing 95% hard fat, 2.5% Tween 20 and 2.5% Tween 60. A conventional sample preparation method did not provide successful results as the recovery of the drug failed to fulfil the validation criterion 95-105%. This was caused by the non-ionic surfactants in the suppository base incorporating some of the drug, preventing its release. As guidance for the formulation from an analytical aspect, we suggest a well defined surfactant content based on the turbidimetric determination of the CMC (critical micelle formation concentration) in the applied methanol-water solvent. Our CMC data correlate well with the results of previous studies. As regards the sample preparation procedure, a study was performed of the effects of ionic strength and pH on the drug recovery with the avoidance of degradation of the drug during the procedure. Aminophenazone and paracetamol were used as model drugs. The optimum conditions for drug release from the molten suppository base were found to be 100 mM NaCl, 20-40 mM NaOH and a 30 min ultrasonic treatment of the final sample solution. As these conditions could cause the degradation of the drugs in the solution, this was followed by NMR spectroscopy, and the results indicated that degradation did not take place. The determined CMCs were 0.08 mM for Tween 20, 0.06 mM for Tween 60 and 0.04 mM for a combined Tween 20, Tween 60 system. Copyright © 2013 Elsevier B.V. All rights reserved.

Metal retention in human transferrin: consequences of solvent composition in analytical sample preparation methods.

PubMed

Quarles, C Derrick; Randunu, K Manoj; Brumaghim, Julia L; Marcus, R Kenneth

2011-10-01

The analysis of metal-binding proteins requires careful sample manipulation to ensure that the metal-protein complex remains in its native state and the metal retention is preserved during sample preparation or analysis. Chemical analysis for the metal content in proteins typically involves some type of liquid chromatography/electrophoresis separation step coupled with an atomic (i.e., inductively coupled plasma-optical emission spectroscopy or -mass spectrometry) or molecular (i.e., electrospray ionization-mass spectrometry) analysis step that requires altered-solvent introduction techniques. UV-VIS absorbance is employed here to monitor the iron content in human holo-transferrin (Tf) under various solvent conditions, changing polarity, pH, ionic strength, and the ionic and hydrophobic environment of the protein. Iron loading percentages (i.e. 100% loading equates to 2 Fe(3+):1 Tf) were quantitatively determined to evaluate the effect of solvent composition on the retention of Fe(3+) in Tf. Maximum retention of Fe(3+) was found in buffered (20 mM Tris) solutions (96 ± 1%). Exposure to organic solvents and deionized H(2)O caused release of ~23-36% of the Fe(3+) from the binding pocket(s) at physiological pH (7.4). Salt concentrations similar to separation conditions used for ion exchange had little to no effect on Fe(3+) retention in holo-Tf. Unsurprisingly, changes in ionic strength caused by additions of guanidine HCl (0-10 M) to holo-Tf resulted in unfolding of the protein and loss of Fe(3+) from Tf; however, denaturing and metal loss was found not to be an instantaneous process for additions of 1-5 M guanidinium to Tf. In contrast, complete denaturing and loss of Fe(3+) was instantaneous with ≥6 M additions of guanidinium, and denaturing and loss of iron from Tf occurred in parallel proportions. Changes to the hydrophobicity of Tf (via addition of 0-14 M urea) had less effect on denaturing and release of Fe(3+) from the Tf binding pocket compared to changes in ionic strength. This journal is © The Royal Society of Chemistry 2011

Effect of ionic strength and presence of serum on lipoplexes structure monitorized by FRET

PubMed Central

Madeira, Catarina; Loura, Luís MS; Prieto, Manuel; Fedorov, Aleksander; Aires-Barros, M Raquel

2008-01-01

Background Serum and high ionic strength solutions constitute important barriers to cationic lipid-mediated intravenous gene transfer. Preparation or incubation of lipoplexes in these media results in alteration of their biophysical properties, generally leading to a decrease in transfection efficiency. Accurate quantification of these changes is of paramount importance for the success of lipoplex-mediated gene transfer in vivo. Results In this work, a novel time-resolved fluorescence resonance energy transfer (FRET) methodology was used to monitor lipoplex structural changes in the presence of phosphate-buffered saline solution (PBS) and fetal bovine serum. 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP)/pDNA lipoplexes, prepared in high and low ionic strength solutions, are compared in terms of complexation efficiency. Lipoplexes prepared in PBS show lower complexation efficiencies when compared to lipoplexes prepared in low ionic strength buffer followed by addition of PBS. Moreover, when serum is added to the referred formulation no significant effect on the complexation efficiency was observed. In physiological saline solutions and serum, a multilamellar arrangement of the lipoplexes is maintained, with reduced spacing distances between the FRET probes, relative to those in low ionic strength medium. Conclusion The time-resolved FRET methodology described in this work allowed us to monitor stability and characterize quantitatively the structural changes (variations in interchromophore spacing distances and complexation efficiencies) undergone by DOTAP/DNA complexes in high ionic strength solutions and in presence of serum, as well as to determine the minimum amount of potentially cytotoxic cationic lipid necessary for complete coverage of DNA. This constitutes essential information regarding thoughtful design of future in vivo applications. PMID:18302788

Interfacial Shear Strength and Adhesive Behavior of Silk Ionomer Surfaces.

PubMed

Kim, Sunghan; Geryak, Ren D; Zhang, Shuaidi; Ma, Ruilong; Calabrese, Rossella; Kaplan, David L; Tsukruk, Vladimir V

2017-09-11

The interfacial shear strength between different layers in multilayered structures of layer-by-layer (LbL) microcapsules is a crucial mechanical property to ensure their robustness. In this work, we investigated the interfacial shear strength of modified silk fibroin ionomers utilized in LbL shells, an ionic-cationic pair with complementary ionic pairing, (SF)-poly-l-glutamic acid (Glu) and SF-poly-l-lysine (Lys), and a complementary pair with partially screened Coulombic interactions due to the presence of poly(ethylene glycol) (PEG) segments and SF-Glu/SF-Lys[PEG] pair. Shearing and adhesive behavior between these silk ionomer surfaces in the swollen state were probed at different spatial scales and pressure ranges by using functionalized atomic force microscopy (AFM) tips as well as functionalized colloidal probes. The results show that both approaches were consistent in analyzing the interfacial shear strength of LbL silk ionomers at different spatial scales from a nanoscale to a fraction of a micron. Surprisingly, the interfacial shear strength between SF-Glu and SF-Lys[PEG] pair with partially screened ionic pairing was greater than the interfacial shear strength of the SF-Glu and SF-Lys pair with a high density of complementary ionic groups. The difference in interfacial shear strength and adhesive strength is suggested to be predominantly facilitated by the interlayer hydrogen bonding of complementary amino acids and overlap of highly swollen PEG segments.

Kinetics and mechanism for platination of thione-containing nucleotides and oligonucleotides: evaluation of the salt dependence.

PubMed

Kjellström, Johan; Elmroth, Sofi K C

2003-01-01

Reactions of cis-[PtCl(NH(3))(CyNH(2))(OH(2))](+) (Cy=cyclohexyl) with thione-containing single-stranded oligonucleotides d(T(8)XT(8)) and d(XT(16)) (X=(s6)I or (s4)U) and the mononucleotides 4-thiouridine ((s4)UMP) and 6-mercaptoinosine ((s6)IMP) have been studied in aqueous solution at pH 4.1. The reaction kinetics was followed using HPLC methodology as a function of ionic strength in the interval 5.0 mM

Rotational dynamics of spin-labeled F-actin during activation of myosin S1 ATPase using caged ATP.

PubMed Central

Ostap, E. M.; Thomas, D. D.

1991-01-01

The most probable source of force generation in muscle fibers in the rotation of the myosin head when bound to actin. This laboratory has demonstrated that ATP induces microsecond rotational motions of spin-labeled myosin heads bound to actin (Berger, C. L. E. C. Svensson, and D. D. Thomas. 1989. Proc. Natl. Acad. Sci. USA. 86:8753-8757). Our goal is to determine whether the observed ATP-induced rotational motions of actin-bound heads are accompanied by changes in actin rotational motions. We have used saturation transfer electron paramagnetic resonance (ST-EPR) and laser-induced photolysis of caged ATP to monitor changes in the microsecond rotational dynamics of spin-labeled F-actin in the presence of myosin subfragment-1 (S1). A maleimide spin label was attached selectively to cys-374 on actin. In the absence of ATP (with or without caged ATP), the ST-EPR spectrum (corresponding to an effective rotational time of approximately 150 microseconds) was essentially the same as observed for the same spin label bound to cys-707 (SH1) on S1, indicating that S1 is rigidly bound to actin in rigor. At normal ionic strength (micro = 186 mM), a decrease in ST-EPR intensity (increase in microsecond F-actin mobility) was clearly indicated upon photolysis of 1 mM caged ATP with a 50-ms, 351-nm laser pulse. This increase in mobility is due to the complete dissociation of Si from the actin filament. At low ionic strength (micro, = 36 mM), when about half the Si heads remain bound during ATP hydrolysis, no change in the actin mobility was detected, despite much faster motions of labeled S1 bound to actin. Therefore, we conclude that the active interaction of Si, actin,and ATP induces rotation of myosin heads relative to actin, but does not affect the microsecond rotational motion of actin itself, as detected at cys-374 of actin. PMID:1651780

The solvent at antigen-binding site regulated C3d-CR2 interactions through the C-terminal tail of C3d at different ion strengths: insights from molecular dynamics simulation.

PubMed

Zhang, Yan; Guo, Jingjing; Li, Lanlan; Liu, Xuewei; Yao, Xiaojun; Liu, Huanxiang

2016-10-01

The interactions of complement receptor 2 (CR2) and the degradation fragment C3d of complement component C3 play important links between the innate and adaptive immune systems. Due to the importance of C3d-CR2 interaction in the design of vaccines and inhibitors, a number of studies have been performed to investigate C3d-CR2 interaction. Many studies have indicated C3d-CR2 interactions are ionic strength-dependent. To investigate the molecular mechanism of C3d-CR2 interaction and the origin of effects of ionic strength, molecular dynamics simulations for C3d-CR2 complex together with the energetic and structural analysis were performed. Our results revealed the increased interactions between charged protein and ions weaken C3d-CR2 association, as ionic strengths increase. Moreover, ion strengths have similar effects on antigen-binding site and CR2 binding site. Meanwhile, Ala17 and Gln20 will transform between the activated and non-activated states mediated by His133 and Glu135 at different ion strengths. Our results reveal the origins of the effects of ionic strengths on C3d-CR2 interactions are due to the changes of water, ion occupancies and distributions. This study uncovers the origin of the effect of ionic strength on C3d-CR2 interaction and deepens the understanding of the molecular mechanism of their interaction, which is valuable for the design of vaccines and small molecule inhibitors. Copyright © 2016 Elsevier B.V. All rights reserved.

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

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

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.

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

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.

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

NASA Astrophysics Data System (ADS)

Ali, H. M.; Iedema, M.; Yu, X.-Y.; Cowin, J. P.

2014-06-01

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium chloride (brine) particles was studied by utilizing a cross flow mini-reactor. The reaction kinetics were followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely CCSEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry's law solubility of H2O2 in brine solutions to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to, eventually, a mixed NaHSO4 plus H2SO4 brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted using established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the dependence of the Henry's law constant of H2O2 on ionic strength.

Osmotic Pressure of Aqueous Chondroitin Sulfate Solution: A Molecular Modeling Investigation

PubMed Central

Bathe, Mark; Rutledge, Gregory C.; Grodzinsky, Alan J.; Tidor, Bruce

2005-01-01

The osmotic pressure of chondroitin sulfate (CS) solution in contact with an aqueous 1:1 salt reservoir of fixed ionic strength is studied using a recently developed coarse-grained molecular model. The effects of sulfation type (4- vs. 6-sulfation), sulfation pattern (statistical distribution of sulfate groups along a chain), ionic strength, CS intrinsic stiffness, and steric interactions on CS osmotic pressure are investigated. At physiological ionic strength (0.15 M NaCl), the sulfation type and pattern, as measured by a standard statistical description of copolymerization, are found to have a negligible influence on CS osmotic pressure, which depends principally on the mean volumetric fixed charge density. The intrinsic backbone stiffness characteristic of polysaccharides such as CS, however, is demonstrated to contribute significantly to its osmotic pressure behavior, which is similar to that of a solution of charged rods for the 20-disaccharide chains considered. Steric excluded volume is found to play a negligible role in determining CS osmotic pressure at physiological ionic strength due to the dominance of repulsive intermolecular electrostatic interactions that maintain chains maximally spaced in that regime, whereas at high ionic-strength steric interactions become dominant due to electrostatic screening. Osmotic pressure predictions are compared to experimental data and to well-established theoretical models including the Donnan theory and the Poisson-Boltzmann cylindrical cell model. PMID:16055525

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

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

Ali, Hashim M.; Iedema, Martin J.; Yu, Xiao-Ying

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium particles was studied by utilizing a crossflow-mini reactor. The reaction kinetics was followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely SEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry’s law solubility of H2O2 to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to eventually a mixed NaHSO4 plus H2SO4more » brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted rates using previously established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the Henry’s law constant of H2O2 dependence on ionic strength.« less

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...

ERRORS IN APPLYING LOW IONIC-STRENGTH ACTIVITY COEFFICIENT ALGORITHMS TO HIGHER IONIC-STRENGTH AQUATIC MEDIA

EPA Science Inventory

The toxicological and regulatory communities are currently exploring the use of the free-ion-activity (FIA) model both alone and in conjunction with the biotic ligand model (BLM) as a means of reducing uncertainties in current methods for assessing metals bioavailability from aqu...

The Properties of HPMC:PEO Extended Release Hydrophilic Matrices and their Response to Ionic Environments.

PubMed

Hu, Anran; Chen, Chen; Mantle, Michael D; Wolf, Bettina; Gladden, Lynn F; Rajabi-Siahboomi, Ali; Missaghi, Shahrzad; Mason, Laura; Melia, Colin D

2017-05-01

Investigate the extended release behaviour of compacts containing mixtures of hydrophilic HPMC and PEO in hydrating media of differing ionic strengths. The extended release behaviour of various HPMC:PEO compacts was investigated using dissolution testing, confocal microscopy and magnetic resonance imaging, with respect to polymer ratio and ionic strength of the hydrating media. Increasing HPMC content gave longer extended release times, but a greater sensitivity to high ionic dissolution environments. Increasing PEO content reduced this sensitivity. The addition of PEO to a predominantly HPMC matrix reduced release rate sensitivity to high ionic environments. Confocal microscopy of early gel layer development showed the two polymers appeared to contribute independently to gel layer structure whilst together forming a coherent and effective diffusion barrier. There was some evidence that poorly swollen HPMC particles added a tortuosity barrier to the gel layer in high ionic strength environments, resulting in prolonged extended release. MRI provides unique, non-invasive spatially resolved information from within the HPMC:PEO compacts that furthers our understanding of USP 1 and USP 4 dissolution data. Confocal microscopy and MRI data show that combinations of HPMC and PEO have advantageous extended release properties, in comparison with matrices containing a single polymer.

Monitoring Insulin Aggregation via Capillary Electrophoresis

PubMed Central

Pryor, Elizabeth; Kotarek, Joseph A.; Moss, Melissa A.; Hestekin, Christa N.

2011-01-01

Early stages of insulin aggregation, which involve the transient formation of oligomeric aggregates, are an important aspect in the progression of Type II diabetes and in the quality control of pharmaceutical insulin production. This study is the first to utilize capillary electrophoresis (CE) with ultraviolet (UV) detection to monitor insulin oligomer formation at pH 8.0 and physiological ionic strength. The lag time to formation of the first detected species in the aggregation process was evaluated by UV-CE and thioflavin T (ThT) binding for salt concentrations from 100 mM to 250 mM. UV-CE had a significantly shorter (5–8 h) lag time than ThT binding (15–19 h). In addition, the lag time to detection of the first aggregated species via UV-CE was unaffected by salt concentration, while a trend toward an increased lag time with increased salt concentration was observed with ThT binding. This result indicates that solution ionic strength impacts early stages of aggregation and β-sheet aggregate formation differently. To observe whether CE may be applied for the analysis of biological samples containing low insulin concentrations, the limit of detection using UV and laser induced fluorescence (LIF) detection modes was determined. The limit of detection using LIF-CE, 48.4 pM, was lower than the physiological insulin concentration, verifying the utility of this technique for monitoring biological samples. LIF-CE was subsequently used to analyze the time course for fluorescein isothiocyanate (FITC)-labeled insulin oligomer formation. This study is the first to report that the FITC label prevented incorporation of insulin into oligomers, cautioning against the use of this fluorescent label as a tag for following early stages of insulin aggregation. PMID:22272138

Structural Characterization of a Thrombin-Aptamer Complex by High Resolution Native Top-Down Mass Spectrometry

NASA Astrophysics Data System (ADS)

Zhang, Jiang; Loo, Rachel R. Ogorzalek; Loo, Joseph A.

2017-09-01

Native mass spectrometry (MS) with electrospray ionization (ESI) has evolved as an invaluable tool for the characterization of intact native proteins and non-covalently bound protein complexes. Here we report the structural characterization by high resolution native top-down MS of human thrombin and its complex with the Bock thrombin binding aptamer (TBA), a 15-nucleotide DNA with high specificity and affinity for thrombin. Accurate mass measurements revealed that the predominant form of native human α-thrombin contains a glycosylation mass of 2205 Da, corresponding to a sialylated symmetric biantennary oligosaccharide structure without fucosylation. Native MS showed that thrombin and TBA predominantly form a 1:1 complex under near physiological conditions (pH 6.8, 200 mM NH4OAc), but the binding stoichiometry is influenced by the solution ionic strength. In 20 mM ammonium acetate solution, up to two TBAs were bound to thrombin, whereas increasing the solution ionic strength destabilized the thrombin-TBA complex and 1 M NH4OAc nearly completely dissociated the complex. This observation is consistent with the mediation of thrombin-aptamer binding through electrostatic interactions and it is further consistent with the human thrombin structure that contains two anion binding sites on the surface. Electron capture dissociation (ECD) top-down MS of the thrombin-TBA complex performed with a high resolution 15 Tesla Fourier transform ion cyclotron resonance (FTICR) mass spectrometer showed the primary binding site to be at exosite I located near the N-terminal sequence of the heavy chain, consistent with crystallographic data. High resolution native top-down MS is complementary to traditional structural biology methods for structurally characterizing native proteins and protein-DNA complexes. [Figure not available: see fulltext.

Na(+) transport, and the E(1)P-E(2)P conformational transition of the Na(+)/K(+)-ATPase.

PubMed Central

Babes, A; Fendler, K

2000-01-01

We have used admittance analysis together with the black lipid membrane technique to analyze electrogenic reactions within the Na(+) branch of the reaction cycle of the Na(+)/K(+)-ATPase. ATP release by flash photolysis of caged ATP induced changes in the admittance of the compound membrane system that are associated with partial reactions of the Na(+)/K(+)-ATPase. Frequency spectra and the Na(+) dependence of the capacitive signal are consistent with an electrogenic or electroneutral E(1)P <--> E(2)P conformational transition which is rate limiting for a faster electrogenic Na(+) dissociation reaction. We determine the relaxation rate of the rate-limiting reaction and the equilibrium constants for both reactions at pH 6.2-8.5. The relaxation rate has a maximum value at pH 7.4 (approximately 320 s(-1)), which drops to acidic (approximately 190 s(-1)) and basic (approximately 110 s(-1)) pH. The E(1)P <--> E(2)P equilibrium is approximately at a midpoint position at pH 6.2 (equilibrium constant approximately 0.8) but moves more to the E(1)P side at basic pH 8.5 (equilibrium constant approximately 0.4). The Na(+) affinity at the extracellular binding site decreases from approximately 900 mM at pH 6.2 to approximately 200 mM at pH 8.5. The results suggest that during Na(+) transport the free energy supplied by the hydrolysis of ATP is mainly used for the generation of a low-affinity extracellular Na(+) discharge site. Ionic strength and lyotropic anions both decrease the relaxation rate. However, while ionic strength does not change the position of the conformational equilibrium E(1)P <--> E(2)P, lyotropic anions shift it to E(1)P. PMID:11053130

Influence of clay particles on the transport and retention of titanium dioxide nanoparticles in quartz sand.

PubMed

Cai, Li; Tong, Meiping; Wang, Xueting; Kim, Hyunjung

2014-07-01

This study investigated the influence of two representative suspended clay particles, bentonite and kaolinite, on the transport of titanium dioxide nanoparticles (nTiO2) in saturated quartz sand in both NaCl (1 and 10 mM ionic strength) and CaCl2 solutions (0.1 and 1 mM ionic strength) at pH 7. The breakthrough curves of nTiO2 with bentonite or kaolinite were higher than those without the presence of clay particles in NaCl solutions, indicating that both types of clay particles increased nTiO2 transport in NaCl solutions. Moreover, the enhancement of nTiO2 transport was more significant when bentonite was present in nTiO2 suspensions relative to kaolinite. Similar to NaCl solutions, in CaCl2 solutions, the breakthrough curves of nTiO2 with bentonite were also higher than those without clay particles, while the breakthrough curves of nTiO2 with kaolinite were lower than those without clay particles. Clearly, in CaCl2 solutions, the presence of bentonite in suspensions increased nTiO2 transport, whereas, kaolinite decreased nTiO2 transport in quartz sand. The attachment of nTiO2 onto clay particles (both bentonite and kaolinite) were observed under all experimental conditions. The increased transport of nTiO2 in most experimental conditions (except for kaolinite in CaCl2 solutions) was attributed mainly to the clay-facilitated nTiO2 transport. The straining of larger nTiO2-kaolinite clusters yet contributed to the decreased transport (enhanced retention) of nTiO2 in divalent CaCl2 solutions when kaolinite particles were copresent in suspensions.

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.

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...

Ionic Strength Effect on the Rate of Reduction of Hexacyanoferrate (III) by Ascorbic Acid: A Physical Chemistry Laboratory Experiment.

ERIC Educational Resources Information Center

Watkins, Kenneth W.; Olson, June A.

1980-01-01

Describes a physical chemistry experiment that allows students to test the effect of ionic strength on the rates of a reaction between ions. The reduction of hexacyanoferrate III by ascorbic acid is detailed. Comparisons with the iodine clock reaction are made. (CS)

CHLORIDEDETERMINATION IN HIGH IONIC STRENGTH SOLUTION OF AMMONIUM ACETATE USING NEGATIVE ION ELECTRON SPRAY IONIZATION (HPLC/MS)

EPA Science Inventory

A precise ion chromatography method has been developed for the determination of chloride in high ionic strength ammonium acetate solutions (10-5 M-5 M) using sodium carbonate/sodium bicarbonate as eluent. Negative ion electrospray ionization (ESI) mass spectrometry was used for q...

State-of-the-Art pH Electrode Quality Control for Measurements of Acidic, Low Ionic Strength Waters.

ERIC Educational Resources Information Center

Stapanian, Martin A.; Metcalf, Richard C.

1990-01-01

Described is the derivation of the relationship between the pH measurement error and the resulting percentage error in hydrogen ion concentration including the use of variable activity coefficients. The relative influence of the ionic strength of the solution on the percentage error is shown. (CW)

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.

Chain Conformation of Phosphorycholine-based Zwitterionic Polymer Brushes in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Mao, Jun; Yu, Jing; Lee, Sungsik; Yuan, Guangcui; Satija, Sushil; Chen, Wei; Tirrell, Matthew

Polyzwitterionic brushes are resistant to nonspecific accumulation of proteins and microorganisms, making them excellent candidates for antifouling applications. It is well-known that polyzwitterions exhibit the so-called antipolyelectrolyte effect: Polyzwitterionic brushes would adopt a collapsed conformation at a low ionic strength due to the electrostatic inter/intra-chain association; whereas at a high ionic strength, they would exhibit an extended conformation because the electrostatic inter/intra-chain dipole-dipole interaction is weakened. However, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) is a unique member in polyzwitterionic families. Its ultrahigh affinity to water leads to no detectable shrinks in aqueous solutions even at low ionic strengths. In this study, we synthesized highly dense PMPC brushes via surface initiated radical polymerization and systematically investigate their conformational behaviors at solid-liquid interfaces in the presence of multivalent counterions, combining X-ray and neutron scattering and force measurements. We have demonstrated that despite no obvious changes of the entire lengths of extended PMPC brushes in aqueous solutions, the chain conformations including, but not limited to, polyzwitterion distribution and charge correlation, varied, dependent on salt types, ionic strengths and ion valences.

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.

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

Large heat capacity change in a protein-monovalent cation interaction.

PubMed

Guinto, E R; Di Cera, E

1996-07-09

Current views about protein-ligand interactions state that electrostatic forces drive the binding of charged species and that burial of hydrophobic and polar surfaces controls the heat capacity change associated with the reaction. For the interaction of a protein with a monovalent cation the electrostatic components are expected to be significant due to the ionic nature of the ligand, whereas the heat capacity change is expected to be small due to the size of the surface area involved in the recognition event. The physiologically important interaction of Na+ with thrombin was studied over the temperature range from 5 to 45 degrees C and the ionic strength range from 50 to 800 mM. These measurements reveal an unanticipated result that bears quite generally on studies of molecular recognition and protein folding. Binding of Na+ to thrombin is characterized by a modest dependence on ionic strength but a large and negative heat capacity change of -1.1 +/- 0.1 kcal mol-1 K-1. The small electrostatic coupling can be explained in terms of a minimal perturbation of the ionic atmosphere of the protein upon Na+ binding. The large heat capacity change, however, is difficult to reconcile with current views on the origin of this effect from surface area changes or large folding transitions coupled to binding. It is proposed that this change is linked to burial of a large cluster of water molecules in the Na+ binding pocket upon Na+ binding. Due to their reduced mobility and highly ordered structure, water molecules sequestered in the interior of a protein must have a lower heat capacity compared to those on the surface of a protein or in the bulk solvent. Hence, a binding or folding event where water molecules are buried may result in significant heat capacity changes independent of changes in exposed hydrophobic surface or coupled conformational transitions.

Polyelectrolyte layer-by-layer deposition in cylindrical nanopores.

PubMed

Lazzara, Thomas D; Lau, K H Aaron; Abou-Kandil, Ahmed I; Caminade, Anne-Marie; Majoral, Jean-Pierre; Knoll, Wolfgang

2010-07-27

Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.

Effects of molecular model, ionic strength, divalent ions, and hydrophobic interaction on human neurofilament conformation

NASA Astrophysics Data System (ADS)

Lee, Joonseong; Kim, Seonghoon; Chang, Rakwoo; Jayanthi, Lakshmi; Gebremichael, Yeshitila

2013-01-01

The present study examines the effects of the model dependence, ionic strength, divalent ions, and hydrophobic interaction on the structural organization of the human neurofilament (NF) brush, using canonical ensemble Monte Carlo (MC) simulations of a coarse-grained model with the amino-acid resolution. The model simplifies the interactions between the NF core and the sidearm or between the sidearms by the sum of excluded volume, electrostatic, and hydrophobic interactions, where both monovalent salt ions and solvents are implicitly incorporated into the electrostatic interaction potential. Several important observations are made from the MC simulations of the coarse-grained model NF systems. First, the mean-field type description of monovalent salt ions works reasonably well in the NF system. Second, the manner by which the NF sidearms are arranged on the surface of the NF backbone core has little influence on the lateral extension of NF sidearms. Third, the lateral extension of the NF sidearms is highly affected by the ionic strength of the system: at low ionic strength, NF-M is most extended but at high ionic strength, NF-H is more stretched out because of the effective screening of the electrostatic interaction. Fourth, the presence of Ca2 + ions induces the attraction between negatively charged residues, which leads to the contraction of the overall NF extension. Finally, the introduction of hydrophobic interaction does not change the general structural organization of the NF sidearms except that the overall extension is contracted.

Coupled factors influencing detachment of nano- and micro-sized particles from primary minima.

PubMed

Shen, Chongyang; Lazouskaya, Volha; Jin, Yan; Li, Baoguo; Ma, Zhiqiang; Zheng, Wenjuan; Huang, Yuanfang

2012-06-01

This study examined the detachments of nano- and micro-sized colloids from primary minima in the presence of cation exchange by laboratory column experiments. Colloids were initially deposited in columns packed with glass beads at 0.2 M CaCl(2) in the primary minima of Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energies. Then, the columns were flushed with NaCl solutions with different ionic strengths (i.e., 0.001, 0.01, 0.1 and 0.2 M). Detachments were observed at all ionic strengths and were particularly significant for the nanoparticle. The detachments increased with increasing electrolyte concentration for the nanoparticle whereas increased from 0.001 M to 0.01 M and decreased with further increasing electrolyte concentration for the micro-sized colloid. The observations were attributed to coupled influence of cation exchange, short-range repulsion, surface roughness, surface charge heterogeneity, and deposition in the secondary minima. The detachments of colloids from primary minima challenge the common belief that colloid interaction in primary minimum is irreversible and resistant to disturbance in solution ionic strength and composition. Although the significance of surface roughness, surface charge heterogeneity, and secondary minima on colloid deposition has been widely recognized, our study implies that they also play important roles in colloid detachment. Whereas colloid detachment is frequently associated with decrease of ionic strength, our results show that increase of ionic strength can also cause detachment due to influence of cation exchange. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

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

Transport and remobilization of multi-walled carbon nanotubes in porous media during dynamic saturation change

NASA Astrophysics Data System (ADS)

Sharma, P.

2012-04-01

Nanotechnology is one of the most important technologies in this century and it is evoking a new industrial revolution. Carbon nanotubes (CNTs) are important engineered nanoparticles with unique and beneficial properties. As a result, CNT has been used in a wide range of commercial products including electronics, optical devices and drug delivery leading to their disposal in the natural environment. Literature studies have investigated the mobility of CNTs in saturated porous media under differing physical and chemical conditions. However CNT transport in temporarily changing porous media water content has not been investigated thus far (a common scenario with rainfall/infiltration events in the vadose zone). This study investigated the mobilization of multi-walled CNTs (MCNTs) in repeated wetting and drying cycles with varying flow rates and ionic strength of the inflow solution. Imbibition-drainage-imbibition cycle experiments suggest that MCNTs mobilization increased with increase in flow rates. MCNTs mobilization occurred only with first imbibition events at low ionic strengths however less mobilization happened for higher ionic strength inflow solution in the first imbibition cycle and additional MCNTs were found in the outflow solution in second imbibition cycle, using low ionic strength solution. This observation was likely due to the attachment force between MCNTs and sand surface. Most of the MCNT mobilization occurred during liquid-gas interface movement with less chance of MCNTs to jump the energy barrier at higher ionic strength solution. As a result, less detachment of MCNTs occurred from the sand surface during drainage.

The dual exo/endo-type mode and the effect of ionic strength on the mode of catalysis of chitinase 60 (CHI60) from Serratia sp. TU09 and its mutants.

PubMed

Kuttiyawong, K; Nakapong, S; Pichyangkura, R

2008-11-03

Mutations of the tryptophan residues in the tryptophan-track of the N-terminal domain (W33F/Y and W69F/Y) and in the catalytic domain (W245F/Y) of Serratia sp. TU09 Chitinase 60 (CHI60) were constructed, as single and double point substitutions to either phenylalanine or tyrosine. The enzyme-substrate interaction and mode of catalysis, exo/endo-type, of wild type CHI60 and mutant enzymes on soluble (partially N-acetylated chitin), amorphous (colloidal chitin), and crystalline (β-chitin) substrates were studied. All CHI60 mutants exhibited a reduced substrate binding activity on colloidal chitin. CHI60 possesses a dual mode of catalysis with both exo- and endo-type activities allowing the enzyme to work efficiently on various substrate types. CHI60 preferentially uses the endo-type mode on soluble and amorphous substrates and the exo-type mode on crystalline substrate. However, the prevalent mode of hydrolysis mediated by CHI60 is regulated by ionic strength. Slightly elevated ionic strength, 0.1-0.2M NaCl, which promotes enzyme-substrate interactions, enhances CHI60 hydrolytic activity on amorphous substrate and, interestingly, on partially N-acetylated chitin. High ionic strength, 0.5-2.0M NaCl, prevents the enzyme from dissociating from amorphous substrate, occupying the enzyme in an enzyme-substrate non-productive complex. However, on crystalline substrates, the activity of CHI60 was only inhibited approximately 50% at high ionic strength, suggesting that the enzyme hydrolyzes crystalline substrates with an exo-type mode processively while remaining tightly bound to the substrate. Moreover, substitution of Trp-33 to either phenylalanine or tyrosine reduced the activity of the enzyme at high ionic strength, suggesting an important role of Trp-33 on enzyme processivity.

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.

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.

Sorption of Metal Ions on Clay Minerals.

PubMed

Schlegel; Charlet; Manceau

1999-12-15

The mechanism of Co uptake from aqueous solution onto hectorite (a magnesian smectite) and its impact on the stability of this clay mineral were investigated as a function of Co concentration (TotCo = 20 to 200 µM, 0.3 M NaNO(3)) and ionic strength (0.3 and 0.01 M NaNO(3), TotCo = 100 µM) by combining kinetics measurements and Co K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The morphology of the sorbent phase was characterized by atomic force microscopy (AFM) and consists of lath-type particles bounded by large basal planes and layer edges. At low ionic strength (0.01 M NaNO(3)), important Co uptake occurred within the first 5 min of reaction, consistent with Co adsorption on exchange sites of hectorite basal planes. Thereafter, the sorption rate dramatically decreased. In contrast, at high ionic strength (0.3 M NaNO(3)), Co uptake rate was much slower within the first 5 min and afterward higher than at 0.01 M NaNO(3), consistent with Co adsorption on specific surface sites located on the edges of hectorite. Time-dependent isotherms for Co uptake at high ionic strength indicated the existence of several sorption mechanisms having distinct equilibration times. The dissolution of hectorite was monitored before and after Co addition. A congruent dissolution regime was observed prior to Co addition. Just after Co addition, an excess release of Mg relatively to congruent dissolution rates occurred at both high and low ionic strengths. At high ionic strength, this excess release nearly equaled the amount of sorbed Co. The dissolution rate of hectorite then decreased at longer Co sorption times. EXAFS spectra of hectorite reacted with Co at high and low ionic strengths and for reaction times longer than 6 h, exhibited similar features, suggesting that the local structural environments of Co atoms are similar. Spectral simulations revealed the occurrence of approximately 2 Mg and approximately 2 Si neighboring cations at interatomic distances characteristic of edge-sharing linkages between Co and Mg octahedra and corner-sharing linkages between Co octahedra and Si tetrahedra, respectively. This local structure is characteristic of inner sphere mononuclear surface complexes at layer edges of hectorite platelets. The occurrence of these complexes even at low ionic strength apparently conflicts with kinetics results, as exchangeable divalent cations are known to form outer sphere surface complexes. To clarify this issue, the amount of Co adsorbed on exchange sites was calculated from the solute Co concentration, assuming that cation exchange was always at equilibrium. These calculations showed that sorbed Co was transferred within 48 h from exchange sites to edge sorption sites. Copyright 1999 Academic Press.

SORPTION OF CU AND ZN TO KAOLINITE AND IRON OXIDE: EFFECTS OF HUMIC ACID AND IONIC STRENGTH AND IMPLICATIONS FOR STORMWATER RUNOFF

EPA Science Inventory

Heavy metals are common pollutants in wet weather flows and urban waterways. Changes in ionic strength, whether from mixing with saline waters, road salt, or from the large osmotic adjustment needed for the Microtox toxicity assay, affect the aqueous chemistry of stormwater runof...

Acceptor-type hydroxide graphite intercalation compounds electrochemically formed in high ionic strength solutions.

PubMed

Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi

2017-09-05

The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.

Sequestration of U(VI) from Acidic, Alkaline, and High Ionic-Strength Aqueous Media by Functionalized Magnetic Mesoporous Silica Nanoparticles: Capacity and Binding Mechanisms

EPA Science Inventory

Uranium (VI) exhibits little adsorption onto sediment minerals in acidic, alkaline or high ionic-strength aqueous media that often occur in U mining or contaminated sites, which makes U(VI) very mobile and difficult to sequester. In this work, magnetic mesoporous silica nanoparti...

Salting out of proteins using ammonium sulfate precipitation.

PubMed

Duong-Ly, Krisna C; Gabelli, Sandra B

2014-01-01

Protein solubility is affected by ions. At low ion concentrations (<0.5 M), protein solubility increases along with ionic strength. Ions in the solution shield protein molecules from the charge of other protein molecules in what is known as 'salting-in'. At a very high ionic strength, protein solubility decreases as ionic strength increases in the process known as 'salting-out'. Thus, salting out can be used to separate proteins based on their solubility in the presence of a high concentration of salt. In this protocol, ammonium sulfate will be added incrementally to an E. coli cell lysate to isolate a recombinantly over-expressed protein of 20 kDa containing no cysteine residues or tags. © 2014 Elsevier Inc. All rights reserved.

Controlled formation of emulsion gels stabilized by salted myofibrillar protein under malondialdehyde (MDA)-induced oxidative stress.

PubMed

Zhou, Feibai; Sun, Weizheng; Zhao, Mouming

2015-04-15

This study presented the cold-set gelation of emulsions stabilized by salted myofibrillar protein (MP) under oxidative stress originated from malondialdehyde (MDA). Gel properties were compared over a range of MDA/NaCl concentrations including gel viscoelastic properties, strength, water-holding capacity (WHC), amount of protein entrapped, and microstructure. The oxidative stability of emulsion gels as indicated by lipid hydroperoxide was further determined and compared. Results indicated that emulsion stabilized by MP at swollen state under certain ionic strengths (0.2-0.6 M) was the premise of gel formation under MDA. In the presence of intermediate MDA concentrations (2.5-10 mM), the emulsion gels showed an improved elasticity, strength, WHC, and oxidative stability. This improvement should be mainly attributed to the enhanced protein-protein cross-linkings via MDA, which were homogeneously formed among absorbed and/or unabsorbed proteins, entrapping a greater amount and fractions of protein within network. Therefore, the oil droplets were better adherent to the gel matrix. Nevertheless, addition of high MDA concentrations (25-50 mM) led to the formation of excessive covalent bonds, which might break protein-protein bonds and trigger the desorption of protein from the interface. This ultimately caused "oil leak" phenomena as well as the collapse of gel structure and, thus, overall decreased gel properties and oxidative stability.

Microfludic Device for Creating Ionic Strength Gradients over DNA Microarrays for Efficient DNA Melting Studies and Assay Development

PubMed Central

Petersen, Jesper; Poulsen, Lena; Birgens, Henrik; Dufva, Martin

2009-01-01

The development of DNA microarray assays is hampered by two important aspects: processing of the microarrays is done under a single stringency condition, and characteristics such as melting temperature are difficult to predict for immobilized probes. A technical solution to these limitations is to use a thermal gradient and information from melting curves, for instance to score genotypes. However, application of temperature gradients normally requires complicated equipment, and the size of the arrays that can be investigated is restricted due to heat dissipation. Here we present a simple microfluidic device that creates a gradient comprising zones of defined ionic strength over a glass slide, in which each zone corresponds to a subarray. Using this device, we demonstrated that ionic strength gradients function in a similar fashion as corresponding thermal gradients in assay development. More specifically, we noted that (i) the two stringency modulators generated melting curves that could be compared, (ii) both led to increased assay robustness, and (iii) both were associated with difficulties in genotyping the same mutation. These findings demonstrate that ionic strength stringency buffers can be used instead of thermal gradients. Given the flexibility of design of ionic gradients, these can be created over all types of arrays, and encompass an attractive alternative to temperature gradients, avoiding curtailment of the size or spacing of subarrays on slides associated with temperature gradients. PMID:19277213

Microfludic device for creating ionic strength gradients over DNA microarrays for efficient DNA melting studies and assay development.

PubMed

Petersen, Jesper; Poulsen, Lena; Birgens, Henrik; Dufva, Martin

2009-01-01

The development of DNA microarray assays is hampered by two important aspects: processing of the microarrays is done under a single stringency condition, and characteristics such as melting temperature are difficult to predict for immobilized probes. A technical solution to these limitations is to use a thermal gradient and information from melting curves, for instance to score genotypes. However, application of temperature gradients normally requires complicated equipment, and the size of the arrays that can be investigated is restricted due to heat dissipation. Here we present a simple microfluidic device that creates a gradient comprising zones of defined ionic strength over a glass slide, in which each zone corresponds to a subarray. Using this device, we demonstrated that ionic strength gradients function in a similar fashion as corresponding thermal gradients in assay development. More specifically, we noted that (i) the two stringency modulators generated melting curves that could be compared, (ii) both led to increased assay robustness, and (iii) both were associated with difficulties in genotyping the same mutation. These findings demonstrate that ionic strength stringency buffers can be used instead of thermal gradients. Given the flexibility of design of ionic gradients, these can be created over all types of arrays, and encompass an attractive alternative to temperature gradients, avoiding curtailment of the size or spacing of subarrays on slides associated with temperature gradients.

Improved thermodynamic model for interaction of EDTA with trivalent actinides and lanthanide to ionic strength of 6.60 m

NASA Astrophysics Data System (ADS)

Thakur, Punam; Xiong, Yongliang; Borkowski, Marian; Choppin, Gregory R.

2014-05-01

The dissociation constants of ethylenediaminetetraacetic acid (H4EDTA), and the stability constants of Am3+, Cm3+and Eu3+ with EDTA4- have been determined at 25 °C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and an extraction technique, respectively. The formation of only 1:1 complex, M(EDTA)-, where (M = Am3+, Cm3+ and Eu3+), was observed under the experimental conditions. The observed ionic strength dependencies of the dissociation constants and the stability constants have been described successfully over the entire ionic strength range using the Pitzer model. The thermodynamic stability constant: logβ1010=20.55±0.18 for Am3+, logβ1010=20.43±0.20 for Cm3+ and logβ1010=20.65±0.19 for Eu3+ were calculated by extrapolation of data to zero ionic strength in an NaClO4 medium. In addition, logβ1010 of 20.05 ± 0.40 for Am3+ was obtained by simultaneously modeling data both in NaCl and NaClO4 media. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters β(0), β(1), and Cϕ determined in this work. The improved model presented in this work would enable researchers to model accurately the potential mobility of actinides (III) and light rare earth elements to ionic strength of 6.60 m in low temperature environments in the presence of EDTA.

Influence of ionic strength and surfactant concentration on electrostatic surfacial assembly of cetyltrimethylammonium bromide-capped gold nanorods on fully immersed glass.

PubMed

Ferhan, Abdul Rahim; Guo, Longhua; Kim, Dong-Hwan

2010-07-20

The effect of ionic strength as well as surfactant concentration on the surface assembly of cetyltrimethylammonium bromide (CTAB)-capped gold nanorods (GNRs) has been studied. Glass substrates were modified to yield a net negative charge through electrostatic coating of polystyrenesulfonate (PSS) over a self-assembled monolayer (SAM) of positively charged aminopropyltriethoxysilane (APTS). The substrates were then fully immersed in GNR solutions at different CTAB concentrations and ionic strengths. Under slightly excess CTAB concentrations, it was observed that the density of GNRs immobilized on a substrate was predictably tunable through the adjustment of NaCl concentration over a wide range. Motivated by the experimental observation, we hypothesize that electrostatic shielding of charges around the GNRs affects the density of GNR immobilization. This model ultimately explains that at moderate to high CTAB concentrations a second electrostatic shielding effect contributed by excess CTAB molecules occurs, resulting in a parabolic trend of nanorod surface density when ionic strength is continually increased. In contrast, at a low CTAB concentration, the effect of ionic strength becomes much less significant due to insufficient CTAB molecules to provide for the second electrostatic shielding effect. The tunability of electrostatic-based surface assembly of GNRs enables the attainment of a dense surface assembly of nanorods without significant removal of CTAB or any other substituted stabilizing agent, both of which could compromise the stability and morphology of GNRs in solution. An additional study performed to investigate the robustness of such electrostatic-based surface assembly also proved its reliability to be used as biosensing platforms.

Quantitative Comparison of Protein Adsorption and Conformational Changes on Dielectric-Coated Nanoplasmonic Sensing Arrays.

PubMed

Ferhan, Abdul Rahim; Jackman, Joshua A; Sut, Tun Naw; Cho, Nam-Joon

2018-04-22

Nanoplasmonic sensors are a popular, surface-sensitive measurement tool to investigate biomacromolecular interactions at solid-liquid interfaces, opening the door to a wide range of applications. In addition to high surface sensitivity, nanoplasmonic sensors have versatile surface chemistry options as plasmonic metal nanoparticles can be coated with thin dielectric layers. Within this scope, nanoplasmonic sensors have demonstrated promise for tracking protein adsorption and substrate-induced conformational changes on oxide film-coated arrays, although existing studies have been limited to single substrates. Herein, we investigated human serum albumin (HSA) adsorption onto silica- and titania-coated arrays of plasmonic gold nanodisks by localized surface plasmon resonance (LSPR) measurements and established an analytical framework to compare responses across multiple substrates with different sensitivities. While similar responses were recorded on the two substrates for HSA adsorption under physiologically-relevant ionic strength conditions, distinct substrate-specific behavior was observed at lower ionic strength conditions. With decreasing ionic strength, larger measurement responses occurred for HSA adsorption onto silica surfaces, whereas HSA adsorption onto titania surfaces occurred independently of ionic strength condition. Complementary quartz crystal microbalance-dissipation (QCM-D) measurements were also performed, and the trend in adsorption behavior was similar. Of note, the magnitudes of the ionic strength-dependent LSPR and QCM-D measurement responses varied, and are discussed with respect to the measurement principle and surface sensitivity of each technique. Taken together, our findings demonstrate how the high surface sensitivity of nanoplasmonic sensors can be applied to quantitatively characterize protein adsorption across multiple surfaces, and outline broadly-applicable measurement strategies for biointerfacial science applications.

The influence of ionic strength on carbonate-based spectroscopic barometry for aqueous fluids: an in-situ Raman study on Na2CO3-NaCl solutions

PubMed Central

Wu, Jia; Wang, Shixia; Zheng, Haifei

2016-01-01

The Raman wavenumber of the symmetric stretching vibration of carbonate ion (ν1-CO32−) was measured in three aqueous solutions containing 2.0 mol·L−1 Na2CO3 and 0.20, 0.42, or 0.92 mol·L−1 NaCl, respectively, from 122 to 1538 MPa at 22 °C using a moissanite anvil cell. The ν1 Raman signal linearly shifted to higher wavenumbers with increasing pressure. Most importantly, the slope of ν1-CO32− Raman frequency shift (∂ν1/∂P)I was independent of NaCl concentration. Moreover, elevated ionic strength was found to shift the apparent outline of the carbonate peak toward low wavenumbers, possibly by increasing the proportion of the contact ion pair NaCO3−. Further investigations revealed no cross-interaction between the pressure effect and the ionic strength effect on the Raman spectra, possibly because the distribution of different ion-pair species in the carbonate equilibrium was largely pressure-independent. These results suggested that the ionic strength should be incorporated as an additional constraint for measuring the internal pressure of various solution-based systems. Combining the ν1-CO32− Raman frequency slope with the pressure herein with the values for the temperature or the ionic strength dependencies determined from previous studies, we developed an empirical equation that can be used to estimate the pressure of carbonate-bearing aqueous solutions. PMID:27982064

Systematic Approach for Calculating the Concentrations of Chemical Species in Multiequilibrium Problems: Inclusion of the Ionic Strength Effects

ERIC Educational Resources Information Center

Baeza-Baeza, Juan J.; Garcia-Alvarez-Coque, M. Celia

2012-01-01

A general systematic approach including ionic strength effects is proposed for the numerical calculation of concentrations of chemical species in multiequilibrium problems. This approach extends the versatility of the approach presented in a previous article and is applied using the Solver option of the Excel spreadsheet to solve real problems…

Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Porous Media: Influence of Solution pH, Ionic Strength, and the Presence of Humic Acid

EPA Science Inventory

The influence of solution pH, ionic strength, and varying concentrations of the Suwannee River Humic Acid (SRHA) on the transport of titanium dioxide (TiO2, rutile) nanoparticle aggregates (nTiO2) in saturated porous media was investigated through systematically examining the tra...

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.

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.

[Verification of a decrease in the rigidity of the phage lambda DNA polymeric chain in low ionic strength aqueous solutions by testing the polymer-polymer interlink interactions].

PubMed

Arutiunian, A V; Ivanova, M A; Kurliand, D I; Kapshin, Iu S; Landa, S B; Poshekhonov, S T; Drobchenko, E A; Shevelev, I V

2011-01-01

Changes in the rigidity of the polymetric chain of phage lambda double-strand DNA have been studied by laser correlation spectroscopy. It was shown that, as the ionic strength increases, the effect of the screening of the hydrodynamic interaction of the links of the polymeric chain specific for polymeric coils arises in a DNA solution. It is assumed that the screening occurs when the threshold of the overlapping of DNA coils is achieved. The overlapping of coils is the result of a previously observed significant rise of DNA coil size from abnormally small DNA coils in low ionic strength buffers (about 10(-2) M Na+ or less) to maximum possible large coils in the 5SSC and 5SSC-like buffers. Further analysis of the far interlink interactions in linear lambda phage DNA coils in similar buffers at pH 7 and 4 confirms the earlier proposal about the role of H+ ions in the appearance of abnormally small DNA coils. The abnormal decrease in the DNA coil size in low ionic strength buffers is not a specific feature of lambda phage DNA only.

Solubilization of myofibrillar proteins in water or low ionic strength media: Classical techniques, basic principles, and novel functionalities.

PubMed

Chen, Xing; Tume, Ron K; Xu, Xinglian; Zhou, Guanghong

2017-10-13

The qualitative characteristics of meat products are closely related to the functionality of muscle proteins. Myofibrillar proteins (MPs), comprising approximately 50% of total muscle proteins, are generally considered to be insoluble in solutions of low ionic strength (< 0.2 M), requiring high concentrations of salt (> 0.3 M) for solubilization. These soluble proteins are the ones which determine many functional properties of meat products, including emulsification and thermal gelation. In order to increase the utilization of meat and meat products, many studies have investigated the solubilization of MPs in water or low ionic strength media and determining their functionality. However, there still remains a lack of systematic information on the functional properties of MPs solubilized in this manner. Hence, this review will explore some typical techniques that have been used. The main procedures used for their solubilization, the fundamental principles and their functionalities in water (low ionic strength medium) are comprehensively discussed. In addition, advantages and disadvantages of each technique are summarized. Finally, future considerations are presented to facilitate progress in this new area and to enable water soluble muscle MPs to be utilized as novel meat ingredients in the food industry.

A precision structured smart hydrogel for sensing applications

NASA Astrophysics Data System (ADS)

Menges, J.; Kleinschmidt, P.; Bart, H.-J.; Oesterschulze, E.

2017-10-01

We report on a macroinitiator based smart hydrogel film applied on a microcantilever for sensing applications. The studied hydrogel features a comparatively wide dynamic range for changes in the electrolyte's ionic strength. Furthermore, it offers a simple spin coating process for thin film deposition as well as the capability to obtain high aspect ratio microstructures by reactive ion etching. This makes the hydrogel compatible to microelectromechanical system integration. As a proof of concept, we study the response of hydrogel functionalized cantilevers in aqueous sodium chloride solutions of varying ionic strength. In contrast to the majority of hydrogel materials reported in the literature, we found that our hydrogel still responds in high ionic strength environments. This may be of future interest for sensing e.g., in sea water or physiological environments like urine.

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.

Divalent cation and ionic strength effects on Vinca alkaloid-induced tubulin self-association.

PubMed

Lobert, S; Boyd, C A; Correia, J J

1997-01-01

We present here a systematic study of ionic strength and divalent cation effects on Vinca alkaloid-induced tubulin spiral formation. We used sedimentation velocity experiments and quantitative fitting of weight-average sedimentation coefficients versus free drug concentrations to obtain thermodynamic parameters under various solution conditions. The addition of 50-150 mM NaCl to our standard buffer (10 mM piperazine-N,N'-bis(2-ethanesulfonic acid), 1 mM Mg, 50 microM GDP or GTP, pH 6.9) enhances overall vinblastine- or vincristine-induced tubulin self-association. As demonstrated in previous studies, GDP enhances overall self-association more than GTP, although in the presence of salt, GDP enhancement is reduced. For example, in 150 mM NaCl, GDP enhancement is 0.24 kcal/mol for vinblastine and 0.36 kcal/mol for vincristine versus an average enhancement of 0.87 (+/- 0.34) kcal/mol for the same drugs in the absence of salt. Wyman linkage analysis of experiments with vinblastine or vincristine over a range of NaCl concentrations showed a twofold increase in the change in NaCl bound to drug-induced spirals in the presence of GTP compared to GDP. These data indicate that GDP enhancement of Vinca alkaloid-induced tubulin self-association is due in part to electrostatic inhibition in the GTP state. In the absence of NaCl, we found that vinblastine and 1 mM Mn2+ or Ca2+ causes immediate condensation of tubulin. The predominant aggregates observed by electron microscopy are large sheets. This effect was not found with 1 mM Mg2+. At 100 microM cation concentrations (Mn2+, Mg2+, or Ca2+), GDP enhances vinblastine-induced spiral formation by 0.55 (+/- 0.26) kcal/mol. This effect is found only in K2, the association of liganded heterodimers at the ends of growing spirals. There is no GDP enhancement of K1, the binding of drug to heterodimer, although K1 is dependent upon the divalent cation concentration. NaCl diminishes tubulin condensation, probably by inhibiting lateral association, and allows an investigation of higher divalent cation concentrations. In the presence of 150 mM NaCl plus 1 mM divalent cations (Mn2+, Mg2+, or Ca2+) GDP enhances vinblastine-induced spiral formation by 0.35 (+/- 0.21) kcal/mol. Relaxation times determined by stopped-flow light scattering experiments in the presence of 150 mM NaCl and vincristine are severalfold longer than those in the presence of vinblastine, consistent with a mechanism involving the redistribution of longer polymers. Unlike previous results in the absence of NaCl, relaxation times in the presence of NaCl are only weekly protein concentration dependent, suggesting the absence of annealing or an additional rate-limiting step in the mechanism.

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 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.

The electronegativity equalization method fused with molecular mechanics: a fluctuating charge and flexible body potential function for [Emim][Gly] ionic liquids.

PubMed

Wu, Yang; Li, Yao; Hu, Na; Hong, Mei

2014-02-14

Recently, experimental and theoretical studies on amino acid ionic liquid (AAIL) systems have attracted much attention. A transferable intermolecular potential approach that includes fluctuating charges and a flexible body based on a combination of the electronegativity equalization method and molecular mechanics (EEM/MM), and its application to an AAIL system containing 1-ethyl-3-methylimidazolium ([Emim](+)) and glycine ([Gly](-)) are explored and tested in this study. A consistent integration of EEM with MM requires the input of the EEM charges of all atoms into the MM intermolecular electrostatic interaction term. Compared with ionic liquid (IL) force fields, the EEM/MM model has an outstanding feature: the EEM/MM model not only presents the electrostatic interaction of atoms and their changes in response to different ambient environments but also introduces "the H-bond interaction region" in which a new parameter kHB(RHB) is used to describe the electrostatic interaction of hydrogen atoms in [Emim](+) and oxygen atoms in [Gly](-), which can form hydrogen bonds. The EEM/MM model gives quite accurate predictions for gas-phase state properties of [Emim](+), [Gly](-), and ion pairs, such as optimized geometries, dipole moments, vibrational frequencies, and cluster interaction energies. Due to its explicit description of charges and hydrogen bonds, the EEM/MM model also performs well for the liquid-phase properties of [Emim][Gly] under ambient conditions. The calculated properties, such as density, heat of vaporization, the self-diffusion coefficient, and ionic conductivity, are fairly consistent with available experimental results.

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)

Conformation of chromatin oligomers. A new argument for a change with the hexanucleosome.

PubMed

Marion, C; Bezot, P; Hesse-Bezot, C; Roux, B; Bernengo, J C

1981-11-01

Quasielastic laser light scattering measurements have been made on chromatin oligomers to obtain information on the transition in their electrooptical properties, previously observed for the hexameric structures [Marion, C. and Roux, B. (1978) Nucleic Acids Res. 5, 4431-4449]. Translational diffusion coefficients were determined for mononucleosomes to octanucleosomes containing histone H1 over a range of ionic strength. At high ionic strength, oligomers show a linear dependence of the logarithm of diffusion coefficient upon the logarithm of number of nucleosomes. At low ionic strength a change occurs between hexamer and heptamer. Our results agree well with the recent sedimentation data of Osipova et al. [Eur. J. Biochem. (1980) 113, 183-188] and of Butler and Thomas [J. Mol. Biol. (1980) 140, 505-529] showing a change in stability with hexamer. Various models for the arrangements of nucleosomes in the superstructure of chromatin are discussed. All calculations clearly indicate a conformational change with the hexanucleosome and the results suggest that, at low ionic strength, the chromatin adopts a loosely helical structure of 28-nm diameter and 22-nm pitch. These results are also consistent with a discontinuity every sixth nucleosome, corresponding to a turn of the helix. This discontinuity may explain the recent electric dichroism data of Lee et al. [Biochemistry (1981) 20, 1438-1445]. The hexanucleosome structure which we have previously suggested, with the faces of nucleosomes arranged radially to the helical axis has been recently confirmed by Mc Ghee et al. [Cell (1980) 22, 87-96]. With an increase of ionic strength, the helix becomes more regular and compact with a slightly reduced outer diameter and a decreased pitch, the dimensions resembling those proposed for solenoid models.

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.

Supramolecular "Big Bang" in a Single-Ionic Surfactant/Water System Driven by Electrostatic Repulsion: From Vesicles to Micelles.

PubMed

Leclercq, Loïc; Bauduin, Pierre; Nardello-Rataj, Véronique

2017-04-11

In aqueous solution, dimethyldi-n-octylammonium chloride, [DiC 8 ][Cl], spontaneously forms dimers at low concentrations (1-10 mM) to decrease the strength of the hydrophobic-water contact. Dimers represent ideal building blocks for the abrupt edification of vesicles at 10 mM. These vesicles are fully characterized by dynamic and static light scattering, self-diffusion nuclear magnetic resonance, and freeze-fracture transmission electron microscopy. An increase in concentration leads to electrostatic repulsion between vesicles that explode into small micelles at 30 mM. These transitions are detected by means of surface tension, conductivity, and solubility of hydrophobic solutes as well as by isothermal titration microcalorimetry. These unusual supramolecular transitions emerge from the surfactant chemical structure that combines two contradictory features: (i) the double-chain structure tending to form low planar aggregates with low water solubility and (ii) the relatively short chains giving high hydrophilicity. The well-balanced hydrophilic-hydrophobic character of [DiC 8 ][Cl] is then believed to be at the origin of the unusual supramolecular sequence offering new opportunities for drug delivery systems.

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

Effect of ionic strength on the thermodynamic characteristics of complexation between Fe(III) ion and nicotinamide in water-ethanol and water-dimethyl sulfoxide mixtures

NASA Astrophysics Data System (ADS)

Gamov, G. A.; Grazhdan, K. V.; Gavrilova, M. A.; Dushina, S. V.; Sharnin, V. A.; Baranski, A.

2013-06-01

Solutions of iron(III) perchlorate in water, water-ethanol, and water-dimethyl sulfoxide solvents (x_{H_2 O} = 0.7 and 0.25 mole fractions) at ionic strength values I = 0.1, 0.25, and 0.5 are studied by IR spectroscopy. Analysis of the absorption bands of perchlorate ion shows that it does not participate in association processes. It is demonstrated that in the range of ionic strength values between 0 and 0.5 (NaClO4), it affects neither the results from potentiometric titration to determine the stability constants of the iron(III)-nicotinamide complex nor the thermal effects of complexation determined via direct calorimetry in a binary solvent containing 0.3 mole fractions (m.f.) of a non-aqueous component.

Long-Term Experimental Determination of Solubilities of Micro-Crystalline Nd(III) Hydroxide in High Ionic Strength Solutions: Applications to Nuclear Waste Management [A Pitzer Model for Am(III)/Nd(III) hydroxide solubility in NaCl-H 2O at 298.15 K to high ionic strengths: Experimental validation and model applications

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

Xiong, Yongliang; Kirkes, Leslie Dawn; Marrs, Cassandra

In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3(micro cr), avoiding the possibility of phase change.

Long-Term Experimental Determination of Solubilities of Micro-Crystalline Nd(III) Hydroxide in High Ionic Strength Solutions: Applications to Nuclear Waste Management [A Pitzer Model for Am(III)/Nd(III) hydroxide solubility in NaCl-H 2O at 298.15 K to high ionic strengths: Experimental validation and model applications

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie Dawn; Marrs, Cassandra

2017-12-01

In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3(micro cr), avoiding the possibility of phase change.

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.

Adsorption of a Textile Dye on Commercial Activated Carbon: A Simple Experiment to Explore the Role of Surface Chemistry and Ionic Strength

ERIC Educational Resources Information Center

Martins, Angela; Nunes, Nelson

2015-01-01

In this study, an adsorption experiment is proposed using commercial activated carbon as adsorbent and a textile azo dye, Mordant Blue-9, as adsorbate. The surface chemistry of the activated carbon is changed through a simple oxidation treatment and the ionic strength of the dye solution is also modified, simulating distinct conditions of water…

A Simplified Undergraduate Laboratory Experiment to Evaluate the Effect of the Ionic Strength on the Equilibrium Concentration Quotient of the Bromcresol Green Dye

ERIC Educational Resources Information Center

Rodriguez, Hernan B.; Mirenda, Martin

2012-01-01

A modified laboratory experiment for undergraduate students is presented to evaluate the effects of the ionic strength, "I", on the equilibrium concentration quotient, K[subscript c], of the acid-base indicator bromcresol green (BCG). The two-step deprotonation of the acidic form of the dye (sultone form), as it is dissolved in water, yields…

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.

Quantifying particulate and colloidal release of radionuclides in waste-weathered hanford sediments.

PubMed

Perdrial, Nicolas; Thompson, Aaron; LaSharr, Kelsie; Amistadi, Mary Kay; Chorover, Jon

2015-05-01

At the Hanford Site in the state of Washington, leakage of hyperalkaline, high ionic strength wastewater from underground storage tanks into the vadose zone has induced mineral transformations and changes in radionuclide speciation. Remediation of this wastewater will decrease the ionic strength of water infiltrating to the vadose zone and could affect the fate of the radionuclides. Although it was shown that radionuclide host phases are thermodynamically stable in the presence of waste fluids, a decrease in solution ionic strength and pH could alter aggregate stability and remobilize radionuclide-bearing colloids and particulate matter. We quantified the release of particulate, colloidal, and truly dissolved Sr, Cs, and I from hyperalkaline-weathered Hanford sediments during a low ionic strength pore water leach and characterized the released particles and colloids using electron microscopy and X-ray diffraction. Although most of the Sr, Cs, and I was released in dissolved form, between 3 and 30% of the Sr and 4 to 18% of the Cs was associated with a dominantly zeolitic mobile particulate fraction. Thus, the removal of hyperalkaline wastewater will likely induce Sr and Cs mobilization that will be augmented by particulate- and colloid-facilitated transport. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

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.

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.

DNA surface hybridization regimes

PubMed Central

Gong, Ping; Levicky, Rastislav

2008-01-01

Surface hybridization reactions, in which sequence-specific recognition occurs between immobilized and solution nucleic acids, are routinely carried out to quantify and interpret genomic information. Although hybridization is fairly well understood in bulk solution, the greater complexity of an interfacial environment presents new challenges to a fundamental understanding, and hence application, of these assays. At a surface, molecular interactions are amplified by the two-dimensional nature of the immobilized layer, which focuses the nucleic acid charge and concentration to levels not encountered in solution, and which impacts the hybridization behavior in unique ways. This study finds that, at low ionic strengths, an electrostatic balance between the concentration of immobilized oligonucleotide charge and solution ionic strength governs the onset of hybridization. As ionic strength increases, the importance of electrostatics diminishes and the hybridization behavior becomes more complex. Suppression of hybridization affinity constants relative to solution values, and their weakened dependence on the concentration of DNA counterions, indicate that the immobilized strands form complexes that compete with hybridization to analyte strands. Moreover, an unusual regime is observed in which the surface coverage of immobilized oligonucleotides does not significantly influence the hybridization behavior, despite physical closeness and hence compulsory interactions between sites. These results are interpreted and summarized in a diagram of hybridization regimes that maps specific behaviors to experimental ranges of ionic strength and probe coverage. PMID:18381819

Effects of polarizability on the structural and thermodynamics properties of [C{sub n}mim][Gly] ionic liquids (n = 1–4) using EEM/MM molecular dynamic simulations

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

Wu, Yang; Hu, Na; Yue, Lili

2015-02-14

An extended electronegativity equalization method/molecular mechanics (EEM/MM) model for ionic liquids is used to investigate the structures and properties of 1-alkyl-3-methylimidazolium glycine ionic liquids [C{sub n}mim][Gly] (n = 1–4) with alkyl substituents of different lengths. The EEM/MM model describes the electrostatic interactions of atoms and their changes in different ambient environments. This property is the most outstanding characteristic of the model. EEM parameters (i.e., valence electronegativities and valence hardness parameters) are calibrated using linear regression and least-squares methods, which can accurately predict the gas-phase properties of [C{sub n}mim]{sup +}, [Gly]{sup −}, and [C{sub n}mim][Gly] ion pairs. We utilize the EEM/MMmore » force field to systematically investigate the effects of polarizability on the accuracy of [C{sub n}mim][Gly] properties predicted through the molecular dynamic simulations. EEM/MM explicitly describes the atom-based polarizability of [C{sub n}mim][Gly]; thus, the densities, enthalpies of vaporization, self-diffusion coefficients, and conductivities of the [C{sub n}mim][Gly] are consistent with the experimental values. The calculated radial distribution functions provide a mechanistic understanding of the effects of polarizability on ionic aggregations in amino acid ionic liquids. The effects of alkyl chain length on the diffusion coefficient and conductivity are also discussed.« less

Novel double-confined polymeric ionic liquids as sorbents for solid-phase microextraction with enhanced stability and durability in high-ionic-strength solution.

PubMed

Feng, Juanjuan; Sun, Min; Xu, Lili; Wang, Shuai; Liu, Xia; Jiang, Shengxiang

2012-12-14

Because of the occurrence of ion exchange between high-ionic-strength solution and anions of polymeric ionic liquids (PILs), PILs based solid-phase microextraction (SPME) fibers were rarely used in direct immersion mode to high-salt-added samples. In this work, a novel double-confined PIL sorbent was prepared by co-polymerization of cation and anion of 1-vinyl-3-octylimidzaolium p-styrenesulfonate (VOIm(+)SS(-)). The poly(VOIm(+)-SS(-)) was chemically bonded onto functionalized stainless steel wire via surface radical chain-transfer reaction. Stability of poly(VOIm(+)-SS(-)) in high-ionic-strength solution was investigated and compared with that of poly(1-vinyl-3-octylimidzaolium benzenesulfonate) (poly(VOIm(+)BS(-))) by elemental analysis of sulfur element, and results turned out that the poly(VOIm(+)-SS(-)) was more stable. Coupled to gas chromatography (GC), the poly(VOIm(+)-SS(-)) fiber was used to extract three sorts of compounds including anilines, phenols and phthalate esters in aqueous solution. The as-established method showed good linearity, low detection limits, and acceptable repeatability. The direct immersion SPME-GC method was applied to determine the model phthalate esters in bottled mineral water. The determination results were satisfactory. Copyright © 2012 Elsevier B.V. All rights reserved.

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

Ultrathin nanoporous membranes for insulator-based dielectrophoresis.

PubMed

Mukaibo, Hitomi; Wang, Tonghui; Perez-Gonzalez, Victor H; Getpreecharsawas, Jirachai; Wurzer, Jack; Lapizco-Encinas, Blanca H; McGrath, James L

2018-06-08

Insulator-based dielectrophoresis (iDEP) is a simple, scalable mechanism that can be used for directly manipulating particle trajectories in pore-based filtration and separation processes. However, iDEP manipulation of nanoparticles presents unique challenges as the dielectrophoretic force [Formula: see text] exerted on the nanoparticles can easily be overshadowed by opposing kinetic forces. In this study, a molecularly thin, SiN-based nanoporous membrane (NPN) is explored as a breakthrough technology that enhances [Formula: see text] By numerically assessing the gradient of the electric field square [Formula: see text]-a common measure for [Formula: see text] magnitude-it was found that the unique geometrical features of NPN (pore tapering, sharp pore corner and ultrathin thickness) act in favor of intensifying the overall [Formula: see text] A comparative study indicated that [Formula: see text] generated in NPN are four orders of magnitude larger than track-etched polycarbonate membranes with comparable pore size. The stronger [Formula: see text] suggests that iDEP can be conducted under lower voltage bias with NPN: reducing joule heating concerns and enabling solutions to have higher ionic strength. Enabling higher ionic strength solutions may also extend the opportunities of iDEP applications under physiologically relevant conditions. This study also highlights the effects of [Formula: see text] induced by the ion accumulation along charged surfaces (electric-double layer (EDL)). EDL-based [Formula: see text] exists along the entire charged surface, including locations where geometry-based iDEP is negligible. The high surface-to-volume ratio of NPN offers a unique platform for exploiting such EDL-based DEP systems. The EDL-based [Formula: see text] was also found to offset the geometry-based [Formula: see text] but this effect was easily circumvented by reducing the EDL thickness (e.g. increasing the ionic strength from 0.1 to 100 mM). The results from this study imply the potential application of iDEP as a direct, in-operando antifouling mechanism for ultrafiltration technology, and also as an active tuning mechanism to control the cut-off size limit for continuous selectivity of nanomembrane-based separations.

Controls of ionic strength and macromolecule chemistry on calcite nucleation: Salinity and ion hydration as levers for regulating biomineralization

NASA Astrophysics Data System (ADS)

Dove, P. M.; Giuffre, A. J.; Mergelsberg, S. T.; Han, N.; De Yoreo, J. J.

2016-12-01

Organisms form shells and skeletons with remarkable fidelity by controlling the timing and placement of the minerals that nucleate and subsequently grow. An extensive effort has identified features of the organic matrix that regulate this process. Recent measurements from our group show the energy barrier to nucleation onto polysaccharide (PS) substrates is dependent upon hydrophilicity through functional group chemistry and suggest that free energy of the macromolecule-liquid interface influences where and when mineral nucleation occurs (Giuffre et al., 2013, PNAS). The importance of interfacial free energy in regulating nucleation raises the question of whether local changes in salinity or electrolyte composition can be tuned to further modulate the onset of calcite nucleation. Using alginate (negatively charged by carboxyl groups) and chitosan (small positive charge by amine groups), the rate of calcite nucleation was measured at controlled supersaturations and pH as a function of NaCl concentration (65-600 mM). Analyses of the data show the thermodynamic barrier to calcite nucleation onto both types of PS increases with ionic strength. The evidence suggests this effect arises from an increasing concentration of solvated ions at the PS-water interface while also increasing the hydrophilic character of that interface; thus decreasing the substrate-liquid interfacial free energy. To test this explanation, a second group of nucleation experiments used a suite of electrolytes (alkali chlorides for alginate and sodium halides for chitosan) while holding ionic strength constant. Indeed, the nucleation barriers for calcite formation are electrolyte-specific and correlated with the hydration free energy of the ion. This suggests solvated electrolyte ions indirectly regulate calcite nucleation onto substrates through their competition with the substrate for water thereby influencing net interfacial free energy. These effects are consistent with the long-established salting-in phenomena of the Hofmeister series. The new insights from this experimental study reiterate the importance of electrolytes in reactions involving mineral-water interfaces and suggest a role for seemingly inert `spectator' ions in regulating the local timing and placement of minerals during biomineralization.

Preparation of Copper Telluride Films by Co-Reduction of Cu(I) and Te(IV) Ions in Choline Chloride: Ethylene Glycol Ionic Liquid

NASA Astrophysics Data System (ADS)

Golgovici, Florentina; Catrangiu, Adriana-Simona; Stoian, Andrei Bogdan; Anicai, Liana; Visan, Teodor

2016-07-01

Cathodic processes of direct co-reduction of Cu+ and Te4+ ions on Pt electrode at 60°C were investigated using cyclic voltammetry and electrochemical impedance spectroscopy techniques. The ionic liquid as background electrolyte consisted of a mixture of choline chloride and ethylene glycol (ChCl-EG 1:2 mol ratio) in which 5-20 mM CuCl and 8 mM TeO2 were dissolved. The voltammograms exhibited the following successive cathodic processes: Cu2+/Cu+ reduction, Te underpotential deposition, simultaneous deposition of Cu metal and CuTe compound, and deposition of Te-rich CuTe compound at the most negative potentials (from -0.5 V to -0.8 V). Corresponding dissolution or oxidation peaks were recorded on the anodic branch. The voltammetric results were confirmed by electrochemical impedance spectra. Copper telluride films have been synthesized on platinum substrate via potentiostatic electrodeposition at 60°C. It was found from atomic force microscopy that CuTe film samples prepared from ChCl-EG + 5 mM CuCl + 8 mM TeO2 ionic liquid have high growth rates. The x-ray diffraction patterns of the deposited films from ChCl-EG + 10 mM CuCl + 8 mM TeO2 ionic liquid indicated the presence of a Cu2Te phase for film deposited at -0.7 V and a Cu0.656Te0.344 phase for film deposited at -0.6 V.

The influence of ionic strength on DNA diffusion in gel networks

NASA Astrophysics Data System (ADS)

Fu, Yuanxi; Jee, Ah-Young; Kim, Hyeong-Ju; Granick, Steve

Cations are known to reduce the rigidity of the DNA molecules by screening the negative charge along the sugar phosphate backbone. This was established by optical tweezer pulling experiment of immobilized DNA strands. However, little is known regarding the influence of ions on the motion of DNA molecules as they thread through network meshes. We imaged in real time the Brownian diffusion of fluorescent labeled lambda-DNA in an agarose gel network in the presence of salt with monovalent or multivalent cations. Each movie was analyzed using home-written program to yield a trajectory of center of the mass and the accompanying history of the shape fluctuations. One preliminary finding is that ionic strength has a profound influence on the slope of the trace of mean square displacement (MSD) versus time. The influence of ionic strength on DNA diffusion in gel networks.

Evaluating Rotavirus and Norovirus transport processes in standardised and natural soil-water columns experiments

NASA Astrophysics Data System (ADS)

Gamazo, Pablo; Schijven, Jack; Victoria, Matias; Alvareda, Elena; López Tort, Fernando; Ramos, Julián; Lizasoain, Andrés; Sapriza, Gonzalo; Castells, Matias; Colina, Rodney

2017-04-01

In Uruguay, as in many developed and developing countries, rotavirus and norovirus are major causes of diarrhea and others symptoms of acute gastroenteritis. In some areas of Uruguay, groundwater is the only source of water for human consumption. In the rural area of the Salto district, virus contamination has been detected in several groundwater wells. Because sewer coverage is low, the most probable sources of contamination are nearby septic systems. This work aims to evaluate the transport of rotavirus and norovirus from clinic samples in two sets of column experiments under saturated conditions: 6.7-cm columns with quartz sand (ionic strength 1mM, pH 7.0) and with sand from the Salto aquifer (Uruguay) (9,2% coarse sand, 47,8% medium sand, 40,5% fine sand, magnesium/calcium bicarbonate water, Ionic strength 15.1 mM, pH 7.2). Both viruses were seeded for 2 pore volumes onto the columns. Samples were collected at the column outlet and viruses were enumerated by Q-PRCR. Breakthrough curves were constructed and fitted to a two-site kinetic attachment/detachment model, including blocking using Hydrus-1D. In the quartz sand column, both rotavirus and norovirus were removed two orders in magnitude. In the Salto sand column, rotavirus was removed 2 log10 as well, but norovirus was removed 4 log10. The fitting of the breakthrough curves indicated that blocking played a role for rotavirus in the Salto sand column. These results are consistent with the field observation where only rotavirus was detected in the Salto aquifer, while similar concentrations in Salto sewer effluent were measured for both viruses. This work, besides reporting actual parameters values for human virus transport modelling, shows the significant differences in transport that human viruses can have in standardised and natural soil-water systems.

Kinetics of interprotein electron transfer between cytochrome c6 and the soluble CuA domain of cyanobacterial cytochrome c oxidase.

PubMed

Paumann, Martina; Feichtinger, Markus; Bernroitner, Margit; Goldfuhs, Judith; Jakopitsch, Christa; Furtmüller, Paul G; Regelsberger, Günther; Peschek, Günter A; Obinger, Christian

2004-10-08

Cytochrome c6 is a soluble metalloprotein located in the periplasmic space and the thylakoid lumen of many cyanobacteria and is known to carry electrons from cytochrome b6f to photosystem I. The CuA domain of cytochrome c oxidase, the terminal enzyme which catalyzes the four-electron reduction of molecular oxygen in the respiratory chains of mitochondria and many bacteria, also has a periplasmic location. In order to test whether cytochrome c6 could also function as a donor for cytochrome c oxidase, we investigated the kinetics of the electron transfer between recombinant cytochrome c6 (produced in high yield in Escherichia coli by coexpressing the maturation proteins encoded by the ccmA-H gene cluster) and the recombinant soluble CuA domain (i.e., the donor binding and electron entry site) of subunit II of cytochrome c oxidase from Synechocystis PCC 6803. The forward and the reverse electron transfer reactions were studied by the stopped-flow technique and yielded apparent bimolecular rate constants of (3.3 +/- 0.3) x 10(5) M(-1) s(-1) and (3.9 +/- 0.1) x 10(6) M(-1) s(-1), respectively, in 5 mM potassium phosphate buffer, pH 7, containing 20 mM potassium chloride and 25 degrees C. This corresponds to an equilibrium constant Keq of 0.085 in the physiological direction (DeltarG'0 = 6.1 kJ/mol). The reduction of the CuA fragment by cytochrome c6 is almost independent on ionic strength, which is in contrast to the reaction of the CuA domain with horse heart cytochrome c, which decreases with increasing ionic strength. The findings are discussed with respect to the potential role of cytochrome c6 as mobile electron carrier in both cyanobacterial electron transport pathways. Copyright 2004 Federation of European Biochemical Societies

Competing Hydrophobic and Screened-Coulomb Interactions in Hepatitis B Virus Capsid Assembly

PubMed Central

Kegel, Willem K.; Schoot, Paul van der

2004-01-01

Recent experiments show that, in the range from ∼15 to 45°C, an increase in the temperature promotes the spontaneous assembly into capsids of the Escherichia coli-expressed coat proteins of hepatitis B virus. Within that temperature interval, an increase in ionic strength up to five times that of standard physiological conditions also acts to promote capsid assembly. To explain both observations we propose an interaction of mean force between the protein subunits that is the sum of an attractive hydrophobic interaction, driving the self-assembly, and a repulsive electrostatic interaction, opposing the self-assembly. We find that the binding strength of the capsid subunits increases with temperature virtually independently of the ionic strength, and that, at fixed temperature, the binding strength increases with the square root of ionic strength. Both predictions are in quantitative agreement with experiment. We point out the similarities of capsid assembly in general and the micellization of surfactants. Finally we make plausible that electrostatic repulsion between the native core subunits of a large class of virus suppresses the formation in vivo of empty virus capsids, that is, without the presence of the charge-neutralizing nucleic acid. PMID:15189887

A trap potential model investigation of the optical activity induced in dye-DNA intercalation complexes

NASA Astrophysics Data System (ADS)

Kamiya, Mamoru

1988-02-01

The fundamental features of the optical activity induced in dye-DNA intercalation complexes are studied by application of the trap potential model which is useful to evaluate the induced rotational strength without reference to detailed geometrical information about the intercalation complexes. The specific effect of the potential depth upon the induced optical activity is explained in terms of the relative magnitudes of the wave-phase and helix-phase variations in the path of an electron moving on a restricted helical segment just like an exciton trapped around the dye intercalation site. The parallel and perpendicular components of the induced rotational strength well reflect basic properties of the helicity effects about the longitudinal and tangential axes of the DNA helical cylinder. The trap potential model is applied to optimize the potential parameters so as to reproduce the ionic strength effect upon the optical activity induced to proflavine-DNA intercalation complexes. From relationships between the optimized potential parameters and ionic strengths, it is inferred that increase in the ionic strength contributes to the optical activity induced by the nearest-neighbour interaction between intercalated proflavine and DNA base pairs.

Mechanical properties and XRD of Nafion modified by 2-hydroxyethylammonium ionic liquids

NASA Astrophysics Data System (ADS)

Garaev, V.; Pavlovica, S.; Reinholds, I.; Vaivars, G.

2013-12-01

In this work, the Nafion 112 membrane impregnated with 2-hydroxyethylammonium carboxylate ionic liquids have been investigated. The used ionic liquids were 2-hydroxyethylammonium formate [HEA]F, acetate [HEA]A and lactate [HEA]L. Prepared composite membranes Nafion/ionic liquid are characterized by mechanical testing, such as tensile test and creep test. It is found that ionic liquids decrease elastic modulus and creep compliance, but do not have significant effect on the tensile strength. Also, composite membranes were studied by wide angle X-ray diffraction. All ionic liquids shift the peak maximum to the lower angle. In this work, only biodegradable ionic liquids were used for composite preparation.

Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing

DOEpatents

Van Calcar, Pamela; Mackay, Richard; Sammells, Anthony F.

2002-01-01

The invention relates to mixed phase materials for the preparation of catalytic membranes which exhibit ionic and electronic conduction and which exhibit improved mechanical strength compared to single phase ionic and electronic conducting materials. The mixed phase materials are useful for forming gas impermeable membranes either as dense ceramic membranes or as dense thin films coated onto porous substrates. The membranes and materials of this invention are useful in catalytic membrane reactors in a variety of applications including synthesis gas production. One or more crystalline second phases are present in the mixed phase material at a level sufficient to enhance the mechanical strength of the mixture to provide membranes for practical application in CMRs.

Unraveling the complexity of the interactions of DNA nucleotides with gold by single molecule force spectroscopy

NASA Astrophysics Data System (ADS)

Bano, Fouzia; Sluysmans, Damien; Wislez, Arnaud; Duwez, Anne-Sophie

2015-11-01

Addressing the effect of different environmental factors on the adsorption of DNA to solid supports is critical for the development of robust miniaturized devices for applications ranging from biosensors to next generation molecular technology. Most of the time, thiol-based chemistry is used to anchor DNA on gold - a substrate commonly used in nanotechnology - and little is known about the direct interaction between DNA and gold. So far there have been no systematic studies on the direct adsorption behavior of the deoxyribonucleotides (i.e., a nitrogenous base, a deoxyribose sugar, and a phosphate group) and on the factors that govern the DNA-gold bond strength. Here, using single molecule force spectroscopy, we investigated the interaction of the four individual nucleotides, adenine, guanine, cytosine, and thymine, with gold. Experiments were performed in three salinity conditions and two surface dwell times to reveal the factors that influence nucleotide-Au bond strength. Force data show that, at physiological ionic strength, adenine-Au interactions are stronger, asymmetrical and independent of surface dwell time as compared to cytosine-Au and guanine-Au interactions. We suggest that in these conditions only adenine is able to chemisorb on gold. A decrease of the ionic strength significantly increases the bond strength for all nucleotides. We show that moderate ionic strength along with longer surface dwell period suggest weak chemisorption also for cytosine and guanine.Addressing the effect of different environmental factors on the adsorption of DNA to solid supports is critical for the development of robust miniaturized devices for applications ranging from biosensors to next generation molecular technology. Most of the time, thiol-based chemistry is used to anchor DNA on gold - a substrate commonly used in nanotechnology - and little is known about the direct interaction between DNA and gold. So far there have been no systematic studies on the direct adsorption behavior of the deoxyribonucleotides (i.e., a nitrogenous base, a deoxyribose sugar, and a phosphate group) and on the factors that govern the DNA-gold bond strength. Here, using single molecule force spectroscopy, we investigated the interaction of the four individual nucleotides, adenine, guanine, cytosine, and thymine, with gold. Experiments were performed in three salinity conditions and two surface dwell times to reveal the factors that influence nucleotide-Au bond strength. Force data show that, at physiological ionic strength, adenine-Au interactions are stronger, asymmetrical and independent of surface dwell time as compared to cytosine-Au and guanine-Au interactions. We suggest that in these conditions only adenine is able to chemisorb on gold. A decrease of the ionic strength significantly increases the bond strength for all nucleotides. We show that moderate ionic strength along with longer surface dwell period suggest weak chemisorption also for cytosine and guanine. Electronic supplementary information (ESI) available: Details of the data analysis; Fig. S1-S5 histograms of rupture lengths; histograms for Au-adenine and Au-amine interactions; Force-extension curve for MCH-Au interactions; normalized force-extension curves; theoretical length of the DNA oligomers. See DOI: 10.1039/c5nr05695k

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.

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.

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.

Soft poly(2-chloroaniline)/pectin hydrogel and its electromechanical properties.

PubMed

Kongkaew, Wanar; Sangwan, Watchara; Lerdwijitjarud, Wanchai; Sirivat, Anuvat

2018-01-01

Pectin hydrogels were successfully fabricated with various physical crosslinkers and concentrations for soft actuator applications. A small amount of synthesized P2ClAn was added as a dispersed phase into the pectin matrix. The electromechanical properties of the pectin hydrogels and blends were investigated under the effects of electric field strength, ionic crosslinker type and concentration, and P2ClAn concentration. The electromechanical properties of the pectin hydrogel as crosslinked by Fe 2+ were superior to other pectin hydrogels. The pristine pectin hydrogel and the P2ClAn/Pectin hydrogel blended with 0.10%v/v P2ClAn provided the high storage modulus sensitivity values of 8.61 and 14.01, respectively, under the electric field strength of 800 V/mm. The P2ClAn/Pectin hydrogel blend responded to the electric field with higher dielectrophoretic forces, but lower deflections relative to the pristine pectin hydrogel due to the additional P2ClAn polarization and the latter lower rigidity.

Ion Association, Solubilities, and Reduction Potentials in Aqueous Solution.

ERIC Educational Resources Information Center

Russo, Steven O.; Hanania, George I. H.

1989-01-01

Incorporates the combined effects of ionic strength and ion association to show how calculations involving ionic equilibria are carried out. Examines the variability of reduction potential data for two aqueous redox systems. Provides several examples. (MVL)

Specific detection of biomolecules in physiological solutions using graphene transistor biosensors

PubMed Central

Gao, Ning; Gao, Teng; Yang, Xiao; Dai, Xiaochuan; Zhou, Wei; Zhang, Anqi; Lieber, Charles M.

2016-01-01

Nanomaterial-based field-effect transistor (FET) sensors are capable of label-free real-time chemical and biological detection with high sensitivity and spatial resolution, although direct measurements in high–ionic-strength physiological solutions remain challenging due to the Debye screening effect. Recently, we demonstrated a general strategy to overcome this challenge by incorporating a biomolecule-permeable polymer layer on the surface of silicon nanowire FET sensors. The permeable polymer layer can increase the effective screening length immediately adjacent to the device surface and thereby enable real-time detection of biomolecules in high–ionic-strength solutions. Here, we describe studies demonstrating both the generality of this concept and application to specific protein detection using graphene FET sensors. Concentration-dependent measurements made with polyethylene glycol (PEG)-modified graphene devices exhibited real-time reversible detection of prostate specific antigen (PSA) from 1 to 1,000 nM in 100 mM phosphate buffer. In addition, comodification of graphene devices with PEG and DNA aptamers yielded specific irreversible binding and detection of PSA in pH 7.4 1x PBS solutions, whereas control experiments with proteins that do not bind to the aptamer showed smaller reversible signals. In addition, the active aptamer receptor of the modified graphene devices could be regenerated to yield multiuse selective PSA sensing under physiological conditions. The current work presents an important concept toward the application of nanomaterial-based FET sensors for biochemical sensing in physiological environments and thus could lead to powerful tools for basic research and healthcare. PMID:27930344

Specific detection of biomolecules in physiological solutions using graphene transistor biosensors.

PubMed

Gao, Ning; Gao, Teng; Yang, Xiao; Dai, Xiaochuan; Zhou, Wei; Zhang, Anqi; Lieber, Charles M

2016-12-20

Nanomaterial-based field-effect transistor (FET) sensors are capable of label-free real-time chemical and biological detection with high sensitivity and spatial resolution, although direct measurements in high-ionic-strength physiological solutions remain challenging due to the Debye screening effect. Recently, we demonstrated a general strategy to overcome this challenge by incorporating a biomolecule-permeable polymer layer on the surface of silicon nanowire FET sensors. The permeable polymer layer can increase the effective screening length immediately adjacent to the device surface and thereby enable real-time detection of biomolecules in high-ionic-strength solutions. Here, we describe studies demonstrating both the generality of this concept and application to specific protein detection using graphene FET sensors. Concentration-dependent measurements made with polyethylene glycol (PEG)-modified graphene devices exhibited real-time reversible detection of prostate specific antigen (PSA) from 1 to 1,000 nM in 100 mM phosphate buffer. In addition, comodification of graphene devices with PEG and DNA aptamers yielded specific irreversible binding and detection of PSA in pH 7.4 1x PBS solutions, whereas control experiments with proteins that do not bind to the aptamer showed smaller reversible signals. In addition, the active aptamer receptor of the modified graphene devices could be regenerated to yield multiuse selective PSA sensing under physiological conditions. The current work presents an important concept toward the application of nanomaterial-based FET sensors for biochemical sensing in physiological environments and thus could lead to powerful tools for basic research and healthcare.

Two-stage DNA compaction induced by silver ions suggests a cooperative binding mechanism

NASA Astrophysics Data System (ADS)

Jiang, Wen-Yan; Ran, Shi-Yong

2018-05-01

The interaction between silver ions and DNA plays an important role in the therapeutic use of silver ions and in related technologies such as DNA sensors. However, the underlying mechanism has not been fully understood. In this study, the dynamics of Ag+-DNA interaction at a single-molecule level was studied using magnetic tweezers. AgNO3 solutions with concentrations ranging from 1 μM to 20 μM led to a 1.4-1.8 μm decrease in length of a single λ-DNA molecule, indicating that Ag+ has a strong binding with DNA, causing the DNA conformational change. The compaction process comprises one linear declining stage and another sigmoid-shaped stage, which can be attributed to the interaction mechanism. Considering the cooperative effect, the sigmoid trend was well explained using a phenomenological model. By contrast, addition of silver nanoparticle solution induced no detectable transition of DNA. The dependence of the interaction on ionic strength and DNA concentration was examined via morphology characterization and particle size distribution measurement. The size of the Ag+-DNA complex decreased with an increase in Ag+ ionic strength ranging from 1 μM to 1 mM. Morphology characterization confirmed that silver ions induced DNA to adopt a compacted globular conformation. At a fixed [AgNO3]:[DNA base pairs] ratio, increasing DNA concentration led to increased sizes of the complexes. Intermolecular interaction is believed to affect the Ag+-DNA complex formation to a large extent.

NaCl strongly modifies the physicochemical properties of aluminum hydroxide vaccine adjuvants.

PubMed

Art, Jean-François; Vander Straeten, Aurélien; Dupont-Gillain, Christine C

2017-01-30

The immunostimulation capacity of most vaccines is enhanced through antigen adsorption on aluminum hydroxide (AH) adjuvants. Varying the adsorption conditions, i.e. pH and ionic strength (I), changes the antigen adsorbed amount and therefore the ability of the vaccine to stimulate the immune system. Vaccine formulations are thus resulting from an empirical screening of the adsorption conditions. This work aims at studying the physicochemical effects of adjusting the ionic strength of commercial AH adjuvant particles suspensions with sodium chloride (NaCl). X-ray photoelectron spectroscopy data show that AH particles surface chemical composition is neither altered by I adjustment with NaCl nor by deposition on gold surfaces. The latter result provides the opportunity to use AH-coated gold surfaces as a platform for advanced surface analysis of adjuvant particles, e.g. by atomic force microscopy (AFM). The morphology of adjuvant particles recovered from native and NaCl-treated AH suspensions, as studied by scanning electron microscopy and AFM, reveals that AH particles aggregation state is significantly altered by NaCl addition. This is further confirmed by nitrogen adsorption experiments: I adjustment to 150mM with NaCl strongly promotes AH particles aggregation leading to a strong decrease of the developed specific surface area. This work thus evidences the effect of NaCl on AH adjuvant structure, which may lead to alteration of formulated vaccines and to misinterpretation of data related to antigen adsorption on adjuvant particles. Copyright © 2016 Elsevier B.V. All rights reserved.

Reversible and non-reversible thermal denaturation of lysozyme with varying pH at low ionic strength.

PubMed

Blumlein, Alice; McManus, Jennifer J

2013-10-01

DSC analysis has been used to quantify the reversibility of unfolding following thermal denaturation of lysozyme. Since the temperature at which protein unfolding occurs, Tm, varies with different solution conditions, the effect on the melting temperature and the degree of refolding after thermal denaturation in low ionic strength sodium phosphate buffers (5-1000mM) over a range of pH (5-9) in the presence/absence of disaccharides is examined. This study compares the enthalpies of unfolding during successive heating cycles to quantify reversibility following thermal denaturation. The disaccharides, trehalose and maltose were used to assess if the disaccharide induced increase in Tm is reflected in the reversibility of thermally induced denaturation. There was extensive overlap between the Tm values where non-reversible and reversible thermal denaturation occurred. Indeed, for pH6, at the highest and lowest Tm, no refolding was observed whereas refolding was observed for intermediate values, but with similar Tm values having different proportions of refolded protein. We established a method to measure the degree of reversible unfolding following thermal denaturation and hence indirectly, the degree to which protein is lost to irreversible aggregation, and show that solution conditions which increase melt transition temperatures do not automatically confer an increase in reversibility. This type of analysis may prove useful in assessing the stability of proteins in both the biopharmaceutical and food industries. Copyright © 2013 Elsevier B.V. All rights reserved.

Thermodynamics study of the dimerization equilibria of rhodamine B and 6G in different ionic strengths by photometric titration and chemometrics method

NASA Astrophysics Data System (ADS)

Ghasemi, Jahanbakhsh; Niazi, Ali; Kubista, Mikael

2005-11-01

The dimerization constants of rhodamine B and 6G have been determined by studying the dependence of their absorption spectra on the temperature in the range 20-80 °C at different total concentrations of rhodamine B (5.89 × 10 -6 to 2.36 × 10 -4 M) and rhodamine 6G (2.34 × 10 -5 to 5.89 × 10 -4 M) and in different concentrations of LiCl, NaCl and KCl salts as supporting electrolytes. The monomer-dimer equilibrium of rhodamine B and 6G have been determined by chemometrics refinement of the absorption spectra obtained by thermometric titrations performed at different ionic strengths. The quantitative analysis of the data of undefined mixtures, was carried out by simultaneous resolution of the overlapping spectral bands in the whole set of absorption spectra. The dimerization constants are varied by changing the ionic strength and the degree of dimerization are decreased by increasing of the ionic strength of the medium. The enthalpy and entropy of the dimerization reactions were determined from the dependence of the equilibrium constants on the temperature (van't Hoff equation). From the thermodynamic results the TΔ S°-Δ H° plot was sketched. It shows a fairly good positive correlation which indicates the enthalpy-entropy compensation in the dimerization reactions (compensation effect).

Thermodynamics study of the dimerization equilibria of rhodamine B and 6G in different ionic strengths by photometric titration and chemometrics method.

PubMed

Ghasemi, Jahanbakhsh; Niazi, Ali; Kubista, Mikael

2005-11-01

The dimerization constants of rhodamine B and 6G have been determined by studying the dependence of their absorption spectra on the temperature in the range 20-80 degrees C at different total concentrations of rhodamine B (5.89 x 10(-6) to 2.36 x 10(-4)M) and rhodamine 6G (2.34 x 10(-5) to 5.89 x 10(-4)M) and in different concentrations of LiCl, NaCl and KCl salts as supporting electrolytes. The monomer-dimer equilibrium of rhodamine B and 6G have been determined by chemometrics refinement of the absorption spectra obtained by thermometric titrations performed at different ionic strengths. The quantitative analysis of the data of undefined mixtures, was carried out by simultaneous resolution of the overlapping spectral bands in the whole set of absorption spectra. The dimerization constants are varied by changing the ionic strength and the degree of dimerization are decreased by increasing of the ionic strength of the medium. The enthalpy and entropy of the dimerization reactions were determined from the dependence of the equilibrium constants on the temperature (van't Hoff equation). From the thermodynamic results the TDeltaS degrees -DeltaH degrees plot was sketched. It shows a fairly good positive correlation which indicates the enthalpy-entropy compensation in the dimerization reactions (compensation effect).

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.

High ionic strength narrows the population of sites participating in protein ion-exchange adsorption: A single-molecule study

PubMed Central

Kisley, Lydia; Chen, Jixin; Mansur, Andrea P.; Dominguez-Medina, Sergio; Kulla, Eliona; Kang, Marci; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Dhamane, Sagar; Willson, Richard C.; Landes, Christy F.

2014-01-01

The retention and elution of proteins in ion-exchange chromatography is routinely controlled by adjusting the mobile phase salt concentration. It has repeatedly been observed, as judged from adsorption isotherms, that the apparent heterogeneity of adsorption is lower at more-eluting, higher ionic strength. Here, we present an investigation into the mechanism of this phenomenon using a single-molecule, super-resolution imaging technique called motion-blur Points Accumulation for Imaging in Nanoscale Topography (mbPAINT). We observed that the number of functional adsorption sites was smaller at high ionic strength and that these sites had reduced desorption kinetic heterogeneity, and thus narrower predicted elution profiles, for the anion-exchange adsorption of α-lactalbumin on an agarose-supported, clustered-charge ligand stationary phase. Explanations for the narrowing of the functional population such as inter-protein interactions and protein or support structural changes were investigated through kinetic analysis, circular dichroism spectroscopy, and microscopy of agarose microbeads, respectively. The results suggest the reduction of heterogeneity is due to both electrostatic screening between the protein and ligand and tuning the steric availability within the agarose support. Overall, we have shown that single molecule spectroscopy can aid in understanding the influence of ionic strength on the population of functional adsorbent sites participating in the ion-exchange chromatographic separation of proteins. PMID:24751557

[Optimized isolation and purification of non-typeable Haemophilus influenzae Haps protein].

PubMed

Li, Wan-yi; Kuang, Yu; Li, Ming-yuan; Yang, Yuan; Jiang, Zhong-hua; Yao, Feng; Chen, Chang-chun

2007-12-01

To optimize the isolation and purification conditions for Hap(s) protein of non-typeable Haemophilus influenzae. Hap(s) protein was purified by ammonium sulfate precipitation, dialysis desalting and Hitrap weak cation exchange columns of CM Sepharose Fast Flow. The condition of the elution was optimized for pH and ionic strength, the absorbance at 280 nm of the elution samples were detected, and the targeted protein band in the collected samples was observed by SDS-PAGE electrophoresis. The Hitrap ion exchange column was eluted with buffer 1, which resulted in a baseline distribution of absorbance at 280 nm. Buffer 2 elution of the column resulted in the presence of peak absorbance with trails, which was identified to be constituted by some low molecular weight bands by subsequent SDS-PAGE. In serial column elution with buffer 3 with different ionic strength, a peak absorbance was observed with the ionic strength of 100 mmol/L NaCl, and SDS-PAGE confirmed that the peak was generated by the target protein. No obvious peaks or bands in SDS-PAGE occurred with the other ionic strengths. The pH of the buffer only affect the elution of the irrelevant proteins rather than the Hap(s) protein, and elution with the buffer containing 100 mmol/L NaCl can be optimal for eluting the Hap(s) protein.

Sorption of triclosan onto activated carbon, kaolinite and montmorillonite: effects of pH, ionic strength, and humic acid.

PubMed

Behera, Shishir Kumar; Oh, Seok-Young; Park, Hung-Suck

2010-07-15

Sorption of triclosan on three sorbents, viz., activated carbon, kaolinite and montmorillonite was studied as a function of pH, ionic strength and humic acid (HA) concentration through controlled batch experiments. Triclosan sorption was found to be higher in the acidic pH range, as varying pH showed significant influence on the surface charge of the sorbents and degree of ionization of the sorbate. Sorption capacity of the sorbents increased with an increase in the ionic strength of solution. At low pH (pH 3), the overall increase in triclosan sorption was 1.2, approximately 4 and 3.5 times, respectively for activated carbon, kaolinite and montmorillonite when ionic strength was increased from 1x10(-3) to 5x10(-1) M. Triclosan sorption onto activated carbon decreased from 31.4 to 10.6 mg g(-1) by increasing the HA concentration to 200 mg C L(-1). However, during sorption onto kaolinite and montmorillonite, the effect of HA was very complex probably due to (i) hydrophobicity (log K(ow)=4.76) of triclosan; and (ii) complexation of HA with triclosan. Though triclosan sorption onto activated carbon is higher, the potential of kaolinite and montmorillonite in controlling the transport of triclosan in subsurface environment can still be appreciable. 2010 Elsevier B.V. All rights reserved.

Electroosmotic Flow Reversal Outside Glass Nanopores

PubMed Central

2015-01-01

We report observations of a striking reversal in the direction of electroosmotic flow (EOF) outside a conical glass nanopore as a function of salt concentration. At high ionic strengths (>100 mM), we observe EOF in the expected direction as predicted by classical electrokinetic theory, while at low salt concentrations (<1 mM) the direction of the flow is reversed. The critical crossover salt concentration depends on the pore diameter. Finite-element simulations indicate a competition between the EOF generated from the inner and outer walls of the pore, which drives flows in opposite directions. We have developed a simple analytical model which reveals that, as the salt concentration is reduced, the flow rates inside the pore are geometrically constrained, whereas there is no such limit for flows outside the pore. This model captures all of the essential physics of the system and explains the observed data, highlighting the key role the external environment plays in determining the overall electroosmotic behavior. PMID:25490120

Membrane-bound dd-carboxypeptidases from Bacillus megaterium KM. General properties, substrate specificity and sensitivity to penicillins, cephalosporins and peptide inhibitors of the activity at pH5

PubMed Central

Diaz-Mauriño, Teresa; Nieto, Manuel; Perkins, Harold R.

1974-01-01

1. The membrane from Bacillus megaterium KM contained a dd-carboxypeptidase with optimum activity under the following conditions: pH5.2, bivalent cation, 3mm; ionic strength, 40mm; temperature, 35°C. It was inactivated by treatment with p-chloromercuribenzoate but was fairly insensitive to 2-mercaptoethanol. 2. The enzyme was inhibited by penicillins and cephalosporins. The inhibition of this enzyme was partially reversed on dialysis but 0.2m-2-mercaptoethanol could neither prevent nor reverse the inhibition. 3. The enzyme was extremely sensitive to changes in the configuration and size of the side chain of the C-terminal dipeptide of the substrate. An aliphatic side chain of a well-defined length and polarity was required in the residue that precedes the C-terminal dipeptide. 4. The enzyme was inhibited by a wide range of analogues of the peptidic portion of the natural substrate. PMID:4218954

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.

Binding Rate Constants Reveal Distinct Features of Disordered Protein Domains.

PubMed

Dogan, Jakob; Jonasson, Josefin; Andersson, Eva; Jemth, Per

2015-08-04

Intrinsically disordered proteins (IDPs) are abundant in the proteome and involved in key cellular functions. However, experimental data about the binding kinetics of IDPs as a function of different environmental conditions are scarce. We have performed an extensive characterization of the ionic strength dependence of the interaction between the molten globular nuclear co-activator binding domain (NCBD) of CREB binding protein and five different protein ligands, including the intrinsically disordered activation domain of p160 transcriptional co-activators (SRC1, TIF2, ACTR), the p53 transactivation domain, and the folded pointed domain (PNT) of transcription factor ETS-2. Direct comparisons of the binding rate constants under identical conditions show that the association rate constant, kon, for interactions between NCBD and disordered protein domains is high at low salt concentrations (90-350 × 10(6) M(-1) s(-1) at 4 °C) but is reduced significantly (10-30-fold) with an increasing ionic strength and reaches a plateau around physiological ionic strength. In contrast, the kon for the interaction between NCBD and the folded PNT domain is only 7 × 10(6) M(-1) s(-1) (4 °C and low salt) and displays weak ionic strength dependence, which could reflect a distinctly different association that relies less on electrostatic interactions. Furthermore, the basal rate constant (in the absence of electrostatic interactions) is high for the NCBD interactions, exceeding those typically observed for folded proteins. One likely interpretation is that disordered proteins have a large number of possible collisions leading to a productive on-pathway encounter complex, while folded proteins are more restricted in terms of orientation. Our results highlight the importance of electrostatic interactions in binding involving IDPs and emphasize the significance of including ionic strength as a factor in studies that compare the binding properties of IDPs to those of ordered proteins.

Formation and stability of manganese-doped ZnS quantum dot monolayers determined by QCM-D and streaming potential measurements.

PubMed

Oćwieja, Magdalena; Matras-Postołek, Katarzyna; Maciejewska-Prończuk, Julia; Morga, Maria; Adamczyk, Zbigniew; Sovinska, Svitlana; Żaba, Adam; Gajewska, Marta; Król, Tomasz; Cupiał, Klaudia; Bredol, Michael

2017-10-01

Manganese-doped ZnS quantum dots (QDs) stabilized by cysteamine hydrochloride were successfully synthesized. Their thorough physicochemical characteristics were acquired using UV-Vis absorption and photoluminescence spectroscopy, X-ray diffraction, dynamic light scattering (DLS), transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS) and Fourier transform infrared (FT-IR) spectroscopy. The average particle size, derived from HR-TEM, was 3.1nm, which agrees with the hydrodynamic diameter acquired by DLS, that was equal to 3-4nm, depending on ionic strength. The quantum dots also exhibited a large positive zeta potential varying between 75 and 36mV for ionic strength of 10 -4 and 10 -2 M, respectively (at pH 6.2) and an intense luminescent emission at 590nm. The quantum yield was equal to 31% and the optical band gap energy was equal to 4.26eV. The kinetics of QD monolayer formation on silica substrates (silica sensors and oxidized silicon wafers) under convection-controlled transport was quantitatively evaluated by the quartz crystal microbalance (QCM) and the streaming potential measurements. A high stability of the monolayer for ionic strength 10 -4 and 10 -2 M was confirmed in these measurements. The experimental data were adequately reflected by the extended random sequential adsorption model (eRSA). Additionally, thorough electrokinetic characteristics of the QD monolayers and their stability for various ionic strengths and pH were acquired by streaming potential measurements carried out under in situ conditions. These results were quantitatively interpreted in terms of the three-dimensional (3D) electrokinetic model that furnished bulk zeta potential of particles for high ionic strengths that is impractical by other experimental techniques. It is concluded that these results can be used for designing of biosensors of controlled monolayer structure capable to bind various ligands via covalent as well as electrostatic interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

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

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.

Colloidal stability of carbonate-coated silver nanoparticles in synthetic and natural freshwater.

PubMed

Piccapietra, Flavio; Sigg, Laura; Behra, Renata

2012-01-17

To gain important information on fate, mobility, and bioavailability of silver nanoparticles (AgNP) in aquatic systems, the influence of pH, ionic strength, and humic substances on the stability of carbonate-coated AgNP (average diameter 29 nm) was systematically investigated in 10 mM carbonate and 10 mM MOPS buffer, and in filtered natural freshwater. Changes in the physicochemical properties of AgNP were measured using nanoparticle tracking analysis, dynamic light scattering, and ultraviolet-visible spectroscopy. According to the pH-dependent carbonate speciation, below pH 4 the negatively charged surface of AgNP became positive and increased agglomeration was observed. Electrolyte concentrations above 2 mM Ca(2+) and 100 mM Na(+) enhanced AgNP agglomeration in the synthetic media. In the considered concentration range of humic substances, no relevant changes in the AgNP agglomeration state were measured. Agglomeration of AgNP exposed in filtered natural freshwater was observed to be primarily controlled by the electrolyte type and concentration. Moreover, agglomerated AgNP were still detected after 7 days of exposure. Consequently, slow sedimentation and high mobility of agglomerated AgNP could be expected under the considered natural conditions. A critical evaluation of the different methods used is presented as well.

Impact of self-assembled surfactant structures on rheology of concentrated nanoparticle dispersions.

PubMed

Zaman, A A; Singh, P; Moudgil, B M

2002-07-15

Rheological behavior of surfactant-stabilized colloidal dispersions of silica particles under extreme conditions (low pH, high ionic strength) has been investigated in relation to interparticle forces and stability of the dispersion. The surfactant used as the dispersing agent was C(12)TAB, a cationic surfactant. Stability analysis through turbidity measurements indicated that there is a sharp increase in the stability of the dispersion when the surfactant concentration is in the range of 8 to 10 mM in the system. The state of the dispersion changes from an unstable regime to a stable regime above a critical concentration of C(12)TAB in the system. In the case of interaction forces measured between the silica substrate and AFM tip, no repulsive force was observed up to a surfactant concentration of 8 mM and a transition from no repulsive forces to steric repulsive forces occurred between 8 and 10 mM. Rheological measurements as a function of C(12)TAB concentration indicated a significant decrease in the viscosity and linear viscoelastic functions of the dispersion over the same range of surfactant concentration (8 to 10 mM C(12)TAB), showing a strong correlation between the viscosity behavior, interparticle forces, and structure development in the dispersion.

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.

Ionic Liquid Epoxy Resin Monomers

NASA Technical Reports Server (NTRS)

Paley, Mark S. (Inventor)

2013-01-01

Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

Simulating chemical reactions in ionic liquids using QM/MM methodology.

PubMed

Acevedo, Orlando

2014-12-18

The use of ionic liquids as a reaction medium for chemical reactions has dramatically increased in recent years due in large part to the numerous reported advances in catalysis and organic synthesis. In some extreme cases, ionic liquids have been shown to induce mechanistic changes relative to conventional solvents. Despite the large interest in the solvents, a clear understanding of the molecular factors behind their chemical impact is largely unknown. This feature article reviews our efforts developing and applying mixed quantum and molecular mechanical (QM/MM) methodology to elucidate the microscopic details of how these solvents operate to enhance rates and alter mechanisms for industrially and academically important reactions, e.g., Diels-Alder, Kemp eliminations, nucleophilic aromatic substitutions, and β-eliminations. Explicit solvent representation provided the medium dependence of the activation barriers and atomic-level characterization of the solute-solvent interactions responsible for the experimentally observed "ionic liquid effects". Technical advances are also discussed, including a linear-scaling pairwise electrostatic interaction alternative to Ewald sums, an efficient polynomial fitting method for modeling proton transfers, and the development of a custom ionic liquid OPLS-AA force field.

Biosorption removal of benzene and toluene by three dried macroalgae at different ionic strength and temperatures: Algae biochemical composition and kinetics.

PubMed

Flores-Chaparro, Carlos E; Chazaro Ruiz, Luis Felipe; Alfaro de la Torre, Ma Catalina; Huerta-Diaz, Miguel Angel; Rangel-Mendez, Jose Rene

2017-05-15

Release of low-molecular aromatic hydrocarbons (HC) into natural waters brings severe consequences to our environment. Unfortunately very limited information is available regarding the treatment of these pollutants. This work evaluated the use of brown, green and red macroalgae biomass as biosorbents of benzene and toluene, two of the most soluble HC. Raw seaweed biomasses were completely characterized, then evaluated under different temperatures and ionic strengths to assess their potential as biosorbents and to elucidate the biosorption mechanisms involved. Brown macroalgae registered the highest removal capacities for benzene and toluene (112 and 28 mg·g -1 , respectively), and these were not affected at ionic strength < 0.6 M. Langmuir and Sips isotherm equations well described biosorption data, and the pseudo-second order model provided the best fit to the kinetics rate. Hydrocarbons are adsorbed onto the diverse chemical components of the cell wall by London forces and hydrophobic interactions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Beyond the Debye length in high ionic strength solution: direct protein detection with field-effect transistors (FETs) in human serum.

PubMed

Chu, Chia-Ho; Sarangadharan, Indu; Regmi, Abiral; Chen, Yen-Wen; Hsu, Chen-Pin; Chang, Wen-Hsin; Lee, Geng-Yen; Chyi, Jen-Inn; Chen, Chih-Chen; Shiesh, Shu-Chu; Lee, Gwo-Bin; Wang, Yu-Lin

2017-07-12

In this study, a new type of field-effect transistor (FET)-based biosensor is demonstrated to be able to overcome the problem of severe charge-screening effect caused by high ionic strength in solution and detect proteins in physiological environment. Antibody or aptamer-immobilized AlGaN/GaN high electron mobility transistors (HEMTs) are used to directly detect proteins, including HIV-1 RT, CEA, NT-proBNP and CRP, in 1X PBS (with 1%BSA) or human sera. The samples do not need any dilution or washing process to reduce the ionic strength. The sensor shows high sensitivity and the detection takes only 5 minutes. The designs of the sensor, the methodology of the measurement, and the working mechanism of the sensor are discussed and investigated. A theoretical model is proposed based on the finding of the experiments. This sensor is promising for point-of-care, home healthcare, and mobile diagnostic device.

Influence of electrostatic forces on particle propulsion in the evanescent field of silver ion-exchanged waveguides.

PubMed

Gebennikov, Dmytro; Mittler, Silvia

2013-02-26

The effect of electrostatic interaction between carboxylate- and amino-functionalized polystyrene particles and a charged waveguide surface on the propulsion speed in optical tweezers is considered to be a function of the pH and ionic strength. It was shown that with the variation of the pH of the aqueous solution in which the particles were immersed, a systematic change in propulsion speed with a maximum speed could be achieved. The appearance of a maximum speed was ascribed to changes in the particle-waveguide separation as a result of the combination of two forces: Coulomb repulsion/attraction and induced dipole forces. The highest maximum speed at low ionic strength was around 12 μm/s. Changes in the ionic strength of the solution influenced the gradient of the dielectric constant near the involved surfaces and also led to a slightly reduced hydrodynamic radius of the particles. The combination of these effects subsequently increased the maximum speed to about 23 μm/s.

Extension of nanoconfined DNA: Quantitative comparison between experiment and theory

NASA Astrophysics Data System (ADS)

Iarko, V.; Werner, E.; Nyberg, L. K.; Müller, V.; Fritzsche, J.; Ambjörnsson, T.; Beech, J. P.; Tegenfeldt, J. O.; Mehlig, K.; Westerlund, F.; Mehlig, B.

2015-12-01

The extension of DNA confined to nanochannels has been studied intensively and in detail. However, quantitative comparisons between experiments and model calculations are difficult because most theoretical predictions involve undetermined prefactors, and because the model parameters (contour length, Kuhn length, effective width) are difficult to compute reliably, leading to substantial uncertainties. Here we use a recent asymptotically exact theory for the DNA extension in the "extended de Gennes regime" that allows us to compare experimental results with theory. For this purpose, we performed experiments measuring the mean DNA extension and its standard deviation while varying the channel geometry, dye intercalation ratio, and ionic strength of the buffer. The experimental results agree very well with theory at high ionic strengths, indicating that the model parameters are reliable. At low ionic strengths, the agreement is less good. We discuss possible reasons. In principle, our approach allows us to measure the Kuhn length and the effective width of a single DNA molecule and more generally of semiflexible polymers in solution.

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.

Evidence for Intramolecular Antiparallel Beta-Sheet Structure in Alpha-Synuclein Fibrils from a Combination of Two-Dimensional Infrared Spectroscopy and Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Roeters, Steven J.; Iyer, Aditya; Pletikapić, Galja; Kogan, Vladimir; Subramaniam, Vinod; Woutersen, Sander

2017-01-01

The aggregation of the intrinsically disordered protein alpha-synuclein (αS) into amyloid fibrils is thought to play a central role in the pathology of Parkinson’s disease. Using a combination of techniques (AFM, UV-CD, XRD, and amide-I 1D- and 2D-IR spectroscopy) we show that the structure of αS fibrils varies as a function of ionic strength: fibrils aggregated in low ionic-strength buffers ([NaCl] ≤ 25 mM) have a significantly different structure than fibrils grown in higher ionic-strength buffers. The observations for fibrils aggregated in low-salt buffers are consistent with an extended conformation of αS molecules, forming hydrogen-bonded intermolecular β-sheets that are loosely packed in a parallel fashion. For fibrils aggregated in high-salt buffers (including those prepared in buffers with a physiological salt concentration) the measurements are consistent with αS molecules in a more tightly-packed, antiparallel intramolecular conformation, and suggest a structure characterized by two twisting stacks of approximately five hydrogen-bonded intermolecular β-sheets each. We find evidence that the high-frequency peak in the amide-I spectrum of αS fibrils involves a normal mode that differs fundamentally from the canonical high-frequency antiparallel β-sheet mode. The high sensitivity of the fibril structure to the ionic strength might form the basis of differences in αS-related pathologies.

Evidence for Intramolecular Antiparallel Beta-Sheet Structure in Alpha-Synuclein Fibrils from a Combination of Two-Dimensional Infrared Spectroscopy and Atomic Force Microscopy

PubMed Central

Roeters, Steven J.; Iyer, Aditya; Pletikapić, Galja; Kogan, Vladimir; Subramaniam, Vinod; Woutersen, Sander

2017-01-01

The aggregation of the intrinsically disordered protein alpha-synuclein (αS) into amyloid fibrils is thought to play a central role in the pathology of Parkinson’s disease. Using a combination of techniques (AFM, UV-CD, XRD, and amide-I 1D- and 2D-IR spectroscopy) we show that the structure of αS fibrils varies as a function of ionic strength: fibrils aggregated in low ionic-strength buffers ([NaCl] ≤ 25 mM) have a significantly different structure than fibrils grown in higher ionic-strength buffers. The observations for fibrils aggregated in low-salt buffers are consistent with an extended conformation of αS molecules, forming hydrogen-bonded intermolecular β-sheets that are loosely packed in a parallel fashion. For fibrils aggregated in high-salt buffers (including those prepared in buffers with a physiological salt concentration) the measurements are consistent with αS molecules in a more tightly-packed, antiparallel intramolecular conformation, and suggest a structure characterized by two twisting stacks of approximately five hydrogen-bonded intermolecular β-sheets each. We find evidence that the high-frequency peak in the amide-I spectrum of αS fibrils involves a normal mode that differs fundamentally from the canonical high-frequency antiparallel β-sheet mode. The high sensitivity of the fibril structure to the ionic strength might form the basis of differences in αS-related pathologies. PMID:28112214

Effect of dipolar moments in domain sizes of lipid bilayers and monolayers

NASA Astrophysics Data System (ADS)

Travesset, A.

2006-08-01

Lipid domains are found in systems such as multicomponent bilayer membranes and single component monolayers at the air-water interface. It was shown by Keller et al. [J. Phys. Chem. 91, 6417 (1987)] that in monolayers, the size of the domains results from balancing the line tension, which favors the formation of a large single circular domain, against the electrostatic cost of assembling the dipolar moments of the lipids. In this paper, we present an exact analytical expression for the electric potential, ion distribution, and electrostatic free energy for different problems consisting of three different slabs with different dielectric constants and Debye lengths, with a circular homogeneous dipolar density in the middle slab. From these solutions, we extend the calculation of domain sizes for monolayers to include the effects of finite ionic strength, dielectric discontinuities (or image charges), and the polarizability of the dipoles and further generalize the calculations to account for domains in lipid bilayers. In monolayers, the size of the domains is dependent on the different dielectric constants but independent of ionic strength. In asymmetric bilayers, where the inner and outer leaflets have different dipolar densities, domains show a strong size dependence with ionic strength, with molecular-sized domains that grow to macroscopic phase separation with increasing ionic strength. We discuss the implications of the results for experiments and briefly consider their relation to other two dimensional systems such as Wigner crystals or heteroepitaxial growth.

Study on epoxy resin modified by polyether ionic liquid

NASA Astrophysics Data System (ADS)

Jin, X. C.; Guo, L. Y.; Deng, L. L.; Wu, H.

2017-06-01

Chloride 1-carboxyl polyether-3-methyl imidazole ionic liquid (PIIL) was synthesized. Then blended with epoxy resin(EP) to prepare the composite materials of PIIL/EP, which cured with aniline curing agent. The structure and curing performance of PIIL/EP were determined by FT-IR and DSC. The effects of the content of PIIL on strength of EP were studied. The results show that the PIIL was the target product. The strength was improved significantly with increase of the PIIL content. The obvious rubber elasticity of PIIL/EP after cured was showed when the content of PIIL accounts for 40% and the impact strength was up to 15.95kJ/m2.

Effect of Micellization on the Adsorption Kinetics of Polymeric Surfactants to the Solid/Water Interface

NASA Astrophysics Data System (ADS)

Toomey, Ryan; Tirrell, Matthew

2002-03-01

We have studied the adsorption kinetics of two classes of hydrophobic/ionic diblock copolymer surfactants in aqueous environments to understand the role that micellization plays in the adsorption process. The two systems studied were poly(t-butyl styrene)-block-poly(styrene sulfonate) (PtBS-b-PSS) and polystyrene-block-poly(acrylic acid) (PS-b-PAA). It is found that by changing the hydrophobicity of the adsorbing surface, micelle adsorption can be turned on or off. When micelle adsorption occurs, the initial adsorption rate is always slower than the supply rate of micelles to the surface, indicating “reaction-limited” adsorption. Since these micelles have essentially frozen cores, the adsorption cannot be explained by the release of unimers from the micelles. Rather, micelles directly adsorb, and they have to overcome the potential barrier imposed by their corona. Due to micellization, the adsorption rate can also be a complex function of ionic strength. A regime was found where the initial adsorption rate decreased with increasing ionic strength. This anomaly can be explained by the onset of micellization. As the salt concentration is increased, more micelles are formed. However micelles adsorb roughly an order of magnitude slower than free chains. Therefore, if increasing the ionic strength produces more micelles, the adsorption rate will simultaneously decrease.

Dissecting ion-specific from electrostatic salt effects on amyloid fibrillation: A case study of insulin.

PubMed

Kutsch, Miriam; Hortmann, Pascal; Herrmann, Christian; Weibels, Sebastian; Weingärtner, Hermann

2016-03-03

Diseases like Alzheimer, type II diabetes mellitus, and others go back to fibril formation of partially unfolded proteins. The impact of sodium, potassium, choline, guanidinium, and 1-ethyl-3-methylimidazolium chloride on the fibrillation kinetics of insulin in an acid-denaturing solvent environment is studied by fluorescence spectroscopy using thioflavin T as a fibril-specific stain. The fibrillation kinetics reveal a sigmoidal behavior, characterized by the lag time τlag and the maximum elongation rate k of the fibrils. Up to ionic strengths of about 70 mM, the elongation rate increases with salt concentration. This increase is nonspecific with regard to the salts. Below ionic strengths of ∼50 mM, it can be explained by a Debye-Hückel type model, indicating a dominant role of Coulomb interactions between the charged reactants and products screened by the ionic environment. At higher ionic strength, the elongation rates pass maxima, followed by a Hofmeister type ion-specific decrease. There is a correlation between the lag time τlag and the inverse elongation rate k, which can be described by a power law of the form τlag ∝  aτ(α) with a sublinear exponent α ≅ 1/2.

Theoretical studies on structural, magnetic, and spintronic characteristics of sandwiched Eu(n)COT(n+1) (n = 1-4) clusters.

PubMed

Zhang, Xiuyun; Ng, Man-Fai; Wang, Yanbiao; Wang, Jinlan; Yang, Shuo-Wang

2009-09-22

Europium (Eu)-cyclootetatrene (COT = C(8)H(8)) multidecker clusters (Eu(n)COT(n+1), n = 1-4) are studied by relativistic density functional theory calculations. These clusters are found to be thermodynamically stable with freely rotatable COT rings, and their total magnetic moments (MMs) increase linearly along with the number of Eu atoms. Each Eu atom contributes about 7 mu(B) to the cluster. Meanwhile, the internal COT rings have little MM contribution while the external COT rings have about 1 mu(B) MM aligned in opposite direction to that of the Eu atoms. The total MM of the Eu(n)COT(n+1) clusters can thus be generalized as 7n - 2 mu(B) where n is the number of Eu atoms. Besides, the ground states of these clusters are ferromagnetic and energetically competitive with the antiferromagnetic states, meaning that their spin states are very unstable, especially for larger clusters. More importantly, we uncover an interesting bonding characteristic of these clusters in which the interior ionic structure is capped by two hybrid covalent-ionic terminals. We suggest that such a characteristic makes the Eu(n)COT(n+1) clusters extremely stable. Finally, we reveal that for the positively charged clusters, the hybrid covalent-ionic terminals will tip further toward the interior part of the clusters to form deeper covalent-ionic caps. In contrast, the negatively charged clusters turn to pure ionic structures.

Fabrication of an ionic-liquid-based polymer monolithic column and its application in the fractionation of proteins from complex biosamples.

PubMed

Zhang, Doudou; Zhang, Qian; Bai, Ligai; Han, Dandan; Liu, Haiyan; Yan, Hongyuan

2018-05-01

An ionic-liquid-based polymer monolithic column was synthesized by free radical polymerization within the confines of a stainless-steel column (50 mm × 4.6 mm id). In the processes, ionic liquid and stearyl methacrylate were used as dual monomers, ethylene glycol dimethacrylate as the cross-linking agent, and polyethylene glycol 200 and isopropanol as co-porogens. Effects of the prepolymerization solution components on the properties of the resulting monoliths were studied in detail. Scanning electron microscopy, nitrogen adsorption-desorption measurements, and mercury intrusion porosimetry were used to investigate the morphology and pore size distribution of the prepared monoliths, which showed that the homemade ionic-liquid-based monolith column possessed a relatively uniform macropore structure with a total macropore specific surface area of 44.72 m 2 /g. Compared to a non-ionic-liquid-based monolith prepared under the same conditions, the ionic-liquid-based monolith exhibited excellent selectivity and high performance for separating proteins from complex biosamples, such as egg white, snailase, bovine serum albumin digest solution, human plasma, etc., indicating promising applications in the fractionation and analysis of proteins from the complex biosamples in proteomics research. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamics of triple helix formation: spectrophotometric studies on the d(A)10.2d(T)10 and d(C+3T4C+3).d(G3A4G3).d(C3T4C3) triple helices.

PubMed Central

Pilch, D S; Brousseau, R; Shafer, R H

1990-01-01

We have stabilized the d(A)10.2d(T)10 and d(C+LT4C+3).d(G3A4G3).d(C3T4C3) triple helices with either NaCl or MgCl2 at pH 5.5. UV mixing curves demonstrate a 1:2 stoichiometry of purine to pyrimidine strands under the appropriate conditions of pH and ionic strength. Circular dichroic titrations suggest a possible sequence-independent spectral signature for triplex formation. Thermal denaturation profiles indicate the initial loss of the third strand followed by dissociation of the underlying duplex with increasing temperature. Depending on the base sequence and ionic conditions, the binding affinity of the third strand for the duplex at 25 degrees C is two to five orders of magnitude lower than that of the two strands forming the duplex. Thermodynamic parameters for triplex formation were determined for both sequences in the presence of 50 mM MgCl2 and/or 2.0 M NaCl. Hoogsteen base pairs are 0.22-0.64 kcal/mole less stable than Watson-Crick base pairs, depending on ionic conditions and base composition. C+.G and T.A Hoogsteen base pairs appear to have similar stability in the presence of Mg2+ ions at low pH. PMID:2216768

Soft and flexible PEDOT/PSS films for applications to soft actuators

NASA Astrophysics Data System (ADS)

Li, Yuechen; Tanigawa, Ryo; Okuzaki, Hidenori

2014-07-01

Stretchable and highly conductive PEDOT/PSS/Xyl films were prepared by casting an aqueous dispersion of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT/PSS) as colloidal gel particles containing xylitol (Xyl) and subsequent heating. The electrical conductivity of the PEDOT/PSS/Xyl film containing 50 wt% of xylitol significantly increased from 115 S cm-1 to 407 S cm-1 by heating at 140 °C in air for 1 h. It was found that the xylitol had two functions as (i) a plasticizer to weaken hydrogen bonds between PSS of colloidal particles by replacing with that between xylitol and PSS and (ii) the additional capability of increasing the mobility of charge carriers between the colloidal particles. The transparent ionic liquid/polyurethane (IL/PU) gels were fabricated by dissolving thermoplastic polyurethane and ionic liquid of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. By increasing the IL content from 0 wt% to 70 wt%, both ionic conductivity and electric-double-layer capacitance under an electric field increased, while Young’s modulus, strength and elongation at break decreased. The IL/PU/PEDOT/PSS/Xyl composites were fabricated by sandwiching the IL/PU gel between two soft and flexible PEDOT/PSS/Xyl films. Upon application of 2 V, the IL/PU/PEDOT/PSS/Xyl composite (IL = 70%) showed quick and intensive bending toward anode, where the bending displacement at 0.1 Hz attained 2.9 mm, corresponding to the strain of 0.15%, and still worked at frequencies higher than 50 Hz.

Soluble minerals in chemical evolution. II - Characterization of the adsorption of 5-prime-AMP and 5-prime-CMP on a variety of soluble mineral salts

NASA Technical Reports Server (NTRS)

Chan, Stephen; Orenberg, James; Lahav, Noam

1987-01-01

The adsorption of 5-prime-AMP and 5-prime-CMP is studied in the saturated solutions of several mineral salts as a function of pH, ionic strength, and surface area of the solid salt. It is suggested that the adsorption which results from the binding between the nucleotide molecule and the salt surface is due to electrostatic forces. The adsorption is reversible in nature and decreases with increasing ionic strength.

Materials Research Society Spring Meeting Symposium KK: Microbial Life on Surfaces: Biofilm-Material Interactions: Life at Interfaces. Held in San Francisco, California on 25-27 April 2011 (Abstracts)

DTIC Science & Technology

2012-05-24

distribution of protein molecules on the cell surface and relative to the substrate on which the bacteria were growing. 9:30AMKKLL3 Effects of the... Temperature and Ionic Strength of Growth Conditions on the Nanoscale Adhesion of L. monocytogenes EGDe to Silicon Nitride. Pinar Gordesli and Nehal Abu...microscopy (AFM) for bacterial cells grown under five different temperatures (10, 20, 30, 37 and 40°C) and five different ionic strengths (0.005

Ionic Association Ion-Selective Electrode Experiment.

ERIC Educational Resources Information Center

Emara, Mostafa M.; And Others

1979-01-01

Describes an experiment that, using a commercially available solid-state selective electrode in conjunction with a pH-meter, determines the stability constants of sodium sulfate while varying the ionic strength of the media using sodium chloride. Detailed reproducible procedures of both the measurements and calculations are described. (BT)

Self-assembled vertically aligned Au nanorod arrays for surface-enhanced Raman scattering (SERS) detection of Cannabinol

NASA Astrophysics Data System (ADS)

Milliken, Sarah; Fraser, Jeff; Poirier, Shawn; Hulse, John; Tay, Li-Lin

2018-05-01

Self-assembled multi-layered vertically aligned gold nanorod (AuNR) arrays have been fabricated by a simple preparation process that requires a balance between the particle concentration and the ionic strength of the solvent. An experimentally determined critical AuNR concentration of 2.0 nM and 50 mM NaCl produces well-ordered vertically aligned hexagonally close-packed AuNR arrays. We demonstrate surface treatment via UV Ozone cleaning of such samples to allow introduction of analyte molecules (benzenethiol and cannabinol) for effective surface enhanced Raman scattering detection. This is the first demonstration of the SERS analysis of cannabinol. This approach demonstrates a cost-effective, high-yield and simple fabrication route to SERS sensors with application in the screening for the cannabinoids.

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

Minimizing back exchange in the hydrogen exchange-mass spectrometry experiment.

PubMed

Walters, Benjamin T; Ricciuti, Alec; Mayne, Leland; Englander, S Walter

2012-12-01

The addition of mass spectrometry (MS) analysis to the hydrogen exchange (HX) proteolytic fragmentation experiment extends powerful HX methodology to the study of large biologically important proteins. A persistent problem is the degradation of HX information due to back exchange of deuterium label during the fragmentation-separation process needed to prepare samples for MS measurement. This paper reports a systematic analysis of the factors that influence back exchange (solution pH, ionic strength, desolvation temperature, LC column interaction, flow rates, system volume). The many peptides exhibit a range of back exchange due to intrinsic amino acid HX rate differences. Accordingly, large back exchange leads to large variability in D-recovery from one residue to another as well as one peptide to another that cannot be corrected for by reference to any single peptide-level measurement. The usual effort to limit back exchange by limiting LC time provides little gain. Shortening the LC elution gradient by 3-fold only reduced back exchange by ~2%, while sacrificing S/N and peptide count. An unexpected dependence of back exchange on ionic strength as well as pH suggests a strategy in which solution conditions are changed during sample preparation. Higher salt should be used in the first stage of sample preparation (proteolysis and trapping) and lower salt (<20 mM) and pH in the second stage before electrospray injection. Adjustment of these and other factors together with recent advances in peptide fragment detection yields hundreds of peptide fragments with D-label recovery of 90% ± 5%.

Fluorescence and electron paramagnetic resonance studies of norfloxacin and N-donor mixed-ligand ternary copper(II) complexes: Stability and interaction with SDS micelles

NASA Astrophysics Data System (ADS)

Vignoli Muniz, Gabriel S.; Incio, Jimmy Llontop; Alves, Odivaldo C.; Krambrock, Klaus; Teixeira, Letícia R.; Louro, Sonia R. W.

2018-01-01

The stability of ternary copper(II) complexes of a heterocyclic ligand, L (L being 2,2‧-bipyridine (bipy) or 1,10-phenanthroline (phen)) and the fluorescent antibacterial agent norfloxacin (NFX) as the second ligand was studied at pH 7.4 and different ionic strengths. Fluorescence quenching upon titration of NFX with the binary complexes allowed to obtain stability constants for NFX binding, Kb, as a function of ionic strength. The Kb values vary by more than two orders of magnitude when buffer concentration varies from 0.5 to 100 mM. It was observed that previously synthesized ternary complexes dissociate in buffer according with the obtained stability constants. This shows that equimolar solutions of NFX and binary complexes are equivalent to solutions of synthesized ternary complexes. The interaction of the ternary copper complexes with anionic SDS (sodium dodecyl sulfate) micelles was studied by fluorescence and electron paramagnetic resonance (EPR). Titration of NFX-loaded SDS micelles with the complexes Cu:L allowed to determine the stability constants inside the micelles. Fluorescence quenching demonstrated that SDS micelles increase the stability constants by factors around 50. EPR spectra gave details of the copper(II) local environment, and demonstrated that the structure of the ternary complexes inside SDS micelles is different from that in buffer. Mononuclear ternary complexes formed inside the micelles, while in buffer most ternary complexes are binuclear. The results show that anionic membrane interfaces increase formation of copper fluoroquinolone complexes, which can influence bioavailability, membrane diffusion, and mechanism of action of the antibiotics.

Minimizing Back Exchange in the Hydrogen Exchange-Mass Spectrometry Experiment

NASA Astrophysics Data System (ADS)

Walters, Benjamin T.; Ricciuti, Alec; Mayne, Leland; Englander, S. Walter

2012-12-01

The addition of mass spectrometry (MS) analysis to the hydrogen exchange (HX) proteolytic fragmentation experiment extends powerful HX methodology to the study of large biologically important proteins. A persistent problem is the degradation of HX information due to back exchange of deuterium label during the fragmentation-separation process needed to prepare samples for MS measurement. This paper reports a systematic analysis of the factors that influence back exchange (solution pH, ionic strength, desolvation temperature, LC column interaction, flow rates, system volume). The many peptides exhibit a range of back exchange due to intrinsic amino acid HX rate differences. Accordingly, large back exchange leads to large variability in D-recovery from one residue to another as well as one peptide to another that cannot be corrected for by reference to any single peptide-level measurement. The usual effort to limit back exchange by limiting LC time provides little gain. Shortening the LC elution gradient by 3-fold only reduced back exchange by ~2 %, while sacrificing S/N and peptide count. An unexpected dependence of back exchange on ionic strength as well as pH suggests a strategy in which solution conditions are changed during sample preparation. Higher salt should be used in the first stage of sample preparation (proteolysis and trapping) and lower salt (<20 mM) and pH in the second stage before electrospray injection. Adjustment of these and other factors together with recent advances in peptide fragment detection yields hundreds of peptide fragments with D-label recovery of 90 % ± 5 %.

An orientation sensitive approach in biomolecule interaction quantitative structure-activity relationship modeling and its application in ion-exchange chromatography.

PubMed

Kittelmann, Jörg; Lang, Katharina M H; Ottens, Marcel; Hubbuch, Jürgen

2017-01-27

Quantitative structure-activity relationship (QSAR) modeling for prediction of biomolecule parameters has become an established technique in chromatographic purification process design. Unfortunately available descriptor sets fail to describe the orientation of biomolecules and the effects of ionic strength in the mobile phase on the interaction with the stationary phase. The literature describes several special descriptors used for chromatographic retention modeling, all of these do not describe the screening of electrostatic potential by the mobile phase in use. In this work we introduce two new approaches of descriptor calculations, namely surface patches and plane projection, which capture an oriented binding to charged surfaces and steric hindrance of the interaction with chromatographic ligands with regard to electrostatic potential screening by mobile phase ions. We present the use of the developed descriptor sets for predictive modeling of Langmuir isotherms for proteins at different pH values between pH 5 and 10 and varying ionic strength in the range of 10-100mM. The resulting model has a high correlation of calculated descriptors and experimental results, with a coefficient of determination of 0.82 and a predictive coefficient of determination of 0.92 for unknown molecular structures and conditions. The agreement of calculated molecular interaction orientations with both, experimental results as well as molecular dynamic simulations from literature is shown. The developed descriptors provide the means for improved QSAR models of chromatographic processes, as they reflect the complex interactions of biomolecules with chromatographic phases. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigating Attachment Behaviors of Cryptosporidium Parvum Oocysts Using Collision Efficiency in Laboratory Column Experiments

NASA Astrophysics Data System (ADS)

Park, Y.; Hou, L.; Atwill, R.; Packman, A. I.; Harter, T.

2009-12-01

Cryptosporidium is one of the most common enteric parasites of humans and domestic animals, and a number of outbreaks of Cryprosporidiosis, a diarrheal disease caused by Cryptosporidium have been reported worldwide. Natural porous media has been demonstrated to be an effective filter for removing Cryptosporidium parvum from contaminated water and the amount of Cryptosporidium filtered is known to be highly dependent on physical and chemical conditions of the porous media and the water. Cryptosporidium deposition in saturated porous media involves two main steps: approach and attachment. In contrast to the approach mechanisms, attachment processes have not been systematically described to predict a priori because theories that represent attachment behavior (colloid stability) such as DLVO are insufficient to explain experimental data. For this reason, attachment efficiency is calculated based on empirical data, typically experimental breakthrough curves in laboratory columns or field experiments. In this study, collision (attachment) efficiencies (α) of C. parvum oocyst were calculated to test the effect of chemical property changes on the association of oocysts with sand grains. The breakthrough curve data obtained from twelve column experiments and three models were employed to calculate single collector efficiency (η) and α. The first ten experiments were conducted by changing ionic strength and pH, and mixing with natural sediments under the same physical properties (same η). Our experiment results show that iron coating or clay/suspended solids mixture drastically enhanced oocyst deposition. The experiments also showed that increase in ionic strength and decrease in pH enhanced the attachment efficiency. However, the experiment with 100mM NaCl resulted in low attachment efficiency and the experiment with pH 8.5 showed similar attachment efficiency to the one at pH 7. Based on the results from two additional experiments with different flow velocities, it appears that attachment efficiency changes when the flow velocity changes, which contradicts CFT. The results prove that predicting attachment efficiency of C. parvum oocyst using ionic strength or pH is inappropriate when non-DLVO interactions are involved. A review of our results and comparison to existing data shows that it is challenging to accurately predict the attachment efficiency using single peak value of breakthrough curve data from geochemical information of porous media.

Aquifer modification: an approach to improve the mobility of nanoscale zero-valent iron particles used for in situ groundwater remediation

NASA Astrophysics Data System (ADS)

MicicBatka, Vesna; Schmid, Doris; Marko, Florian; Velimirovic, Milica; Wagner, Stephan; von der Kammer, Frank; Hofmann, Thilo

2015-04-01

Successful emplacement of nanoscale zero-valent iron (nZVI) within the contaminated source zone is a prerequisite for the use of nZVI technology in groundwater remediation. Emplacement of nZVI is influenced i.e., by the injection technique and the injection velocity applied, as well as by the mobility of nZVI in the subsurface. Whereas processes linked to the injection can be controlled by the remediation practitioners, the mobility of nZVI in the subsurface remains limited. Even though mobility of nZVI is somewhat improved by surface coating with polyelectrolytes, it is still greatly affected by the groundwater composition and physical and chemical heterogeneities of aquifer grains. In order to promote mobility of nZVI it is needed to alter the surface charge heterogeneities of aquifer grains. Modifying the aquifer grain's surfaces by means of polyelectrolyte coating is an approach proposed to increase the overall negative surface charge of the aquifer grain surfaces, hinder deposition of nZVI onto aquifer grains, and finally promote nZVI mobility. In this study the effect of different polyelectrolytes on the nZVI mobility is tested in natural sands deriving from real brownfield sites that are proposed to be remediated using the nZVI technology. Sands collected from brownfield sites were characterized in terms of grain size distribution, mineralogical and chemical composition, and organic carbon content. Furthermore, surface charge of these sands was determined in both, low- and high ionic strength background solutions. Finally, changes of the sand's surface charges were examined after addition of the proposed aquifer modifiers, lignin sulfonate and humic acid. Surface charge of brownfield sands in low ionic strength background solution is more negative compared to that in high ionic strength background solution. An increase in negative surface potential of brownfield sand was recorded when aquifer modifiers were applied in a background solution with low ionic strength, indicating their potential to improve nZVI mobility under comparable environmental conditions. In contrast, no significant change of the surface potential of brownfield sand was observed when aquifer modifiers were applied in a background solution with high ionic strength. The potential of the aquifer modifiers to promote the mobility of nZVI was furthermore tested in flow-through columns, starting with the one filled with natural quartz sand with rough surface, low ionic strength background solutions and pre-injecting lignin sulfonate in concentration of 50 mg/L. The preliminary results showed that the pre-injection of lignin sulfonate does increase mobility of nZVI under this experimental condition. Further mobility tests will be carried out in order to elucidate the potential of the aquifer modifiers to promote the mobility of nZVI in sands with a complex mineralogy and in the background solutions with varying ionic strength, in order to account for the condition that resemble those at polluted sites. This research receives funding from the European Union's Seventh Framework Programme FP7/2007-2013 under grant agreement n°309517.

Surface interactions between nanoscale iron and organic material: Potential uses in water treatment process units

NASA Astrophysics Data System (ADS)

Storms, Max

Membrane systems are among the primary emergent technologies in water treatment process units due to their ease of use, small physical footprint, and high physical rejection. Membrane fouling, the phenomena by which membranes become clogged or generally soiled, is an inhibitor to optimal efficiency in membrane systems. Novel, composite, and modified surface materials must be investigated to determine their efficacy in improving fouling behavior. Ceramic membranes derived from iron oxide nanoparticles called ferroxanes were coated with a superhydrophillic, zwitterionic polymer called poly (sulfobetaine methacrylate) (polySBMA) to form a composite ceramic-polymeric membrane. Membrane samples with and without polySBMA coating were subjected to fouling with a bovine serum albumin solution and fouling was observed by measuring permeate flux at 10 mL intervals. Loss of polySBMA was measured using total organic carbon analysis, and membrane samples were characterized using x-ray diffraction, scanning electron microscopy, and optical profilometry. The coated membrane samples decreased initial fouling rate by 27% and secondary fouling rate by 24%. Similarly, they displayed a 30% decrease in irreversible fouling during the initial fouling stage, and a 27% decrease in irreversible fouling in the secondary fouling stage; however, retention of polySBMA sufficient for improved performance was not conclusive. The addition of chemical disinfectants into drinking water treatment processes results in the formation of compounds called disinfection by-products (DBPs). The formation of DBPs occurs when common chemical disinfectants (i.e. chlorine) react with organic material. The harmful effects of DBP exposure require that they be monitored and controlled for public safety. This work investigated the ability of nanostructured hematite derived from ferroxane nanoparticles to remove organic precursors to DBPs in the form of humic acid via adsorption processes. The results show that pH and ionic strength have an effect on adsorption capacity and mechanism. At lower ionic strengths, the adsorption isotherms are closely correlated with the Freundlich adsorption isotherm model, while at higher ionic strength, the isotherms are closely related to the Langmuir adsorption isotherm model. Lower pH systems facilitate better adsorption capacities than higher pH systems, and lower ionic strength systems facilitate better adsorption than higher ionic strength systems.

Ionic Strength, Surface Charge, and Packing Density Effects on the Properties of Peptide Self-Assembled Monolayers.

PubMed

Leo, Norman; Liu, Juan; Archbold, Ian; Tang, Yongan; Zeng, Xiangqun

2017-02-28

The various environmental parameters of packing density, ionic strength, and solution charge were examined for their effects on the properties of the immobilized peptide mimotope CH19 (CGSGSGSQLGPYELWELSH) that binds with the therapeutic antibody Trastuzumab (Herceptin) on a gold substrate. The immobilization of CH19 onto gold was examined with a quartz crystal microbalance (QCM). The QCM data showed the presence of intermolecular interactions resulting in the increase of viscoelastic properties of the peptide self-assembled monolayer (SAM). The CH19 SAM was diluted with CS7 (CGSGSGS) to decrease the packing density as CH19/CS7. The packing density and ionic strength parameters were evaluated by atomic force microscopy (AFM), ellipsometry, and QCM. AFM and ellipsometry showed a distinct conformational difference between CH19 and CH19/CS7, indicating a relationship between packing density and conformational state of the immobilized peptide. The CH19 SAM thickness was 40 Å with a rough topology, while the CH19/CS7 SAM thickness was 20 Å with a smooth topology. The affinity studies showed that the affinity of CH19 and CH19/CS7 to Trastuzumab were both on the order of 10 7 M -1 in undiluted PBS buffer, while the dilution of the buffer by 1000× increased both SAMs affinities to Trastuzumab to the order of 10 15 M -2 and changed the binding behavior from noncooperative to cooperative binding. This indicated that ionic strength had a more pronounced effect on binding properties of the CH19 SAM than packing density. Electrochemical impedance spectroscopy (EIS) was conducted on the CH19/CS7 SAM, which showed an increase in impedance after each EIS measurement cycle. Cyclic voltammetry on the CH19/CS7 SAM decreased impedance to near initial values. The impact of the packing density, buffer ionic strength, and local charge perturbation of the peptide SAM properties was interpreted based on the titratable sites in CH19 that could participate in the proton transfer and water equilibrium.

Induction of Ca2+-dependent cyclosporin A-insensitive nonspecific permeability of the inner membrane of liver mitochondria and cytochrome c release by α,ω-hexadecanedioic acid in media of varying ionic strength.

PubMed

Dubinin, M V; Vedernikov, A A; Khoroshavina, E I; Samartsev, V N

2014-06-01

In liver mitochondria loaded with Ca2+ or Sr(2+), α,ω-hexadecanedioic acid (HDA) can induce nonspecific permeability of the inner membrane (mitochondrial pore) by the mechanism insensitive to cyclosporin A (CsA). In this work we studied the effect of ionic strength of the incubation medium on the kinetics of the processes that accompany Ca2+-dependent induction of the mitochondrial pore by fatty acid: organelle swelling, Ca2+ release from the matrix, changes in transmembrane potential (Δψ) and rate of oxygen consumption, and the release of cytochrome c from the intermembrane space. Two basic incubation media were used: sucrose medium and isotonic ionic medium containing KCl without sucrose. We found that 200 μM Ca2+ and 20 μM HDA in the presence of CsA effectively induce high-amplitude swelling of mitochondria both in the case of sucrose and in the ionic incubation medium. In the presence of CsA, mitochondria can rapidly absorb Ca2+ and retain it in the matrix for a while without reducing Δψ. Upon incubation in the ionic medium, mitochondria retain most of the added Ca2+ in the matrix for a short time without reducing the Δψ. In both cases the addition of HDA to the mitochondria 2 min after the introduction of Ca2+ leads to the rapid release of these ions from the matrix and total drop in Δψ. The mitochondrial swelling induced by Ca2+ and HDA in non-ionic medium is accompanied by almost maximal stimulation of respiration. Under the same conditions, but during incubation of mitochondria in the ionic medium, it is necessary to add cytochrome c for significant stimulation of respiration. The mitochondrial swelling induced by Ca2+ and HDA leads to the release of cytochrome c in a larger amount in the case of ionic medium than for the sucrose medium. We conclude that high ionic strength of the incubation medium determines the massive release of cytochrome c from mitochondria and liberates it from the respiratory chain, which leads to blockade of electron transport along the respiratory chain and consequently to disruption of the energy functions of the organelles.

Effect of electrolytes on proteins physisorption on ordered mesoporous silica materials.

PubMed

Salis, Andrea; Medda, Luca; Cugia, Francesca; Monduzzi, Maura

2016-01-01

This short review highlights the effect of electrolytes on the performance of proteins-mesoporous silica conjugates which can open interesting perspectives in biotechnological fields, particularly nanomedicine and biocatalysis. Indeed therapeutic proteins and peptides represent a challenging innovation for several kinds of diseases, but since their self-life in biological fluids is very short, they need a stealth protective carrier. Similarly, enzymes need a solid support to improve thermal stability and to allow for recycling. Ordered mesoporous silica materials represent a valid choice as widely demonstrated. Both proteins and silica mesoporous materials possess charged surfaces, and here, the crucial role of pH, buffer, ionic strength and electrolyte type is posed in relation with loading/release of proteins onto/from the silica support through the analysis of adsorption and release processes. A delicate interplay of electrostatic and van der Waals interactions arises from considering electrolytes' effects on the two different charged surfaces. Clear outcomes concern the effect of pH and ionic strength. Protein loading onto the silica matrix is favored by an adsorbing solution having a pH close to the protein pI, and by a high ionic strength that reduces the Debye length. Release is instead favored by an adsorbing solution characterized by an intermediate ionic strength, close to the physiological values. Significant specific ions effects are shown to affect both proteins and silica matrices, as well as protein adsorption onto silica matrices. Further work is needed to quantify specific ion effects on the preservation of the biological activity, and on the release performance. Copyright © 2015 Elsevier B.V. All rights reserved.

Steric and electrostatic surface forces on sulfonated PEG graft surfaces with selective albumin adsorption.

PubMed

Bremmell, Kristen E; Britcher, Leanne; Griesser, Hans J

2013-06-01

Addition of ionized terminal groups to PEG graft layers may cause additional interfacial forces to modulate the net interfacial interactions between PEG graft layers and proteins. In this study we investigated the effect of terminal sulfonate groups, characterizing PEG-aldehyde (PEG-CHO) and sulfonated PEG (PEG-SO3) graft layers by XPS and colloid probe AFM interaction force measurements as a function of ionic strength, in order to determine surface forces relevant to protein resistance and models of bio-interfacial interaction of such graft coatings. On the PEG-CHO surface the measured interaction force does not alter with ionic strength, typical of a repulsive steric barrier coating. An analogous repulsive interaction force of steric origin was also observed on the PEG-SO3 graft coating; however, the net interaction force changed with ionic strength. Interaction forces were modelled by steric and electrical double layer interaction theories, with fitting to a scaling theory model enabling determination of the spacing and stretching of the grafted chains. Albumin, fibrinogen, and lysozyme did not adsorb on the PEG-CHO coating, whereas the PEG graft with terminal sulfonate groups showed substantial adsorption of albumin but not fibrinogen or lysozyme from 0.15 M salt solutions. Under lower ionic strength conditions albumin adsorption was again minimized as a result of the increased electrical double-layer interaction observed with the PEG-SO3 modified surface. This unique and unexpected adsorption behaviour of albumin provides an alternative explanation to the "negative cilia" model used by others to rationalize observed thromboresistance on PEG-sulfonate coatings. Copyright © 2013 Elsevier B.V. All rights reserved.

The effect of humic acid on uranyl sorption onto bentonite at trace uranium levels.

PubMed

Ivanov, Peter; Griffiths, Tamara; Bryan, Nick D; Bozhikov, Gospodin; Dmitriev, Serguei

2012-11-01

The effect of humic acid (HA) on U(VI) sorption on bentonite was studied in batch experiments at room temperature and ambient atmosphere at a (237)U(VI) concentration of 8.4 × 10(-11) M and HA concentration of 100 mg L(-1). The distribution of U(VI) between the liquid and solid phases was studied as a function of pH and ionic strength both in the absence and presence of HA. It was shown that the uranyl sorption on bentonite is strongly dependent on pH and the presence of humics, and the effect of the addition order was negligible. In the absence of HA an enhancement in the uptake with increasing pH was observed and a sharp sorption edge was found to take place between pH 3.2 and 4.2. The presence of HA slightly increases uranium(VI) sorption at low pH and curtails it at moderate pH, compared to the absence of HA. In the basic pH range for both the presence and absence of HA the sorption of uranium is significantly reduced, which could be attributed to the formation of soluble uranyl carbonate complexes. The influence of ionic strength on U(VI) and HA uptake by bentonite were investigated in the range of 0.01-1.0 M, and while there was an enhancement in the sorption of humic acid with increasing ionic strength, no significant effect of the ionic strength on the U(VI) sorption was observed in both the absence and presence of HA.

Transport and abatement of fluorescent silica nanoparticle (SiO2 NP) in granular filtration: effect of porous media and ionic strength

NASA Astrophysics Data System (ADS)

Zeng, Chao; Shadman, Farhang; Sierra-Alvarez, Reyes

2017-03-01

The extensive production and application of engineered silica nanoparticles (SiO2 NPs) will inevitably lead to their release into the environment. Granular media filtration, a widely used process in water and wastewater treatment plants, has the potential for NP abatement. In this work, laboratory-scale column experiments were performed to study the transport and retention of SiO2 NPs on three widely used porous materials, i.e., sand, anthracite, and granular activated carbon (GAC). Synthetic fluorescent core-shell SiO2 NPs (83 nm) were used to facilitate NP detection. Sand showed very low capacity for SiO2 filtration as this material had a surface with limited surface area and a high concentration of negative charge. Also, we found that the stability and transport of SiO2 NP were strongly dependent on the ionic strength of the solution. Increasing ionic strength led to NP agglomeration and facilitated SiO2 NP retention, while low ionic strength resulted in release of captured NPs from the sand bed. Compared to sand, anthracite and GAC showed higher affinity for SiO2 NP capture. The superior capacity of GAC was primarily due to its porous structure and high surface area. A process model was developed to simulate NP capture in the packed bed columns and determine fundamental filtration parameters. This model provided an excellent fit to the experimental data. Taken together, the results obtained indicate that GAC is an interesting material for SiO2 NP filtration.

Radioprotection of Human Cell Nuclear DNA by Polyamines: Radiosensitivity of Chromatin is Influenced by Tightly Bound Spermine

NASA Technical Reports Server (NTRS)

Warters, Raymond L.; Newton, Gerald L.; Olive, Peggy L.; Fahey, Robert C.

1999-01-01

The polyamines putrescine (PUT) and spermine (SPM) were examined for their ability to protect human cell Deoxyribonucleic Acid (DNA) against the formation of radiation-induced double-strand breaks (DSBs). As observed previously, under conditions where polyamines were shown to be almost completely absent, association with nuclear matrix protein into a nucleoid, and organization into chromatin structure, protected DNA from induction of DSBs by factors of 4.5 and 95, respectively. At concentrations below 1 mM, PUT or SPM provided equivalent levels of protection to deproteinized nuclear DNA, consistent with their capacity to scavenge radiation-induced radicals. At constant ionic strength, 5 mM SPM protected deproteinized DNA and nucleoid DNA and DNA in nuclear chromatin by factors of 100 and 26, respectively. At 5 mM, SPM provided 15 times greater protection of deproteinized DNA than did PUT. Under physiologically relevant conditions, 5 mM SPM protected DNA in the intact nucleus from the induction of DSBs by a factor of 2 relative to DNA in the absence of SPM. Studies of SPM binding during cellular fractionation revealed that a significant fraction of the cellular SPM is tightly bound in the nucleus but can be removed by extended washing. Thus the association of SPM with nuclear chromatin appears to be a significant contributor to the resistance of the cell's DNA to the induction of DSBs.

Effect of the interfacial tension and ionic strength on the thermodynamic barrier associated to the benzocaine insertion into a cell membrane.

PubMed

López Cascales, J J; Oliveira Costa, S D

2013-02-01

The insertion of local anaesthetics into a cell membrane is a key aspect for explaining their activity at a molecular level. It has been described how the potency and response time of local anaesthetics is improved (for clinical applications) when they are dissolved in a solution of sodium bicarbonate. With the aim of gaining insight into the physico-chemical principles that govern the action mechanism of these drugs at a molecular level, simulations of benzocaine in binary lipid bilayers formed by DPPC/DPPS were carried out for different ionic strengths of the aqueous solution. From these molecular dynamic simulations, we observed how the thermodynamic barrier associated with benzocaine insertion into the lipid bilayers diminished exponentially as the fraction of DPPS in the bilayer increased, especially when the ionic strength of the aqueous solution increased. In line with these results, we also observed how this thermodynamic barrier diminished exponentially with the phospholipid/water interfacial tension. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Influence of cellulose nanocrystals concentration and ionic strength on the elaboration of cellulose nanocrystals-xyloglucan multilayered thin films.

PubMed

Dammak, Abir; Moreau, Céline; Azzam, Firas; Jean, Bruno; Cousin, Fabrice; Cathala, Bernard

2015-12-15

The effect of the variation of CNC concentration on the growth pattern of CNC-XG films is investigated. We found that a transition in the growth slope occurs at a CNC concentration of roughly 3-4gL(-1). A close effect can be obtained by the increase of the ionic strength of the CNC suspensions, suggesting that electrostatic interactions are involved. Static light scattering investigation of CNC dispersions at increasing concentrations demonstrated that the particle-particle interactions change as the CNC concentration increases. Neutron Reflectivity (NR) was used to probe the internal structure of the films. The increase of the CNC concentration as well as the increase of the ionic strength in the CNC suspension were found to induce a densification of the adsorbed CNC layers, even though the mechanisms are not strictly identical in both cases. Small changes in these parameters provide a straightforward way of controlling the architecture of CNC-based multilayered thin films and, as a result, their functional properties. Copyright © 2015 Elsevier Inc. All rights reserved.

Adsorption of Eu(III) onto TiO2: effect of pH, concentration, ionic strength and soil fulvic acid.

PubMed

Tan, Xiaoli; Fang, Ming; Li, Jiaxing; Lu, Yi; Wang, Xiangke

2009-08-30

The effects of pH, initial Eu(III) concentration, ionic strength and fulvic acid (FA) on the adsorption of Eu(III) on TiO(2) are investigated by using batch techniques. The results indicate that the presence of FA strongly enhances the adsorption of Eu(III) on TiO(2) at low pH values. Besides, the adsorption of Eu(III) on TiO(2) is significantly dependent on pH values and independent of ionic strength. The adsorption of Eu(III) on TiO(2) is attributed to inner-sphere surface complexation. The diffuse layer model (DLM) is applied to simulate the adsorption data, and fits the experimental data well with the aid of FITEQL 3.2. X-ray photoelectron spectroscopy (XPS) is performed to study the species of Eu(III) adsorbed on the surfaces of TiO(2)/FA-TiO(2) hybrids at a molecular level, which suggest that FA act as "bridge" between Eu(III) and TiO(2) particles to enhance the ability to adsorb Eu(III) in solution.

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.

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.

Influence of the DNA structure on the free radical induction due to proflavine and light treatment.

PubMed

Piette, J; Calberg-Bacq, C M; Van de Vorst, A

1979-04-30

Induction of peroxide free radicals (detected by Electron Paramagnetic Resonance at 77 K) due to the photodynamic activity of proflavine was measured on bacteriophage phi X174 DNA either single-stranded (ss) as isolated from the virion, or double-stranded supercoiled (RFI) as isolated from the infected bacteria. Comparison was made with calf thymus DNA photosensitization. In order to use equivalent DNA-proflavine complexes, binding of the dye to the three DNA's was first determined under those conditions of high ionic strength favourable to the photodynamic reaction. Free radical induction was maximal for definite amounts of bound proflavine (which varied depending upon the DNA substrate) and at an ionic strength value of 0.5. The level of the maximal reaction increased in the following order: from phi Xss DNA to calf thymus DNA and finally to phi XRFI DNA. The conformation of the proflavine-DNA complex was thus a determinant for the efficiency of the photodynamic process. The ionic strength effect could not be explained by the evolution of the proflavine triplet state in irradiated proflavine-calf thymus DNA complexes.

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.

Purification of inulinases by changing the ionic strength of the medium and precipitation with alcohols.

PubMed

Golunski, Simone; Silva, Marceli F; Marques, Camila T; Rosseto, Vanusa; Kaizer, Rosilene R; Mossi, Altemir J; Rigo, Diane; Dallago, Rogério M; DI Luccio, Marco; Treichel, Helen

2017-01-01

The present study evaluated the purification of inulinase by changing the ionic strength of the medium by addition of NaCl and CaCl2 followed by precipitation with n-propyl alcohol or iso-propyl alcohol. The effects of the concentration of alcohols and the rate of addition of alcohols in the crude extract on the purification yield and purification factor were evaluated. Precipitation caused an activation of enzyme and allowed purification factors up to 2.4-fold for both alcohols. The purification factor was affected positively by the modification of the ionic strength of the medium to 0.5 mol.L-1 NaCl before precipitation with the alcohol (n-propyl or iso-propyl). A purification factor of 4.8-fold and an enzyme yield of 78.1 % could be achieved by the addition of 0.5 mol.L-1 of NaCl to the crude extract, followed by the precipitation with 50 % (v/v) of n-propyl alcohol, added at a flow rate of 19.9 mL/min.

Salinity-dependent diatom biosilicification implies an important role of external ionic strength

PubMed Central

Vrieling, Engel G.; Sun, Qianyao; Tian, Mingwen; Kooyman, Patricia J.; Gieskes, Winfried W. C.; van Santen, Rutger A.; Sommerdijk, Nico A. J. M.

2007-01-01

The role of external ionic strength in diatom biosilica formation was assessed by monitoring the nanostructural changes in the biosilica of the two marine diatom species Thalassiosira punctigera and Thalassiosira weissflogii that was obtained from cultures grown at two distinct salinities. Using physicochemical methods, we found that at lower salinity the specific surface area, the fractal dimensions, and the size of mesopores present in the biosilica decreased. Diatom biosilica appears to be denser at the lower salinity that was applied. This phenomenon can be explained by assuming aggregation of smaller coalescing silica particles inside the silica deposition vesicle, which would be in line with principles in silica chemistry. Apparently, external ionic strength has an important effect on diatom biosilica formation, making it tempting to propose that uptake of silicic acid and other external ions may take place simultaneously. Uptake and transport of reactants in the proximity of the expanding silica deposition vesicle, by (macro)pinocytosis, are more likely than intracellular stabilization and transport of silica precursors at the high concentrations that are necessary for the formation of the siliceous frustule components. PMID:17563373

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.

Octanol-water distribution of engineered nanomaterials.

PubMed

Hristovski, Kiril D; Westerhoff, Paul K; Posner, Jonathan D

2011-01-01

The goal of this study was to examine the effects of pH and ionic strength on octanol-water distribution of five model engineered nanomaterials. Distribution experiments resulted in a spectrum of three broadly classified scenarios: distribution in the aqueous phase, distribution in the octanol, and distribution into the octanol-water interface. Two distribution coefficients were derived to describe the distribution of nanoparticles among octanol, water and their interface. The results show that particle surface charge, surface functionalization, and composition, as well as the solvent ionic strength and presence of natural organic matter, dramatically impact this distribution. Distributions of nanoparticles into the interface were significant for nanomaterials that exhibit low surface charge in natural pH ranges. Increased ionic strengths also contributed to increased distributions of nanoparticle into the interface. Similarly to the octanol-water distribution coefficients, which represent a starting point in predicting the environmental fate, bioavailability and transport of organic pollutants, distribution coefficients such as the ones described in this study could help to easily predict the fate, bioavailability, and transport of engineered nanomaterials in the environment.

The influence of ionic strength and organic compounds on nanoparticle TiO2 (n-TiO2) aggregation.

PubMed

Lee, Jaewoong; Bartelt-Hunt, Shannon L; Li, Yusong; Gilrein, Erica Jeanne

2016-07-01

This study investigated the aggregation of n-TiO2 in the presence of humic acid (HA) and/or 17β-estradiol (E2) under high ionic strength conditions simulating levels detected in landfill leachate. Aggregation of n-TiO2 was strongly influenced by ionic strength as well as ionic valence in that divalent cations (Ca(2+)) were more effective than monovalent (Na(+)) at the surface modification. HA or E2 enhanced aggregation of n-TiO2 in 20 mM CaCl2, however little aggregation was observed in 100 mM NaCl. Similarly, we observed only the increased aggregation of n-TiO2 in the presence of HA/E2. These results showed the critical role of particles' surface charges on the aggregation behaviors of n-TiO2 that HA plays more significantly than E2. However, the slightly increased zeta potential and aggregation of n-TiO2 in the combination of HA and E2 at both 20 mM CaCl2 and 100 mM NaCl means that E2 has influenced on the surface modification of n-TiO2 by adsorption. Based on the aggregation of n-TiO2 under high ionic strength with HA and/or E2, we simulated the mobility of aggregated n-TiO2 in porous media. As a result, we observed that the mobility distance of aggregated n-TiO2 was dramatically influenced by the surface modification with both HA and/or E2 between particles and media. Furthermore, larger mobility distance was observed with larger aggregation of n-TiO2 particles that can be explained by clean bed filtration (CFT) theory. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling bipolar stimulation of cardiac tissue

NASA Astrophysics Data System (ADS)

Galappaththige, Suran K.; Gray, Richard A.; Roth, Bradley J.

2017-09-01

Unipolar stimulation of cardiac tissue is often used in the design of cardiac pacemakers because of the low current required to depolarize the surrounding tissue at rest. However, the advantages of unipolar over bipolar stimulation are not obvious at shorter coupling intervals when the tissue near the pacing electrode is relatively refractory. Therefore, this paper analyzes bipolar stimulation of cardiac tissue. The strength-interval relationship for bipolar stimulation is calculated using the bidomain model and a recently developed parsimonious ionic current model. The strength-interval curves obtained using different electrode separations and arrangements (electrodes placed parallel to the fibers versus perpendicular to the fibers) indicate that bipolar stimulation results in more complex activation patterns compared to unipolar stimulation. An unusually low threshold stimulus current is observed when the electrodes are close to each other (a separation of 1 mm) because of break excitation. Unlike for unipolar stimulation, anode make excitation is not present during bipolar stimulation, and an abrupt switch from anode break to cathode make excitation can cause dramatic changes in threshold with very small changes in the interval. These results could impact the design of implantable pacemakers and defibrillators.

Development of conductometric biosensor array for simultaneous determination of maltose, lactose, sucrose and glucose.

PubMed

Soldatkin, O O; Peshkova, V M; Saiapina, O Y; Kucherenko, I S; Dudchenko, O Y; Melnyk, V G; Vasylenko, O D; Semenycheva, L M; Soldatkin, A P; Dzyadevych, S V

2013-10-15

The aim of this work was to develop an array of biosensors for simultaneous determination of four carbohydrates in solution. Several enzyme systems selective to lactose, maltose, sucrose and glucose were immobilised on the surface of four conductometric transducers and served as bio-recognition elements of the biosensor array. Direct enzyme analysis carried out by the developed biosensors was highly sensitive to the corresponding substrates. The analysis lasted 2 min. The dynamic range of substrate determination extended from 0.001 mM to 1.0-3.0mM, and strongly depended on the enzyme system used. An effect of the solution pH, ionic strength and buffer capacity on the biosensors responses was investigated; the conditions of simultaneous operation of all biosensors were optimised. The data on cross-impact of the substrates of all biosensors were obtained; the biosensor selectivity towards possible interfering carbohydrates was tested. The developed biosensor array showed good signal reproducibility and storage stability. The biosensor array is suited for simultaneous, quick, simple, and selective determination of maltose, lactose, sucrose and glucose. © 2013 Elsevier B.V. All rights reserved.

The globular domain of histone H5 is internally located in the 30 nm chromatin fiber: an immunochemical study.

PubMed Central

Dimitrov, S I; Russanova, V R; Pashev, I G

1987-01-01

The location of the globular domain of histone H5 relative to the axis of the 30 nm chromatin fiber was investigated by following the accessibility of this region of the molecule in chicken erythrocyte chromatin to specific antibodies as a function of chromatin structure. Antibodies to the globular domain of H5 as well as their Fab fragments were found to react with chromatin at ionic strengths ranging from 1-80 mM NaCl, the reaction gradually decreasing upon increase of salt concentration. If, however, Fab fragments were conjugated to ferritin, no reaction of the complex with chromatin was observed at salt concentrations higher than 20 mM. The accessibility of the globular part of H5 in unfolded chromatin to the Fab-ferritin complex was also demonstrated with trypsin-digested chromatin. The experiments were carried out by both solid-phase immunoassay and inhibition experiments. The data obtained are consistent with a structure in which the globular domain of H5 is internally located in the 30 nm chromatin fiber. Images Fig. 1. Fig. 2. PMID:2444434

A label-free impedimetric DNA sensing chip integrated with AC electroosmotic stirring.

PubMed

Wu, Ching-Chou; Yang, Dong-Jie

2013-05-15

AC electroosmosis (ACEO) flow and label-free electrochemical impedance spectroscopy are employed to increase the hybridization rate and specifically detect target DNA (tDNA) concentrations. A low-ionic-strength solution, 6.1μS/cm 1mM Tris (pH 9.3), was used to produce ACEO and proved the feasibility of hybridization. Adequate voltage parameters for the simultaneous ACEO driving and DNA hybridization in the 1mM Tris solution were 1.5 Vpp and 200Hz. Moreover, an electrode set with a 1:4 ring width-to-disk diameter ratio exhibited a larger ACEO velocity above the disk electrode surface to improve collecting efficiency. The ACEO-integrated DNA sensing chips could reach 90% saturation hybridization within 117s. The linear range and detection limit of the sensors was 10aM-10pM and 10aM, respectively. The label-free impedimetric DNA sensing chips with integrated ACEO stirring can perform rapid hybridization and highly-sensitive detections to specifically measure tDNA concentrations. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Towards understanding the effects of van der Waals strengths on the electric double-layer structures and capacitive behaviors

NASA Astrophysics Data System (ADS)

Yang, Huachao; Bo, Zheng; Yang, Jinyuan; Yan, Jianhua; Cen, Kefa

2017-10-01

Solid-liquid interactions are considered to play a crucial role in charge storage capability of electric double-layer capacitors (EDLCs). In this work, effects of van der Waals (VDW) strengths on the EDL structures and capacitive performances within two representative electrolytes of solvated aqueous solutions and solvent-free ionic liquids are illuminated by molecular dynamics simulations. Single crystalline metals with similar lattice constant but diverse VDW potentials are employed as electrodes. Upon enhancing VDW strengths, capacitance of aqueous electrolytes first increases conspicuously by ∼34.0% and then descends, manifesting a non-monotonic trend, which goes beyond traditional perspectives. Such unusual observation is interpreted by the excluded-volume effects stemmed from ion-solvent competitions. Stimulated by predominant coulombic interactions, more ions are aggregated at the interface despite of the increasing VDW potentials, facilitating superior screening efficiency and capacitance. However, further enhancing strengths preferentially attracts more solvents instead of ions to the electrified surface, which in turn strikingly repels ions from Helmholtz layers, deteriorating electrode capacitance. An essentially similar feather is also recognized for ionic liquids, while the corresponding mechanisms are prominently ascribed to the suppressed ionic separations issued from cation-anion competitions. We highlight that constructing electrode materials with a moderate-hydrophilicity could further advance the performances of EDLCs.

Comparison of Rotavirus and Norovirus transport in standardised and natural soil-water systems

NASA Astrophysics Data System (ADS)

Gamazo, P. A.; Schijven, J. F.; Victoria, M.; Alvareda, E.; Lopez, F.; Ramos, J.; Lizasoain, A.; Sapriza-Azuri, G.; Castells, M.; Colina, R.

2016-12-01

Rotavirus and Norovirus are waterborne viruses that are major causes of diarrhea and others symptoms of acute gastroenteritis. An important pathway of these viruses is groundwater. In Uruguay, as in many developed and developing countries, there are areas where the only source of water for human consumption is groundwater. In the rural area of the Salto district, groundwater is commonly used without any treatment, as it is traditionally considered as a safe source. However, virus contamination have been detected in several wells in the area. The most probable source of contamination are nearby septic systems, since the sewer coverage is scarce. This work aims to evaluate and compare the virus transport processes for a standardised soil-water systems and for the Salto aquifer system. For this, the transport of Rotavirus and Norovirus from clinic samples was studied in two sets of column experiments: 6.7 cm columns with quartz sand under saturated conditions (ionic strength 1mM, pH 7.0) and with sand from the Salto aquifer (Uruguay) (9,2% coarse sand, 47,8% medium sand, 40,5% fine sand, magnesium/calcium bicarbonate water, Ionic strength 15.1 mM, pH 7.2). Both viruses were seeded for 2 pore volumes on the columns. Samples were collected at the column outlet and viruses were enumerated by Q-PRCR. Breakthrough curves were constructed and fitted to a two-site kinetic attachment/detachment model, including blocking using Hydrus-1D. In the quartz sand column, both Rotavirus and Norovirus were removed two orders in magnitude. In the Salto sand column, Rotavirus was removed 2 log10 as well, but Norovirus was removed 4 log10. The fitting of the breakthrough curves indicated that blocking played a role for Rotavirus in the Salto sand column. These results are consistent with field observation where only Rotavirus was detected in the Salto aquifer, while similar concentrations in Salto sewer effluent was measured for these two viruses. This work, besides reporting actual parameters values for human virus transport modelling, shows the significant differences in transport that human viruses can have in standardised and natural soil-water systems.

Silver nanoparticles coated with natural polysaccharides as models to study AgNP aggregation kinetics using UV-Visible spectrophotometry upon discharge in complex environments.

PubMed

Lodeiro, Pablo; Achterberg, Eric P; Pampín, Joaquín; Affatati, Alice; El-Shahawi, Mohammed S

2016-01-01

This study provides quantitative information on the aggregation and dissolution behaviour of silver nanoparticles (AgNPs) upon discharge in fresh and sea waters, represented here as NaCl solutions of increasing ionic strength (up to 1M) and natural fjord waters. Natural polysaccharides, sodium alginate (ALG) and gum Arabic (GA), were used as coatings to stabilize the AgNPs and the compounds acted as models to study AgNP aggregation kinetics. The DLVO theory was used to quantitatively describe the interactions between the AgNPs. The stability of AgNPs was established using UV-Visible spectrophotometry, including unique information collected during the first seconds of the aggregaton process. Alginate coating resulted in a moderate stabilization of AgNPs in terms of critical coagulation concentration (~82mM NaCl) and a low dissolution of <10% total Ag in NaCl solutions up to 1M. Gum Arabic coated AgNPs were more strongly stabilized, with ~7-30% size increase up to 77mM NaCl, but only when the silver ion content initially present in solution was low (<10% total Ag). The ALG and GA coated AgNPs showed a strongly enhanced stability in natural fjord waters (ca. 5h required to reduce the area of the surface plasmon resonance band (SPRB) by two fold) compared with NaCl at an equivalent ionic strength (1-2min period for a two fold SPRB reduction). This is ascribed to a stabilizing effect from dissolved organic matter present in natural fjord waters. Interestingly, for AgNP-GA solutions with 40% of total silver present as unreacted silver ions in the NP stock solution, fast aggregation kinetics were observed in NaCl solutions (SPRB area was reduced by ca. 50% within 40-150min), with even more rapid removal in fjord waters, attributed to the high amount of silver-chloride charged species, that interact with the NP coating and/or organic matter and reduce the NPs stabilization. Copyright © 2015 Elsevier B.V. All rights reserved.

Reconstitution of a kidney chloride channel and its identification by covalent labeling.

PubMed

Breuer, W

1990-02-28

The basolateral membrane of the thick ascending loop of Henle (TALH) of the mammalian kidney is characterized by its high content of Na+/K(+)-ATPase and a Cl- conductance, which function in parallel in salt reabsorption. In order to reconstitute the Cl- channels, TALH membrane vesicles were solubilized in 1% sodium cholate in buffer containing 200 mM KCl, followed by dilution with soybean lipids (final ratio of protein/detergent/lipid of 1:3:15 in mg) and removal of the detergent by gel filtration on Sephadex G-50. Cl- channel activity in the liposomes was determined by a 36Cl- uptake assay where the accumulation of the radioactive tracer against its chemical gradient is driven by the membrane potential (positive inside) generated by an outward Cl- gradient. The 36Cl- uptake by the KCl-loaded liposomes was dependent on the inclusion of membrane protein and was abolished by valinomycin, indicating the involvement of a conductive pathway. It was also inhibited by 36% by 100 microM 4,4'-diisothiocyanostilbene-2,2'-disulfonate (DIDS) and 5-nitro-2-(3-phenylpropylamino)benzoic acid (NPPB). Solubilization of the Cl- channels in cholate was optimal in the presence of 200 mm KCl, but was found to decrease markedly at low ionic strength. SDS-PAGE analysis of the proteins extracted by cholate at high and low salt concentrations showed that the Cl- channel-containing high KCl extract was enriched in the 96 and 55 kDa alpha- and beta-subunits of the Na+/K(+)-ATPase (the major proteins in the membrane preparation) and several minor protein bands. Treatment of the membrane vesicles with the radioactive analogue of DIDS, [3H]2DIDS, labeled primarily a 65 and a 31 kDa protein. The solubilization of the 31 kDa protein by cholate depended markedly on the ionic strength and thus paralleled the solubilization pattern of Cl- channel activity. Furthermore, the labeling of the 31 kDa protein was prevented by nonradioactive DIDS and by NPPB but not by other compounds, indicating that it may be a Cl- channel component.

Strength of mortar containing rubber tire particle

NASA Astrophysics Data System (ADS)

Jusoh, M. A.; Abdullah, S. R.; Adnan, S. H.

2018-04-01

The main focus in this investigation is to determine the strength consist compressive and tensile strength of mortar containing rubber tire particle. In fact, from the previous study, the strength of mortar containing waste rubber tire in mortar has a slightly decreases compare to normal mortar. In this study, rubber tire particle was replacing on volume of fine aggregate with 6%. 9% and 12%. The sample were indicated M0 (0%), M6 (6%), M9 (9%) and M12 (12%). In this study, two different size of sample used with cube 100mm x 100mm x 100mm for compressive strength and 40mm x 40mm x 160mm for flexural strength. Morphology test was conducted by using Scanning electron microscopic (SEM) were done after testing compressive strength test. The concrete sample were cured for day 3, 7 and 28 before testing. Results compressive strength and flexural strength of rubber mortar shown improved compare to normal mortar.

Exploring the ionic strength effects on the photochemical degradation of pyruvic acid in atmospheric deliquescent aerosol particles

NASA Astrophysics Data System (ADS)

Mekic, Majda; Brigante, Marcello; Vione, Davide; Gligorovski, Sasho

2018-07-01

There is increasing evidence that aqueous-phase atmospheric chemistry is an important source of secondary organic aerosols (SOA), but the related processes are currently not adequately represented in atmospheric chemistry models. Here we show that the absorption spectrum of pyruvic acid (PA) exhibits both an increase of the absorption intensity and a red shift of 13 nm while going from a dilute aqueous phase to a solution containing the inert salt sodium perchlorate (5M NaClO4). If this phenomenon turns out to be more general, many compounds that do not absorb actinic light in clouds and fog could become light absorbers at elevated salt concentrations in aerosol deliquescent particles. Compared to the direct photolysis of PA in dilute aqueous solution, the photolysis rate is increased by three times at high ionic strength (5M NaClO4). Such a considerable enhancement can be rationalized in the framework of the Debye-McAulay approach for reactions of ionic + neutral (or neutral + neutral) species, considering that the PA direct photolysis likely involves interaction between the photogenerated triplet state and water. This is, to our knowledge, the first report of a significant effect of the ionic strength on the rate of an atmospheric photochemical reaction. The phenomenon has important implications for the fate of PA and, potentially, of other organic compounds in atmospheric aerosol deliquescent particles.

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

A novel approach to bar adsorptive microextraction: Cork as extractor phase for determination of benzophenone, triclocarban and parabens in aqueous samples.

PubMed

Dias, Adriana Neves; da Silva, Ana Cristine; Simão, Vanessa; Merib, Josias; Carasek, Eduardo

2015-08-12

This study describes the use of cork as a new coating for bar adsorptive microextraction (BAμE) and its application in determining benzophenone, triclocarban and parabens in aqueous samples by HPLC-DAD. In this study bars with 7.5 and 15 mm of length were used. The extraction and liquid desorption steps for BAμE were optimized employing multivariate and univariate procedures. The desorption time and solvent used for liquid desorption were optimized by univariate and multivariate studies, respectively. For the extraction step the sample pH was optimized by univariate experiments while the parameters extraction time and ionic strength were evaluated using the Doehlert design. The optimum extraction conditions were sample pH 5.5, NaCl concentration 25% and extraction time 90 min. Liquid desorption was carried out for 30 min with 250 μL (bar length of 15 mm) or 100 μL (bar length of 7.5 mm) of ACN:MeOH (50:50, v/v). The quantification limits varied between 1.6 and 20 μg L(-1) (bar length of 15 mm) and 0.64 and 8 μg L(-1) (bar length of 7.5 mm). The linear correlation coefficients were higher than 0.98 for both bars. The method with 7.5 mm bar length showed recovery values between 65 and 123%. The bar-to-bar reproducibility and the repeatability were lower than 13% (n = 2) and 14% (n = 3), respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Ionic strength and temperature induced conformational changes in mononucleosomes and oligonucleosomes. [Chromatin

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

Schmitz, K.S.; Kent, J.C.; Parthasarathy, N.

1980-10-01

Chromatin is a nucleohistone complex which exhibits a repeat unit structure as inferred from nuclease digestion studies. The repeat unit, or nucleosome, is defined as approx. 200 base pairs of DNA wrapped about the surface of an octameric histone complex (two copies each of the histones H2A, H2B, H3, and H4). We report in this communication preliminary studies on the conformation of chromatin mononucleosomes and oligonucleosomes as a function of temperature and ionic strength. The methods used were conductivity, fluorescence of bound proflavine, and quasielastic light scattering.

Electronegativity, charge transfer, crystal field strength, and the point charge model revisited.

PubMed

Tanner, Peter A; Ning, Lixin

2013-02-21

Although the optical spectra of LnCl(6)(3-) systems are complex, only two crystal field parameters, B(40) and B(60), are required to model the J-multiplet crystal field splittings in octahedral symmetry. It is found that these parameters exhibit R(-5) and R(-7) dependence, respectively, upon the ionic radius Ln(3+)(VI), but not upon the Ln-Cl distance. More generally, the crystal field strengths of LnX(6) systems (X = Br, Cl, F, O) exhibit linear relationships with ligand electronegativity, charge transfer energy, and fractional ionic character of the Ln-X bond.

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

Yield stress and scaling of polyelectrolyte multilayer modified suspensions: effect of polyelectrolyte conformation during multilayer assembly.

PubMed

Hess, Andreas; Aksel, Nuri

2013-09-10

The yield stress of polyelectrolyte multilayer modified suspensions exhibits a surprising dependence on the polyelectrolyte conformation of multilayer films. The rheological data scale onto a universal master curve for each polyelectrolyte conformation as the particle volume fraction, φ, and the ionic strength of the background fluid, I, are varied. It is shown that rough films with highly coiled, brushy polyelectrolytes significantly enhance the yield stress. Moreover, via the ionic strength I of the background fluid, the dynamic yield stress of brushy polyelectrolyte multilayers can be finely adjusted over 2 decades.

Effect of oxidation state and ionic strength on sorption of actinides (Th, U, Np, Am) to geologic media [Abstract and References Only

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

Dittrich, Timothy M.; Richmann, Michael K.; Reed, Donald T.

2015-10-30

The degree of conservatism in the estimated sorption partition coefficients (K ds) used in a performance assessment model is being evaluated based on a complementary batch and column method. The main focus of this work is to investigate the role of ionic strength, solution chemistry, and oxidation state (III-VI) in actinide sorption to dolomite rock. Based on redox conditions and solution chemistry expected at the WIPP, possible actinide species include Pu(III), Pu(IV), U(IV), U(VI), Np(IV), Np(V), Am(III), and Th(IV).

Higher-order structures assembly of gold nanorods caused by captopril in high ionic strength solutions.

PubMed

Shen, Sufen; Zhao, Huawen; Huang, Chengzhi; Wu, Liping

2010-02-01

The ability to construct self-assembled architectures is essential for the exploration of nanoparticle-structured properties. It is one of good strategies by employing molecule-modificated nanoparticles to prepare new materials with particular properties. Herein, we found that captopril (Cap), a biocompatible medicament, could adjust and control the formation of self-assembled gold nanorods (Au-NRs) in high ionic strength solutions. The assembly is in higher-order structures containing both end-to-end and side-by-side orientations. Furthermore, these structures of Au-NRs could be served as plasmonic waveguide in future biological nanodevices.

Purification and characterization of chromatin-bound DNA-dependent RNA polymerase I from parsley (Petroselinum crispum). Influence of nucleoside triphosphates.

PubMed Central

Grossmann, K; Friedrich, H; Seitz, U

1980-01-01

The isolation and purification of DNA-dependent RNA polymerase I (EC 2.7.7.6) from parsley (Petroselinum crispum) callus cells grown in suspension culture is described. The enzyme was solubilized from isolated chromatin. Purification was achieved by using DEAE- and phospho-cellulose in batches, followed by column chromatography on DEAE- and phospho-cellulose (two columns) and density-gradient centrifugation. The highly purified enzyme was stable over several months. The properties of purified parsley RNA polymerase I were investigated. Optimum concentration for Mn2+ was 1 mM, and for Mg2+ 4-6 mM, Mn2+ was slightly more stimulatory than Mg2+. The enzyme was most active at low ionic strengths [10-20 mM-(NH4)SO4]. The influence of various phosphates was tested: pyrophosphate inhibited RNA polymerase at low concentrations, whereas orthophosphate had no effect on the enzyme activity. ADP was slightly inhibitory, and AMP had no effect on the enzyme reaction. Nucleoside triphosphates and bivalent cations in equimolar concentrations in the range 4-11 mM did not influence the RNA synthesis in vitro. Free nucleoside triphosphates in excess of this 1:1 ratio inhibited the enzyme activity, unlike free bivalent cations, which stimulated RNA polymerase I. PMID:7470092

Quantifying intermolecular interactions of ionic liquids using cohesive energy densities.

PubMed

Lovelock, Kevin R J

2017-12-01

For ionic liquids (ILs), both the large number of possible cation + anion combinations and their ionic nature provide a unique challenge for understanding intermolecular interactions. Cohesive energy density, ced , is used to quantify the strength of intermolecular interactions for molecular liquids, and is determined using the enthalpy of vaporization. A critical analysis of the experimental challenges and data to obtain ced for ILs is provided. For ILs there are two methods to judge the strength of intermolecular interactions, due to the presence of multiple constituents in the vapour phase of ILs. Firstly, ced IP , where the ionic vapour constituent is neutral ion pairs, the major constituent of the IL vapour. Secondly, ced C+A , where the ionic vapour constituents are isolated ions. A ced IP dataset is presented for 64 ILs. For the first time an experimental ced C+A , a measure of the strength of the total intermolecular interaction for an IL, is presented. ced C+A is significantly larger for ILs than ced for most molecular liquids, reflecting the need to break all of the relatively strong electrostatic interactions present in ILs. However, the van der Waals interactions contribute significantly to IL volatility due to the very strong electrostatic interaction in the neutral ion pair ionic vapour. An excellent linear correlation is found between ced IP and the inverse of the molecular volume. A good linear correlation is found between IL ced IP and IL Gordon parameter (which are dependent primarily on surface tension). ced values obtained through indirect methods gave similar magnitude values to ced IP . These findings show that ced IP is very important for understanding IL intermolecular interactions, in spite of ced IP not being a measure of the total intermolecular interactions of an IL. In the outlook section, remaining challenges for understanding IL intermolecular interactions are outlined.

Quantifying intermolecular interactions of ionic liquids using cohesive energy densities

PubMed Central

2017-01-01

For ionic liquids (ILs), both the large number of possible cation + anion combinations and their ionic nature provide a unique challenge for understanding intermolecular interactions. Cohesive energy density, ced, is used to quantify the strength of intermolecular interactions for molecular liquids, and is determined using the enthalpy of vaporization. A critical analysis of the experimental challenges and data to obtain ced for ILs is provided. For ILs there are two methods to judge the strength of intermolecular interactions, due to the presence of multiple constituents in the vapour phase of ILs. Firstly, cedIP, where the ionic vapour constituent is neutral ion pairs, the major constituent of the IL vapour. Secondly, cedC+A, where the ionic vapour constituents are isolated ions. A cedIP dataset is presented for 64 ILs. For the first time an experimental cedC+A, a measure of the strength of the total intermolecular interaction for an IL, is presented. cedC+A is significantly larger for ILs than ced for most molecular liquids, reflecting the need to break all of the relatively strong electrostatic interactions present in ILs. However, the van der Waals interactions contribute significantly to IL volatility due to the very strong electrostatic interaction in the neutral ion pair ionic vapour. An excellent linear correlation is found between cedIP and the inverse of the molecular volume. A good linear correlation is found between IL cedIP and IL Gordon parameter (which are dependent primarily on surface tension). ced values obtained through indirect methods gave similar magnitude values to cedIP. These findings show that cedIP is very important for understanding IL intermolecular interactions, in spite of cedIP not being a measure of the total intermolecular interactions of an IL. In the outlook section, remaining challenges for understanding IL intermolecular interactions are outlined. PMID:29308254

Effects of ionic strength and temperature on the aggregation and deposition of multi-walled carbon nanotubes.

PubMed

Wang, Lixin; Yang, Xuezhi; Wang, Qi; Zeng, Yuxuan; Ding, Lei; Jiang, Wei

2017-01-01

The aggregation and deposition of carbon nanotubes (CNTs) determines their transport and fate in natural waters. Therefore, the aggregation kinetics of humic-acid treated multi-walled carbon nanotubes (HA-MWCNTs) was investigated by time-resolved dynamic light scattering in NaCl and CaCl 2 electrolyte solutions. Increased ionic strength induced HA-MWCNT aggregation due to the less negative zeta potential and the reduced electrostatic repulsion. The critical coagulation concentration (CCC) values of HA-MWCNTs were 80mmol/L in NaCl and 1.3mmol/L in CaCl 2 electrolyte, showing that Ca 2+ causes more serious aggregation than Na + . The aggregation behavior of HA-MWCNTs was consistent with Derjaguin-Landau-Verwey-Overbeek theory. The deposition kinetics of HA-MWCNTs was measured by the optical absorbance at 800nm. The critical deposition concentrations for HA-MWCNT in NaCl and CaCl 2 solutions were close to the CCC values, therefore the rate of deposition cannot be increased by changing the ionic strength in the diffusion-limited aggregation regime. The deposition process was correlated to the aggregation since larger aggregates increased gravitational deposition and decreased random Brownian diffusion. HA-MWCNTs hydrodynamic diameters were evaluated at 5, 15 and 25°C. Higher temperature caused faster aggregation due to the reduced electrostatic repulsion and increased random Brownian motion and collision frequency. HA-MWCNTs aggregate faster at higher temperature in either NaCl or CaCl 2 electrolyte due to the decreased electrostatic repulsion and increased random Brownian motion. Our results suggest that CNT aggregation and deposition are two correlated processes governed by the electrolyte, and CNT transport is favored at low ionic strength and low temperature. Copyright © 2016. Published by Elsevier B.V.

Deposition kinetics of extracellular polymeric substances (EPS) on silica in monovalent and divalent salts.

PubMed

Zhu, Pingting; Long, Guoyu; Ni, Jinren; Tong, Meiping

2009-08-01

The deposition kinetics of extracellular polymeric substances (EPS) on silica surfaces were examined in both monovalent and divalent solutions under a variety of environmentally relevant ionic strength and pH conditions by employing a quartz crystal microbalance with dissipation (DCM-D). Soluble EPS (SEPS) and bound EPS (BEPS) were extracted from four bacterial strains with different characteristics. Maximum favorable deposition rates (k(fa)) were observed for all EPS at low ionic strengths in both NaCl and CaCl2 solutions. With the increase of ionic strength, k(fa) decreased due to the simultaneous occurrence of EPS aggregation in solutions. Deposition efficiency (alpha; the ratio of deposition rates obtained under unfavorable versus corresponding favorable conditions) for all EPS increased with increasing ionic strength in both NaCl and CaCl2 solutions, which agreed with the trends of zeta potentials and was consistent with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Comparison of alpha for SEPS and BEPS extracted from the same strain showed that the trends of alpha did not totally agree with trends of zeta potentials, indicating the deposition kinetics of EPS on silica surfaces were not only controlled by DLVO interactions, but also non-DLVO forces. Close comparison of alpha for EPS extracted from different sources showed alpha increased with increasing proteins to polysaccharides ratio. Subsequent experiments for EPS extracted from the same strain but with different proteins to polysaccharides ratios and from activated sludge also showed that alpha were largest for EPS with greatest proteins to polysaccharides ratio. Additional experiments for pure protein and solutions with different pure proteins to pure saccharides ratios further corroborated that larger proteins to polysaccharides ratio resulted in greater EPS deposition.

Determination of perchlorate in drinking water by ion chromatography using macrocycle-based concentration and separation methods.

PubMed

Lamb, John D; Simpson, David; Jensen, Bryce D; Gardner, Joseph S; Peterson, Quinn P

2006-06-16

Macrocycle-based ion chromatography provides a convenient, reliable method for the determination of perchlorate ion, which is currently of great interest to the environmental community. This study shows that effective perchlorate determinations can be made using standard conductimetric detection by combining an 18-crown-6-based mobile phase with an underivatized reversed-phase mobile phase ion chromatography (MPIC) column. One unique feature of this method is the flexibility in column capacity that is achieved through simple variations in eluent concentrations of 18-crown-6 and KOH, facilitating the separation of target analyte anions such as perchlorate. Using a standard anion exchange column as concentrator makes possible the determination of perchlorate as low as 0.2 ug/L in low ionic strength matrices. Determination of perchlorate at the sub-ug/L level in pure water and in spiked local city hard water samples with high background ion concentrations can be achieved this way. However, like other IC techniques, this method is challenged to achieve analyses at the ug/L level in the demanding high ionic strength matrix described by the United States Environmental Protection Agency (EPA) (1,000 mg/L chloride, sulfate and carbonate). We approached this challenge by use of the Cryptand C1 concentrator column, provided by Dionex Corporation, to effectively preconcentrate perchlorate while reducing background ion concentrations in the high ionic strength matrix. The retention characteristics of the concentrator column were studied in order to maximize its effectiveness for perchlorate determinations. The method makes possible the determination of perchlorate at the 5 ug/L level in the highest ionic strength matrix described by the EPA.

Modeling the effects of variable groundwater chemistry on adsorption of molybdate

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1995-01-01

Laboratory experiments were used to identify and quantify processes having a significant effect on molybdate (MoO42−) adsorption in a shallow alluvial aquifer on Cape Cod, assachusetts. Aqueous chemistry in the aquifer changes as a result of treated sewage effluent mixing with groundwater. Molybdate adsorption decreased as pH, ionic strength, and the concentration of competing anions increased. A diffuse-layer surface complexation model was used to simulate adsorption of MoO42−, phosphate (PO43−), and sulfate (SO42−) on aquifer sediment. Equilibrium constants for the model were calculated by calibration to data from batch experiments. The model was then used in a one-dimensional solute transport program to successfully simulate initial breakthrough of MoO42− from column experiments. A shortcoming of the solute transport program was the inability to account for kinetics of physical and chemical processes. This resulted in a failure of the model to predict the slow rate of desorption of MoO42− from the columns. The mobility of MoO42− ncreased with ionic strength and with the formation of aqueous complexes with calcium, magnesium, and sodium. Failure to account for MoO42− speciation and ionic strength in the model resulted in overpredicting MoO42− adsorption. Qualitatively, the laboratory data predicted the observed behavior of MoO42− in the aquifer, where retardation of MoO42− was greatest in uncontaminated roundwater having low pH, low ionic strength, and low concentrations of PO43− and SO42−.

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.

Chemical modeling for precipitation from hypersaline hydrofracturing brines.

PubMed

Zermeno-Motante, Maria I; Nieto-Delgado, Cesar; Cannon, Fred S; Cash, Colin C; Wunz, Christopher C

2016-10-15

Hypersaline hydrofracturing brines host very high salt concentrations, as high as 120,000-330,000 mg/L total dissolved solids (TDS), corresponding to ionic strengths of 2.1-5.7 mol/kg. This is 4-10 times higher than for ocean water. At such high ionic strengths, the conventional equations for computing activity coefficients no longer apply; and the complex ion-interactive Pitzer model must be invoked. The authors herein have used the Pitzer-based PHREEQC computer program to compute the appropriate activity coefficients when forming such precipitates as BaSO4, CaSO4, MgSO4, SrSO4, CaCO3, SrCO3, and BaCO3 in hydrofracturing waters. The divalent cation activity coefficients (γM) were computed in the 0.1 to 0.2 range at 2.1 mol/kg ionic strength, then by 5.7 mol/kg ionic strength, they rose to 0.2 for Ba(2+), 0.6 for Sr(2+), 0.8 for Ca(2+), and 2.1 for Mg(2+). Concurrently, the [Formula: see text] was 0.02-0.03; and [Formula: see text] was 0.01-0.02. While employing these Pitzer-derived activity coefficients, the authors then used the PHREEQC model to characterize precipitation of several of these sulfates and carbonates from actual hydrofracturing waters. Modeled precipitation matched quite well with actual laboratory experiments and full-scale operations. Also, the authors found that SrSO4 effectively co-precipitated radium from hydrofracturing brines, as discerned when monitoring (228)Ra and other beta-emitting species via liquid scintillation; and also when monitoring gamma emissions from (226)Ra. Copyright © 2016 Elsevier Ltd. All rights reserved.

Self-assembled vertically aligned Au nanorod arrays for surface-enhanced Raman scattering (SERS) detection of Cannabinol.

PubMed

Milliken, Sarah; Fraser, Jeff; Poirier, Shawn; Hulse, John; Tay, Li-Lin

2018-05-05

Self-assembled multi-layered vertically aligned gold nanorod (AuNR) arrays have been fabricated by a simple preparation process that requires a balance between the particle concentration and the ionic strength of the solvent. An experimentally determined critical AuNR concentration of 2.0nM and 50mM NaCl produces well-ordered vertically aligned hexagonally close-packed AuNR arrays. We demonstrate surface treatment via UV Ozone cleaning of such samples to allow introduction of analyte molecules (benzenethiol and cannabinol) for effective surface enhanced Raman scattering detection. This is the first demonstration of the SERS analysis of cannabinol. This approach demonstrates a cost-effective, high-yield and simple fabrication route to SERS sensors with application in the screening for the cannabinoids. Copyright © 2018. Published by Elsevier B.V.

Kinetic deuterium isotope effects in glucocorticoid receptor activation

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

Aranyi, P.

1984-01-01

Activation and deactivation of the chick thymus glucocorticoid receptor protein was studied in ordinary and heavy water by DNA-cellulose binding of the tritiated triamcinolone acetonide-receptor complex. Activation was significantly slower in heavy water if it was promoted by incubation at elevated temperature in buffers of low ionic strength. In the presence of 300 mM KC1 or after separation from the low molecular weight cytosol constituents, the complex was activated at the same rate in both solvents. Deactivation (time dependent loss of DNA-binding capacity) was much faster in ordinary than in heavy water regardless of gel filtration or the presence ofmore » KC1. A model of receptor activation-deactivation was constructed on the basis of these data that accounts for the observed kinetic deuterium isotope effects and reveals some submolecular details of the process.« less

Pickering emulsions stabilized by whey protein nanoparticles prepared by thermal cross-linking.

PubMed

Wu, Jiande; Shi, Mengxuan; Li, Wei; Zhao, Luhai; Wang, Ze; Yan, Xinzhong; Norde, Willem; Li, Yuan

2015-03-01

A Pickering (o/w) emulsion was formed and stabilized by whey protein isolate nanoparticles (WPI NPs). Those WPI NPs were prepared by thermal cross-linking of denatured WPI proteins within w/o emulsion droplets at 80°C for 15 min. During heating of w/o emulsions containing 10% (w/v) WPI proteins in the water phase, the emulsions displayed turbid-transparent-turbid phase transitions, which is ascribed to the change in the size of the protein-containing water droplets caused by thermal cross-linking between denatured protein molecules. The transparent stage indicated the formation of WPI NPs. WPI NPs of different sizes were obtained by varying the mixing speed. WPI NPs of 200-500 nm were selected to prepare o/w Pickering emulsions because of their good stability against coalescence. By Confocal Laser Scanning Microscopy, it was observed that WPI NPs were closely packed and distributed at the surface of the emulsion droplets. By measuring water contact angles of WPI NPs films, it was found that under most conditions WPI NPs present good partial wetting properties, but that at the isoelectric point (pI) and high ionic strength the particles become more hydrophobic, resulting in less stable Pickering emulsion. Thus, at pH above and below the pI of WPI NPs and low to moderate ionic strengths (1-10 mM), and with a WPI NPs concentration of 2% (w/v), a stable Pickering emulsion can be obtained. The results may provide useful information for applications of WPI NPs in environmentally friendly and food grade applications, notably in food, pharmaceutical and cosmetic products. Copyright © 2015 Elsevier B.V. All rights reserved.

Zeta potential orientation dependence of sapphire substrates.

PubMed

Kershner, Ryan J; Bullard, Joseph W; Cima, Michael J

2004-05-11

The zeta potential of planar sapphire substrates for three different crystallographic orientations was measured by a streaming potential technique in the presence of KCl and (CH3)4NCl electrolytes. The streaming potential was measured for large single crystalline C-plane (0001), A-plane (1120), and R-plane (1102) wafers over a full pH range at three or more ionic strengths ranging from 1 to 100 mM. The roughness of the epi-polished wafers was verified using atomic force microscopy to be on the order of atomic scale, and X-ray photoelectron spectroscopy (XPS) was used to ensure that the samples were free of silica and other contaminants. The results reveal a shift in the isoelectric point (iep) of the three samples by as much as two pH units, with the R-plane surface exhibiting the most acidic behavior and the C-plane samples having the highest iep. The iep at all ionic strengths was tightly centered around a single pH for each wafer. These values of iep are substantially different from the range of pH 8-10 consistently reported in the literature for alpha-Al2O3 particles. Particle zeta potential measurements were performed on a model powder using phase analysis light scattering, and the iep was confirmed to occur at pH 8. Modified Auger parameters (MAP) were calculated from XPS spectra of a monolayer of iridium metal deposited on the sapphire by electron beam deposition. A shift in MAP consistent with the observed differences in iep of the surfaces confirms the effect of surface structure on the transfer of charge between the Ir and sapphire, hence accounting for the changes in acidity as a function of crystallographic orientation.

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.

Transport and retention of surfactant- and polymer-stabilized engineered silver nanoparticles in silicate-dominated aquifer material.

PubMed

Adrian, Yorck F; Schneidewind, Uwe; Bradford, Scott A; Simunek, Jirka; Fernandez-Steeger, Tomas M; Azzam, Rafig

2018-05-01

Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca 2+ . The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled. Copyright © 2018 Elsevier Ltd. All rights reserved.

Increasing the Analytical Sensitivity by Oligonucleotides Modified with Para- and Ortho-Twisted Intercalating Nucleic Acids – TINA

PubMed Central

Schneider, Uffe V.; Géci, Imrich; Jøhnk, Nina; Mikkelsen, Nikolaj D.; Pedersen, Erik B.; Lisby, Gorm

2011-01-01

The sensitivity and specificity of clinical diagnostic assays using DNA hybridization techniques are limited by the dissociation of double-stranded DNA (dsDNA) antiparallel duplex helices. This situation can be improved by addition of DNA stabilizing molecules such as nucleic acid intercalators. Here, we report the synthesis of a novel ortho-Twisted Intercalating Nucleic Acid (TINA) amidite utilizing the phosphoramidite approach, and examine the stabilizing effect of ortho- and para-TINA molecules in antiparallel DNA duplex formation. In a thermal stability assay, ortho- and para-TINA molecules increased the melting point (Tm) of Watson-Crick based antiparallel DNA duplexes. The increase in Tm was greatest when the intercalators were placed at the 5′ and 3′ termini (preferable) or, if placed internally, for each half or whole helix turn. Terminally positioned TINA molecules improved analytical sensitivity in a DNA hybridization capture assay targeting the Escherichia coli rrs gene. The corresponding sequence from the Pseudomonas aeruginosa rrs gene was used as cross-reactivity control. At 150 mM ionic strength, analytical sensitivity was improved 27-fold by addition of ortho-TINA molecules and 7-fold by addition of para-TINA molecules (versus the unmodified DNA oligonucleotide), with a 4-fold increase retained at 1 M ionic strength. Both intercalators sustained the discrimination of mismatches in the dsDNA (indicated by ΔTm), unless placed directly adjacent to the mismatch – in which case they partly concealed ΔTm (most pronounced for para-TINA molecules). We anticipate that the presented rules for placement of TINA molecules will be broadly applicable in hybridization capture assays and target amplification systems. PMID:21673988

Heteroaggregation of lipid droplets coated with sodium caseinate and lactoferrin.

PubMed

de Figueiredo Furtado, Guilherme; Michelon, Mariano; de Oliveira, Davi Rocha Bernardes; da Cunha, Rosiane Lopes

2016-11-01

Formation and characterization of droplet heteroaggregates were investigated by mixing two emulsions previously stabilized by proteins oppositely charged. Emulsions were composed of 5vol.% of sunflower oil and 95vol.% of sodium caseinate or lactoferrin aqueous dispersions. They were produced using ultrasound with fixed power (300W) and sonication time (6min). Different volume ratios (0-100%) of sodium caseinate-stabilized emulsion (droplet diameter around 1.75μm) to lactoferrin-stabilized emulsion (droplet diameter around 1.55μm) were mixed under conditions that both proteins showed opposite charges (pH7). Influence of ionic strength (0-400mM NaCl) on the heteroaggregates stability was also evaluated. Creaming stability, zeta potential, microstructure, mean particle diameter and rheological properties of the heteroaggregates were measured. These properties depended on the volume ratio (0-100%) of sodium caseinate to lactoferrin-stabilized emulsion (C:L) and the ionic strength. In the absence of salt, different zeta potential values were obtained, rheological properties (viscosity and elastic moduli) were improved and the largest heteroaggregates were formed at higher content of lactoferrin-stabilized emulsion (60-80%). The system containing 40 and 60vol.% of sodium caseinate and lactoferrin stabilized emulsion, respectively, presented good stability against phase separation besides showing enhanced rheological and size properties due to extensive droplets aggregation. Phase separation was observed only in the absence of sodium caseinate, demonstrating the higher susceptibility of lactoferrin to NaCl. The heteroaggregates produced may be useful functional agents for texture modification and controlled release since different rheological properties and sizes can be achieved depending on protein concentrations. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hydraulic pressures generated in magnetic ionic liquids by paramagnetic fluid/air interfaces inside of uniform tangential magnetic fields.

PubMed

Scovazzo, Paul; Portugal, Carla A M; Rosatella, Andreia A; Afonso, Carlos A M; Crespo, João G

2014-08-15

Magnetic Ionic Liquid (MILs), novel magnetic molecules that form "pure magnetic liquids," will follow the Ferrohydrodynamic Bernoulli Relationship. Based on recent literature, the modeling of this fluid system is an open issue and potentially controversial. We imposed uniform magnetic fields parallel to MIL/air interfaces where the capillary forces were negligible, the Quincke Problem. The size and location of the bulk fluid as well as the size and location of the fluid/air interface inside of the magnetic field were varied. MIL properties varied included the density, magnetic susceptibility, chemical structure, and magnetic element. Uniform tangential magnetic fields pulled the MILs up counter to gravity. The forces per area were not a function of the volume, the surface area inside of the magnetic field, or the volume displacement. However, the presence of fluid/air interfaces was necessary for the phenomena. The Ferrohydrodynamic Bernoulli Relationship predicted the phenomena with the forces being directly related to the fluid's volumetric magnetic susceptibility and the square of the magnetic field strength. [emim][FeCl4] generated the greatest hydraulic head (64-mm or 910 Pa at 1.627 Tesla). This work could aid in experimental design, when free surfaces are involved, and in the development of MIL applications. Copyright © 2014 Elsevier Inc. All rights reserved.

Insulation of the conduction pathway of muscle transverse tubule calcium channels from the surface charge of bilayer phospholipid

PubMed Central

1986-01-01

Functional calcium channels present in purified skeletal muscle transverse tubules were inserted into planar phospholipid bilayers composed of the neutral lipid phosphatidylethanolamine (PE), the negatively charged lipid phosphatidylserine (PS), and mixtures of both. The lengthening of the mean open time and stabilization of single channel fluctuations under constant holding potentials was accomplished by the use of the agonist Bay K8644. It was found that the barium current carried through the channel saturates as a function of the BaCl2 concentration at a maximum current of 0.6 pA (at a holding potential of 0 mV) and a half-saturation value of 40 mM. Under saturation, the slope conductance of the channel is 20 pS at voltages more negative than -50 mV and 13 pS at a holding potential of 0 mV. At barium concentrations above and below the half-saturation point, the open channel currents were independent of the bilayer mole fraction of PS from XPS = 0 (pure PE) to XPS = 1.0 (pure PS). It is shown that in the absence of barium, the calcium channel transports sodium or potassium ions (P Na/PK = 1.4) at saturating rates higher than those for barium alone. The sodium conductance in pure PE bilayers saturates as a function of NaCl concentration, following a curve that can be described as a rectangular hyperbola with a half-saturation value of 200 mM and a maximum conductance of 68 pS (slope conductance at a holding potential of 0 mV). In pure PS bilayers, the sodium conductance is about twice that measured in PE at concentrations below 100 mM NaCl. The maximum channel conductance at high ionic strength is unaffected by the lipid charge. This effect at low ionic strength was analyzed according to J. Bell and C. Miller (1984. Biophysical Journal. 45:279- 287) and interpreted as if the conduction pathway of the calcium channel were separated from the bilayer lipid by approximately 20 A. This distance thereby effectively insulates the ion entry to the channel from the bulk of the bilayer lipid surface charge. Current vs. voltage curves measured in NaCl in pure PE and pure PS show that similarly small surface charge effects are present in both inward and outward currents. This suggests that the same conduction insulation is present at both ends of the calcium channel. PMID:2425043

Molecular crowders and cosolutes promote folding cooperativity of RNA under physiological ionic conditions

PubMed Central

Strulson, Christopher A.; Boyer, Joshua A.; Whitman, Elisabeth E.; Bevilacqua, Philip C.

2014-01-01

Folding mechanisms of functional RNAs under idealized in vitro conditions of dilute solution and high ionic strength have been well studied. Comparatively little is known, however, about mechanisms for folding of RNA in vivo where Mg2+ ion concentrations are low, K+ concentrations are modest, and concentrations of macromolecular crowders and low-molecular-weight cosolutes are high. Herein, we apply a combination of biophysical and structure mapping techniques to tRNA to elucidate thermodynamic and functional principles that govern RNA folding under in vivo–like conditions. We show by thermal denaturation and SHAPE studies that tRNA folding cooperativity increases in physiologically low concentrations of Mg2+ (0.5–2 mM) and K+ (140 mM) if the solution is supplemented with physiological amounts (∼20%) of a water-soluble neutral macromolecular crowding agent such as PEG or dextran. Low-molecular-weight cosolutes show varying effects on tRNA folding cooperativity, increasing or decreasing it based on the identity of the cosolute. For those additives that increase folding cooperativity, the gain is manifested in sharpened two-state-like folding transitions for full-length tRNA over its secondary structural elements. Temperature-dependent SHAPE experiments in the absence and presence of crowders and cosolutes reveal extent of cooperative folding of tRNA on a nucleotide basis and are consistent with the melting studies. Mechanistically, crowding agents appear to promote cooperativity by stabilizing tertiary structure, while those low molecular cosolutes that promote cooperativity stabilize tertiary structure and/or destabilize secondary structure. Cooperative folding of functional RNA under physiological-like conditions parallels the behavior of many proteins and has implications for cellular RNA folding kinetics and evolution. PMID:24442612

[The effect of core veneer thickness ratio on the flexural strength of diatomite-based dental ceramic].

PubMed

Jiang, Jie; Zhang, Xin; Gao, Mei-qin; Zhang, Fei-min; Lu, Xiao-li

2015-06-01

To evaluate the effect of different core veneer thickness ratios on the flexural strength and failure mode of bilayered diatomite-based dental ceramics. Diatomite-based dental ceramics blocks (16 mm×5.4 mm×1 mm) were sintered with different thickness of veneer porcelains: 0 mm (group A), 0.6 mm (group B), 0.8 mm (group C) and 1.0 mm (group D). Flexural strength was detected and scanning electron microscope was used to observe the interface microstructure. Statistical analysis was performed using SPSS 17.0 software package. With the increase of the thickness of the veneer porcelain, flexural strength of group C showed highest flexural strength up to (277.24±5.47) MPa. Different core veneer thickness ratios can significantly influence the flexural strength of bilayered diatomite-based dental ceramics. Supported by Science and Technology Projects of Nantong City (HS2013010).

Quartz dissolution. I - Negative crystal experiments and a rate law. II - Theory of rough and smooth surfaces

NASA Technical Reports Server (NTRS)

Gratz, Andrew J.; Bird, Peter

1993-01-01

The range of the measured quartz dissolution rates, as a function of temperature and pOH, extent of saturation, and ionic strength, is extended to cover a wider range of solution chemistries, using the negative crystal methodology of Gratz et al. (1990) to measure the dissolution rate. A simple rate law describing the quartz dissolution kinetics above the point of zero charge of quartz is derived for ionic strengths above 0.003 m. Measurements were performed on some defective crystals, and the mathematics of step motion was developed for quartz dissolution and was compared with rough-face behavior using two different models.

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.

Solution structure of detergent micelles at conditions relevant to membrane protein crystallization.

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

Littrell, K.; Thiyagarajan, P.; Tiede, D.

1999-07-02

In this study small angle neutron scattering was used to characterize the formation of micelles in aqueous solutions of the detergents DMG and SPC as a function of detergent concentration and ionic strength of the solvent. The effects on the micelle structure of the additives glycerol and PEG, alone as well as in combination typical for actual membrane protein crystallization, were also explored. This research suggests that the micelles are cigar-like in form at the concentrations studied. The size of the micelles was observed to increase with increasing ionic strength but decrease with the addition of glycerol or PEG.

Characterization of cross-linked cellulosic ion-exchange adsorbents: 2. Protein sorption and transport.

PubMed

Angelo, James M; Cvetkovic, Aleksandar; Gantier, Rene; Lenhoff, Abraham M

2016-03-18

Adsorption behavior in the HyperCel family of cellulosic ion-exchange materials (Pall Corporation) was characterized using methods to assess, quantitatively and qualitatively, the dynamics of protein uptake as well as static adsorption as a function of ionic strength and protein concentration using several model proteins. The three exchangers studied all presented relatively high adsorptive capacities under low ionic strength conditions, comparable to commercially available resins containing polymer functionalization aimed at increasing that particular characteristic. The strong cation- and anion-exchange moieties showed higher sensitivity to increasing salt concentrations, but protein affinity on the salt-tolerant STAR AX HyperCel exchanger remained strong at ionic strengths normally used in downstream processing to elute material fully during ion-exchange chromatography. Very high uptake rates were observed in both batch kinetics experiments and time-series confocal laser scanning microscopy, suggesting low intraparticle transport resistances relative to external film resistance, even at higher bulk protein concentrations where the opposite is typically observed. Electron microscopy imaging of protein adsorbed phases provided additional insight into particle structure that could not be resolved in previous work on the bare resins. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

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.

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.

New recommendations for measuring collagen solubility.

PubMed

Latorre, María E; Lifschitz, Adrian L; Purslow, Peter P

2016-08-01

The heat-solubility of intramuscular collagen is usually conducted in 1/4 Ringer's solution at pH7.4, despite this ionic strength and pH being inappropriate for post-rigor meat. The current work studied the percentage of soluble collagen and hydrothermal isometric tension characteristics of perimysial strips on bovine semitendinosus muscles in either 1/4 Ringer's solution, distilled water, PBS, or a solution of the same salt concentration as 1/4 Ringer's but at pH5.6. Values of % soluble collagen were lower at pH7.4 than 5.6. Increasing ionic strength reduced % soluble collagen. The maximum perimysial isometric tension was independent of the bathing medium, but the percent relaxation was higher at pH7.4 than at pH5.6, and increased with ionic strength of the media. It is recommended that future measurements of collagen solubility and tests on connective tissue components of post-rigor meat should be carried out in a solution of concentrations NaCl and KCl equivalent to those in 1/4 Ringer's, but at pH5.6, a pH relevant to post-rigor meat. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of natural organic matter on transport and retention of polymer coated silver nanoparticles in porous media.

PubMed

Yang, Xinyao; Lin, Shihong; Wiesner, Mark R

2014-01-15

Interactions between organic matter (OM) and engineered polymer coatings as they affect the retention of polyvinylpyrrolidone (PVP) polymer-coated silver nanoparticles (AgNPs) were studied. Two distinct types of OM-cysteine representing low molecular weight multivalent functional groups, and Suwannee River Humic Acid (HA) representing high molecular weight polymers, were investigated with respect to their effects on particle stability in aggregation and deposition. Aggregation of the PVP coated AgNPs (PVP-AgNPs) was enhanced by cysteine addition at high ionic strengths, which was attributed to cysteine binding to the AgNPs and replacing the otherwise steric stabilizing agent PVP. In contrast the addition of HA did not increase aggregation rates and decreased PVP-AgNP deposition to the silica porous medium, consistent with enhanced electrosteric stabilization by the HA. Although cysteine also reduced deposition in the porous medium, the mechanisms of reduced deposition appear to be enhanced electric double layer (EDL) interaction at low ionic strengths. At higher ionic strengths, aggregation was favored leading to lower deposition due to smaller diffusion coefficients and single collector efficiencies despite the reduced EDL interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

Fractionation of poly(methacrylic acid) and poly(vinyl pyridine) in aqueous and organic mobile phases by multidetector thermal field-flow fractionation.

PubMed

Greyling, Guilaume; Pasch, Harald

2017-08-25

Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

NASA Astrophysics Data System (ADS)

Bryan, Allison L.; Dong, Shuofei; Wilkes, Elise B.; Wasylenki, Laura E.

2015-05-01

Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Δ66/64Znadsorbed-dissolved ∼ -0.2‰). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Δ66/64Znadsorbed-dissolved was indistinguishable from zero (+0.05 ± 0.08‰). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Δ66/64Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Δ66/64Znadsorbed-dissolved ranged from nearly +3‰ at low surface loading to +0.16‰ at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation that ferromanganese sediments are enriched in heavier isotopes of Zn relative to deep seawater. This represents a step towards building a robust mass balance model for Zn isotopes in the oceans and potentially using Zn isotopes to trace biogeochemical cycling of this important element in the modern and ancient oceans.

A molecular model of proteoglycan-associated electrostatic forces in cartilage mechanics.

PubMed

Buschmann, M D; Grodzinsky, A J

1995-05-01

Measured values of the swelling pressure of charged proteoglycans (PG) in solution (Williams RPW, and Comper WD; Biophysical Chemistry 36:223, 1990) and the ionic strength dependence of the equilibrium modulus of PG-rich articular cartilage (Eisenberg SR, and Grodzinsky AJ; J Orthop Res 3: 148, 1985) are compared to the predictions of two models. Each model is a representation of electrostatic forces arising from charge present on spatially fixed macromolecules and spatially mobile micro-ions. The first is a macroscopic continuum model based on Donnan equilibrium that includes no molecular-level structure and assumes that the electrical potential is spatially invariant within the polyelectrolyte medium (i.e. zero electric field). The second model is based on a microstructural, molecular-level solution of the Poisson-Boltzmann (PB) equation within a unit cell containing a charged glycosaminoglycan (GAG) molecule and its surrounding atmosphere of mobile ions. This latter approach accounts for the space-varying electrical potential and electrical field between the GAG constituents of the PG. In computations involving no adjustable parameters, the PB-cell model agrees with the measured pressure of PG solutions to within experimental error (10%), whereas the ideal Donnan model overestimates the pressure by up to 3-fold. In computations involving one adjustable parameter for each model, the PB-cell model predicts the ionic strength dependence of the equilibrium modulus of articular cartilage. Near physiological ionic strength, the Donnan model overpredicts the modulus data by 2-fold, but the two models coincide for low ionic strengths (C0 < 0.025M) where the spatially invariant Donnan potential is a closer approximation to the PB potential distribution. The PB-cell model result indicates that electrostatic forces between adjacent GAGs predominate in determining the swelling pressure of PG in the concentration range found in articular cartilage (20-80 mg/ml). The PB-cell model is also consistent with data (Eisenberg and Grodzinsky, 1985, Lai WM, Hou JS, and Mow VC; J Biomech Eng 113: 245, 1991) showing that these electrostatic forces account for approximately 1/2 (290kPa) the equilibrium modulus of cartilage at physiological ionic strength while absolute swelling pressures may be as low as approximately 25-100kPa. This important property of electrostatic repulsion between GAGs that are highly charged but spaced a few Debye lengths apart allows cartilage to resist compression (high modulus) without generating excessive intratissue swelling pressures.

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.

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.

Capillary isotachophoresis for the analysis of ionic liquid entities.

PubMed

Markowska, Aleksandra; Stepnowski, Piotr

2010-07-01

Simple, selective and sensitive isotachophoretic methods for the analysis of ionic liquid (IL) compartments were developed in this study. A leading electrolyte containing 10 mM L-histidine + 10 mM histidine hydrochloride and a terminating electrolyte containing 5 mM glutamic acid + 5 mM L-histidine were selected to separate nitrate(V), chlorate(V), hexafluorophosphate, dicyanimide, trifluoromethanesulfonate, phosphate(V) and bis(trifluoromethanesulfonyl)imide in anionic mode. In contrast, seven short-chain alkylimidazolium, alkylpyrrolidinium, alkylpyridinium and non-chromophoric tetraalkylammonium and tetraalkylphosphonium IL cations were separated with 10 mM potassium hydroxide + 10 mM acetic acid as leading electrolyte, and 10 mM beta-alanine + 10 mM acetate as terminating electrolyte. Both methods were optimized and validated with good analytical performance parameters. LOD was about 3-5 microM, and the repeatability lay in the range of 1.06-5.59%. These methods were evaluated for their applicability to the analysis of soil samples and freshwater contaminated with ILs. In light of hitherto the absence of reports on the determination of non-chromophoric IL cations, this study delivers for the first time a universal method enabling analysis of these species. Moreover, as there is still significant lack of methodologies of IL anion analysis, the obtained results offer an interesting alternative in that matter.

Glucose biosensing using glassy carbon electrode modified with polyhydroxy-C60, glucose oxidase and ionic-liquid.

PubMed

Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, BaoLin; Hong, Jun

2014-01-01

Direct electrochemistry of glucose oxidase (GOD) was achieved when an ionic liquid/GOD-Polyhydroxy-C60 functional membrane was confined on a glassy carbon electrode (GCE). The cyclic voltammograms (CVs) of the modified GCE showed a pair of redox peaks with a formal potential (E°') of - 329 ± 2 mV. The heterogeneous electron transfer constant (k(s)) was 1.43 s-1. The modified GCE response to glucose was linear in the range from 0.02 to 2.0 mM. The detection limit was 1 μM. The apparent Michaelis-Menten constant (K(m)(app)) was 1.45 mM.

Experimental Study on the Strength Characteristics and Water Permeability of Hybrid Steel Fibre Reinforced Concrete

PubMed Central

Singh, M. P.; Singh, S. P.; Singh, A. P.

2014-01-01

Results of an investigation conducted to study the effect of fibre hybridization on the strength characteristics such as compressive strength, split tensile strength, and water permeability of steel fibre reinforced concrete (SFRC) are presented. Steel fibres of different lengths, that is, 12.5 mm, 25 mm, and 50 mm, having constant diameter of 0.6 mm, were systematically combined in different mix proportions to obtain mono, binary, and ternary combinations at each of 0.5%, 1.0%, and 1.5% fibre volume fraction. A concrete mix containing no fibres was also cast for reference purpose. A total number of 1440 cube specimens of size 100∗100∗100 mm were tested, 480 each for compressive strength, split tensile strength, and water permeability at 7, 28, 90, and 120 days of curing. It has been observed from the results of this investigation that a fibre combination of 33% 12.5 mm + 33% 25 mm + 33% 50 mm long fibres can be adjudged as the most appropriate combination to be employed in hybrid steel fibre reinforced concrete (HySFRC) for optimum performance in terms of compressive strength, split tensile strength and water permeability requirements taken together. PMID:27379298

Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

NASA Astrophysics Data System (ADS)

Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

2018-04-01

Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

Self-Healing Natural Rubber with Tailorable Mechanical Properties Based on Ionic Supramolecular Hybrid Network.

PubMed

Xu, Chuanhui; Cao, Liming; Huang, Xunhui; Chen, Yukun; Lin, Baofeng; Fu, Lihua

2017-08-30

In most cases, the strength of self-healing supramolecular rubber based on noncovalent bonds is in the order of KPa, which is a challenge for their further applications. Incorporation of conventional fillers can effectively enhance the strength of rubbers, but usually accompanied by a sacrifice of self-healing capability due to that the filler system is independent of the reversible supramolecular network. In the present work, in situ reaction of methacrylic acid (MAA) and excess zinc oxide (ZnO) was realized in natural rubber (NR). Ionic cross-links in NR matrix were obtained by limiting the covalent cross-linking of NR molecules and allowing the in situ polymerization of MAA/ZnO. Because of the natural affinity between Zn 2+ ion-rich domains and ZnO, the residual nano ZnO participated in formation of a reversible ionic supramolecular hybrid network, thus having little obstructions on the reconstruction of ionic cross-links. Meanwhile, the well dispersed residual ZnO could tailor the mechanical properties of NR by changing the MAA/ZnO molar ratios. The present study thus provides a simple method to fabricate a new self-healing NR with tailorable mechanical properties that may have more potential applications.

Maximizing recovery of water-soluble proteins through acetone precipitation.

PubMed

Crowell, Andrew M J; Wall, Mark J; Doucette, Alan A

2013-09-24

Solvent precipitation is commonly used to purify protein samples, as seen with the removal of sodium dodecyl sulfate through acetone precipitation. However, in its current practice, protein loss is believed to be an inevitable consequence of acetone precipitation. We herein provide an in depth characterization of protein recovery through acetone precipitation. In 80% acetone, the precipitation efficiency for six of 10 protein standards was poor (ca. ≤15%). Poor recovery was also observed for proteome extracts, including bacterial and mammalian cells. As shown in this work, increasing the ionic strength of the solution dramatically improves the precipitation efficiency of individual proteins, and proteome mixtures (ca. 80-100% yield). This is obtained by including 1-30 mM NaCl, together with acetone (50-80%) which maximizes protein precipitation efficiency. The amount of salt required to restore the recovery correlates with the amount of protein in the sample, as well as the intrinsic protein charge, and the dielectric strength of the solution. This synergistic approach to protein precipitation in acetone with salt is consistent with a model of ion pairing in organic solvent, and establishes an improved method to recover proteins and proteome mixtures in high yield. Copyright © 2013 Elsevier B.V. All rights reserved.

Transport of viruses through saturated and unsaturated columns packed with sand

USGS Publications Warehouse

Anders, R.; Chrysikopoulos, C.V.

2009-01-01

Laboratory-scale virus transport experiments were conducted in columns packed with sand under saturated and unsaturated conditions. The viruses employed were the male-specific RNA coliphage, MS2, and the Salmonella typhimurium phage, PRD1. The mathematical model developed by Sim and Chrysikopoulos (Water Resour Res 36:173-179, 2000) that accounts for processes responsible for removal of viruses during vertical transport in one-dimensional, unsaturated porous media was used to fit the data collected from the laboratory experiments. The liquid to liquid-solid and liquid to air-liquid interface mass transfer rate coefficients were shown to increase for both bacteriophage as saturation levels were reduced. The experimental results indicate that even for unfavorable attachment conditions within a sand column (e.g., phosphate-buffered saline solution; pH = 7.5; ionic strength = 2 mM), saturation levels can affect virus transport through porous media. ?? Springer Science+Business Media B.V. 2008.

Sodium caseinate stabilized zein colloidal particles.

PubMed

Patel, Ashok R; Bouwens, Elisabeth C M; Velikov, Krassimir P

2010-12-08

The present work deals with the preparation and stabilization of zein colloidal particles using sodium caseinate as electrosteric stabilizer. Colloidal particles with well-defined size range (120-150 nm) and negative surface potential (-29 to -47 mV) were obtained using a simple antisolvent precipitation method. Due to the presence of caseinate, the stabilized colloidal particles showed a shift of isoelectric point (IEP) from 6.0 to around pH 5.0 and thus prevent the aggregation of zein near its native IEP (pH 6.2). The particles also showed good stability to varying ionic strength (15 mM-1.5 M NaCl). Furthermore, stabilized particles retained the property of redispersibility after drying. In vitro protein hydrolysis study confirmed that the presence of caseinate did not alter the digestibility of zein. Such colloidal particles could potentially serve as all-natural delivery systems for bioactive molecules in food, pharmaceutical, and agricultural formulations.

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

Effect of carboxymethyl cellulose and ionic strength on stability of mineral suspensions in potash ore flotation systems.

PubMed

Pawlik, M; Laskowski, J S; Ansari, A

2003-04-15

The adsorption of sodium carboxymethyl cellulose from aqueous solutions varying in ionic strength from that of distilled water to 50% NaCl/KCl brine (about 3.5 mol/dm(3)) onto illite and dolomite has been studied. The purpose of this work was to investigate the solvency effects in the phenomena underlying the potash flotation process that is carried out in saturated brine. Based on viscosity measurements, the adsorption results were analyzed in terms of a simple model of polymer macromolecules in solution. Suspension stability measurements carried out concomitantly with adsorption tests showed the ranges of carboxymethyl cellulose concentration over which the tested suspensions either were aggregated or were restabilized.

Chromatographic Separation, and Characteristics of Nucleic Acids from HeLa Cells

PubMed Central

Philipson, Lennart

1961-01-01

The application of the phenol-duponol method to extraction of nucleic acids from HeLa cells is described. Chromatography of the phenol extract on an esterified bovine serum albumin column with a salt gradient of sodium chloride gives separation of soluble RNA, DNA, and two different high molecular RNA fractions. Ultracentrifugation of the DNA eluted from the column gives a sedimentation coefficient (s 20 o,w) of 38, which agrees with ultracentrifugation data on the phenol extract. The eluted RNA appears polydisperse at low ionic strength, but at high ionic strength and after alcohol precipitation two fractions with the sedimentation coefficients of 16 and 25 to 29, respectively, were obtained. PMID:13735276

Experimental determination of solubilities of di-calcium ethylenediaminetetraacetic acid hydrate [Ca2C10H12N2O8·7H2O(s)] in NaCl and MgCl2 solutions to high ionic strengths and its Pitzer model: Applications to geological disposal of nuclear waste and other low temperature environments

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie; Westfall, Terry

2017-04-01

In this study, solubility measurements on di-calcium ethylenediaminetetraacetic acid [Ca 2C 10H 12N 2O 8(s), abbreviated as Ca 2EDTA(s)] as a function of ionic strength are conducted in NaCl solutions up to I = 5.0 mol•kg –1 and in MgCl 2 solutions up to I = 7.5 mol•kg –1, at room temperature (22.5 ± 0.5oC).

The detection of Rh antigens (D,C,c,E,e) on bloodstains by a micro-elution technique using low ionic strength solution (LISS) and papain-treated red cells.

PubMed

Bargagna, M; Sabelli, M; Giacomelli, C

1982-01-01

Ninety experimental bloodstains, were examined, with the intention of detecting the principal Rh antigens, by using a micro-elution method improved by the use of low ionic strength solution (LISS) and papain-treated red cells. This method makes it possible to employ most commercially produced sera in routine forensic haematology laboratory work. The antigens could regularly be detected in stains of the following ages: D, C and c in stains of at least 6 months, E in stains of at least 4 months, and e in stains of at least 2 months.

Effects of lability of metal complex on free ion measurement using DMT.

PubMed

Weng, Liping; Van Riemsdijk, Willem H; Temminghoff, Erwin J M

2010-04-01

Very low concentrations of free metal ion in natural samples can be measured using the Donnan membrane technique (DMT) based on ion transport kinetics. In this paper, the possible effects of slow dissociation of metal complexes on the interpretation of kinetic DMT are investigated both theoretically and experimentally. The expressions of the lability parameter, Lgrangian , were derived for DMT. Analysis of new experimental studies using synthetic solution containing NTA as the ligand and Cu(2+) ions shows that when the ionic strength is low (

Structure of human thymidylate synthase under low-salt conditions.

PubMed

Lovelace, Leslie L; Minor, Wladek; Lebioda, Lukasz

2005-05-01

Human thymidylate synthase, a target in cancer chemotherapy, was crystallized from PEG 3350 with 30 mM ammonium sulfate (AS) in the crystallization medium. The crystals are isomorphous with the high-salt crystals ( approximately 2.0 M AS) and the structure has been solved and refined (R = 22.6%, R(free) = 24.3%) at 1.8 A resolution. The high- and low-AS-concentration structures are quite similar, with loop 181-197 is in the inactive conformation. Also, residues 95-106 and 129-135 (eukaryotic inserts region) show high mobility as assessed by poor electron density and high values of crystallographic temperature factors (residues 1-25 and 108-129 are disordered in both structures). The high mobility of this region may reflect the situation at physiological ionic strength. Of the four sulfate ions observed bound at 2.0 M AS, only two are present at 30 mM AS. The inactive conformation appears to be stabilized by the side chain of Val3 or a leucine residue from the disordered regions. The low-salt conditions of these crystals should be much more suitable for the study of thymidylate synthase inhibitors, especially those that utilize sulfate-binding sites to stabilize the inactive conformation of loop 181-197.

Anomalous frequency-dependent ionic conductivity of lesion-laden human-brain tissue

NASA Astrophysics Data System (ADS)

Emin, David; Akhtari, Massoud; Fallah, Aria; Vinters, Harry V.; Mathern, Gary W.

2017-10-01

We study the effect of lesions on our four-electrode measurements of the ionic conductivity of (˜1 cm3) samples of human brain excised from patients undergoing pediatric epilepsy surgery. For most (˜94%) samples, the low-frequency ionic conductivity rises upon increasing the applied frequency. We attributed this behavior to the long-range (˜0.4 mm) diffusion of solvated sodium cations before encountering intrinsic impenetrable blockages such as cell membranes, blood vessels, and cell walls. By contrast, the low-frequency ionic conductivity of some (˜6%) brain-tissue samples falls with increasing applied frequency. We attribute this unusual frequency-dependence to the electric-field induced liberation of sodium cations from traps introduced by the unusually severe pathology observed in samples from these patients. Thus, the anomalous frequency-dependence of the ionic conductivity indicates trap-producing brain lesions.

Soft but Powerful Artificial Muscles Based on 3D Graphene-CNT-Ni Heteronanostructures.

PubMed

Kim, Jaehwan; Bae, Seok-Hu; Kotal, Moumita; Stalbaum, Tyler; Kim, Kwang J; Oh, Il-Kwon

2017-08-01

Bioinspired soft ionic actuators, which exhibit large strain and high durability under low input voltages, are regarded as prospective candidates for future soft electronics. However, due to the intrinsic drawback of weak blocking force, the feasible applications of soft ionic actuators are limited until now. An electroactive artificial muscle electro-chemomechanically reinforced with 3D graphene-carbon nanotube-nickel heteronanostructures (G-CNT-Ni) to improve blocking force and bending deformation of the ionic actuators is demonstrated. The G-CNT-Ni heteronanostructure, which provides an electrically conductive 3D network and sufficient contact area with mobile ions in the polymer electrolyte, is embedded as a nanofiller in both ionic polymer and conductive electrodes of the ionic actuators. An ionic exchangeable composite membrane consisting of Nafion, G-CNT-Ni and ionic liquid (IL) shows improved tensile modulus and strength of up to 166% and 98%, respectively, and increased ionic conductivity of 0.254 S m -1 . The ionic actuator exhibits enhanced actuation performances including three times larger bending deformation, 2.37 times higher blocking force, and 4 h durability. The electroactive artificial muscle electro-chemomechanically reinforced with 3D G-CNT-Ni heteronanostructures offers improvements over current soft ionic actuator technologies and can advance the practical engineering applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid and deep eutectic solvent-activated CelA2 variants generated by directed evolution.

PubMed

Lehmann, Christian; Bocola, Marco; Streit, Wolfgang R; Martinez, Ronny; Schwaneberg, Ulrich

2014-06-01

Chemoenzymatic cellulose degradation is one of the key steps for the production of biomass-based fuels under mild conditions. An effective cellulose degradation process requires diverse physico-chemical dissolution of the biomass prior to enzymatic degradation. In recent years, "green" solvents, such as ionic liquids and, more recently, deep eutectic liquids, have been proposed as suitable alternatives for biomass dissolution by homogenous catalysis. In this manuscript, a directed evolution campaign of an ionic liquid tolerant β-1,4-endoglucanase (CelA2) was performed in order to increase its performance in the presence of choline chloride/glycerol (ChCl:Gly) or 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), as a first step to identify residues which govern ionic strength resistance and obtaining insights for employing cellulases on the long run in homogenous catalysis of lignocellulose degradation. After mutant library screening, variant M4 (His288Phe, Ser300Arg) was identified, showing a dramatically reduced activity in potassium phosphate buffer and an increased activity in the presence of ChCl:Gly or [BMIM]Cl. Further characterization showed that the CelA2 variant M4 is activated in the presence of these solvents, representing a first report of an engineered enzyme with an ionic strength activity switch. Structural analysis revealed that Arg300 could be a key residue for the ionic strength activation through a salt bridge with the neighboring Asp287. Experimental and computational results suggest that the salt bridge Asp287-Arg300 generates a nearly inactive CelA2 variant and activity is regained when ChCl:Gly or [BMIM]Cl are supplemented (~5-fold increase from 0.64 to 3.37 μM 4-MU/h with the addition ChCl:Gly and ~23-fold increase from 3.84 to 89.21 μM 4-pNP/h with the addition of [BMIM]Cl). Molecular dynamic simulations further suggest that the salt bridge between Asp287 and Arg300 in variant M4 (His288Phe, Ser300Arg) modulates the observed salt activation.

Molecular Dynamics Simulations of the Interfacial Region between Boehmite and Gibbsite Basal Surfaces and High Ionic Strength Aqueous Solutions

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

Shen, Zhizhang; Ilton, Eugene S.; Prange, Micah P.

Classical molecular dynamics (MD) simulations were used to study the interactions of up to 2 M NaCl and NaNO3 aqueous solutions with the presumed inert boehmite (010) and gibbsite (001) surfaces. The force field parameters used in these simulations were validated against density functional theory calculations of Na+ and Cl- hydrated complexes adsorbed at the boehmite (010) surface. In all the classical MD simulations and regardless of the ionic strength or the nature of the anion, Na+ ions were found to preferably form inner-sphere complexes over outer-sphere complexes at the aluminum (oxy)hydroxide surfaces, adsorbing closer to the surface than bothmore » water molecules and anions. In contrast, Cl- ions were distributed almost equally between inner- and outer-sphere positions. The resulting asymmetry in adsorption strengths offers molecular-scale evidence for the observed isoelectric point (IEP) shift to higher pH at high ionic strength for aluminum (oxy)hydroxides. As such, the MD simulations also provided clear evidence against the assumption that the basal surfaces of boehmite and gibbsite are inert to background electrolytes. Finally, the MD simulations indicated that, although the adsorption behavior of Na+ in NaNO3 and NaCl solutions was similar, the different affinities of NO3- and Cl- for the aluminum (oxy)hydroxide surfaces might have macroscopic consequences, such as difference in the sensitivity of the IEP to the electrolyte concentration.« less

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

Buchko, Garry W.; Lin, Genyao; Tarasevich, Barbara J.

Amelogenesis imperfecta describes a group of inherited disorders that results in defective tooth enamel. Two disorders associated with human amelogenesis imperfecta are the point mutations T21?I or P40?T in amelogenin, the dominant protein present during the early stages of enamel biomineralization. The biophysical properties of wildtype murine amelogenin (M180) and two proteins containing the equivalent mutations in murine amelogenin, T21?I (M180-I) and P41?T (M180-T), were probed by NMR spectroscopy. At low protein concentration (0.1 mM), M180, M180-I, and M180-T are predomi- nately monomeric at pH 3.0 in 2% acetic acid and neither mutation produces a major structural change. Chemical shiftmore » perturbation studies as a function of protein (0.1–1.8 mM) or NaCl (0–400 mM) concentra- tions show that the mutations affect the self-association properties by causing self-assembly at lower protein or salt concentrations, relative to wildtype amelogenin, with the largest effect observed for M180-I. Under both conditions, the premature self-assembly is initiated near the N-terminus, providing further evidence for the importance of this region in the self-assembly process. The self-association of M180-I and M180-T at lower protein concentrations and lower ionic strengths than wildtype M180 may account for the clinical phenotypes of these mutations, defective enamel formation.« less

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.

Dielectric spectroscopy of single human erythrocytes at physiological ionic strength: dispersion of the cytoplasm.

PubMed Central

Gimsa, J; Müller, T; Schnelle, T; Fuhr, G

1996-01-01

Usually dielectrophoretic and electrorotation measurements are carried out at low ionic strength to reduce electrolysis and heat production. Such problems are minimized in microelectrode chambers. In a planar ultramicroelectrode chamber fabricated by semiconductor technology, we were able to measure the dielectric properties of human red blood cells in the frequency range from 2 kHz to 200 MHz up to physiological ion concentrations. At low ionic strength, red cells exhibit a typical electrorotation spectrum with an antifield rotation peak at low frequencies and a cofield rotation peak at higher ones. With increasing medium conductivity, both electrorotational peaks shift toward higher frequencies. The cofield peak becomes antifield for conductivities higher than 0.5 S/m. Because the polarizability of the external medium at these ionic strengths becomes similar to that of the cytoplasm, properties can be measured more sensitively. The critical dielectrophoretic frequencies were also determined. From our measurements, in the wide conductivity range from 2 mS/m to 1.5 S/m we propose a single-shell erythrocyte model. This pictures the cell as an oblate spheroid with a long semiaxis of 3.3 microns and an axial ratio of 1:2. Its membrane exhibits a capacitance of 0.997 x 10(-2) F/m2 and a specific conductance of 480 S/m2. The cytoplasmic parameters, a conductivity of 0.4 S/m at a dielectric constant of 212, disperse around 15 MHz to become 0.535 S/m and 50, respectively. We attribute this cytoplasmic dispersion to hemoglobin and cytoplasmic ion properties. In electrorotation measurements at about 60 MHz, an unexpectedly low rotation speed was observed. Around 180 MHz, the speed increased dramatically. By analysis of the electric chamber circuit properties, we were able to show that these effects are not due to cell polarization but are instead caused by a dramatic increase in the chamber field strength around 180 MHz. Although the chamber exhibits a resonance around 180 MHz, the harmonic content of the square-topped driving signals generates distortions of electrorotational spectra at far lower frequencies. Possible technological applications of chamber resonances are mentioned. Images FIGURE 1 PMID:8804632

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.

Effects of ionic strength on the antimicrobial photodynamic efficiency of methylene blue.

PubMed

Núñez, Silvia Cristina; Garcez, Aguinaldo Silva; Kato, Ilka Tiemy; Yoshimura, Tania Mateus; Gomes, Laércio; Baptista, Maurício Silva; Ribeiro, Martha Simões

2014-03-01

Antimicrobial photodynamic therapy (APDT) may become a useful clinical tool to treat microbial infections, and methylene blue (MB) is a well-known photosensitizer constantly employed in APDT studies, and although MB presents good efficiency in antimicrobial studies, some of the MB photochemical characteristics still have to be evaluated in terms of APDT. This work aimed to evaluate the role of MB solvent's ionic strength regarding dimerization, photochemistry, and photodynamic antimicrobial efficiency. Microbiological survival fraction assays on Escherichia coli were employed to verify the solution's influence on MB antimicrobial activity. MB was evaluated in deionized water and 0.9% saline solution through optical absorption spectroscopy; the solutions were also analysed via dissolved oxygen availability and reactive oxygen species (ROS) production. Our results show that bacterial reduction was increased in deionized water. Also we demonstrated that saline solution presents less oxygen availability than water, the dimer/monomer ratio for MB in saline is smaller than in water and MB presented a higher production of ROS in water than in 0.9% saline. Together, our results indicate the importance of the ionic strength in the photodynamic effectiveness and point out that this variable must be taken into account to design antimicrobial studies and to evaluate similar studies that might present conflicting results.

Effect of inorganic regenerant properties on pharmaceutical adsorption and desorption performance on polymer anion exchange resin.

PubMed

Zheng, Shaokui; Li, Xiaofeng; Zhang, Xueyu; Wang, Wei; Yuan, Shengliu

2017-09-01

This study investigated the potential effect of four frequently used inorganic regenerant properties (i.e., ionic strength, cation type, anion type, and regeneration solution volume) on the desorption and adsorption performance of 14 pharmaceuticals, belonging to 12 therapeutic classes with different predominant chemical forms and hydrophobicities, using polymeric anion exchange resin (AER)-packed fixed-bed column tests. After preconditioning with NaCl, NaOH, or saline-alkaline (SA) solutions, all resulting mobile counterion types of AERs effectively adsorbed all 14 pharmaceuticals, where the preferential magnitude of OH - -type = Cl -  + OH - -type > Cl - -type. During regeneration, ionic strength (1 M versus 3 M NaCl) had no significant influence on desorption performance for any of the 14 pharmaceuticals, while no regenerant cation (HCl versus NaCl) or anion type (NaCl versus NaOH and SA) achieved higher desorption efficiencies for all pharmaceuticals. A volumetric increase in 1 M or 3 M NaCl solutions significantly improved the desorption efficiencies of most pharmaceuticals, irrespective of ionic strength. The results indicate that regeneration protocols, including regenerant cation type, anion type and volume, should be optimized to improve pharmaceutical removal by AERs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Linear and circular dichroism characterization of thionine binding mode with DNA polynucleotides

NASA Astrophysics Data System (ADS)

Tuite, Eimer Mary; Nordén, Bengt

2018-01-01

The binding mode of thionine (3,7-diamino-5-phenothiazinium) with alternating and non-alternating DNA polynucleotides at low binding ratios was conclusively determined using linear and circular dichroism spectroscopies. The binding to [poly(dG-dC)]2 and poly(dG)·poly(dC) was purely intercalative and was insensitive to ionic strength. Intercalative binding to [poly(dA-dT)]2 is observed at low ionic strength, but a shift of some dye to an non-intercalative mode is observed as the background salt concentration increases. With poly(dA)·poly(dT), intercalative binding is unfavourable, although some dye molecules may intercalate at low ionic strength, and groove binding is strongly promoted with increasing concentration of background salt. However, stacking with bases is observed with single-stranded poly(dA) and with triplex poly(dT)*poly(dA)·poly(dT) which suggests that the unusual structure of poly(dA)·poly(dT) precludes intercalation. Thionine behaves similarly to the related dye methylene blue, and small differences may be attributed either to the ability of thionine to form H-bonds that stabilize intercalation or to its improved stacking interactions in the basepair pocket on steric grounds.

Removal forces and adhesion properties of Saccharomyces cerevisiae on glass substrates probed by optical tweezer

NASA Astrophysics Data System (ADS)

Castelain, Mickaël; Pignon, Frédéric; Piau, Jean-Michel; Magnin, Albert; Mercier-Bonin, Muriel; Schmitz, Philippe

2007-10-01

In agroindustry, the hygiene of solid surfaces is of primary importance in order to ensure that products are safe for consumers. To improve safety, one of the major ways consists in identifying and understanding the mechanisms of microbial cell adhesion to nonporous solid surfaces or filtration membranes. In this paper we investigate the adhesion of the yeast cell Saccharomyces cerevisiae (about 5μm in diameter) to a model solid surface, using well-defined hydrophilic glass substrates. An optical tweezer device developed by Piau [J. Non-Newtonian Fluid Mech. 144, 1 (2007)] was applied to yeast cells in contact with well-characterized glass surfaces. Two planes of observation were used to obtain quantitative measurements of removal forces and to characterize the corresponding mechanisms at a micrometer length scale. The results highlight various adhesion mechanisms, depending on the ionic strength, contact time, and type of yeast. The study has allowed to show a considerable increase of adhering cells with the ionic strength and has provided a quantitative measurement of the detachment forces of cultured yeast cells. Force levels are found to grow with ionic strength and differences in mobility are highlighted. The results clearly underline that a microrheological approach is essential for analyzing the adhesion mechanisms of biological systems at the relevant local scales.

Self-Healable Electrical Insulation for High Voltage Applications

NASA Technical Reports Server (NTRS)

Williams, Tiffany S.

2017-01-01

Polymeric aircraft electrical insulation normally degrades by partial discharge with increasing voltage, which causes excessive localized Joule heating in the material and ultimately leads to dielectric failure of the insulator through thermal breakdown. Developing self-healing insulation could be a viable option to mitigate permanent mechanical degradation, thus increasing the longevity of the insulation. Instead of relying on catalyst and monomer-filled microcapsules to crack, flow, and cure at the damaged sites described in well-published mechanisms, establishment of ionic crosslinks could allow for multiple healing events to occur with the added benefit of achieving full recovery strength under certain thermal environments. This could be possible if the operating temperature of the insulator is the same as or close to the temperature where ionic crosslinks are formed. Surlyn, a commercial material with ionic crosslinks, was investigated as a candidate self-healing insulator based off prior demonstrations of self-healing behavior. Thin films of varying thicknesses were investigated and the effects of thickness on the dielectric strength were evaluated and compared to representative polymer insulators. The effects of thermal conditioning on the recovery strength and healing were observed as a function of time following dielectric breakdown. Moisture absorption was also studied to determine if moisture absorption rates in Surlyn were lower than that of common polyimides.

Colloid-Mediated Transport of Pharmaceutical and Personal Care Products through Porous Media

NASA Astrophysics Data System (ADS)

Xing, Yingna; Chen, Xijuan; Chen, Xin; Zhuang, Jie

2016-10-01

Pharmaceutical and personal care products (PPCPs) enter soils through reclaimed water irrigation and biosolid land applications. Colloids, such as clays, that are present in soil may interact with PPCPs and thus affect their fate and transport in the subsurface environment. This study addresses the influence of soil colloids on the sorption and transport behaviors of PPCPs through laboratory column experiments. Results show that the affinities of PPCPs for colloids vary with their molecular chemistry and solution ionic strength. The presence of colloids promotes the breakthrough of ciprofloxacin (over 90% sorbed on colloids) from ~4% to 30-40%, and the colloid-facilitated effect was larger at lower ionic strength (e.g., 2 mM). In comparison, the net effect of colloids on the transport of tetracycline (~50% sorbed on colloids) could be facilitation or inhibition, depending on solution chemistry. This dual effect of colloids is primarily due to the opposite response of migration of dissolved and colloid-bound tetracycline to the change in solution ionic strength. Colloids could also facilitate the transport of ibuprofen (~10% sorbed on colloids) by ~50% due likely to exclusion of dispersion pathways by colloid straining. This study suggests that colloids are significant carriers or transport promoters of some PPCPs in the subsurface environment and could affect their off-site environmental risks.

Experimental determination of lead carbonate solubility at high ionic strengths: A Pitzer model description

DOE PAGES

Xiong, Yongliang

2015-05-06

In this article, solubility measurements of lead carbonate, PbCO 3(cr), cerussite, as a function of total ionic strengths are conducted in the mixtures of NaCl and NaHCO 3 up to I = 1.2 mol•kg –1 and in the mixtures of NaHCO 3 and Na 2CO 3 up to I = 5.2 mol•kg –1, at room temperature (22.5 ± 0.5 °C). The solubility constant (log K sp) for cerussite, PbCO 3(cr) = Pb 2+ + CO 3 2- was determined as –13.76 ± 0.15 (2σ) with a set of Pitzer parameters describing the specific interactions of PbCO 3(aq), Pb(CO 3) 2more » 2-, and Pb(CO 3)Cl – with the bulk-supporting electrolytes, based on the Pitzer model. The model developed in this work can reproduce the experimental results including model-independent solubility values from the literature over a wide range of ionic strengths with satisfactory accuracy. The model is expected to find applications in numerous fields, including the accurate description of chemical behavior of lead in geological repositories, the modeling of formation of oxidized Pb–Zn ore deposits, and the environmental remediation of lead contamination.« less

Colloid-Mediated Transport of Pharmaceutical and Personal Care Products through Porous Media

PubMed Central

Xing, Yingna; Chen, Xijuan; Chen, Xin; Zhuang, Jie

2016-01-01

Pharmaceutical and personal care products (PPCPs) enter soils through reclaimed water irrigation and biosolid land applications. Colloids, such as clays, that are present in soil may interact with PPCPs and thus affect their fate and transport in the subsurface environment. This study addresses the influence of soil colloids on the sorption and transport behaviors of PPCPs through laboratory column experiments. Results show that the affinities of PPCPs for colloids vary with their molecular chemistry and solution ionic strength. The presence of colloids promotes the breakthrough of ciprofloxacin (over 90% sorbed on colloids) from ~4% to 30–40%, and the colloid-facilitated effect was larger at lower ionic strength (e.g., 2 mM). In comparison, the net effect of colloids on the transport of tetracycline (~50% sorbed on colloids) could be facilitation or inhibition, depending on solution chemistry. This dual effect of colloids is primarily due to the opposite response of migration of dissolved and colloid-bound tetracycline to the change in solution ionic strength. Colloids could also facilitate the transport of ibuprofen (~10% sorbed on colloids) by ~50% due likely to exclusion of dispersion pathways by colloid straining. This study suggests that colloids are significant carriers or transport promoters of some PPCPs in the subsurface environment and could affect their off-site environmental risks. PMID:27734948

Strength properties of interlocking compressed earth brick units

NASA Astrophysics Data System (ADS)

Saari, S.; Bakar, B. H. Abu; Surip, N. A.

2017-10-01

This study presents a laboratory investigation on the properties of interlocking compressed earth brick (ICEB) units. Compressive strength, which is one of the most important properties in masonry structures, is used to determine masonry performance. The compressive strength of the ICEB units was determined by applying a compressive strength test for 340 units from four types of ICEB. To analyze the strength of the ICEB units, each unit was capped by a steel plate at the top and bottom to create a flat surface, and then ICEB was loaded until failure. The average compressive strength of the corresponding ICEB units are as follows: wall brick, 19.15 N/mm2; beam brick, 16.99 N/mm2; column brick, 13.18 N/mm2; and half brick, 11.79 N/mm2. All the ICEB units had compressive strength of over 5 N/mm2, which is the minimum strength for a load-bearing brick. This study proves that ICEB units may be used as load-bearing bricks. The strength of ICEBs is equal to that of other common bricks and blocks that are currently available in the market.

On the influence of hydrated ionic liquids on the dynamical structure of model proteins: a computational study.

PubMed

Haberler, Michael; Steinhauser, Othmar

2011-10-28

The solvation of the protein ubiquitin (PDB entry "1UBQ") in hydrated molecular ionic liquids was studied for varying water content or, equivalently, a diversity of ionic strengths. The cations and anions were 1-ethyl-3-methylimidazolium and trifluoromethanesulfonate, respectively. The protein's shape and stability as well as the solvation structure, the shell dynamics and the shell resolved dielectric properties were investigated by means of molecular dynamics simulations. The respective simulation trajectories covered 200 nanoseconds. Besides the characteristic point already found for the zinc finger motif at the transition from the pure aqueous environment to the ionic solution an even more pronounced state is found where several properties show extremal behaviour (maximum or minimum). This second characteristic point occurs at the transition from the ionic solution to the hydrated ionic melt where water changes its role from a solvent to a co-solvent. Most of the data analysis presented here is based on the Voronoi decomposition of space. This journal is © the Owner Societies 2011

Synthesis and anti-microbial potencies of 1-(2-hydroxyethyl)-3-alkylimidazolium chloride ionic liquids: microbial viabilities at different ionic liquids concentrations.

PubMed

Hossain, M Ismail; El-Harbawi, Mohanad; Alitheen, Noorjahan Banu Mohamed; Noaman, Yousr Abdulhadi; Lévêque, Jean-Marc; Yin, Chun-Yang

2013-01-01

Three 1-(2-hydroxyethyl)-3-alkylimidazolium chloride room temperature ionic liquids (ILs) [2OHimC(n)][Cl]; (n=0, 1, 4) have been synthesized from the appropriate imidazole precursors and characterized by IR and NMR spectroscopies and elemental analysis. Their anti-microbial activities were investigated using the well-diffusion method. The viabilities of Escherichia coli, Aeromonas hydrophila, Listeria monocytogenes and Salmonella enterica as a function of IL concentrations were studied. The minimal inhibitory concentrations (MICs) and EC₅₀ values for the present ILs were within the concentration range from 60 to 125 mM and 23 to 73 mM. The anti-microbial potencies of the present ILs were compared to a standard antibiotic, gentamicin. The finding affords additional perspective on the level of ILs toxicity to aquatic lifeforms and yet, this characteristic can be readily harnessed to detect microbial growth and activity. Copyright © 2012 Elsevier Inc. 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.

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.

Impact of Carrier Fluid Composition on Recovery of Nanoparticles and Proteins in Flow Field Flow Fractionation

PubMed Central

Schachermeyer, Samantha; Ashby, Jonathan; Kwon, MinJung; Zhong, Wenwan

2012-01-01

Flow field flow fractionation (F4) is an invaluable separation tool for large analytes, including nanoparticles and biomolecule complexes. However, sample loss due to analyte-channel membrane interaction limits extensive usage of F4 at present, which could be strongly affected by the carrier fluid composition. This work studied the impacts of carrier fluid (CF) composition on nanoparticle (NP) recovery in F4, with focus on high ionic strength conditions. Successful analysis of NPs in a biomolecules-friendly environment could expand the applicability of F4 to the developing field of nanobiotechnology. Recovery of the unfunctionalized polystyrene NPs of 199-, 102-, and 45-nm in CFs with various pH (6.2, 7.4 and 8.2), increasing ionic strength (0–0.1 M), and different types of co- and counter-ions, were investigated. Additionally, elution of the 85-nm carboxylate NPs and two proteins, human serum albumin (HSA) and immunoglobulin (IgG), at high ionic strengths (0–0.15 M) was investigated. Our results suggested that; 1) Electrostatic repulsion between the negatively charged NPs and the regenerated cellulose membrane was the main force to avoid particle adsorption on the membrane; 2) Larger particles experienced higher attractive force and thus were influenced more by variation in CF composition; and 3) Buffers containing weak anions or NPs with weak anion as the surface functional groups provided higher tolerance to the increase in ionic strength, owing to more anions being trapped inside the NP porous structure. Protein adsorption onto the membrane was also briefly investigated in salted CFs, using human serum albumin and immunoglobulin. We believe our findings could help to identify the basic carrier fluid composition for higher sample recovery in F4 analysis of nanoparticles in a protein-friendly environment, which will be useful for applying F4 in bioassays and in nanotoxicology studies. PMID:23058938

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.

Colloid transport in porous media: impact of hyper-saline solutions.

PubMed

Magal, Einat; Weisbrod, Noam; Yechieli, Yoseph; Walker, Sharon L; Yakirevich, Alexander

2011-05-01

The transport of colloids suspended in natural saline solutions with a wide range of ionic strengths, up to that of Dead Sea brines (10(0.9) M) was explored. Migration of microspheres through saturated sand columns of different sizes was studied in laboratory experiments and simulated with mathematical models. Colloid transport was found to be related to the solution salinity as expected. The relative concentration of colloids at the columns outlet decreased (after 2-3 pore volumes) as the solution ionic strength increased until a critical value was reached (ionic strength > 10(-1.8) M) and then remained constant above this level of salinity. The colloids were found to be mobile even in the extremely saline brines of the Dead Sea. At such high ionic strength no energetic barrier to colloid attachment was presumed to exist and colloid deposition was expected to be a favorable process. However, even at these salinity levels, colloid attachment was not complete and the transport of ∼ 30% of the colloids through the 30-cm long columns was detected. To further explore the deposition of colloids on sand surfaces in Dead Sea brines, transport was studied using 7-cm long columns through which hundreds of pore volumes were introduced. The resulting breakthrough curves exhibited a bimodal shape whereby the relative concentration (C/C(0)) of colloids at the outlet rose to a value of 0.8, and it remained relatively constant (for the ∼ 18 pore volumes during which the colloid suspension was flushed through the column) and then the relative concentration increased to a value of one. The bimodal nature of the breakthrough suggests different rates of colloid attachment. Colloid transport processes were successfully modeled using the limited entrapment model, which assumes that the colloid attachment rate is dependent on the concentration of the attached colloids. Application of this model provided confirmation of the colloid aggregation and their accelerated attachment during transport through soil in high salinity solution. Copyright © 2011 Elsevier Ltd. All rights reserved.

Experimental and Modeling Study on Detachment of Silver Nanoparticles in Saturated Granular Media

NASA Astrophysics Data System (ADS)

Kim, I.; Jeon, C. H.; Lawler, D. F.

2017-12-01

The detachment of citrate-capped silver nanoparticles (AgNPs) previously captured in a column packed with 350-μm glass beads was investigated either by increasing the hydrodynamic force (filtration velocity) or by reducing electrosteric attraction. Overall, the physical enforcement showed negligible (0.4 0.7%) release of attached AgNPs while the chemically-driven force resulted in the noticeable release up to 25.5% of attached AgNPs. Among the chemical parameters tested in this study, Na ionic strength reduction clearly demonstrated the reversible deposition in the secondary energy minimum of classical DLVO theory, yielding the most significant release of the attached AgNPs. The immediate and transient AgNP release after the ionic strength reduction further corroborated the weak deposition. However, an insignificant release was observed with Ca ionic strength reduction due to the strong Ca-citrate complexation and the subsequent deposition in the primary energy minimum; calculations indicated that the depth of the secondary energy minimum was only 1/10 that of the Na ion case. The natural organic matter (NOM) coating on both AgNPs and granular media resulted in approximately 6.1% greater AgNP release compared to the case without NOM coating, indicating additional weak deposition due to the reduced steric attraction between AgNPs and granular media. A modified filtration model in agreement with the experimental data provided the estimated detachment coefficient as a transient AgNP releasing capacity independent of the amount of attached AgNPs. The marginal difference between the detachment coefficients from Na ionic strength reduction and NOM coating indicates the release potential by NOM coating was possibly underestimated in the experimental study due to a lesser amount of the initially attached AgNPs. The findings provide insights into chemical factors on possible reentrainment behavior of the engineered nanoparticles in soil and groundwater contamination.

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

2007-01-01

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Effect of citrate on Aspergillus niger phytase adsorption and catalytic activity in soil

NASA Astrophysics Data System (ADS)

Mezeli, Malika; Menezes-Blackburn, Daniel; Zhang, Hao; Giles, Courtney; George, Timothy; Shand, Charlie; Lumsdon, David; Cooper, Patricia; Wendler, Renate; Brown, Lawrie; Stutter, Marc; Blackwell, Martin; Darch, Tegan; Wearing, Catherine; Haygarth, Philip

2015-04-01

Current developments in cropping systems that promote mobilisation of phytate in agricultural soils, by exploiting plant-root exudation of phytase and organic acids, offer potential for developments in sustainable phosphorus use. However, phytase adsorption to soil particles and phytate complexion has been shown to inhibit phytate dephosphorylation, thereby inhibiting plant P uptake, increasing the risk of this pool contributing to diffuse pollution and reducing the potential benefits of biotechnologies and management strategies aimed to utilise this abundant reserve of 'legacy' phosphorus. Citrate has been seen to increase phytase catalytic efficiency towards complexed forms of phytate, but the mechanisms by which citrate promotes phytase remains poorly understood. In this study, we evaluated phytase (from Aspergillus niger) inactivation, and change in catalytic properties upon addition to soil and the effect citrate had on adsorption of phytase and hydrolysis towards free, precipitated and adsorbed phytate. A Langmuir model was fitted to phytase adsorption isotherms showing a maximum adsorption of 0.23 nKat g-1 (19 mg protein g-1) and affinity constant of 435 nKat gˉ1 (8.5 mg protein g-1 ), demonstrating that phytase from A.niger showed a relatively low affinity for our test soil (Tayport). Phytases were partially inhibited upon adsorption and the specific activity was of 40.44 nKat mgˉ1 protein for the free enzyme and 25.35 nKat mgˉ1 protein when immobilised. The kinetics of adsorption detailed that most of the adsorption occurred within the first 20 min upon addition to soil. Citrate had no effect on the rate or total amount of phytase adsorption or loss of activity, within the studied citrate concentrations (0-4mM). Free phytases in soil solution and phytase immobilised on soil particles showed optimum activity (>80%) at pH 4.5-5.5. Immobilised phytase showed greater loss of activity at pH levels over 5.5 and lower activities at the secondary peak at pH 2.5 when compared to the free enzymes or in soil solution. The effect of ionic strength on enzyme activity was studied by increasing NaCl concentration on the activity buffer. A significant loss of activity was seen at ionic strengths over 0.6 M but enzymes in soil solution showed increased loss of activity on initial increase in ionic strength. No significant effect of citrate on phytase catalytic efficiency was observed towards free, adsorbed and precipitated (Al, Fe, Ca) phytate, except for the free phytase towards adsorbed phytase which showed a ~160% increase in P release with the addition of citric acid. This data suggest that citrate addition has no impact on the adsorption or catalytic activity of phytase in soil solution or that immobilised on soil particles, suggesting that its impact is associated with the availability of the substrate rather than effects on the enzyme per se. The ionic strength of soil solution does, however, have an impact on phytase activity suggesting that both wetting/drying cycles and fertilisation will have discrete impacts on the activity of phytases once released to soil and thus their ability to make organic P available for uptake by plants and microbes.

Design and synthesis of magnetic nanoparticles with gold shells for single particle optical tracking

NASA Astrophysics Data System (ADS)

Lim, Jitkang

The design, synthesis, and characterization of iron oxide core, gold shell nanoparticles are studied in this thesis. Firstly, nanoparticles with 18 +/- 1.7 nm diameter iron oxide cores with ˜5 nm thick gold shells were synthesized via a new seed-mediated electroless deposition method. The nanoparticles were superparamagnetic at room temperature and could be reversibly collected by a permanent magnet. These nanoparticles displayed a sharp localized surface plasmon resonance peak at 605 nm, as predicted by scattering theory, and their large scattering cross-section allowed them to be individually resolved in darkfield optical microscopy while undergoing Brownian motion in aqueous suspension. Later, commercially available 38 +/- 3.8 nm diameter spherical iron oxide nanoparticles (from Ocean Nanotech, Inc) were employed to make core-shell particles. These particles were decorated with cationic poly(diallyldimethylammonium chloride) (PDDA) which further promotes the attachment of small gold clusters. After gold seeding, the average hydrodynamic diameter of the core-shell particles is 172 +/- 65.9 nm. The magnetophoretic motion of these particles was guided by a piece of magnetized mu-metal. Individual particle trajectories were observed by darkfield optical microscopy. The typical magnetophoretic velocity achieved was within the range of 1--10 mum/sec. Random walk analysis performed on these particles while undergoing Brownian motion confirmed that individual particles were indeed being imaged. The particle size variation within the observed sample obtained through random walk analysis was within the size distribution obtained by dynamic light scattering. When the current to the solenoid used to magnetize the mu-metal was turned off, all the collected core-shell particles were readily redispersed by diffusion back into the surrounding environment. A Peclet number analysis was performed to probe the convective motion of nanospheres and nanorods under the influence of magnetophoresis and diffusion. Under most circumstances, magnetophoretic behavior dominates diffusion for nanorods, as the magnetic field lines tend to align the magnetic moment along the rod axis. The synthesis and dispersion of fluorophore-tagged nanorods are described. Fluorescence microscopy was employed to image the nanorod motion in a magnetic field gradient. The preliminary experimental data are consistent with the Peclet number analysis. Lastly, the colloidal stability of iron oxide core, gold shell nanoparticles in high ionic strength media was investigated. Such particles are sufficiently charged to be stable against flocculation without modification in low ionic strength media, but they require surface modification to be stably dispersed in elevated ionic strength media that are appropriate for biotechnological applications. Dynamic light scattering and ultraviolet-visible spectrophotometry were used to monitor the colloidal stability of core-shell particles in pH 7.4, 150 mM ionic strength phosphate buffered saline (PBS). While uncoated particles flocculated immediately upon being introduced into PBS, core-shell particles with adsorbed layers of bovine serum albumin or the amphiphilic triblock copolymers Pluronic F127 and Pluronic F68 resist flocculation after more than five days in PBS. Adsorbed dextran allowed flocculation that was limited to the formation of small clusters, while poly(ethylene glycol) homopolymers ranging in molecular weight from 6,000 to 100,000 were ineffective steric stabilizers. The effectiveness of adsorbed Pluronic copolymers as steric stabilizers was interpreted in terms of the measured adsorbed layer thickness and extended DLVO theory predictions of the interparticle interactions.

Effect of Aperture Field Variability, Flow Rate, and Ionic Strength on Colloid Transport in Single Fractures: Laboratory-Scale Experiments and Numerical Simulation

NASA Astrophysics Data System (ADS)

Zheng, Q.; Dickson, S.; Guo, Y.

2007-12-01

A good understanding of the physico-chemical processes (i.e., advection, dispersion, attachment/detachment, straining, sedimentation etc.) governing colloid transport in fractured media is imperative in order to develop appropriate bioremediation and/or bioaugmentation strategies for contaminated fractured aquifers, form management plans for groundwater resources to prevent pathogen contamination, and identify suitable radioactive waste disposal sites. However, research in this field is still in its infancy due to the complex heterogeneous nature of fractured media and the resulting difficulty in characterizing this media. The goal of this research is to investigate the effects of aperture field variability, flow rate and ionic strength on colloid transport processes in well characterized single fractures. A combination of laboratory-scale experiments, numerical simulations, and imaging techniques were employed to achieve this goal. Transparent replicas were cast from natural rock fractures, and a light transmission technique was employed to measure their aperture fields directly. The surface properties of the synthetic fractures were characterized by measuring the zeta-potential under different ionic strengths. A 33 (3 increased to the power of 3) factorial experiment was implemented to investigate the influence of aperture field variability, flow rate, and ionic strength on different colloid transport processes in the laboratory-scale fractures, specifically dispersion and attachment/detachment. A fluorescent stain technique was employed to photograph the colloid transport processes, and an analytical solution to the one-dimensional transport equation was fit to the colloid breakthrough curves to calculate the average transport velocity, dispersion coefficient, and attachment/detachment coefficient. The Reynolds equation was solved to obtain the flow field in the measured aperture fields, and the random walk particle tracking technique was employed to model the colloid transport experiments. The images clearly show the development of preferential pathways for colloid transport in the different aperture fields and under different flow conditions. Additionally, a correlation between colloid deposition and fracture wall topography was identified. This presentation will demonstrate (1) differential transport between colloid and solute in single fractures, and the relationship between differential transport and aperture field statistics; (2) the relationship between the colloid dispersion coefficient and aperture field statistics; and (3) the relationship between attachment/detachment, aperture field statistics, fracture wall topography, flow rate, and ionic strength. In addition, this presentation will provide insight into the application of the random walk particle tracking technique for modeling colloid transport in variable-aperture fractures.

Ionic strength effects on silicic acid (H4SiO4) sorption and oligomerization on an iron oxide surface: an interesting interplay between electrostatic and chemical forces.

PubMed

Hamid, Rossuriati Dol; Swedlund, Peter J; Song, Yantao; Miskelly, Gordon M

2011-11-01

The effect of ionic strength on reactions at aqueous interfaces can provide insights into the nature of the chemistry involved. The adsorption of H(4)SiO(4) on iron oxides at low surface silicate concentration (Γ(Si)) forms monomeric silicate complexes with Fe-O-Si linkages, but as Γ(Si) increases silicate oligomers with Si-O-Si linkages become increasingly prevalent. In this paper, the effect of ionic strength (I) on both Γ(Si) and the extent of silicate oligomerization on the ferrihydrite surface is determined at pH 4, 7, and 10, where the surface is, respectively, positive, nearly neutral, and negatively charged. At pH 4, an increase in ionic strength causes Γ(Si) to decrease at a given H(4)SiO(4) solution concentration, while the proportion of oligomers on the surface at a given Γ(Si) increases. At pH 10, the opposite is observed; Γ(Si) increases as I increases, while the proportion of surface oligomers at a given Γ(Si) decreases. Ionic strength has only a small effect on the surface chemistry of H(4)SiO(4) at pH 7, but at low Γ(Si) this effect is in the direction observed at pH 4 while at high Γ(Si) the effect is in the direction observed at pH 10. The pH where the surface has zero charge decreases from ≈8 to 6 as Γ(Si) increases so that the surface potential (Ψ) is positive at pH 4 for all Γ(Si) and at pH 7 with low Γ(Si). Likewise, Ψ < 0 at pH 10 for all Γ(Si) and at pH 7 with high Γ(Si). The diffuse layer model is used to unravel the complex and subtle interactions between surface potential (Ψ) and chemical parameters that influence interfacial silicate chemistry. This analysis reveals that the decrease in the absolute value of Ψ as I increases causes Γ(Si) to decrease or increase where Ψ is, respectively, positive or negative. Therefore, at a given Γ(Si), the solution H(4)SiO(4) concentration changes with I, and because oligomerization has a higher H(4)SiO(4) stoichiometry coefficient than monomer adsorption, this results in the observed dependence of the extent of silicate oligomerization on I.

Potential of Zero Charge and Its Temperature Derivative for Au(111) Electrode|Alkanethiol SAM|1.0 M Aqueous Electrolyte Solution Interfaces: Impact of Electrolyte Solution Ionic Strength and Its Effect on the Structure of the Modified Electrode|Electrolyte Solution Interface

DOE PAGES

Smalley, John F.

2017-04-06

In this study, we demonstrate how small and rapid temperature perturbations (produced by the indirect laser-induced temperature jump (ILIT) technique) of solid metal electrode|electrolyte solution interfaces may be used to determine the potential of zero (total) charge (E pzc) and its temperature derivativemore » $$\\left(\\frac{dEpzc}{dT}\\right)$$ of Au(111) electrode surfaces modified by alkanethiol self-assembled monolayers in contact with high ionic strength (i.e., 1.0 M) aqueous electrolyte solutions. The E pzc’s measured for two different types of SAMs (made from either HS(CH 2) n-1CH 3 (5 ≤ n ≤ 12, E pzc = -(0.99 ± 0.12) V vs SSCE) or HS(CH 2) nOH (3 ≤ n ≤ 16, E pzc = (0.46 ± 0.22) V vs SSCE)) are considerably different than those measured previously at much lower electrolyte solution ionic strengths. For mixed monolayers made from both HS(CH 2) n-1CH 3 and HS(CH 2) nFc (where Fc refers to ferrocene), the difference in Epzc decreases as a function of the surface concentration of the Fc moiety (i.e., [Fc]), and it completely disappears at a surprisingly small [Fc] (~4.0 × 10 –11 mol cm –2). These observations for the Au(111)|hydrophobic (neat and mixed) SAM|aqueous electrolyte solution interfaces, along with the surface potentials (g Sml(dip)) evaluated for the contacting electrolyte solution surfaces of these interfaces, are consistent with a structure for the water molecule components of these surfaces where there is a net orientation of the dipoles of these molecules. Accordingly, the negative (oxygen) ends of these molecules point toward the SAM surface. The positive values of g Sml(dip) evaluated for hydrophilic SAM (e.g., made from HS(CH 2) nOH)|aqueous electrolyte solution interfaces) also indicate that the structure of these interfaces is similar to that of the hydrophobic interfaces. However, g Sml(dip) decreases with increasing ionic strength for the hydrophilic interfaces, while it increases with increasing ionic strength for the hydrophobic interfaces. The data (and calculations) reported in the present work and other studies of hydrophobic (and hydrophilic)|aqueous solution interfaces are as yet insufficient to support a complete explanation for the effects of ionic strength observed in the present study. Nevertheless, an analysis based upon the value of $$\\left(\\frac{dEpzc}{dT}\\right)$$ (= (0.51 ± 0.12) mV/K, essentially the same for SAMs made from both HS(CH 2) n-1CH 3 and HS(CH 2) nOH), determined in the present study provides a further indication that upon formation of the SAM there is a partial charge transfer of electrons from the relevant gold atoms on the Au(111) surface to the sulfur atoms of the alkanethiols.« less

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.

Resilient self-assembling hydrogels from block copolypeptide amphiphiles

NASA Astrophysics Data System (ADS)

Nowak, Andrew Paul

The ability to produce well defined synthetic polypeptides has been greatly improved by the discovery of transition metal species that mediate the controlled polymerization of N-carboxyanhydrides (NCAs). These metal species create a living polymerization system by producing control over chain length, low polydispersities, and the ability to form complex block architectures. We have applied this system to the synthesis of block copolypeptide amphiphiles. Initial block copolymers synthesized were composed of hydrophilic, cationic poly(L-Lysine) combined with hydrophobic, alpha-helical poly(L-Leucine). These Lysine- block-Leucine copolypeptides were found to form stiff, clear hydrogels at low concentration (˜1 wt%) in low ionic strength water. Based on this unexpected result we used the flexibility of our transition metal polymerization chemistry to better understand the nature and mechanisms of gel formation in these materials. Systematic changes to the original Lysine-block-Leucine copolypeptides were made by altering overall chain size, relative block length, polyelectrolyte charge, and hydrophobic secondary structure. Rheological characterization revealed that the strength of these hydrogels was primarily dependent on degree of polymerization, relative block length, and a well ordered secondary structure in the hydrophobic segment. The Lysine-block-Leucine hydrogels were formed by direct addition of water to dry polypeptide material which swelled to homogeneously fill the entire volume of liquid with no special processing. CryoTEM showed a percolating cellular network at ˜100nm that appears to be comprised of both membranes and fibers. Larger length scales studied with Laser Scanning Confocal Microscopy revealed a spontaneously formed microporous network with large (˜10mum) water rich voids. These hydrogels also displayed interesting mechanical properties including rapid recovery of solid like behavior after being sheared to a liquid and mechanical stability with increased temperature (˜90°C). The behavior of the Lysine- block-Leucine system with salt was also thoroughly investigated. With proper tuning of the relative block composition it was found that hydrogels could be optimized to possess good solubility and mechanical strength in many useful ionic solutions (˜100--200mM) such as pH buffers and cell culture media.

Conductometry of electrolyte solutions

NASA Astrophysics Data System (ADS)

Safonova, Lyubov P.; Kolker, Arkadii M.

1992-09-01

A review is given of the theories of the electrical conductance of electrolyte solutions of different ionic strengths and concentrations, and of the models of ion association. An analysis is made of the methods for mathematical processing of experimental conductometric data. An account is provided of various theories describing the dependence of the limiting value of the ionic electrical conductance on the properties of the solute and solvent. The bibliography includes 115 references.

On the pH of Aqueous Attoliter-Volume Droplets

NASA Astrophysics Data System (ADS)

Ramos, Kieran P.; Velpula, Samson S.; Demille, Trevor B.; Pajela, Ryan; Goldner, Lori S.

Droplets of water dispersed in perfluorinated liquids have widespread use including microfluidics, drug delivery and single-molecule measurements. Perfluorinated liquids are distinctly biocompatible due to their stability, low surface tension, lipophobicity, and hydrophobicity. For this reason, the effect of the perfluorinated surface on droplet contents is usually ignored. However, as the droplet diameter is reduced, we expect that any effect of the water/oil interface on droplet contents will become more obvious. We studied the pH of attoliter-volume aqueous droplets in perfluorinated liquids using pH-sensing fluorescent dyes. Droplets were prepared either by sonication or extrusion from buffer and perfluorinated liquids (FC40 or FC77). A non-ionic surfactant was used to stabilize the droplets. Buffer strength, ionic strength, and pH of the aqueous phase were varied and resulting droplet pH compared to the pH of the buffer from which they were formed. Preliminary data are consistent with a pH in droplets that depends on the concentration of non-ionic surfactant. At low surfactant concentrations, the pH in droplets is distinctly lower than the stock buffer. However, as the concentration of non-ionic surfactant is increased the change in pH decreases. This work was funded by NSF/DBI-1152386.

Effects of alkyl chain length and solvents on thermodynamic dissociation constants of the ionic liquids with one carboxyl group in the alkyl chain of imidazolium cations.

PubMed

Chen, Yuehua; Wang, Huiyong; Wang, Jianji

2014-05-01

Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

Dynamics at Lys-553 of the acto-myosin interface in the weakly and strongly bound states.

PubMed Central

MacLean, J J; Chrin, L R; Berger, C L

2000-01-01

Lys-553 of skeletal muscle myosin subfragment 1 (S1) was specifically labeled with the fluorescent probe FHS (6-[fluorescein-5(and 6)-carboxamido]hexanoic acid succinimidyl ester) and fluorescence quenching experiments were carried out to determine the accessibility of this probe at Lys-553 in both the strongly and weakly actin-bound states of the MgATPase cycle. Solvent quenchers of varying charge [nitromethane, (2,2,6, 6-tetramethyl-1-piperinyloxy) (TEMPO), iodide (I(-)), and thallium (Tl(+))] were used to assess both the steric and electrostatic accessibilities of the FHS probe at Lys-553. In the strongly bound rigor (nucleotide-free) and MgADP states, actin offered no protection from solvent quenching of FHS by nitromethane, TEMPO, or thallium, but did decrease the Stern-Volmer constant by almost a factor of two when iodide was used as the quencher. The protection from iodide quenching was almost fully reversed with the addition of 150 mM KCl, suggesting this effect is ionic in nature rather than steric. Conversely, actin offered no protection from iodide quenching at low ionic strength during steady-state ATP hydrolysis, even with a significant fraction of the myosin heads bound to actin. Thus, the lower 50 kD subdomain of myosin containing Lys-553 appears to interact differently with actin in the weakly and strongly bound states. PMID:10692329

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

Parameters of tensile strength, elongation, and tenacity of 70mm IIaO spectroscopic film

NASA Technical Reports Server (NTRS)

Hammond, Ernest C., Jr.; Peters, Kevin A.

1989-01-01

The 70mm IIaO spectroscopic film was tested to determine its tensile strength, elongation, and breaking strength, using an Instron (strength and compression) 4201 Test Instrument. These data provide information leading to the upper and lower limits of the above parameters for 70mm IIaO spectroscopic film. This film will be developed by a commercial developing machine after the Ultraviolet Telescope Space Shuttle Mission returns to the Earth in the early 1990's; thus, it is necessary to understand these force parameters. Several test strips of approximately 200mm in length were used. The results indicate that when a stress load of 100 kg was applied, the film elongated approximately 1.06mm and the break strength was 19.45 kilograms.

Unraveling the complexities of the velocity dependency of E. coli retention and release parameters in saturated porous media.

PubMed

Sasidharan, Salini; Bradford, Scott A; Torkzaban, Saeed; Ye, Xueyan; Vanderzalm, Joanne; Du, Xinqiang; Page, Declan

2017-12-15

Escherichia coli transport and release experiments were conducted to investigate the pore-water velocity (v) dependency of the sticking efficiency (α), the fraction of the solid surface area that contributed to retention (S f ), the percentage of injected cells that were irreversibly retained (M irr ), and cell release under different (10-300mM) ionic strength (IS) conditions. Values of α, S f , and M irr increased with increasing IS and decreasing v, but the dependency on v was greatest at intermediate IS (30 and 50mM). Following the retention phase, successive increases in v up to 100 or 150mday -1 and flow interruption of 24h produced negligible amounts of cell release. However, excavation of the sand from the columns in excess electrolyte solution resulted in the release of >80% of the retained bacteria. These observations were explained by: (i) extended interaction energy calculations on a heterogeneous sand collector; (ii) an increase in adhesive strength with the residence time; and (iii) torque balance consideration on rough surfaces. In particular, α, S f , and M irr increased with IS due to lower energy barriers and stronger primary minima. The values of α, S f , and M irr also increased with decreasing v because the adhesive strength increased with the residence time (e.g., an increased probability to diffuse over the energy barrier) and lower hydrodynamic forces diminished cell removal. The controlling influence of lever arms at microscopic roughness locations and grain-grain contacts were used to explain negligible cell removal with large increases in v and large amounts of cell recovery following sand excavation. Results reveal the underlying causes (interaction energy, torque balance, and residence time) of the velocity dependency of E. coli retention and release parameters (k sw , α, and S f ) that are not accounted for in colloid filtration theory. Copyright © 2017 Elsevier B.V. All rights reserved.

Submicrometer Emitter ESI Tips for Native Mass Spectrometry of Membrane Proteins in Ionic and Nonionic Detergents

NASA Astrophysics Data System (ADS)

Susa, Anna C.; Lippens, Jennifer L.; Xia, Zijie; Loo, Joseph A.; Campuzano, Iain D. G.; Williams, Evan R.

2018-01-01

Native mass spectrometry (native-MS) of membrane proteins typically requires a detergent screening protocol, protein solubilization in the preferred detergent, followed by protein liberation from the micelle by collisional activation. Here, submicrometer nano-ESI emitter tips are used for native-MS of membrane proteins solubilized in both nonionic and ionic detergent solutions. With the submicrometer nano-ESI emitter tips, resolved charge-state distributions of membrane protein ions are obtained from a 150 mM NaCl, 25 mM Tris-HCl with 1.1% octyl glucoside solution. The relative abundances of NaCl and detergent cluster ions at high m / z are significantly reduced with the submicrometer emitters compared with larger nano-ESI emitters that are commonly used. This technique is beneficial for significantly decreasing the abundances (by two to three orders of magnitude compared with the larger tip size: 1.6 μm) of detergent cluster ions formed from aqueous ammonium acetate solutions containing detergents that can overlap with the membrane protein ion signal. Resolved charge-state distributions of membrane protein ions from aqueous ammonium acetate solutions containing ionic detergents were obtained with the submicrometer nano-ESI emitters; this is the first report of native-MS of membrane proteins solubilized by ionic detergents. [Figure not available: see fulltext.

Submicrometer Emitter ESI Tips for Native Mass Spectrometry of Membrane Proteins in Ionic and Nonionic Detergents.

PubMed

Susa, Anna C; Lippens, Jennifer L; Xia, Zijie; Loo, Joseph A; Campuzano, Iain D G; Williams, Evan R

2018-01-01

Native mass spectrometry (native-MS) of membrane proteins typically requires a detergent screening protocol, protein solubilization in the preferred detergent, followed by protein liberation from the micelle by collisional activation. Here, submicrometer nano-ESI emitter tips are used for native-MS of membrane proteins solubilized in both nonionic and ionic detergent solutions. With the submicrometer nano-ESI emitter tips, resolved charge-state distributions of membrane protein ions are obtained from a 150 mM NaCl, 25 mM Tris-HCl with 1.1% octyl glucoside solution. The relative abundances of NaCl and detergent cluster ions at high m /z are significantly reduced with the submicrometer emitters compared with larger nano-ESI emitters that are commonly used. This technique is beneficial for significantly decreasing the abundances (by two to three orders of magnitude compared with the larger tip size: 1.6 μm) of detergent cluster ions formed from aqueous ammonium acetate solutions containing detergents that can overlap with the membrane protein ion signal. Resolved charge-state distributions of membrane protein ions from aqueous ammonium acetate solutions containing ionic detergents were obtained with the submicrometer nano-ESI emitters; this is the first report of native-MS of membrane proteins solubilized by ionic detergents. Graphical Abstract.

A Molecular Dynamics-Quantum Mechanics Theoretical Study of DNA-Mediated Charge Transport in Hydrated Ionic Liquids.

PubMed

Meng, Zhenyu; Kubar, Tomas; Mu, Yuguang; Shao, Fangwei

2018-05-08

Charge transport (CT) through biomolecules is of high significance in the research fields of biology, nanotechnology, and molecular devices. Inspired by our previous work that showed the binding of ionic liquid (IL) facilitated charge transport in duplex DNA, in silico simulation is a useful means to understand the microscopic mechanism of the facilitation phenomenon. Here molecular dynamics simulations (MD) of duplex DNA in water and hydrated ionic liquids were employed to explore the helical parameters. Principal component analysis was further applied to capture the subtle conformational changes of helical DNA upon different environmental impacts. Sequentially, CT rates were calculated by a QM/MM simulation of the flickering resonance model based upon MD trajectories. Herein, MD simulation illustrated that the binding of ionic liquids can restrain dynamic conformation and lower the on-site energy of the DNA base. Confined movement among the adjacent base pairs was highly related to the increase of electronic coupling among base pairs, which may lead DNA to a CT facilitated state. Sequentially combining MD and QM/MM analysis, the rational correlations among the binding modes, the conformational changes, and CT rates illustrated the facilitation effects from hydrated IL on DNA CT and supported a conformational-gating mechanism.

Influence of collector surface composition and water chemistry on the deposition of cerium dioxide nanoparticles: QCM-D and column experiment approaches.

PubMed

Liu, Xuyang; Chen, Gexin; Su, Chunming

2012-06-19

The deposition behavior of cerium dioxide (CeO(2)) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied in quartz crystal microbalance with dissipation (QCM-D) to examine the effect of these mineral phases on CeO(2) deposition in NaCl solution (1-200 mM). Frequency and dissipation shift followed the order: silica > iron oxide > alumina in 10 mM NaCl at pH 4.0. No significant deposition was observed at pH 6.0 and 8.5 on any of the tested sensors. However, ≥ 94.3% of CeO(2) NPs deposited onto Ottawa sand in columns in 10 mM NaCl at pH 6.0 and 8.5. The inconsistency in the different experimental approaches can be mainly attributed to NP aggregation, surface heterogeneity of Ottawa sand, and flow geometry. In QCM-D experiments, the deposition kinetics was found to be qualitatively consistent with the predictions based on the classical colloidal stability theory. The presence of low levels (1-6 mg/L) of Suwannee River humic acid, fulvic acid, alginate, citric acid, and carboxymethyl cellulose greatly enhanced the stability and mobility of CeO(2) NPs in 1 mM NaCl at pH 6.5. The poor correlation between the transport behavior and electrophoretic mobility of CeO(2) NPs implies that the electrosteric effect of OM was involved.

Mechanical properties of polymer-modified porous concrete

NASA Astrophysics Data System (ADS)

Ariffin, N. F.; Jaafar, M. F. Md.; Shukor Lim, N. H. Abdul; Bhutta, M. A. R.; Hussin, M. W.

2018-04-01

In this research work, polymer-modified porous concretes (permeable concretes) using polymer latex and redispersible polymer powder with water-cement ratio of 30 %, polymer-cement ratios of 0 to 10 % and cement content of 300 kg/m3 are prepared. The porous concrete was tested for compressive strength, flexural strength, water permeability and void ratio. The cubes size of specimen is 100 mm ×100 mm × 100 mm and 150 mm × 150 mm × 150 mm while the beam size is 100 mm × 100 mm × 500 mm was prepared for particular tests. The tests results show that the addition of polymer as a binder to porous concrete gives an improvement on the strength properties and coefficient of water permeability of polymer-modified porous concrete. It is concluded from the test results that increase in compressive and flexural strengths and decrease in the coefficient of water permeability of the polymer-modified porous concrete are clearly observed with increasing of polymer-cement ratio.

Modeling the controllable pH-responsive swelling and pore size of networked alginate based biomaterials.

PubMed

Chan, Ariel W; Neufeld, Ronald J

2009-10-01

Semisynthetic network alginate polymer (SNAP), synthesized by acetalization of linear alginate with di-aldehyde, is a pH-responsive tetrafunctionally linked 3D gel network, and has potential application in oral delivery of protein therapeutics and active biologicals, and as tissue bioscaffold for regenerative medicine. A constitutive polyelectrolyte gel model based on non-Gaussian polymer elasticity, Flory-Huggins liquid lattice theory, and non-ideal Donnan membrane equilibria was derived, to describe SNAP gel swelling in dilute and ionic solutions containing uni-univalent, uni-bivalent, bi-univalent or bi-bi-valent electrolyte solutions. Flory-Huggins interaction parameters as a function of ionic strength and characteristic ratio of alginates of various molecular weights were determined experimentally to numerically predict SNAP hydrogel swelling. SNAP hydrogel swells pronouncedly to 1000 times in dilute solution, compared to its compact polymer volume, while behaving as a neutral polymer with limited swelling in high ionic strength or low pH solutions. The derived model accurately describes the pH-responsive swelling of SNAP hydrogel in acid and alkaline solutions of wide range of ionic strength. The pore sizes of the synthesized SNAP hydrogels of various crosslink densities were estimated from the derived model to be in the range of 30-450 nm which were comparable to that measured by thermoporometry, and diffusion of bovine serum albumin. The derived equilibrium swelling model can characterize hydrogel structure such as molecular weight between crosslinks and crosslinking density, or can be used as predictive model for swelling, pore size and mechanical properties if gel structural information is known, and can potentially be applied to other point-link network polyelectrolytes such as hyaluronic acid gel.

Gel polymer electrolytes for batteries

DOEpatents

Balsara, Nitash Pervez; Eitouni, Hany Basam; Gur, Ilan; Singh, Mohit; Hudson, William

2014-11-18

Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at 25.degree. C.

Electromechanical engineering in SnO2 nanoparticle tethered hybrid ionic liquid

NASA Astrophysics Data System (ADS)

Deb, Debalina; Bhattacharya, Subhratanu

2017-05-01

Challenge of developing electrolytes comprising synergic properties of high mechanical strength with superior electrical and electrochemical properties has so far been unmet towards the application of secondary storage devices. In this research, we have engineered the electromechanical properties of 2-(trimethylamino) ethyl methacrylate bis(trifluoromethylsulfonyl) imide [TMEM]TFSI ionic liquid by tethering silane modified SnO2 nanoparticles within it. Different percentages of tethering are employed to achieve improved ionic conductivity, better discharge/ charging ratio (40%) along with gel like mechanical properties. Our findings appear to provide an optimal solution towards the future prospects in application in a number of areas, notably in energy-related technologies.

Temperature dependency of virus and nanoparticle transport and retention in saturated porous media

NASA Astrophysics Data System (ADS)

Sasidharan, Salini; Torkzaban, Saeed; Bradford, Scott A.; Cook, Peter G.; Gupta, Vadakattu V. S. R.

2017-01-01

The influence of temperature on virus (PRD1 and ΦX174) and carboxyl-modified latex nanoparticle (50 and 100 nm) attachment was examined in sand-packed columns under various physiochemical conditions. When the solution ionic strength (IS) equaled 10 and 30 mM, the attachment rate coefficient (katt) increased up to 109% (p < 0.0002) and the percentage of the sand surface area that contributed to attachment (Sf) increased up to 160% (p < 0.002) when the temperature was increased from 4 to 20 °C. Temperature effects at IS = 10 and 30 mM were also dependent on the system hydrodynamics; i.e., enhanced retention at a lower pore water velocity (0.1 m/day). Conversely, this same temperature increase had a negligible influence on katt and Sf values when IS was 1 mM or > 50 mM. An explanation for these observations was obtained from extended interaction energy calculations that considered nanoscale roughness and chemical heterogeneity on the sand surface. Interaction energy calculations demonstrated that the energy barrier to attachment in the primary minimum (ΔΦa) decreased with increasing IS, chemical heterogeneity, and temperature, especially in the presence of small amounts of nanoscale roughness (e.g., roughness fraction of 0.05 and height of 20 nm in the zone of influence). Temperature had a negligible effect on katt and Sf when the IS = 1 mM because of the large energy barrier, and at IS = 50 mM because of the absence of an energy barrier. Conversely, temperature had a large influence on katt and Sf when the IS was 10 and 30 mM because of the presence of a small ΔΦa on sand with nanoscale roughness and a chemical (positive zeta potential) heterogeneity. This has large implications for setting parameters for the accurate modeling and transport prediction of virus and nanoparticle contaminants in ground water systems.

The use of physiological solutions or media in calcium phosphate synthesis and processing.

PubMed

Tas, A Cuneyt

2014-05-01

This review examined the literature to spot uses, if any, of physiological solutions/media for the in situ synthesis of calcium phosphates (CaP) under processing conditions (i.e. temperature, pH, concentration of inorganic ions present in media) mimicking those prevalent in the human hard tissue environments. There happens to be a variety of aqueous solutions or media developed for different purposes; sometimes they have been named as physiological saline, isotonic solution, cell culture solution, metastable CaP solution, supersaturated calcification solution, simulated body fluid or even dialysate solution (for dialysis patients). Most of the time such solutions were not used as the aqueous medium to perform the biomimetic synthesis of calcium phosphates, and their use was usually limited to the in vitro testing of synthetic biomaterials. This review illustrates that only a limited number of research studies used physiological solutions or media such as Earle's balanced salt solution, Bachra et al. solutions or Tris-buffered simulated body fluid solution containing 27mM HCO3(-) for synthesizing CaP, and these studies have consistently reported the formation of X-ray-amorphous CaP nanopowders instead of Ap-CaP or stoichiometric hydroxyapatite (HA, Ca10(PO4)6(OH)2) at 37°C and pH 7.4. By relying on the published articles, this review highlights the significance of the use of aqueous solutions containing 0.8-1.5 mMMg(2+), 22-27mM HCO3(-), 142-145mM Na(+), 5-5.8mM K(+), 103-133mM Cl(-), 1.8-3.75mM Ca(2+), and 0.8-1.67mM HPO4(2-), which essentially mimic the composition and the overall ionic strength of the human extracellular fluid (ECF), in forming the nanospheres of X-ray-amorphous CaP. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Dielectric breakdown of additively manufactured polymeric materials

DOE PAGES

Monzel, W. Jacob; Hoff, Brad W.; Maestas, Sabrina S.; ...

2016-01-11

Dielectric strength testing of selected Polyjet-printed polymer plastics was performed in accordance with ASTM D149. This dielectric strength data is compared to manufacturer-provided dielectric strength data for selected plastics printed using the stereolithography (SLA), fused deposition modeling (FDM), and selective laser sintering (SLS) methods. Tested Polyjet samples demonstrated dielectric strengths as high as 47.5 kV/mm for a 0.5 mm thick sample and 32.1 kV/mm for a 1.0 mm sample. As a result, the dielectric strength of the additively manufactured plastics evaluated as part of this study was lower than the majority of non-printed plastics by at least 15% (with themore » exception of polycarbonate).« less

Dielectric breakdown of additively manufactured polymeric materials

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

Monzel, W. Jacob; Hoff, Brad W.; Maestas, Sabrina S.

Dielectric strength testing of selected Polyjet-printed polymer plastics was performed in accordance with ASTM D149. This dielectric strength data is compared to manufacturer-provided dielectric strength data for selected plastics printed using the stereolithography (SLA), fused deposition modeling (FDM), and selective laser sintering (SLS) methods. Tested Polyjet samples demonstrated dielectric strengths as high as 47.5 kV/mm for a 0.5 mm thick sample and 32.1 kV/mm for a 1.0 mm sample. As a result, the dielectric strength of the additively manufactured plastics evaluated as part of this study was lower than the majority of non-printed plastics by at least 15% (with themore » exception of polycarbonate).« less

Effects of porcelain thickness on the flexural strength and crack propagation in a bilayered zirconia system.

PubMed

Figueiredo, Viviane Maria Gonçalves de; Pereira, Sarina Maciel Braga; Bressiani, Eduardo; Valera, Márcia Carneiro; Bottino, Marco Antônio; Zhang, Yu; Melo, Renata Marques de

2017-01-01

This study evaluated the influence of porcelain (VM9, VITA Zahnfabrik, Germany) thickness on the flexural strength and crack propagation in bilayered zirconia systems (YZ, VITA Zahnfabrik, Germany). Thirty zirconia bars (20.0x4.0x1.0 mm) and six zirconia blocks (12.0x7.5x1.2 mm) were prepared and veneered with porcelain with different thickness: 1 mm, 2 mm, or 3 mm. The bars of each experimental group (n=10) were subjected to four-point flexural strength testing. In each ceramic block, a Vickers indentation was created under a load of 10 kgf for 10 seconds, for the propagation of cracks. The results of flexural strength were evaluated by One-way ANOVA and Tukey's test, with a significance level of 5%. The factor "thickness of the porcelain" was statistically significant (p=0.001) and the l-mm group presented the highest values of flexural strength. The cracks were predominant among the bending specimens with 1 and 2 mm of porcelain, and catastrophic failures were found in 50% of 3-mm-thick porcelain. After the indentation of blocks, the most severe defects were observed in blocks with 3-mm-thick porcelain. The smallest (1 mm) thickness of porcelain on the zirconia infrastructure presented higher values of flexural strength. Better resistance to defect propagation was observed near the porcelain/ zirconia interface for all groups. Higher flexural strength was found for a thinner porcelain layer in a bilayered zirconia system. The damage caused by a Vickers indentation near and far the interface with the zirconia shows that the stress profiles are different.

Effects of porcelain thickness on the flexural strength and crack propagation in a bilayered zirconia system

PubMed Central

de Figueiredo, Viviane Maria Gonçalves; Pereira, Sarina Maciel Braga; Bressiani, Eduardo; Valera, Márcia Carneiro; Bottino, Marco Antônio; Zhang, Yu; de Melo, Renata Marques

2017-01-01

Abstract Objective: This study evaluated the influence of porcelain (VM9, VITA Zahnfabrik, Germany) thickness on the flexural strength and crack propagation in bilayered zirconia systems (YZ, VITA Zahnfabrik, Germany). Material and Methods: Thirty zirconia bars (20.0x4.0x1.0 mm) and six zirconia blocks (12.0x7.5x1.2 mm) were prepared and veneered with porcelain with different thickness: 1 mm, 2 mm, or 3 mm. The bars of each experimental group (n=10) were subjected to four-point flexural strength testing. In each ceramic block, a Vickers indentation was created under a load of 10 kgf for 10 seconds, for the propagation of cracks. Results: The results of flexural strength were evaluated by One-way ANOVA and Tukey's test, with a significance level of 5%. The factor “thickness of the porcelain” was statistically significant (p=0.001) and the l-mm group presented the highest values of flexural strength. The cracks were predominant among the bending specimens with 1 and 2 mm of porcelain, and catastrophic failures were found in 50% of 3-mm-thick porcelain. After the indentation of blocks, the most severe defects were observed in blocks with 3-mm-thick porcelain. Conclusion: The smallest (1 mm) thickness of porcelain on the zirconia infrastructure presented higher values of flexural strength. Better resistance to defect propagation was observed near the porcelain/ zirconia interface for all groups. Higher flexural strength was found for a thinner porcelain layer in a bilayered zirconia system. The damage caused by a Vickers indentation near and far the interface with the zirconia shows that the stress profiles are different. PMID:29069155

[Comparison of wear resistance and flexural strength of three kinds of bulk-fill composite resins].

PubMed

Zhang, Huan; Zhang, Meng-Long; Qiu, Li-Hong; Yu, Jing-Tao; Zhan, Fu-Liang

2016-06-01

To compare the abrasion resistance and flexure strength of three bulk-fill resin composites with an universal nano-hybrid composite resins. The specimens were prepared with three kinds of bulk fill composites (SDR , sonicfill, Tetric N-Ceram Bulk Fill) and an universal nano-hybrid composite resins(Herculite Precis). 10 mm in diameter × 2mm in height specimens were prepared for abrasion resistance, while 2 mm in width × 2 mm in depth×25 mm in length specimens were prepared for flexure strength. The specimens were mounted in a bal1-on-disc wear testing machine and abraded with the media artificial saliva(50 N loads, 10000 cycles).Flexural test was performed with an Universal Testing Machine at a cross-head speed of 1mm/min. One-way variance analysis was used to determine the statistical differences of volume loss and flexural strength among groups with SPSS 13.0 software package(P<0.05). The volume loss was as follows: SDR (1.2433±0.11) mm30.05). With regard to wear resistance and flexural strength, Tetric N-Ceram Bulk Fill is recommended as an alternative for posterior restorations.

Acid-Base Chemistry of White Wine: Analytical Characterisation and Chemical Modelling

PubMed Central

Prenesti, Enrico; Berto, Silvia; Toso, Simona; Daniele, Pier Giuseppe

2012-01-01

A chemical model of the acid-base properties is optimized for each white wine under study, together with the calculation of their ionic strength, taking into account the contributions of all significant ionic species (strong electrolytes and weak one sensitive to the chemical equilibria). Coupling the HPLC-IEC and HPLC-RP methods, we are able to quantify up to 12 carboxylic acids, the most relevant substances responsible of the acid-base equilibria of wine. The analytical concentration of carboxylic acids and of other acid-base active substances was used as input, with the total acidity, for the chemical modelling step of the study based on the contemporary treatment of overlapped protonation equilibria. New protonation constants were refined (L-lactic and succinic acids) with respect to our previous investigation on red wines. Attention was paid for mixed solvent (ethanol-water mixture), ionic strength, and temperature to ensure a thermodynamic level to the study. Validation of the chemical model optimized is achieved by way of conductometric measurements and using a synthetic “wine” especially adapted for testing. PMID:22566762

Pharmacological and ionic characterizations of the muscarinic receptors modulating (/sup 3/H)acetylcholine release from rat cortical synaptosomes

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

Meyer, E.M.; Otero, D.H.

The muscarinic receptors that modulate acetylcholine release from rat cortical synaptosomes were characterized with respect to sensitivity to drugs that act selectively at M1 or M2 receptor subtypes, as well as to changes in ionic strength and membrane potential. The modulatory receptors appear to be of the M2 type, since they are activated by carbachol, acetylcholine, methacholine, oxotremorine, and bethanechol, but not by pilocarpine, and are blocked by atropine, scopolamine, and gallamine (at high concentrations), but not by pirenzepine or dicyclomine. The ED50S for carbachol, acetylcholine, and oxotremorine are less than 10 microM, suggesting that the high affinity state ofmore » the receptor is functional. High ionic strength induced by raising the NaCl concentration has no effect on agonist (oxotremorine) potency, but increases the efficacy of this compound, which disagrees with receptor-binding studies. On the other hand, depolarization with either KCl or with veratridine (20 microM) reduces agonist potencies by approximately an order of magnitude, suggesting a potential mechanism for receptor regulation.« less

Acid-base chemistry of white wine: analytical characterisation and chemical modelling.

PubMed

Prenesti, Enrico; Berto, Silvia; Toso, Simona; Daniele, Pier Giuseppe

2012-01-01

A chemical model of the acid-base properties is optimized for each white wine under study, together with the calculation of their ionic strength, taking into account the contributions of all significant ionic species (strong electrolytes and weak one sensitive to the chemical equilibria). Coupling the HPLC-IEC and HPLC-RP methods, we are able to quantify up to 12 carboxylic acids, the most relevant substances responsible of the acid-base equilibria of wine. The analytical concentration of carboxylic acids and of other acid-base active substances was used as input, with the total acidity, for the chemical modelling step of the study based on the contemporary treatment of overlapped protonation equilibria. New protonation constants were refined (L-lactic and succinic acids) with respect to our previous investigation on red wines. Attention was paid for mixed solvent (ethanol-water mixture), ionic strength, and temperature to ensure a thermodynamic level to the study. Validation of the chemical model optimized is achieved by way of conductometric measurements and using a synthetic "wine" especially adapted for testing.

Effects of the background electrolyte on Th(IV) sorption to muscovite mica

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

Schmidt, Moritz; Hellebrandt, Stefan; Knope, Karah E.

2015-09-01

The adsorption of tetravalent thorium on the muscovite mica (001) basal plane was studied by X-ray crystal truncation rod (CTR), and resonant anomalous X-ray reflectivity (RAXR) measurements and alpha spectrometry in the presence of perchlorate background electrolytes LiClO 4, NaClO 4, and KClO 4 ([Th(IV)] = 0.1 mM, I = 0.1 M or 0.01 M, pH = 3.3 ± 0.3). RAXR data directly reveal a strong influence of the background electrolyte on the actinide sorption. No significant Th adsorption was observed in 0.1 M NaClO 4, i.e., the Th coverage θ(Th), the number of Th per unit cell area ofmore » the muscovite surface (A UC = 46.72 Å 2), was ≤ 0.01 Th/A UC, whereas limited uptake (θ(Th) ~ 0.04 Th/A UC) was detected at a lower ionic strength (I = 0.01 M). These results are in stark contrast to the behavior of Th in 0.1 M NaCl which showed a coverage of 0.4 Th/A UC (Schmidt et al., 2012a). Th uptake was also influenced by the electrolyte cation. Weak adsorption was observed in 0.1M KClO 4 (θ(Th) ~ 0.07 Th/AUC) similar to the results in NaClO 4 at lower ionic strength. In contrast, strong adsorption was found in 0.1 M LiClO 4, with θ(Th) = 4.9 Th/A UC, a ~10-fold increase compared with that previously reported in NaCl. These differences are confirmed independently by ex situ alpha spectrometry, which shows no measurable Th coverage in 0.1 M NaClO 4 background in contrast to a large coverage of 1.6 Th/A UC in 0.1 M LiClO 4. The CTR/RAXR analyses of Th-LiClO 4 show the sorption structure consisting of Th species that are broadly distributed, centered at heights of 4.1 Å and 29 Å distance from the interface. Neither the very large distribution height of the second species nor the high coverage can be explained with (hydrated) ionic adsorption, suggesting that the enhanced uptake is presumably due to the formation and sorption of Th nanoparticles.« less

Chromatin ionic atmosphere analyzed by a mesoscale electrostatic approach.

PubMed

Gan, Hin Hark; Schlick, Tamar

2010-10-20

Characterizing the ionic distribution around chromatin is important for understanding the electrostatic forces governing chromatin structure and function. Here we develop an electrostatic model to handle multivalent ions and compute the ionic distribution around a mesoscale chromatin model as a function of conformation, number of nucleosome cores, and ionic strength and species using Poisson-Boltzmann theory. This approach enables us to visualize and measure the complex patterns of counterion condensation around chromatin by examining ionic densities, free energies, shielding charges, and correlations of shielding charges around the nucleosome core and various oligonucleosome conformations. We show that: counterions, especially divalent cations, predominantly condense around the nucleosomal and linker DNA, unburied regions of histone tails, and exposed chromatin surfaces; ionic screening is sensitively influenced by local and global conformations, with a wide ranging net nucleosome core screening charge (56-100e); and screening charge correlations reveal conformational flexibility and interactions among chromatin subunits, especially between the histone tails and parental nucleosome cores. These results provide complementary and detailed views of ionic effects on chromatin structure for modest computational resources. The electrostatic model developed here is applicable to other coarse-grained macromolecular complexes. Copyright © 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Effect of thickness and surface modifications on flexural strength of monolithic zirconia.

PubMed

Ozer, Fusun; Naden, Andrew; Turp, Volkan; Mante, Francis; Sen, Deniz; Blatz, Markus B

2017-10-14

A recommended minimum thickness for monolithic zirconia restorations has not been reported. Assessing a proper thickness that has the necessary load-bearing capacity but also conserves dental hard tissues is essential. The purpose of this in vitro study was to evaluate the effect of thickness and surface modifications on monolithic zirconia after simulated masticatory stresses. Monolithic zirconia disks (10 mm in diameter) were fabricated with 1.3 mm and 0.8 mm thicknesses. For each thickness, 21 disks were fabricated. The specimens of each group were further divided into 3 subgroups (n=7) according to the surface treatments applied: untreated (control), airborne-particle abrasion with 50-μm Al 2 O 3 particles at a pressure of 400 kPa at 10 mm, and grinding with a diamond rotary instrument followed by polishing. The biaxial flexure strength was determined by using a piston-on-3-balls technique in a universal testing machine. Flexural loading was applied with a 1.4-mm diameter steel cylinder, centered on the disk, at a crosshead speed of 0.5 mm/min until fracture occurred. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses were performed. The data were statistically analyzed with 2-way ANOVA, Tamhane T2, 1-way ANOVA, and Student t tests (α=.05). The 1.3-mm specimens had significantly higher flexural strength than the 0.8-mm specimens (P<.05). Airborne-particle abrasion significantly increased the flexural strength (P<.05). Grinding and polishing did not affect the flexural strength of the specimens (P>.05). The mean flexural strength of 0.8-mm and 1.3-mm thick monolithic zirconia was greater than reported masticatory forces. Airborne-particle abrasion increased the flexural strength of monolithic zirconia. Grinding did not affect flexural strength if subsequently polished. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Self-consistent-field calculations of proteinlike incorporations in polyelectrolyte complex micelles

NASA Astrophysics Data System (ADS)

Lindhoud, Saskia; Stuart, Martien A. Cohen; Norde, Willem; Leermakers, Frans A. M.

2009-11-01

Self-consistent field theory is applied to model the structure and stability of polyelectrolyte complex micelles with incorporated protein (molten globule) molecules in the core. The electrostatic interactions that drive the micelle formation are mimicked by nearest-neighbor interactions using Flory-Huggins χ parameters. The strong qualitative comparison with experimental data proves that the Flory-Huggins approach is reasonable. The free energy of insertion of a proteinlike molecule into the micelle is nonmonotonic: there is (i) a small repulsion when the protein is inside the corona; the height of the insertion barrier is determined by the local osmotic pressure and the elastic deformation of the core, (ii) a local minimum occurs when the protein molecule is at the core-corona interface; the depth (a few kBT ’s) is related to the interfacial tension at the core-corona interface and (iii) a steep repulsion (several kBT ) when part of the protein molecule is dragged into the core. Hence, the protein molecules reside preferentially at the core-corona interface and the absorption as well as the release of the protein molecules has annealed rather than quenched characteristics. Upon an increase of the ionic strength it is possible to reach a critical micellization ionic (CMI) strength. With increasing ionic strength the aggregation numbers decrease strongly and only few proteins remain associated with the micelles near the CMI.

Elucidation of release characteristics of highly soluble drug trimetazidine hydrochloride from chitosan-carrageenan matrix tablets.

PubMed

Li, Liang; Wang, Linlin; Shao, Yang; Tian, Ye; Li, Conghao; Li, Ying; Mao, Shirui

2013-08-01

The aim of this study was to better understand the underlying drug release characteristics from matrix tablets based on the combination of chitosan (CS) and different types of carrageenans [kappa (κ)-CG, iota (ι)-CG, and lambda (λ)-CG]. Highly soluble trimetazidine hydrochloride (TH) was used as a model drug. First, characteristics of drug release from different formulations were investigated, and then in situ complexation capacity of CG with TH and CS was studied by differential scanning calorimetry and Fourier transform infrared spectroscopy. Erosion and swelling of matrix were also characterized to better understand the drug-release mechanisms. Effects of pH and ionic strength on drug release were also studied. It was found that not only ι-CG and λ-CG could reduce the burst release of TH by the effect of TH-CG interaction, CS-ι-CG- and CS-λ-CG-based polyelectrolyte film could further modify the controlled-release behavior, but not CS-κ-CG. High pH and high ionic strength resulted in faster drug release from CS-κ-CG- and CS-ι-CG-based matrix, but drug release from CS-λ-CG-based matrix was less sensitive to pH and ionic strength. In conclusion, CS-λ-CG-based matrix tablets are quite promising as controlled-release drug carrier based on multiple mechanisms. Copyright © 2013 Wiley Periodicals, Inc.

Evolution of carboxymethyl cellulose layer morphology on hydrophobic mineral surfaces: variation of polymer concentration and ionic strength.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka; Beattie, David A

2010-06-15

The adsorption of carboxymethyl cellulose (CMC) on the basal planes of talc and molybdenite has been studied using in situ atomic force microscope (AFM) imaging. These experiments were partnered with quantitative adsorption isotherm determinations on particulate samples. The isotherms revealed a clear increase of the CMC adsorbed amount upon increasing the solution ionic strength for adsorption on both minerals. In addition, the shapes of the isotherms changed in response to the change in the electrolyte concentration, with CMC on talc displaying stepped (10(-3) M KCl), Langmuir (10(-2) M KCl), then Freundlich isotherm shapes (10(-1) M KCl), and CMC on molybdenite displaying stepped (10(-3) M KCl), Freundlich (10(-2) M KCl), then Langmuir isotherm shapes (10(-1) M KCl). AFM imaging of the polymer layer on the mineral surfaces with varying solution conditions mirrored and confirmed the conclusions from the isotherms: as the polymer solution concentration increased, coverage on the basal plane increased; as the ionic strength increased, coverage on the basal plane increased and the morphology of the layer changed from isolated well-distributed polymer domains to extensive adsorption and formation of dense, uneven polymer domains/features. In addition, comparison of the talc and molybdenite datasets points toward the presence of different binding mechanisms for CMC adsorption on the talc and molybdenite basal plane surfaces. 2010 Elsevier Inc. All rights reserved.

Electroviscous Effects in Ceramic Nanofiltration Membranes.

PubMed

Farsi, Ali; Boffa, Vittorio; Christensen, Morten Lykkegaard

2015-11-16

Membrane permeability and salt rejection of a γ-alumina nanofiltration membrane were studied and modeled for different salt solutions. Salt rejection was predicted by using the Donnan-steric pore model, in which the extended Nernst-Planck equation was applied to predict ion transport through the pores. The solvent flux was modeled by using the Hagen-Poiseuille equation by introducing electroviscosity instead of bulk viscosity. γ-Alumina particles were used for ζ-potential measurements. The ζ-potential measurements show that monovalent ions did not adsorb on the γ-alumina surface, whereas divalent ions were highly adsorbed. Thus, for divalent ions, the model was modified, owing to pore shrinkage caused by ion adsorption. The ζ-potential lowered the membrane permeability, especially for membranes with a pore radius lower than 3 nm, a ζ-potential higher than 20 mV, and an ionic strength lower than 0.01 m. The rejection model showed that, for a pore radius lower than 3 nm and for solutions with ionic strengths lower than 0.01 m, there is an optimum ζ-potential for rejection, because of the concurrent effects of electromigration and convection. Hence, the model can be used as a prediction tool to optimize membrane perm-selectivity by designing a specific pore size and surface charge for application at specific ionic strengths and pH levels. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Site-Specific Modulation of Charge Controls the Structure and Stimulus Responsiveness of Intrinsically Disordered Peptide Brushes.

PubMed

Bhagawati, Maniraj; Rubashkin, Matt G; Lee, Jessica P; Ananthanarayanan, Badriprasad; Weaver, Valerie M; Kumar, Sanjay

2016-06-14

Intrinsically disordered proteins (IDPs) are an important and emerging class of materials for tailoring biointerfaces. While the importance of chain charge and resultant electrostatic interactions in controlling conformational properties of IDPs is beginning to be explored through in silico approaches, there is a dearth of experimental studies motivated toward a systematic study of these effects. In an effort to explore this relationship, we measured the conformations of two peptides derived from the intrinsically disordered neurofilament (NF) side arm domain: one depicting the wild-type sequence with four lysine-serine-proline repeats (KSP peptide) and another in which the serine residues were replaced with aspartates (KDP peptide), a strategy sometimes used to mimic phosphorylation. Using a variety of biophysical measurements including a novel application of scanning angle interference microscopy, we demonstrate that the KDP peptide assumes comparatively more expanded conformations in solution and forms significantly thicker brushes when immobilized on planar surfaces at high densities. In both settings, the peptides respond to changes in ambient ionic strength, with each peptide showing distinct stimulus-responsive characteristics. While the KDP peptide undergoes compaction with increasing ionic strength as would be expected for a polyampholyte, the KSP peptide shows biphasic behavior, with an initial compaction followed by an expanded state at a higher ionic strength. Together these results support the notion that modulation of charge on IDPs can regulate conformational and interfacial properties.

Sensitivity of the acid-base properties of clays to the methods of preparation and measurement. 2. Evidence from continuous potentiometric titrations.

PubMed

Duc, Myriam; Gaboriaud, Fabien; Thomas, Fabien

2005-09-01

The effects of experimental procedures on the acid-base consumption titration curves of montmorillonite suspension were studied using continuous potentiometric titration. For that purpose, the hysteresis amplitudes between the acid and base branches were found to be useful to systematically evaluate the impacts of storage conditions (wet or dried), the atmosphere in titration reactor, the solid-liquid ratio, the time interval between successive increments, and the ionic strength. In the case of storage conditions, the increase of the hysteresis was significantly higher for longer storage of clay in suspension and drying procedures compared to "fresh" clay suspension. The titration carried out under air demonstrated carbonate contamination that could only be cancelled by performing experiments under inert gas. Interestingly, the increase of the time intervals between successive increments of titrant strongly emphasized the amplitude of hysteresis, which could be correlated with the slow kinetic process specifically observed for acid addition in acid media. Thus, such kinetic behavior is probably associated with dissolution processes of clay particles. However, the resulting curves recorded at different ionic strengths under optimized conditions did not show the common intersection point required to define point of zero charge. Nevertheless, the ionic strength dependence of the point of zero net proton charge suggested that the point of zero charge of sodic montmorillonite could be estimated as lower than 5.

Surface acid-base behaviors of Chinese loess.

PubMed

Chu, Zhaosheng; Liu, Wenxin; Tang, Hongxiao; Qian, Tianwei; Li, Shushen; Li, Zhentang; Wu, Guibin

2002-08-15

Acid-base titration was applied to investigate the surface acid-base properties of a Chinese loess sample at different ionic strengths. The acidimetric supernatant was regarded as the system blank of titration to correct the influence of particle dissolution on the estimation of proton consumption. The titration behavior of the system blank could be described by the hydrolysis of Al3+ and Si(OH)4 in aqueous solution as well as the production of hydroxyaluminosilicates. The formation of Al-Si species on homogeneous surface sites by hydrous aluminum and silicic acid, released from solid substrate during the acidic titration, was considered in the model description of the back-titration procedure. A surface reaction model was suggested as follows: >SOH<-->SO(-)+H+, pK(a)(int)=3.48-3.98;>SOH+Al(3+)+H4SiO4<-->SOAl(OSi(OH)3(+)+2H+, pK(SC)=3.48-4.04. Two simple surface complexation models accounted for the interfacial structure, i.e., the constant capacitance model (CCM) and the diffuse layer model (DLM), and gave a satisfactory description of the experimental data. Considering the effect of ionic strength on the electrostatic profile at the solid-aqueous interface, the DLM was appropriate at the low concentrations (0.01 and 0.005 mol/L) of background electrolyte (NaNO3 in this study), while the CCM was preferable in the case of high ionic strength (0.1 mol/L).

Solubility and modeling acid-base properties of adrenaline in NaCl aqueous solutions at different ionic strengths and temperatures.

PubMed

Bretti, Clemente; Cigala, Rosalia Maria; Crea, Francesco; De Stefano, Concetta; Vianelli, Giuseppina

2015-10-12

Solubility and acid-base properties of adrenaline were studied in NaCl aqueous solutions at different ionic strengths (0