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.

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

PubMed

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

2010-08-15

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

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

PubMed

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

2016-01-28

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

Application of quartz crystal microbalance to study the impact of pH and ionic strength on protein-silicone oil interactions.

PubMed

Dixit, Nitin; Maloney, Kevin M; Kalonia, Devendra S

2011-06-30

In this study, we have used quartz crystal microbalance (QCM) to quantitate the adsorption of a protein on silicone oil coated surfaces as a function of protein concentration, pH and ionic strength using a 5 MHz quartz crystal. Protein adsorption isotherms were generated at different solution pH and ionic strengths. Surface saturation concentrations were selected from adsorption isotherms and used to generate adsorption profiles from pH 3.0 to 9.0, and at ionic strengths of 10 mM and 150 mM. At low ionic strength (10mM) and pH 5.0 (close to the isoelectric point of the protein), maximum adsorption of protein to the silicone oil surface was observed. At higher ionic strength (150 mM), no significant pH influence on adsorption was observed. QCM could be used as a reliable technique to study the binding of proteins to silicone oil coated surfaces. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

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

PubMed

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

2018-06-14

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

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

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

PubMed

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

2017-09-28

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-12-14

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

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

PubMed

Pourret, Olivier; Houben, David

2018-02-01

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

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

PubMed

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

2015-01-01

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

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.

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.

Effects of ionic strength, temperature, and pH on degradation of selected antibiotics

USGS Publications Warehouse

Loftin, K.A.; Adams, C.D.; Meyer, M.T.; Surampalli, R.

2008-01-01

Aqueous degradation rates, which include hydrolysis and epimerization, for chlorretracycline (CTC), oxytetracycline (OTC), tetracycline (TET), lincomycin (LNC), sulfachlorpyridazine (SCP), sulfadimethoxine (SDM), sulfathiazole (STZ), trimethoprim (TRM), and tylosin A (TYL) were studied as a function of ionic strength (0.0015, 0.050, or 0.084 mg/L as Na2HPO4), temperature (7, 22, and 35??C), and pH (2, 5, 7, 9, and 11). Multiple linear regression revealed that ionic strength did not significantly affect (?? = 0.05) degradation rates for all compounds, but temperature and pH affected rates for CTC, OTC, and TET significandy (?? = 0.05). Degradation also was observed for TYL at pH 2 and 11. No significant degradation was observed for LNC, SCR SDM, STZ, TRM, and TYL (pH 5, 7, and 9) under study conditions. Pseudo first-order rate constants, half-lives, and Arrhenius coefficients were calculated where appropriate. In general, hydrolysis rates for CTC, OTC, and TET increased as pH and temperature increased following Arrhenius relationships. Known degradation products were used to confirm that degradation had occurred, but these products were not quantified. Half-lives ranged from less than 6 h up to 9.7 wk for the tetracyclines and for TYL (pH 2 and 11), but no degradation of LIN, the sulfonamides, or TRM was observed during the study period. These results indicate that tetracyclines and TYL at pH 2 and 11 are prone to pH-mediated transformation and hydrolysis in some cases, but not the sulfonamides, LIN nor TRM are inclined to degrade under study conditions. This indicates that with the exception of CTC OTC, and TET, pH-mediated reactions such as hydrolysis and epimerization are not likely removal mechanisms in surface water, anaerobic swine lagoons, wastewater, and ground water. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

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.

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.

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

PubMed

Dong, Shunan; Sun, Yuanyuan; Gao, Bin; Shi, Xiaoqing; Xu, Hongxia; Wu, Jianfeng; Wu, Jichun

2017-08-01

In this work, column experiments were conducted to investigate the transport characteristics of graphene oxide (GO) nanoparticles in limestone media under various electrolytes, solution pH, and humic acid (HA) concentration conditions. In the limestone media, GO exhibited relatively low mobility with the mass recovery rate lower than 65.2%, even when solution ionic strength was low. The presence of HA enhanced its mobility. In addition, the presence of S 2- , a divalent anion, also promoted GO transport in limestone media compared to Cl - under similar ionic strength conditions through neutralizing more positive charge and thus diminishing the cation bridging. Solution pH showed slight effect on the transport of GO in limestone with the mass recovery range from 40.3% to 51.7%. Over all, decreases in solution pH, HA concentration and increases in solution ionic strength reduced the mobility of GO in the limestone media under the tested conditions. These results indicated both environmental conditions and media characteristics played important roles in controlling GO fate and transport in porous media. The one-site kinetic deposition model was applied to describe the interactions between the GO and limestone media and model simulations fitted the observed experimental data very well. As limestone is an important component of aquiferous media in subsurface, findings from this study elucidated the key factors and processes controlling the fate of GO particles in limestone media, which can inform the prediction and assessment of the risks of GO in groundwater environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Anions adsorption onto nanoparticles: effects on colloid stability and mobility in the environment

NASA Astrophysics Data System (ADS)

Missana, Tiziana; Benedicto, Ana; Mayordomo, Natalia; Alonso, Ursula

2013-04-01

Nanoparticles and colloids can enhance the contaminant transport in groundwater, if the contaminant is irreversibly adsorbed onto their surface; additionally colloids must be stable and mobile under the chemical conditions of the environment of interest. Colloid stability and mobility are factors directly related to the chemistry of the water, which determines the charge and size of the particles, but these colloidal properties can also be affected by the contaminant adsorption. This last point, which is potentially very relevant on the overall colloid-driven transport, is scarcely investigated. The evaluation of the stability of a colloidal system is generally carried out by measuring the aggregation kinetic after the change of a specific chemical condition, mainly pH or ionic strength of the aqueous solution. The effect of anion adsorption onto the stability of colloidal systems is mostly neglected. Parameters of the nanoparticles,as the point of zero charge (pH PCZ) or the isoelectric point (pH IEP) are determined with "inert" electrolytes and this might not be representative of their real behavior in natural systems. In this work, the effects of the Se(IV) (selenite) adsorption on alumina (Al2O3) nanoparticles have been analyzed. Selenite adsorption was studied in a wide range of pH (2-12) and ionic strengths (0.0005 - 0.1 M in NaClO4) and the effect of the adsorption on the main properties of the colloids (size and charge) were analyzed. Se adsorption on Al2O3 is almost independent of the ionic strength and decreases with increasing pH; sorption data were successfully fit by surface complexation modeling. Selenite adsorption (at medium-high surface occupancies) clearly affected the stability of Al2O3 colloids, with a clear shift of the isoelectric point towards more acid pH and enhancing colloid aggregation when the ionic strength increases. Considering the obtained results, the effect of anions in the chemical composition of natural water, frequently not accounted for in stability studies, will be discussed, as well as their implications on possible colloid-driven selenite transport in the environment.

Nanomechanical properties of the sea-water bacterium Paracoccus seriniphilus--a scanning force microscopy approach.

PubMed

Davoudi, Neda; Müller-Renno, Christine; Ziegler, Christiane; Raid, Indek; Seewig, Jörg; Schlegel, Christin; Muffler, Kai; Ulber, Roland

2015-03-02

The measurement of force-distance curves on a single bacterium provides a unique opportunity to detect properties such as the turgor pressure under various environmental conditions. Marine bacteria are very interesting candidates for the production of pharmaceuticals, but are only little studied so far. Therefore, the elastic behavior of Paracoccus seriniphilus, an enzyme producing marine organism, is presented in this study. After a careful evaluation of the optimal measurement conditions, the spring constant and the turgor pressure are determined as a function of ionic strength and pH. Whereas the ionic strength changes the turgor pressure passively, the results give a hint that the change to acidic pH increases the turgor pressure by an active mechanism. Furthermore, it could be shown, that P. seriniphilus has adhesive protrusions outside its cell wall.

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

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.

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.

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

PubMed Central

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

2017-01-01

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

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.

Study on aggregation behavior of Cytochrome C-conjugated silver nanoparticles using asymmetrical flow field-flow fractionation.

PubMed

Kim, Sun Tae; Lee, Yong-Ju; Hwang, Yu-Sik; Lee, Seungho

2015-01-01

In this study, 40 nm silver nanoparticles (AgNPs) were synthesized using the citrate reduction method and then the surface of AgNPs was modified by conjugating Cytochrome C (Cyto C) to improve stability and to enhance bioactivity and biocompatibility of AgNPs. It is known that Cyto C may undergo conformational changes under various conditions of pH, temperature, ionic strength, etc., resulting in aggregation of the particles. These parameters also affect the size and size distribution of Cyto C-conjugated AgNPs (Cyto C-AgNP). ζ-potential measurement revealed that the adsorption of Cyto C on the surface of AgNPs is saturated at the molar ratio [Cyto C]/[AgNPs] above about 300. Asymmetrical flow field-flow fractionation (AsFlFFF) analysis showed that hydrodynamic diameter of AgNPs increases by about 4 nm when the particle is saturated by Cyto C. The aggregation behavior of Cyto C-AgNP at various conditions of pH, temperature and ionic strength were investigated using AsFlFFF and UV-vis spectroscopy. It was found that the aggregation of Cyto C-AgNP increases with decreasing pH, increasing temperature and ionic strength due to denaturation of Cyto C on AgNPs and reduction in the thickness of electrostatic double layer on the surface of Cyto C-AgNP. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation of ionic-crosslinked chitosan-based gel beads and effect of reaction conditions on drug release behaviors.

PubMed

Chen, Shilan; Liu, Mingzhu; Jin, Shuping; Wang, Bin

2008-02-12

Drug-loaded chitosan (CS) beads were prepared under simple and mild condition using trisodium citrate as ionic crosslinker. The beads were further coated with poly(methacrylic acid) (PMAA) by dipping the beads in PMAA aqueous solution. The surface and cross-section morphology of these beads were observed by scanning electron microscopy and the observation showed that the coating beads had core-shell structure. In vitro release of model drug from these beads obtained under different reaction conditions was investigated in buffer medium (pH 1.8). The results showed that the rapid drug release was restrained by PMAA coating and the optimum conditions for preparing CS-based drug-loaded beads were decided through the effect of reaction conditions on the drug release behaviors. In addition, the drug release mechanism of CS-based drug-loaded beads was analyzed by Peppa's potential equation. According to this study, the ionic-crosslinked CS beads coated by PMAA could serve as suitable candidate for drug site-specific carrier in stomach.

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

PubMed

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

2017-03-24

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

[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.

Effect of rhamnolipid biosurfactant on solubilization of polycyclic aromatic hydrocarbons.

PubMed

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

2015-12-15

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

Solution and surface effects on plasma fibronectin structure

PubMed Central

1983-01-01

As assessed by electron microscopy, the reported shape of the plasma fibronectin molecule ranges from that of a compact particle to an elongated, rod-like structure. In this study, we evaluated the effects of solution and surface conditions on fibronectin shape. Freeze-dried, unstained human plasma fibronectin molecules deposited at pH 7.0-7.4 onto carbon films and examined by scanning transmission electron microscopy appeared relatively compact and pleiomorphic, with approximate average dimensions of 24 nm X 16 nm. Negatively stained molecules also had a similar shape but revealed greater detail in that we observed irregular, yarn-like structures. Glutaraldehyde-induced intramolecular cross-linking did not alter the appearance of plasma fibronectin. Molecules deposited at pH 2.8, pH 9.3, or after succinylation were less compact than those deposited at neutral pH. In contrast, fibronectin molecules sprayed onto mica surfaces at pH 7, rotary shadowed, and examined by transmission electron microscopy were elongated and nodular with a contour length of 120-130 nm. Sedimentation velocity experiments and electron microscopic observations indicate that fibronectin unfolds when it is succinylated, when the ionic strength is raised at pH 7, or when the pH is adjusted to 9.3 or 2.8. Greater unfolding is observed at pH 2.8 at low ionic strength (less than 0.01) compared with material at that pH in 0.15 M NaCl solution. We conclude that (a) the shape assumed by the fibronectin molecule can be strongly affected by solution conditions and by deposition onto certain surfaces; and that (b) the images of fibronectin seen by scanning transmission electron microscopy at neutral pH on carbon film are representative of molecules in physiologic solution. PMID:6417145

The effect of physiological conditions on the surface structure of proteins: Setting the scene for human digestion of emulsions

NASA Astrophysics Data System (ADS)

Maldonado-Valderrama, J.; Gunning, A. P.; Ridout, M. J.; Wilde, P. J.; Morris, V. J.

2009-10-01

Understanding and manipulating the interfacial mechanisms that control human digestion of food emulsions is a crucial step towards improved control of dietary intake. This article reports initial studies on the effects of the physiological conditions within the stomach on the properties of the film formed by the milk protein ( β -lactoglobulin) at the air-water interface. Atomic force microscopy (AFM), surface tension and surface rheology techniques were used to visualize and examine the effect of gastric conditions on the network structure. The effects of changes in temperature, pH and ionic strength on a pre-formed interfacial structure were characterized in order to simulate the actual digestion process. Changes in ionic strength had little effect on the surface properties. In isolation, acidification reduced both the dilatational and the surface shear modulus, mainly due to strong repulsive electrostatic interactions within the surface layer and raising the temperature to body temperature accelerated the rearrangements within the surface layer, resulting in a decrease of the dilatational response and an increase of surface pressure. Together pH and temperature display an unexpected synergism, independent of the ionic strength. Thus, exposure of a pre-formed interfacial β -lactoglobulin film to simulated gastric conditions reduced the surface dilatational modulus and surface shear moduli. This is attributed to a weakening of the surface network in which the surface rearrangements of the protein prior to exposure to gastric conditions might play a crucial role.

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.

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

PubMed

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

2014-10-31

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

Impact of multicomponent ionic transport on pH fronts propagation in saturated porous media

NASA Astrophysics Data System (ADS)

Muniruzzaman, Muhammad; Rolle, Massimo

2016-04-01

Multicomponent ionic interactions have been increasingly recognized as important factors for the displacement of charged species in porous media under both diffusion- [1,2] and advection-dominated flow regimes [3,4]. In this study we investigate the propagation of pH fronts during multicomponent ionic transport in saturated porous media under flow-through conditions. By performing laboratory bench-scale experiments combined with numerical modeling we show the important influence of Coulombic effects on proton transport in the presence of ionic admixtures. The experiments were performed in a quasi two-dimensional flow-through setup under steady-state flow and transport conditions. Dilute solutions of hydrochloric acid with MgCl2 (1:2 strong electrolyte) were used as tracer solutions to experimentally test the effect of electrochemical cross-coupling on the migration of diffusive/dispersive pH fronts. We focus on two experimental scenarios, with different composition of tracer solutions, causing remarkably different effects on the propagation of the acidic fronts with relative differences in the penetration depth of pH fronts of 36% between the two scenarios and of 25% and 15% for each scenario with respect to the transport of ions at liberated state (i.e., without considering the charge effects). Also significant differences in the dilution of the distinct ionic plumes, quantified using the flux-related dilution index at the laboratory bench scale [5], were measured at the outflow of the flow-through system. The dilution of the pH plumes also changed considerably (26% relative difference) in the two flow-through experiments only due to the different composition of the pore water solution and to the electrostatic coupling of the ions in the flow-through setups. Numerical transport simulations were performed to interpret the laboratory experiments. The simulations were based on a multicomponent ionic formulation accurately capturing the Coulombic interactions between the transported ions in the flow-through system. The results of purely forward simulations show a very good agreement with the high-resolution measurements performed at the outlet of the flow-through setup and illustrate the importance of charge effects on pH fronts propagation in porous media. [1] Giambalvo, E. R., C. I. Steefel, A. T. Fisher, N. D. Rosenberg, and C. G. Wheat (2002), Effect of fluid-sediment reaction on hydrothermal fluxes of major elements, eastern flank of the Juan de Fuca Ridge, Geochim. Cosmochim. Acta, 66, 1739-1757. [2] Appelo, C. A. J., and P. Wersin (2007), Multicomponent diffusion modeling in clay systems with application to the diffusion of tritium, iodide, and sodium in opalinus clay, Environ. Sci. Technol., 41, 5002-5007. [3] Rolle, M., M. Muniruzzaman, C. M. Haberer, and P. Grathwohl (2013), Coulombic effects in advection-dominated transport of electrolytes in porous media: Multicomponent ionic dispersion, Geochim. Cosmochim. Acta, 120, 195-205. [4] Muniruzzaman, M., C. M. Haberer, P. Grathwohl, and M. Rolle (2014), Multicomponent ionic dispersion during transport of electrolytes in heterogeneous porous media: Experiments and model-based interpretation, Geochim. Cosmochim. Acta, 141, 656-669. [5] Rolle, M., G. Chiogna, D. L. Hochstetler, and P. K. Kitanidis (2013), On the importance of diffusion and compound-specific mixing for groundwater transport: An investigation from pore to field scale, J. Contam. Hydrol., 153, 51-68.

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

The strong affinity of carbon nanotubes (CNTs) to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength) and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB) from multi-walled carbon nanotubes (MWNTs). The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH < 7 vs. pH > 7). In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs. PMID:28348336

Improved in situ saccharification of cellulose pretreated by dimethyl sulfoxide/ionic liquid using cellulase from a newly isolated Paenibacillus sp. LLZ1.

PubMed

Hu, Dongxue; Ju, Xin; Li, Liangzhi; Hu, Cuiying; Yan, Lishi; Wu, Tianyun; Fu, Jiaolong; Qin, Ming

2016-02-01

A cellulase producing strain was newly isolated from soil samples and identified as Paenibacillus sp. LLZ1. A novel aqueous-dimethyl sulfoxide (DMSO)/1-ethyl-3-methylimidazolium diethyl phosphate ([Emin]DEP)-cellulase system was designed and optimized. In the pretreatment, DMSO was found to be a low-cost substitute of up to 70% ionic liquid to enhance the cellulose dissolution. In the enzymatic saccharification, the optimum pH and temperature of the Paenibacillus sp. LLZ1 cellulase were identified as 6.0 and 40°C, respectively. Under the optimized reaction condition, the conversion of microcrystalline cellulose and bagasse cellulose increased by 39.3% and 37.6%, compared with unpretreated cellulose. Compared to current methods of saccharification, this new approach has several advantages including lower operating temperature, milder pH, and less usage of ionic liquid, indicating a marked progress in environmental friendly hydrolysis of biomass-based materials. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed

Chen, Changlun; Wang, Xiangke

2007-02-01

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

Ionic substitution of Mg2+ for Al3+ and Fe3+ with octahedral coordination in hydroxides facilitate precipitation of layered double hydroxides

NASA Astrophysics Data System (ADS)

Paikaray, Susanta; Essilfie-Dughan, Joseph; Hendry, M. Jim

2018-01-01

Precipitation of hydrotalcite-like layered double hydroxides (HT-LDHs) from CO32--SO42--rich acidic and alkaline aqueous media through ionic substitution of Mg2+ for Al3+ + Fe3+ and vice versa was investigated under ambient conditions. Diffractogram, spectroscopic, microprobe, microscopic, and synchrotron techniques were used to examine the mechanisms involved. The cations facilitated rapid precipitation of HT-LDH in alkaline conditions (pH ≥ 8.2) with SO42- and CO32- as the counter charge balancing interlayer anions, while initial formation of Fe3+- and Al3+-hydroxides in acidic conditions (pH ≥ 2.4) with subsequent transformation to MgAlFe-type HT-LDH (pH ≥ 8.2) occurred through substitution of Mg2+ for Al3+ and Fe3+. Substitution of Al3+ and Fe3+ in Mg2+-hydroxides did not yield HT-LDH, while the reverse, i.e., Mg2+ substitution in Al3+ and Fe3+-hydroxides, produced initial poorly ordered amorphous HT-LDH that gained better crystallinity and crystallite size upon neutralization. Linear combination fit analyses of XANES data suggest schwertmannite constituted the predominant Fe-phase until pH ∼3.7 followed by ferrihydrite and eventually HT-LDH after pH ≥ 10; basaluminite and epsomite constituted the predominant Al and Mg phases until pH ∼4.5, after which HT-LDH with minor Al(OH)3 and HT-LDH with brucite, respectively, predominated. The study highlights that Mg2+ substitution in Al- and Fe-precipitates is the governing mechanism for HT-LDH precipitation in oxic environments through neutralization of acidic cationic aqueous residues.

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.

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

PubMed

Hoggett, J G; Kellett, G L

1976-06-15

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

Electrodeionization method

DOEpatents

Lin, YuPo J.; Hestekin, Jamie; Arora, Michelle; St. Martin, Edward J.

2004-09-28

An electrodeionization method for continuously producing and or separating and/or concentrating ionizable organics present in dilute concentrations in an ionic solution while controlling the pH to within one to one-half pH unit method for continuously producing and or separating and/or concentrating ionizable organics present in dilute concentrations in an ionic solution while controlling the pH to within one to one-half pH unit.

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

PubMed

Odzak, Niksa; Kistler, David; Sigg, Laura

2017-07-01

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

Ionic calcium determination in skim milk with molecular probes and front-face fluorescence spectroscopy: simple linear regression.

PubMed

Gangidi, R R; Metzger, L E

2006-11-01

The purpose of this study was to determine if the ionic calcium content of skim milk could be determined using molecular probes and front-face fluorescence spectroscopy. Current methods for determining ionic calcium are not sensitive, overestimate ionic calcium, or require complex procedures. Molecular probes designed specifically for measuring ionic calcium could potentially be used to determine the ionic calcium content of skim milk. The goal of the current study was to develop foundation methods for future studies to determine ionic calcium directly in skim milk and other dairy products with molecular probes and fluorescence spectroscopy. In this study, the effect of pH on calcium-sensitive fluorescent probe (Rhod-5N and Fluo-5N) performance using various concentrations of skim milk was determined. The pH of diluted skim milk (1.9 to 8.9% skim milk), was adjusted to either 6.2 or 7.0, after which the samples were analyzed with fluorescent probes (1 microM) and front-face fluorescence spectroscopy. The ionic calcium content of each sample was also determined using a calcium ion-selective electrode. The results demonstrated that the ionic calcium content of each sample was highly correlated (R2 > 0.989) with the fluorescence intensities of the probe-calcium adduct using simple linear regression. Higher than suggested ionic calcium contents of 1,207 and 1,973 microM were determined with the probes (Fluo-5N and Rhod-5N) in diluted skim milk with pH 7.0 and 6.2, respectively. The fluorescence intensity of the probe-calcium adduct decreased with a decrease in pH for the same ionic calcium concentration. This study demonstrates that Fluo-5N and Rhod-5N can be used to determine the ionic-calcium content of diluted milk with front-face fluorescence spectroscopy. Furthermore, these probes may also have the potential to determine the ionic calcium content of undiluted skim milk.

Interaction of proteins with weak amphoteric charged membrane surfaces: effect of pH.

PubMed

Matsumoto, Hidetoshi; Koyama, Yoshiyuki; Tanioka, Akihiko

2003-08-01

Weak amphoteric charged membranes were prepared by the graft copolymerization of poly(ethylene glycol) (PEG) derivatives with pendant ionizable groups onto polyethylene (PE) porous membranes. Two types of weak amphoteric charged membranes and two types of weak single charged membranes were prepared. The pH dependence of the protein (fluorescein isothiocyanate-labeled bovine serum albumin, FITC-BSA) adsorption onto the membranes was investigated by fluorescence spectroscopy. The interfacial charge properties of the membranes and protein were also characterized at different pH values by streaming potential and electrophoretic light scattering (ELS) measurements, respectively. The adsorbed amount onto each ionic PEG chain grafted membrane showed a uniform maximum value near the isoelectric point (IEP) of the protein (pH 4.1). On both sides of the IEP (pHs 3.3 and 7.2), the adsorption experiments and zeta (zeta) potential measurements were well correlated: the contribution of electrostatic interaction was dominant for the protein adsorption behavior. In the alkaline condition (pH 10.2), the adsorption experiments contradict the zeta potential measurements. It suggested that the conformational change of protein molecule influenced the adsorption behavior. Finally, these results indicated the potential of controlling the protein-ionic PEG chain interaction on the membrane surfaces by the pH adjustment of the outer solution.

MS-2 and poliovirus transport in porous media: Hydrophobic effects and chemical perturbations

NASA Astrophysics Data System (ADS)

Bales, Roger C.; Li, Shimin; Maguire, Kimberly M.; Yahya, Moyasar T.; Gerba, Charles P.

1993-04-01

In a series of pH 7 continuous-flow column experiments, removal of the bacteriophage MS-2 by attachment to silica beads had a strong, systematic dependence on the amount of hydrophobic surface present on the beads. With no hydrophobic surface, removal of phage at pH 5 was much greater than at pH 7. Release of attached phage at both pH values did occur, but was slow; breakthrough curves exhibited tailing. Poliovirus attached to silica beads at pH 5.5 much more than at pH 7.0, and attachment was also slowly reversible. Time scales for phage and poliovinis attachment were of the order of hours. The sticking efficiency factor (α), reflecting microscaie physicochemical influences on virus attachment, was in the range of 0.0007-0.02. Phage release was small but measurable under steady state conditions. Release was enhanced by lowering ionic strength and by introducing beef extract, a high-ionic-strength protein solution. Results show that viruses experience reversible attachment/detachment (sometimes termed sorption), that large chemical perturbations are needed to induce rapid virus detachment, and that viruses should be quite mobile in sandy porous media. Even small amounts of hydrophobic organic material in the porous media (≥0.001%) can retard virus transport.

Zeta Potential and Aggregation of Virus-Like Particle of Human Norovirus and Feline Calicivirus Under Different Physicochemical Conditions.

PubMed

Samandoulgou, Idrissa; Fliss, Ismaïl; Jean, Julie

2015-09-01

Although the spread of human norovirus reportedly depends on its ability to bind to food materials, the mechanism of the phenomenon remains unknown. Since protein size and electrical charge are reportedly important parameters in their adsorption, the current work is focused on determining human noroviruses isoelectric point (IEP), electrical charge and aggregate size at different pH, ionic strength (IS), and temperature. Using the baculovirus expression vector system, we produced and purified virus-like particles (VLPs) of GI.1 and GII.4 noroviruses and feline calicivirus, determined their IEP, and examined their size and electrical charge using a Zetasizer Nano ZS apparatus. Shape and size were also visualized using transmission electron microscopy. IEPs were found close to pH 4. Net charge increased as the pH deviated from the IEP. VLPs were negatively charged at all IS tested and showed a gradual decrease in charge with increasing IS. At low temperature, VLPs were 20-45 nm in diameter at pH far from their IEP and under almost all IS conditions, while aggregates appeared at or near the IEP. At increased temperatures, aggregates appeared at or near the IEP and at high IS. Aggregation at the IEP was also confirmed by microscopy. This suggests that electrostatic interactions would be the predominant factor in VLPs adhesion at pH far from 4 and at low ionic strength. In contrast, non-electrostatic interactions would prevail at around pH 4 and would be reinforced by aggregates, since size generally favors multiple bonding with sorbents.

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

PubMed

Tansel, Berrin; Lunn, Griffin; Monje, Oscar

2018-03-01

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

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

NASA Astrophysics Data System (ADS)

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

1998-05-01

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

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.

Stability and activity of lysozyme in stoichiometric and non-stoichiometric protic ionic liquid (PIL)-water systems

NASA Astrophysics Data System (ADS)

Wijaya, Emmy C.; Separovic, Frances; Drummond, Calum J.; Greaves, Tamar L.

2018-05-01

There has been a substantial increase in enzyme applications within the biochemical and pharmaceutical industries, for example, as industrial biocatalysts. However, enzymes have narrow marginal stability which makes them prone to become inactive and/or denature with a slight change in the solvent environment. Typically industrial applications require harsher solvent environments than enzyme native environments, and hence there is a need to understand solvent-protein interactions in order to develop strategies to maintain, or enhance, the enzymatic activity under industrially relevant solvent conditions. Previously we have shown that protic ionic liquids (PILs) with water can have a stabilising effect on lysozyme, with a large variation dependent on which PIL ions are present, and the water concentration [E. C. Wijaya et al., Phys. Chem. Chem. Phys. 18(37), 25926-25936 (2016)]. Here we extend on this work using non-stoichiometric aqueous PIL solvents to investigate, and isolate, the role of pH and ionicity on enzymes. We have used the PILs ethylammonium nitrate (EAN) and ethanolammonium formate (EOAF) since our previous work has identified these as good solvents for lysozyme. Solvent libraries were made from these two PILs with an additional precursor acid or base to modify the acidity/basicity of the neutral stoichiometric PIL, and with water added, to have solutions with 4-17 mol. % of the PIL ions in water. Molar ratios of base:acid were varied between 1:1.05 and 2:1 for EAN and 1:1.25 and 2:1 for EOAF, which enabled from highly basic to highly acidic solutions to be obtained. This was to modify the acidity/basicity of the neutral stoichiometric PILs, without the addition of buffers. The structure and stability of hen egg white lysozyme (HEWL) were explored under these solvent conditions using synchrotron small angle X-ray scattering (SAXS), Fourier transform infrared (FTIR), and activity assays. The radius of gyration and Kratky plots obtained from the SAXS data showed little change with varying ionicity or acid:base ratio. FTIR showed that α-helix was maintained in all, except for the most acidic solvent conditions. The activity data show that HEWL was active between pH 0 and 11 for the EA:N-water system and pH 4.4 and 11 for the EOA:F-water system. This work indicates that ionic liquids have the potential to enable enzymes to maintain activity across a broader range of solvent conditions.

Sorption of Eu(III) on granite: EPMA, LA-ICP-MS, batch and modeling studies.

PubMed

Fukushi, Keisuke; Hasegawa, Yusuke; Maeda, Koushi; Aoi, Yusuke; Tamura, Akihiro; Arai, Shoji; Yamamoto, Yuhei; Aosai, Daisuke; Mizuno, Takashi

2013-11-19

Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages.

Analysis of SAT Type Foot-And-Mouth Disease Virus Capsid Proteins and the Identification of Putative Amino Acid Residues Affecting Virus Stability

PubMed Central

Maree, Francois F.; Blignaut, Belinda; de Beer, Tjaart A. P.; Rieder, Elizabeth

2013-01-01

Foot-and-mouth disease virus (FMDV) initiates infection by adhering to integrin receptors on target cells, followed by cell entry and disassembly of the virion through acidification within endosomes. Mild heating of the virions also leads to irreversible dissociation into pentamers, a characteristic linked to reduced vaccine efficacy. In this study, the structural stability of intra- and inter-serotype chimeric SAT2 and SAT3 virus particles to various conditions including low pH, mild temperatures or high ionic strength, was compared. Our results demonstrated that while both the SAT2 and SAT3 infectious capsids displayed different sensitivities in a series of low pH buffers, their stability profiles were comparable at high temperatures or high ionic strength conditions. Recombinant vSAT2 and intra-serotype chimeric viruses were used to map the amino acid differences in the capsid proteins of viruses with disparate low pH stabilities. Four His residues at the inter-pentamer interface were identified that change protonation states at pH 6.0. Of these, the H145 of VP3 appears to be involved in interactions with A141 in VP3 and K63 in VP2, and may be involved in orientating H142 of VP3 for interaction at the inter-pentamer interfaces. PMID:23717387

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.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Effect of preparation conditions on properties and permeability of chitosan-sodium hexametaphosphate capsules.

PubMed

Angelova, N; Hunkeler, D

2001-01-01

Capsules were obtained by interpolymer complexation between chitosan (polycation) and sodium hexametaphosphate (SMP, oligoanion). The effect of the preparation conditions on the capsule characteristics was evaluated. Specifically, the influence of variables such as pH, ionic strength, reagent concentration, and additives on the capsule permeability properties was investigated using dextran as a model permeant. The capsule membrane permeability was found to increase by decreasing the chitosan/SMP ratio as well as adding mannitol to the oligoanion recipient bath. Increasing the ionic strength or the pH of the initial chitosan solution was also found to enhance the membrane permeability, moving the membrane exclusion limit to higher values. Generally, the capsules prepared tinder all tested conditions had a relatively low permeability which rarely exceeded a molecular cut-off of 40 kD based on dextran standards. Furthermore, the diffusion rate showed a strong temporal dependence, indicating that the capsules prepared under various conditions exhibit different apparent pore size densities on the surface. The results indicated that, in order to obtain the desired capsule mass-transfer properties, the preparation conditions should be carefully considered and adjusted. Adding a polyol as well as low salt amount (less than 0.15%) is preferable as a means of modulating the diffusion characteristics, without disturbing the capsule mechanical stability.

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

PubMed

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

2018-02-01

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

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

PubMed

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

2015-12-30

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

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

PubMed

Curtin, Justin Paul; Wang, Minji

2017-08-01

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

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

PubMed

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

2014-07-01

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

Physical gelation of chitosan in the presence of beta-glycerophosphate: the effect of temperature.

PubMed

Cho, Jaepyoung; Heuzey, Marie-Claude; Bégin, André; Carreau, Pierre J

2005-01-01

When adding beta-glycerophosphate (beta-GP), a weak base, to chitosan aqueous solutions, the polymer remains in solution at neutral pH and room temperature, while homogeneous gelation of this system can be triggered upon heating. It is therefore one of the rare true physical chitosan hydrogels. In this study, physicochemical and rheological properties of chitosan solutions in the presence of acetic acid and beta-GP were investigated as a function of temperature in order to gain a better understanding of the gelation mechanisms. The gel structure formed at high temperature was only partially thermoreversible upon cooling to 5 degrees C because of the existence of remaining associations, confirmed by the spontaneous recovery of the gel after breakup at low temperature. Increasing temperature had no effect on the pH values of this system, while conductivity (and calculated ionic strength) increased. Values from the pH measurements were used to estimate the degree of protonation of each species as a function of temperature. The decreasing ratio of -NH3+ in chitosan and -OPO(O-)2 in beta-GP suggested reduced chitosan solubility along with a diminution of ionic interactions such as ionic bridging with increasing temperature. On the other hand, the increased ionic strength as a function of temperature, in the presence of beta-GP, enhanced screening of electrostatic repulsion and increased hydrophobic effect, resulting in favorable conditions for gel formation. Therefore, our study suggests that hydrophobic interactions and reduced solubility are the main driving force for chitosan gelation at high temperature in the presence of beta-GP.

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

PubMed

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

2015-02-25

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

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.

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

USGS Publications Warehouse

Roy, Sujoy B.; Dzombak, David A.

1997-01-01

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

Acid-base characterization of 5-hydroxypyrazine-2-carboxylic acid and the role of ionic equilibria in the optimization of some process conditions for its biocatalytic production.

PubMed

Sak-Bosnar, M; Kovar, K

2005-10-01

This paper describes the use of potentiometric titration to determine the relevant acid-base properties of 5-hydroxypyrazine-2-carboxylic acid (5OH-PYCA), an important intermediate in the production of tuberculostatics. The data obtained were used for calculation of the dissociation constants of 5OH-PYCA. It was found that 5OH-PYCA dissociates in two steps, with the corresponding dissociation constants pK (a1)=3.42 and pK (a2)=7.96, designating 5OH-PYCA as a medium weak acid (1st step). The distribution diagram of dissociated species and the buffer-strength diagram of 5OH-PYCA provide useful information about its behaviour at different pH. The ionic equilibria data obtained can be used for selection of the optimum pH for biotransformation of pyrazine-2-carboxylic acid (PYCA) and for prediction of pH changes during the biotransformation. These data can also be used for selection of the optimum pH for precipitating 5OH-PYCA in downstream processing. All computations have been optimized by mathematical modelling using Solver.

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

PubMed

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

2016-04-01

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

Screening for Cellulase Encoding Clones in Metagenomic Libraries.

PubMed

Ilmberger, Nele; Streit, Wolfgang R

2017-01-01

For modern biotechnology there is a steady need to identify novel enzymes. In biotechnological applications, however, enzymes often must function under extreme and nonnatural conditions (i.e., in the presence of solvents, high temperature and/or at extreme pH values). Cellulases have many industrial applications from the generation of bioethanol, a realistic long-term energy source, to the finishing of textiles. These industrial processes require cellulolytic activity under a wide range of pH, temperature, and ionic conditions, and they are usually carried out by mixtures of cellulases. Investigation of the broad diversity of cellulolytic enzymes involved in the natural degradation of cellulose is necessary for optimizing these processes.

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.

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

PubMed

Chakraborty, Subhashis; Shukla, Dali; Jain, Achint; Mishra, Brahmeshwar; Singh, Sanjay

2009-07-15

The effect of surfactants on the solubility of a new phosphate salt of carvedilol was investigated at different biorelevent pH to evaluate their solubilization capacity. Solutions of different classes of surfactants viz., anionic-sodium dodecyl sulfate (SDS) and sodium taurocholate (STC), cationic-cetyltrimethylammonium bromide (CTAB) and non-ionic-Tween 80 (T80) were prepared in the concentration range of 5-35 mmol dm(-3) in buffer solutions of pH 1.2, 3.0, 4.5, 5.8, 6.8 and 7.2. The solubility data were used to calculate the solubilization characteristics viz. molar solubilization capacity, water micelle partition coefficient, free energy of solubilization and binding constant. Solubility enhancement in basic pH was in following order: CTAB>T80>SDS>STC. CTAB and T80 showed remarkable solubility enhancement in acidic pH as well. Among the anionic surfactants, solubility in acidic medium was retarded except at pH 1.2 in case of SDS. Cationic and non-ionic surfactants were found to be suitable for enhancing the solubility of CP which can be employed for maintaining the in vitro sink condition in the basic dissolution medium. While anionic surfactants showed solubility retardant behavior which may be exploited in increasing the drug entrapment efficiency of a colloidal drug delivery system formulated by emulsification technique.

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

PubMed

Kamran, Sedigheh; Absalan, Ghodratollah; Asadi, Mozaffar

2015-12-01

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

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

EPA Science Inventory

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

Thermodynamics, electrostatics, and ionic current in nanochannels grafted with pH-responsive end-charged polyelectrolyte brushes.

PubMed

Chen, Guang; Das, Siddhartha

2017-03-01

In this paper, we study the thermodynamics, electrostatics, and an external electric field driven ionic current in a pH-responsive, end-charged polyelectrolyte (PE) brush grafted nanochannel. By employing a mean field theory, we unravel a highly nonintuitive interplay of pH and electrolyte salt concentration in dictating the height of the end-charged PE brush. Larger pH or weak hydrogen ion concentration leads to maximum ionization of the charge-producing group-as a consequence, the resulting the electric double layer (EDL) energy get maximized causing a maximum deviation of the brush height from the value (d 0 ) of the uncharged brush. This deviation may result in enhancement or lowering of the brush height as compared to d 0 depending on whether the PE end locates lower or higher than h/2 (h is the nanochannel half height) and the salt concentration. Subsequently, we use this combined PE-brush-configuration-EDL-electrostatics framework to compute the ionic current in the nanochannel. We witness that the ionic current for smaller pH is much larger despite the corresponding magnitude of the EDL electrostatic potential being much smaller-this stems from the presence of a much larger concentration of H+ ions at small pH and the fact that H+ ions have very large mobilities. In fact, this ionic current shows a steep variation with pH that can be useful in exploring new designs for applications involving quantification and characterization of ionic current in PE-brush-grafted nanochannels. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2015-01-01

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

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.

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

PubMed

Salis, Andrea; Boström, Mathias; Medda, Luca; Cugia, Francesca; Barse, Brajesh; Parsons, Drew F; Ninham, Barry W; Monduzzi, Maura

2011-09-20

The points of zero charge/potential of proteins depend not only on pH but also on how they are measured. They depend also on background salt solution type and concentration. The protein isoelectric point (IEP) is determined by electrokinetical measurements, whereas the isoionic point (IIP) is determined by potentiometric titrations. Here we use potentiometric titration and zeta potential (ζ) measurements at different NaCl concentrations to study systematically the effect of ionic strength on the IEP and IIP of bovine serum albumin (BSA) aqueous solutions. It is found that high ionic strengths produce a shift of both points toward lower (IEP) and higher (IIP) pH values. This result was already reported more than 60 years ago. At that time, the only available theory was the purely electrostatic Debye-Hückel theory. It was not able to predict the opposite trends of IIP and IEP with ionic strength increase. Here, we extend that theory to admit both electrostatic and nonelectrostatic (NES) dispersion interactions. The use of a modified Poisson-Boltzmann equation for a simple model system (a charge regulated spherical colloidal particle in NaCl salt solutions), that includes these ion specific interactions, allows us to explain the opposite trends observed for isoelectric point (zero zeta potential) and isoionic point (zero protein charge) of BSA. At higher concentrations, an excess of the anion (with stronger NES interactions than the cation) is adsorbed at the surface due to an attractive ionic NES potential. This makes the potential relatively more negative. Consequently, the IEP is pushed toward lower pH. But the charge regulation condition means that the surface charge becomes relatively more positive as the surface potential becomes more negative. Consequently, the IIP (measuring charge) shifts toward higher pH as concentration increases, in the opposite direction from the IEP (measuring potential). © 2011 American Chemical Society

Recent Development in Chemical Depolymerization of Lignin: A Review

DOE PAGES

Wang, Hai; Tucker, Melvin; Ji, Yun

2013-01-01

This article reviewed recent development of chemical depolymerization of lignins. There were five types of treatment discussed, including base-catalyzed, acid-catalyzed, metallic catalyzed, ionic liquids-assisted, and supercritical fluids-assisted lignin depolymerizations. The methods employed in this research were described, and the important results were marked. Generally, base-catalyzed and acid-catalyzed methods were straightforward, but the selectivity was low. The severe reaction conditions (high pressure, high temperature, and extreme pH) resulted in requirement of specially designed reactors, which led to high costs of facility and handling. Ionic liquids, and supercritical fluids-assisted lignin depolymerizations had high selectivity, but the high costs of ionic liquids recyclingmore » and supercritical fluid facility limited their applications on commercial scale biomass treatment. Metallic catalyzed depolymerization had great advantages because of its high selectivity to certain monomeric compounds and much milder reaction condition than base-catalyzed or acid-catalyzed depolymerizations. It would be a great contribution to lignin conversion if appropriate catalysts were synthesized.« 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...

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.

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.

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

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.

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

PubMed

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

2017-12-01

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

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

PubMed

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

2015-01-01

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

Aggregation and Charge Behavior of Metallic and Nonmetallic Nanoparticles in the Presence of Competing Similarly-Charged Inorganic Ions

EPA Science Inventory

The influence of competing, similarly charged, inorganic ions on the size and charge behavior of suspended titanium-dioxide (nTiO2), silver (nAg) and fullerene (nC60) nanoparticles (NPs) was investigated. Under pH and ionic conditions similar to natural water bodies, Ca2+ induced...

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.

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)

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.

Reversible and strong immobilization of proteins by ionic exchange on supports coated with sulfate-dextran.

PubMed

Fuentes, Manuel; Pessela, Benevides C C; Maquiese, Jorgette V; Ortiz, Claudia; Segura, Rosa L; Palomo, Jose M; Abian, Olga; Torres, Rodrigo; Mateo, Cesar; Fernández-Lafuente, Roberto; Guisán, J M

2004-01-01

New and strong ionic exchange resins have been prepared by the simple and rapid ionic adsorption of anionic polymers (sulfate-dextran) on porous supports activated with the opposite ionic group (DEAE/MANAE). Ionic exchange properties of such composites were strongly dependent on the size of the ionic polymers as well as on the conditions of the ionic coating of the solids with the ionic polymers (optimal conditions were 400 mg of sulfate-dextran 5000 kDa per gram of support). Around 80% of the proteins contained in crude extracts from Escherichia coli and Acetobacter turbidans could be adsorbed on these porous composites even at pH 7. This interaction was stronger than that using conventional carboxymethyl cellulose (CMC) and even others such as supports coated with aspartic-dextran polymer. By means of the sequential use of the new supports and supports coated with polyethyleneimine (PEI), all proteins from crude extracts could be immobilized. In fact, a large percentage (over 50%) could be immobilized on both supports. Finally, some industrially relevant enzymes (beta-galactosidases from Aspergillus oryzae, Kluyveromyces lactis, and Thermussp. strain T2, lipases from Candida antarctica A and B, Candida rugosa, Rhizomucor miehei, and Rhyzopus oryzae and bovine pancreas trypsin and chymotrypsin) have been immobilized on these supports with very high activity recoveries and immobilization rates. After enzyme inactivation, the protein could be fully desorbed from the support, and then the support could be reused for several cycles. Moreover, in some instances the enzyme stability was significantly improved, mainly in the presence of organic solvents, perhaps as a consequence of the highly hydrophilic microenvironment of the support.

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

PubMed

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

2016-12-01

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

Kinetic studies of the acylation of pig muscle–d-glyceraldehyde 3-phosphate dehydrogenase by 1,3-diphosphoglycerate and of proton uptake and release in the overall enzyme mechanism

PubMed Central

Harrigan, P. J.; Trentham, D. R.

1973-01-01

In the presence of NAD+ the acylation by 1,3-diphosphoglycerate of the four active sites of pig muscle d-glyceraldehyde 3-phosphate dehydrogenase can be monitored at 365nm by the disappearance of the absorption band present in the binary complex of NAD+ and the enzyme. A non-specific salt effect decreased the acylation rate 25-fold when the ionic strength was increased from 0.10 to 1.0. This caused acylation to be the rate-limiting process in the enzyme-catalysed reductive dephosphorylation of 1,3-diphosphoglycerate at high ionic strength at pH8. The salt effect permitted investigation of the acylation over a wide range of conditions. Variation of pH from 5.4 to 8.6 produced at most a two-fold change in the acylation rate. One proton was taken up per site acylated at pH8.0. By using a chromophoric H+ indicator the rate of proton uptake could be monitored during the acylation and was also almost invariant in the pH range 5.5–8.5. Transient kinetic studies of the overall enzyme-catalysed reaction indicated that acylation was the process involving proton uptake at pH8.0. The enzyme mechanism is discussed in the light of these results. PMID:4360248

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

PubMed Central

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

2010-01-01

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

Biochemical thermodynamics: applications of Mathematica.

PubMed

Alberty, Robert A

2006-01-01

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

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

PubMed Central

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

2013-01-01

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

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.

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

PubMed

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

2013-04-02

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

Development of an automated experimental setup for the study of ionic-exchange kinetics. Application to the ionic adsorption, equilibrium attainment and dissolution of apatite compounds.

PubMed

Thomann, J M; Gasser, P; Bres, E F; Voegel, J C; Gramain, P

1990-02-01

An ion-selective electrode and microcomputer-based experimental setup for the study of ionic-exchange kinetics between a powdered solid and the solution is described. The equipment is composed of easily available commercial devices and a data acquisition and regularization computer program is presented. The system, especially developed to investigate the ionic adsorption, equilibrium attainment and dissolution of hard mineralized tissues, provides good reliable results by taking into account the volume changes of the reacting solution and the electrode behaviour under different experimental conditions, and by avoiding carbonation of the solution. A second computer program, using the regularized data and the experimental parameters, calculates the quantities of protons consumed and calcium released in the case of equilibrium attainment and dissolution of apatite-like compounds. Finally, typical examples of ion-exchange and dissolution kinetics under constant pH of enamel and synthetic hydroxyapatite are examined.

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

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

PubMed

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

2017-03-01

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

Immobilization of Moniliella spathulata R25L270 Lipase on Ionic, Hydrophobic and Covalent Supports: Functional Properties and Hydrolysis of Sardine Oil.

PubMed

Souza, Lívia T de A; Moreno-Perez, Sonia; Fernández Lorente, Gloria; Cipolatti, Eliane P; de Oliveira, Débora; Resende, Rodrigo R; Pessela, Benevides C

2017-09-25

The oleaginous yeast Moniliella spathulata R25L270 was the first yeast able to grow and produce extracellular lipase using Macaúba ( Acrocomia aculeate ) cake as substrate. The novel lipase was recently identified, and presented promising features for biotechnological applications. The M. spathulata R25L270 lipase efficiently hydrolyzed vegetable and animal oils, and showed selectivity for generating cis -5,8,11,15,17-eicosapentaenoic acid from sardine oil. The enzyme can act in a wide range of temperatures (25-48 °C) and pH (6.5-8.4). The present study deals with the immobilization of M. spathulata R25L270 lipase on hydrophobic, covalent and ionic supports to select the most active biocatalyst capable to obtain omega-3 fatty acids (PUFA) from sardine oil. Nine immobilized agarose derivatives were prepared and biochemically characterized for thermostability, pH stability and catalytic properties (K M and V max ). Ionic supports improved the enzyme-substrate affinity; however, it was not an effective strategy to increase the M. spathulata R25L270 lipase stability against pH and temperature. Covalent support resulted in a biocatalyst with decreased activity, but high thermostability. The enzyme was most stabilized when immobilized on hydrophobic supports, especially Octyl-Sepharose. Compared with the free enzyme, the half-life of the Octyl-Sepharose derivative at 60 °C increased 10-fold, and lipase stability under acidic conditions was achieved. The Octyl-Sepharose derivative was selected to obtain omega-3 fatty acids from sardine oil, and the maximal enzyme selectivity was achieved at pH 5.0.

Effect of acidification on carrot (Daucus carota) juice cloud stability.

PubMed

Schultz, Alison K; Barrett, Diane M; Dungan, Stephanie R

2014-11-26

Effects of acidity on cloud stability in pasteurized carrot juice were examined over the pH range of 3.5-6.2. Cloud sedimentation, particle diameter, and ζ potential were measured at each pH condition to quantify juice cloud stability and clarification during 3 days of storage. Acidification below pH 4.9 resulted in a less negative ζ potential, an increased particle size, and an unstable cloud, leading to juice clarification. As the acidity increased, clarification occurred more rapidly and to a greater extent. Only a weak effect of ionic strength was observed when sodium salts were added to the juice, but the addition of calcium salts significantly reduced the cloud stability.

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

PubMed

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

2017-03-10

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

How pH, Temperature, and Time of Incubation Affect False-Positive Responses and Uncertainty of the LAL Gel-Clot Test.

PubMed

Lourenço, Felipe Rebello; Botelho, Túlia De Souza; Pinto, Terezinha De Jesus Andreoli

2012-01-01

The limulus amebocyte lysate (LAL) test is the simplest and most widely used procedure for detection of endotoxin in parenteral drugs. The LAL test demands optimal pH, ionic strength, temperature, and time of incubation. Slight changes in these parameters may increase the frequency of false-positive responses and the estimated uncertainty of the LAL test. The aim of this paper is to evaluate how changes in the pH, temperature, and time of incubation affect the occurrence of false-positive responses in the LAL test. LAL tests were performed in nominal conditions (37 °C, 60 min, and pH 7) and in different conditions of temperature (36 °C and 38 °C), time of incubation (58 and 62 min), and pH (6 and 8). Slight differences in pH increase the frequency of false-positive responses 5-fold (relative risk 5.0), resulting in an estimated of uncertainty 7.6%. Temperature and time of incubation affect the LAL test less, showing relative risks of 1.5 and 1.0, respectively. Estimated uncertainties in 36 °C or 38 °C temperatures and 58 or 62 min of incubation were found to be 2.0% and 1.0%, respectively. Simultaneous differences in these parameters significantly increase the frequency of false-positive responses. The limulus amebocyte lysate (LAL) gel-clot test is a simple test for detection of endotoxin from Gram-negative bacteria. The test is based on a gel formation when a certain amount of endotoxin is present; it is a pass/fail test. The LAL test requires optimal pH, ionic strength, temperature, and time of incubation. Slight difference in these parameters may increase the frequency of false-positive responses. The aim of this paper is to evaluate how changes in the pH, temperature, and time of incubation affect the occurrence of false-positive responses in the LAL test. We find that slight differences in pH increase the frequency of false-positive responses 5-fold. Temperature and time of incubation affect the LAL test less. Simultaneous differences in these parameters significantly increase the frequency of false-positive responses.

TRLFS study on the complexation of Cm(III) and Eu(III) with SO3-Ph-BTBP.

PubMed

Wagner, Christoph; Müllich, Udo; Geist, Andreas; Panak, Petra J

2015-10-21

The complexation of Cm(iii) and Eu(iii) with a water soluble BTBP (sodium 3,3',3'',3'''-([2,2'-bipyridine]-6,6'-diylbis(1,2,4-triazine-3,5,6-triyl))tetrabenzenesulfonate, SO3-Ph-BTBP) is studied using time resolved laser fluorescence spectroscopy. For the complexation of Cm(iii) the influence of the medium (10(-3) M HClO4→ 0.5 M HNO3) is investigated in detail revealing important impacts of the applied medium (pH, ionic strength, anions) on the speciation and conditional stability constants. SO3-Ph-BTBP forms 1 : 2 complexes with Cm(iii) and Eu(iii). The conditional stability constants of [Cm(SO3-Ph-BTBP)2](5-) and [Eu(SO3-Ph-BTBP)2](5-) in 0.5 M HNO3 are determined to be log β02 = 7.3 ± 0.3 and log β02 = 5.4 ± 0.5, respectively. The difference of 1.9 orders of magnitude is in line with hydrophobic BT(B)P type ligands and shows that the selectivity is not affected by tuning the hydrophilicity using SO3-Ph-side chains.

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

PubMed

Bittencourt, H M; Chaimovich, H

1976-08-01

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

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...

[Bromate reduction by granular activated carbon].

PubMed

Huang, Xin; Gao, Nai-yun; Lu, Pin-pin

2007-10-01

Batch experiments were conducted to evaluate the kinetics of reducing bromate to bromide by granular activated carbon. Solution conditions were studied in details, such as pH, ionic strength, temperature and initial bromate concentration. The results showed the removal capacity of GAC was positively relevant to surface basic functional groups. The whole process was inhibited by other anions in solution and the inhibition sequence was NO3(-) > SO4(2-) > Cl(-). Pseudo-second order rate equation and intraparticle diffusion model were applied to fit the process of bromate reduction and the process of bromide formation, respectively, with regression coefficients higher than 0.97 at most cases. Bromate removal was found to be favored under conditions with low pH value and low ionic strength. Both sorption rate of bromate and formation rate of bromide were decreased, and then increased along with the increase of temperature during 15-42 degree C. In this experiment, the maximum adsorption capacity of GAC is 769.23 micromol/g (98.4 mg/g), whereas the sorption process is slow and easily influenced. It is concluded that the sorption of bromate by the micropore portion of GAC was influenced by the release of bromide.

Impact of physicochemical parameters on in vitro assembly and disassembly kinetics of recombinant triple-layered rotavirus-like particles.

PubMed

Mellado, Maria Candida M; Mena, Jimmy A; Lopes, António; Ramírez, Octavio T; Carrondo, Manuel J T; Palomares, Laura A; Alves, Paula M

2009-11-01

Virus-like particles constitute potentially relevant vaccine candidates. Nevertheless, their behavior in vitro and assembly process needs to be understood in order to improve their yield and quality. In this study we aimed at addressing these issues and for that purpose triple- and double-layered rotavirus-like particles (TLP 2/6/7 and DLP 2/6, respectively) size and zeta potential were measured using dynamic light scattering at different physicochemical conditions, namely pH, ionic strength, and temperature. Both TLP and DLP were stable within a pH range of 3-7 and at 5-25 degrees C. Aggregation occurred at 35-45 degrees C and their disassembly became evident at 65 degrees C. The isoelectric points of TLP and DLP were 3.0 and 3.8, respectively. In vitro kinetics of TLP disassembly was monitored. Ionic strength, temperature, and the chelating agent employed determined disassembly kinetics. Glycerol (10%) stabilized TLP by preventing its disassembly. Disassembled TLP was able to reassemble by dialysis at high calcium conditions. VP7 monomers were added to DLP in the presence of calcium to follow in vitro TLP assembly kinetics; its assembly rate being mostly affected by pH. Finally, DLP and TLP were found to coexist under certain conditions as determined from all reaction products analyzed by capillary electrophoresis. Overall, these results contribute to the design of new strategies for the improvement of TLP yield and quality by reducing the VP7 detachment from TLP. Copyright 2009 Wiley Periodicals, Inc.

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

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2004-01-01

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

pH-sensitive gating by conformational change of a polypeptide brush grafted onto a porous polymer membrane

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

Ito, Yoshihiro; Ochiai, Yasushi; Park, Y.S.

1997-02-19

Benzyl glutamate NCA was graft-polymerized onto a porous poly(tetrafluoroethylene) membrane in order to study the effects of pH and ionic strength on permeation rate. The membrane was first glow-discharged in the presence of ammonia in order to produce amino groups on the surface. Following graft polymerization the graft chains were hydrolyzed to yield poly(glutamic acid). The rate of water permeation through this poly(glutamic acid)-grafted polymer membrane was pH-dependent and found to be slow under high-pH conditions and fast under low-pH conditions. Under high-pH conditions, randomly coiled graft chains extend to close the pores. The chains form a helix structure andmore » open the pores under low-pH conditions. The magnitude of the permeation rate was dependent upon the length and density of graft chains. Ionic strength also affected the permeation rate. 39 refs., 7 figs., 2 tabs.« less

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

PubMed

Seibt, C; Schlichter, D

2001-09-01

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

Destabilization and Treatment of Emulsified Oils in Wastewaters by Electrocoagulation.

PubMed

Genc, Ayten; Bakirci, Busra

2016-11-01

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

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

PubMed Central

Guan, Qian; Noblitt, Scott D.; Henry, Charles S.

2012-01-01

The use of mixtures of ionic and zwitterionic surfactants in poly(dimethylsiloxane) (PDMS) microchips is reported. The effect of surfactant concentration on EOF was studied for a single anionic surfactant (sodium dodecyl sulfate, SDS), a single zwitterionic surfactant (N-tetradecylammonium-N,N-dimethyl-3-ammonio-1-propanesulfonate, TDAPS), and a mixed SDS/TDAPS surfactant system. SDS increased the EOF as reported previously while TDAPS showed an initial increase in EOF followed by a reduction at higher concentrations. When TDAPS was added to a solution containing SDS, the EOF decreased in a concentration dependent manner. The EOF for all three surfactant systems followed expected pH trends, with increasing EOF at higher pH. The mixed surfactant system allowed tuning of the EOF across a range of pH and concentration conditions. After establishing the EOF behavior, the adsorption/desorption kinetics were measured and showed a slower adsorption/desorption rate for TDAPS than SDS. Finally, the separation and electrochemical detection of model catecholamines in buffer and reduced glutathione (GSH) in red blood cell lysate using the mixed surfactant system were explored. The mixed surfactant system provided shorter analysis times and/or improved resolution when compared to the single surfactant systems. PMID:22222982

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 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...

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

PubMed

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

2017-10-15

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

Recent progress in biopolymer nanoparticle and microparticle formation by heat-treating electrostatic protein-polysaccharide complexes.

PubMed

Jones, Owen G; McClements, David Julian

2011-09-14

Functional biopolymer nanoparticles or microparticles can be formed by heat treatment of globular protein-ionic polysaccharide electrostatic complexes under appropriate solution conditions. These biopolymer particles can be used as encapsulation and delivery systems, fat mimetics, lightening agents, or texture modifiers. This review highlights recent progress in the design and fabrication of biopolymer particles based on heating globular protein-ionic polysaccharide complexes above the thermal denaturation temperature of the proteins. The influence of biopolymer type, protein-polysaccharide ratio, pH, ionic strength, and thermal history on the characteristics of the biopolymer particles formed is reviewed. Our current understanding of the underlying physicochemical mechanisms of particle formation and properties is given. The information provided in this review should facilitate the rational design of biopolymer particles with specific physicochemical and functional attributes, as well as stimulate further research in identifying the physicochemical origin of particle formation. Copyright © 2010 Elsevier B.V. All rights reserved.

Solubility and dissolution improvement of ketoprofen by emulsification ionic gelation

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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

PubMed

Sheng, Guodong; Hu, Jun; Wang, Xiangke

2008-10-01

Diatomite has a number of unique physicochemical properties and has diversified industrial uses. Natural diatomite has been tested as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that sorption of Th(IV) is strongly dependent on ionic strength at pH<3, and is independent of ionic strength at pH>3. Outer-sphere complexation or ion exchange may be the main sorption mechanism of Th(IV) to diatomite at low pH values, whereas the sorption of Th(IV) at pH>3 is mainly dominated by inner-sphere complexation or precipitation. The competition for Th(IV) between aqueous or surface adsorbed anions (e.g., herein ClO(4)(-), NO(3)(-) and Cl(-)) and surface functional groups of diatomite is important for Th(IV) sorption. The thermodynamic data (DeltaH(0), DeltaS(0), DeltaG(0)) are calculated from the temperature-dependent sorption isotherms. The results suggest that sorption process of Th(IV) on diatomite is spontaneous and endothermic.

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

PubMed

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

2011-09-15

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

Field measurement of alkalinity and pH

USGS Publications Warehouse

Barnes, Ivan

1964-01-01

The behavior of electrometric pH equipment under field conditions departs from the behavior predicted from Nernst's law. The response is a linear function of pH, and hence measured pH values may be corrected to true pH if the instrument is calibrated with two reference solutions for each measurement. Alkalinity titrations may also be made in terms of true pH. Standard methods, such as colorimetric titrations, were rejected as unreliable or too cumbersome for rapid field use. The true pH of the end point of the alkalinity titration as a function of temperature, ionic strength, and total alkalinity has been calculated. Total alkalinity in potable waters is the most important factor influencing the end point pH, which varies from 5.38 (0 ? C, 5 ppm (parts per million) HC0a-) to 4.32 (300 ppm HC0a-,35 ? C), for the ranges of variables considered. With proper precautions, the pH may be determined to =i:0.02 pH and the alkalinity to =i:0.6 ppm HCO3- for many naturally occurring bodies of fresh water.

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Influence of lidocaine forms (salt vs. freebase) on properties of drug-eudragit® L100-55 extrudates prepared by reactive melt extrusion.

PubMed

Liu, Xu; Ma, Xiangyu; Kun, Eucharist; Guo, Xiaodi; Yu, Zhongxue; Zhang, Feng

2018-06-05

This study examines the preparation of sustained-release lidocaine polyelectrolyte complex using reactive melt extrusion. Eudragit L100-55 was selected as the ionic polymer. The influence of drug forms (freebase vs. hydrochloride salt) on lidocaine-Eudragit L100-55 interactions, physical stability, and dissolution properties of extrudates was investigated. It was confirmed by DSC, FT-IR and Raman spectroscopy that polyelectrolyte could only form via the acid-base reaction between Eudragit L100-55 and lidocaine freebase. Due to this ionic interaction, the lidocaine extrudate was physically more stable than the lidocaine hydrochloride extrudate during the storage under stressed condition. Drug release from lidocaine extrudate was a function of drug solubility, polymer solubility, drug-polymer interaction, and drug-induced microenvironment pH. At 30% drug loading, extrudate exhibited sustained release in aqueous media at pH 1.2 and 4.5. Due to the alkaline microenvironment pH induced by dissolved lidocaine, Eudragit L100-55 was solubilized and sustained-release was not achieved in water and aqueous media at pH 5.5. In comparison, lidocaine hydrochloride induced an acidic microenvironment. Drug release of lidocaine hydrochloride extrudate was similar at pH 1.2, 4.5, 5.5 and water with drug being released over 10 h. The release of lidocaine hydrochloride from the extrudates in these media was primarily controlled by microenvironment pH. It is concluded that different forms of lidocaine resulted in different drug-polymer interactions and distinctive physicochemical properties of extrudates. Copyright © 2018. Published by Elsevier B.V.

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.

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...

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.

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.

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

PubMed Central

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

2017-01-01

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

Enhanced antimicrobial activity and structural transitions of a nanofibrillated cellulose-nisin bio-composite suspension.

PubMed

Weishaupt, Ramon; Heuberger, Lukas; Siqueira, Gilberto; Gutt, Beatrice; Zimmermann, Tanja; Maniura-Weber, Katharina; Salentinig, Stefan; Faccio, Greta

2018-05-16

The occurrence of resistance to antibiotics has posed a high demand for novel strategies to fight bacterial infections. Antimicrobial peptides (AMPs) are a promising alternative to con-ventional antibiotics. However, their poor solubility in water and sensitivity to degradation has limited their application. Here we report the design of a smart, pH-responsive antimicro-bial nanobiocomposite material based on the AMP nisin and oxidized nanofibrillated cellulose (TONFC). Morphological transformations of the nano-scale structure of nisin functionalized TONFC fibrils were discovered at pH values between pH 5.8 and 8.0 using small angle X-ray scattering (SAXS). Complementary zeta potential measurements indicate that electrostatic-attractions between the negatively charged TONFC surface and the positively charged nisin molecules are responsible for the integration of nisin. Contrary, shifting the pH level or in-creasing the ionic strength reduce the nisin binding capacity of TONFC. Biological evaluation studies using a bioluminescence-based reporter strain of Bacillus subtilis and a clinically rele-vant strain of Staphylococcus aureus indicated a significantly higher antimicrobial activity of the TONFC-nisin biocomposite compared to the pure nisin against both strains under physio-logical pH and ionic strength conditions. The in-depth characterization of this new class of an-timicrobial bio-composite material based on nanocellulose and nisin, may guide the rational design of sustainable antimicrobial materials.

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.

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

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

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Sorption of vanadium (V) onto natural soil colloids under various solution pH and ionic strength conditions.

PubMed

Luo, Xiuhua; Yu, Lin; Wang, Changzhao; Yin, Xianqiang; Mosa, Ahmed; Lv, Jialong; Sun, Huimin

2017-02-01

Batch sorption kinetics and isothermal characteristics of V(V) were investigated on three natural soil colloids (manual loessial soil colloid (MSC), aeolian sandy soil colloid (ASC), and cultivated loessial soil colloid (CSC)) under various solution pH and ionic strength (IS) conditions. Colloids were characterized by atomic force microscopy (AFM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). AFM micrographs showed CSC with an aggregated shape with larger particle diameter as compared with ASC and MSC. XRD spectra revealed the presence of different minerals in natural soil colloids including biotite, kaolinite, calcite and quartz, which might contribute to sorption process. The sorption ability decreased with increase of colloidal particle size. The sorption was mainly attributed to complexation by active carboxylate and alcohol groups of colloidal components. Sorption kinetics and isotherms of V(V) onto natural soil colloids were best fitted with Pseudo-second-order and Freundlich models. Langmuir model indicated that sorption capacity of MSC and ASC was comparable (285.7 and 238.1 mg g -1 ); however, CSC exhibited the lowest sorption capacity (41.5 mg g -1 ) due to its larger particle diameter and aggregated shape. The maximum V(V) sorption capacity reached plateau values at a solution pH ranged between 5.0 and 9.0 for MSC and ASC, and 6.0-8.0 for CSC. Sorption capacity of V(V) onto natural soil colloids decreased with increasing IS. Based on result of this study we can conclude that sorption of V(V) onto natural soil colloids is pH- and IS-dependent. These findings provide insights on the remediation of vanadium-contaminated soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistry

NASA Astrophysics Data System (ADS)

Schlautman, Mark A.; Morgan, James J.

1994-10-01

The adsorption of Suwannee River humic substances (HS) on colloidal-size aluminum oxide particles was examined as a function of solution chemistry. The amount of humic acid (HA) or fulvic acid (FA) adsorbed decreased with increasing pH for all solutions of constant ionic strength. In NaCl solutions at fixed pH values, the adsorption of HA and FA increased with increasing ionic strength. The presence of Ca 2+ enhanced the adsorption of HA but had little effect on FA. For identical solution conditions, the amount (by mass) of HA adsorbed to alumina was always greater than FA. Adsorption densities for both HA and FA showed good agreement with the Langmuir equation, and interpretations of adsorption processes were made from the model parameters. For FA, ligand exchange appears to be the dominant adsorption reaction for the conditions studied here. Ligand exchange is also a major adsorption reaction for HA; however, other reactions contribute to adsorption for some solution compositions. At high pH, cation and water bridging become increasingly important for HA adsorption with increasing amounts of Na + and Ca 2+, respectively. At low to neutral pH values, increases in these same two cations make hydrophobic bonding more effective. Calculations of HS carboxyl group densities in the adsorbed layer support the proposed adsorption reactions. From the adsorption data it appears that fewer than 3.3 HS-COO - groups per nm 2 can be bound directly as inner-sphere complexes by the alumina surface. We propose that the influence of aqueous chemistry on HS adsorption reactions, and therefore on the types of HS surface complexes formed, affects the formation and nature of organic coatings on mineral surfaces.

Isolated Potato Virus A coat protein possesses unusual properties and forms different short virus-like particles.

PubMed

Ksenofontov, Alexander L; Dobrov, Eugeny N; Fedorova, Natalia V; Serebryakova, Marina V; Prusov, Andrei N; Baratova, Ludmila A; Paalme, Viiu; Järvekülg, Lilian; Shtykova, Eleonora V

2018-05-01

In our previous study, we have observed that the isolated coat proteins (CP) of the Potyvirus Potato Virus A (PVA) virions exhibit an intrinsic tendency to self-associate into various multimeric forms containing some fractions of cross-β-structure. In this report, we studied the effect of solution conditions on the structure and dissociation of isolated PVA CP using a number of complementary physicochemical methods. Analysis of the structure of PVA CP in solution was performed by limited proteolysis with MALDI-TOF mass spectrometry analysis, transmission electron microscopy, intrinsic fluorescence spectroscopy, and synchrotron small angle X-ray scattering (SAXS). Overall structural characteristics of PVA CP obtained by combination of these methods and ab initio shape reconstruction by SAXS show that PVA CP forms large multi-subunit particles. We demonstrate that a mixture of compact virus-like particles (VLP) longer than 30 nm is assembled on dialysis of isolated CP into neutral pH buffer (at low ionic strength). Under conditions of high ionic strength (0.5 M NaCl) and high pH (pH 10.5), PVA dissociates into low compactness oval-shaped particles of approximately 30 subunits (20-30 nm). The results of limited trypsinolysis of these particles (enzyme/substrate ratio 1:100, 30 min) showed the existence of non-cleavable core-fragment, consisting of 137 amino acid residues. Trypsin treatment removed only a short N-terminal fragment in the intact virions. These particles are readily reassembled into regular VLPs by changing pH back to neutral. It is possible that these particles may represent some kind of intermediate in PVA assembly in vitro and in vivo.

Surface complexation modeling of zinc sorption onto ferrihydrite.

PubMed

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

2004-02-01

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

Column experiments to investigate transport of colloidal humic acid through porous media during managed aquifer recharge

NASA Astrophysics Data System (ADS)

Liu, Dan; Zhou, Jingjing; Zhang, Wenjing; Huan, Ying; Yu, Xipeng; Li, Fulin; Chen, Xuequn

2017-01-01

Colloids act as vectors for pollutants in groundwater, thereby creating a series of environmental problems. While managed aquifer recharge plays an important role in protecting groundwater resources and controlling land subsidence, it has a significant effect on the transport of colloids. In this study, particle size and zeta potential of colloidal humic acid (HA) have been measured to determine the effects of different hydrochemistry conditions. Column experiments were conducted to examine the effects on the transport of colloidal HA under varying conditions of pH (5, 7, 9), ionic strength (<0.0005, 0.02, 0.05 M), cation valence (Na+, Ca2+) and flow rate (0.1, 0.2, 0.4 ml/min) through collectors (glass beads) to model the properties and quality of artificial recharge water and changes in the hydrodynamic field. Breakthrough curves showed that the behavior of colloidal HA being transported varied depending on the conditions. Colloid transport was strongly influenced by hydrochemical and hydrodynamic conditions. With decreasing pH or increasing ionic strength, a decrease in the peak effluent concentration of colloidal HA and increase in deposition could be clearly seen. Comparison of different cation valence tests indicated that changes in transport and deposition were more pronounced with divalent Ca2+ than with monovalent Na+. Changes in hydrodynamic field (flow rate) also had an impact on transportation of colloidal HA. The results of this study highlight the need for further research in this area.

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

PubMed

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

2006-11-01

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

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.

Osmotic Pressure in Ionic Microgel Dispersions

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Tang, Qiyun

2015-03-01

Microgels are microscopic gel particles, typically 10-1000 nm in size, that are swollen by a solvent. Hollow microgels (microcapsules) can encapsulate cargo, such as dye molecules or drugs, in their solvent-filled cavities. Their sensitive response to environmental conditions (e.g., temperature, pH) and influence on flow properties suit microgels to widespread applications in the chemical, pharmaceutical, food, and consumer care industries. When dispersed in water, polyelectrolyte gels become charged through dissociation of counterions. The electrostatic contribution to the osmotic pressure inside and outside of ionic microgels influences particle swelling and bulk materials properties, including thermodynamic, structural, optical, and rheological properties. Within the primitive and cell models of polyelectrolyte solutions, we derive an exact statistical mechanical formula for the contribution of mobile microions to the osmotic pressure within ionic microgels. Using Poisson-Boltzmann theory, we validate this result by explicitly calculating ion distributions across the surface of an ionic microgel and the electrostatic contribution to the osmotic pressure. Within a coarse-grained one-component model, we further chart the limits of the cell model for salty dispersions. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

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.

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

PubMed

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

2016-08-05

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

Interference of 1:1 and 2:1 layered phyllosilicates as excipients with ranitidine.

PubMed

Li, Zhaohui; Fitzgerald, Nicole M; Albert, Zachary; Jiang, Wei-Teh

2016-04-01

As natural ingredients and excipients, kaolinite and talc were frequently studied for their interactions with drugs in pharmaceutical formulations. In this study, the uptake of ranitidine (RT) on these two minerals was studied under different physic-chemical conditions and the mechanism of RT uptake on these two minerals contrasted. Although the thermodynamic and kinetic RT uptake on these two minerals was similar and the RT uptake on both minerals were limited to the external surfaces only, drastic difference in RT uptake was found under different equilibrium solution pH and ionic strength conditions. As cation exchange process was strongly affected by solution pH and ionic strength, the RT uptake on kaolinite was dominated by cation exchange and electrostatic interactions, while the RT uptake on talc was more controlled by inter- and intra- molecular hydrogen bonding interactions. For kaolinite, the limiting factor for RT uptake was the specific surface area due to monolayer RT adsorption. In contract, multilayer RT uptake was found on talc surfaces. No matter which mechanism dominated RT uptake on these minerals, the interaction should not be neglected in pharmaceutical formulations should these minerals be used as additives and/or excipients. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of pH and media composition on suspension stability of silver, zinc oxide, and titanium dioxide nanoparticles and immobilization of Daphnia magna under guideline testing conditions.

PubMed

Cupi, Denisa; Hartmann, Nanna B; Baun, Anders

2016-05-01

In aquatic toxicity testing of engineered nanoparticles (ENPs) the process of agglomeration is very important as it may alter bioavailability and toxicity. In the present study, we aimed to identify test conditions that are favorable for maintaining stable ENP suspensions. We evaluated the influence of key environmental parameters: pH (2-12) and ionic strength using M7, Soft EPA (S EPA) medium, and Very Soft EPA (VS EPA) medium; and observed the influence of these parameters on zeta potential, zeta average, and acute immobilization of Daphnia magna for three different ENPs. Despite being sterically stabilized, test suspensions of silver (Ag) ENPs formed large agglomerates in both VS EPA and M7 media; and toxicity was found to be higher in VS EPA medium due to increased dissolution. Low-agglomerate suspensions for zinc oxide (ZnO) could be obtained at pH 7 in VS EPA medium, but the increase in dissolution caused higher toxicity than in M7 medium. Titanium dioxide (TiO2) ENPs had a point of zero charge in the range of pH 7-8. At pH 7 in VS EPA, agglomerates with smaller hydrodynamic diameters (~200nm) were present compared to the high ionic strength M7 medium where hydrodynamic diameters reached micrometer range. The stable suspensions of TiO2 ENPs caused immobilization of D. magna, 48-h EC50 value of 13.7mgL(-1) (95% CI, 2.4mg-79.1mgL(-1)); whereas no toxicity was seen in the unstable, highly agglomerated M7 medium suspensions, 48-h EC50 >100mgL(-1). The current study provides a preliminary approach for methodology in testing and assessing stability and toxicity of ENPs in aquatic toxicity tests of regulatory relevance. Copyright © 2016 Elsevier Inc. All rights reserved.

The novel acidophilic structure of the killer toxin from halotolerant yeast demonstrates remarkable folding similarity with a fungal killer toxin.

PubMed

Kashiwagi, T; Kunishima, N; Suzuki, C; Tsuchiya, F; Nikkuni, S; Arata, Y; Morikawa, K

1997-01-15

Several strains of yeasts and fungi produce proteinous substances, termed killer toxins, which kill sensitive strains. The SMK toxin, secreted by the halotolerant yeast Pichia farinosa KK1 strain, uniquely exhibits its maximum killer activity under conditions of acidic pH and high salt concentration. The toxin is composed of two distinct subunits, alpha and beta, which tightly interact with each other under acidic conditions. However, they are easily dissociated under neutral conditions and lose the killer activity. The three-dimensional structure of the SMK toxin will provide a better understanding of the mechanism of toxicity of this protein and the cause of its unique pH-dependent stability. Two crystal structures of the SMK toxin have been determined at 1.8 A resolution in different ionic strength conditions. The two subunits, alpha and beta, are jointly folded into an ellipsoidal, single domain structure belonging to the alpha/beta-sandwich family. The folding topology of the SMK toxin is essentially the same as that of the fungal killer toxin, KP4. This shared topology contains two left-handed split betaalphabeta motifs, which are rare in the other proteins. Many acidic residues are clustered at the bottom of the SMK toxin molecule. Some of the carboxyl sidechains interact with each other through hydrogen bonds. The ionic strength difference induces no evident structural change of the SMK toxin except that, in the high ionic strength crystal, a number of sulfate ions are electrostatically bound near the basic residues which are also locally distributed at the bottom of the toxin molecule. The two killer toxins, SMK and KP4, share a unique folding topology which contains a rare structural motif. This observation may suggest that these toxins are evolutionally and/or functionally related. The pH-dependent stability of the SMK toxin is a result of the intensive interactions between the carboxyl groups. This finding is important for protein engineering, for instance, towards stabilization of the toxin molecule in a broader pH range. The present crystallographic study revealed that the structure of the SMK toxin itself is hardly affected by the ionic strength, implying that a high salt concentration affects the sensitivity of the cell against the toxin.

Plasticizing Effects of Polyamines in Protein-Based Films

PubMed Central

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

2017-01-01

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

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

PubMed

Sun, Chencheng; Xiong, Bowen; Pan, Yang; Cui, Hao

2017-02-01

Polyaniline (PANI) prepared by chemical oxidation was studied for adsorption removal of tannic acid (TA) from aqueous solution. Batch adsorption studies were carried out under different adsorbent dosages, pH, ionic strength, initial TA concentration and coexisting anions. Solution pH had an important impact on TA adsorption onto PANI with optimal removal in the pH range of 8-11. TA adsorption on PANI at three ionic strength levels (0.02, 0.2 and 2molL -1 NaCl) could be well described by Langmuir model (monolayer adsorption process) and the maximum adsorption capacity was 230, 223 and 1023mgg -1 , respectively. Kinetic data showed that TA adsorption on PANI fitted well with pseudo-second-order model (controlled by chemical process). Among the coexisting anions tested, PO 4 3- significantly inhibited TA adsorption due to the enhancement of repulsive interaction. Continuous flow adsorption studies indicated good flexibility and adaptability of the PANI adsorbent under different flow rates and influent TA concentrations. The mechanism controlling TA adsorption onto PANI under different operating conditions was analyzed with the combination of electrostatic interactions, hydrogen bonding, π-π interactions and Van der Waals interactions. Copyright © 2016 Elsevier Inc. All rights reserved.

Optimization of oligomeric enzyme activity in ionic liquids using Rhodotorula glutinis yeast phenylalanine ammonia lyase.

PubMed

Barron, Christiaan C; Sponagle, Brandon J D; Arivalagan, Pugazhendhi; D'Cunha, Godwin B

2017-01-01

Phenylalanine ammonia lyase (E.C.4.3.1.24, PAL) activity of Rhodotorula glutinis yeast has been demonstrated in four commonly used ionic liquids. PAL forward reaction was carried out in 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO 4 ]), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ]), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF 6 ]) and 1-butyl-3-methylimidazolium lactate ([BMIM][lactate]). Our experiments have revealed that PAL is catalytically active in ionic liquids and the enzyme activity in ([BMIM][PF 6 ]) is comparable to that obtained in aqueous buffer medium. Different conditions were optimized for maximal PAL forward activity including time of incubation (30.0min) L -phenylalanine substrate concentration (30.0mM), nature of buffer (50.0mM Tris-HCl), pH (9.0), temperature (37°C), and speed of agitation (100 rev min -1 ). Under these optimized conditions, about 83% conversion of substrate to product was obtained for the PAL forward reaction that was determined using UV spectroscopy at 290nm. PAL reverse reaction in ([BMIM][PF 6 ]) was determined spectrophotometrically at 520nm; and about 59% substrate conversion was obtained. This data provides further knowledge in enzyme biocatalysis in non-aqueous media, and may be of importance when studying the function of other oligomeric/multimeric proteins and enzymes in ionic liquids. Copyright © 2016 Elsevier Inc. All rights reserved.

Ultrasound-assisted magnetic solid-phase extraction based ionic liquid-coated Fe3O4@graphene for the determination of nitrobenzene compounds in environmental water samples.

PubMed

Cao, Xiaoji; Shen, Lingxiao; Ye, Xuemin; Zhang, Feifei; Chen, Jiaoyu; Mo, Weimin

2014-04-21

An ultrasound-assisted magnetic solid-phase extraction procedure with the [C7MIM][PF6] ionic liquid-coated Fe3O4-grafted graphene nanocomposite as the magnetic adsorbent has been developed for the determination of five nitrobenzene compounds (NBs) in environmental water samples, in combination with high performance liquid chromatography-photodiode array detector (HPLC-PDA). Several significant factors that affect the extraction efficiency, such as the types of magnetic nanoparticle and ionic liquid, the volume of ionic liquid and the amount of magnetic nanoparticles, extraction time, ionic strength, and solution pH, were investigated. With the assistance of ultrasound, adsorbing nitrobenzene compounds by ionic liquid and self-aggregating ionic liquid onto the surface of the Fe3O4-grafted graphene proceeded synchronously, which made the extraction achieved the maximum within 20 min using only 144 μL [C7MIM][PF6] and 3 mg Fe3O4-grafted graphene. Under the optimized conditions, satisfactory linearities were obtained for all NBs with correlation coefficients larger than 0.9990. The mean recoveries at two spiked levels ranged from 80.35 to 102.77%. Attributed to the convenient magnetic separation, the Fe3O4-grafted graphene could be recycled many times. The proposed method was demonstrated to be feasible, simple, solvent-saving and easy to operate for the trace analysis of NBs in environmental water samples.

Determination of metal ions in tea samples using task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction coupled to liquid chromatography with ultraviolet detection.

PubMed

Werner, Justyna

2016-04-01

Task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction was used for the preconcentration of cadmium(II), cobalt(II), and lead(II) ions in tea samples, which were subsequently analyzed by liquid chromatography with UV detection. The proposed method of preconcentration is free of volatile organic compounds, which are often used as extractants and dispersing solvents in classic techniques of microextraction. A task-specific ionic liquid trioctylmethylammonium thiosalicylate was used as an extractant and a chelating agent. Ultrasound was used to disperse the ionic liquid. After microextraction, the phases were separated by centrifugation, and the ionic liquid phase was solubilized in methanol and directly injected into the liquid chromatograph. Selected microextraction parameters, such as the volume of ionic liquid, the pH of the sample, the duration of ultrasound treatment, the speed and time of centrifugation, and the effect of ionic strength, were optimized. Under optimal conditions an enrichment factor of 200 was obtained for each analyte. The limits of detection were 0.002 mg/kg for Cd(II), 0.009 mg/kg for Co(II), and 0.013 mg/kg for Pb(II). The accuracy of the proposed method was evaluated by an analysis of the Certified Reference Materials (INCT-TL-1, INCT-MPH-2) with the recovery values in the range of 90-104%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave-assisted liquid-liquid microextraction based on solidification of ionic liquid for the determination of sulfonamides in environmental water samples.

PubMed

Song, Ying; Wu, Lijie; Lu, Chunmei; Li, Na; Hu, Mingzhu; Wang, Ziming

2014-12-01

An easy, quick, and green method, microwave-assisted liquid-liquid microextraction based on solidification of ionic liquid, was first developed and applied to the extraction of sulfonamides in environmental water samples. 1-Ethy-3-methylimidazolium hexafluorophosphate, which is a solid-state ionic liquid at room temperature, was used as extraction solvent in the present method. After microwave irradiation for 90 s, the solid-state ionic liquid was melted into liquid phase and used to finish the extraction of the analytes. The ionic liquid and sample matrix can be separated by freezing and centrifuging. Several experimental parameters, including amount of extraction solvent, microwave power and irradiation time, pH of sample solution, and ionic strength, were investigated and optimized. Under the optimum experimental conditions, good linearity was observed in the range of 2.00-400.00 μg/L with the correlation coefficients ranging from 0.9995 to 0.9999. The limits of detection for sulfathiazole, sulfachlorpyridazine, sulfamethoxazole, and sulfaphenazole were 0.39, 0.33, 0.62, and 0.85 μg/L, respectively. When the present method was applied to the analysis of environmental water samples, the recoveries of the analytes ranged from 75.09 to 115.78% and relative standard deviations were lower than 11.89%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2014-10-01

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

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

PubMed

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

2017-06-01

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

Multilayer nanoparticles with a magnetite core and a polycation inner shell as pH-responsive carriers for drug delivery

NASA Astrophysics Data System (ADS)

Guo, Miao; Yan, Yu; Liu, Xiaozhou; Yan, Husheng; Liu, Keliang; Zhang, Hongkai; Cao, Youjia

2010-03-01

Nanocarriers with multilayer core-shell architecture were prepared by coating a superparamagnetic Fe3O4 core with a triblock copolymer. The first block of the copolymer formed the biocompatible outermost shell of the nanocarrier. The second block that contains amino groups and hydrophobic moiety formed the inner shell. The third block bound tightly onto the Fe3O4 core. Chlorambucil (an anticancer agent) and indomethacin (an anti-inflammation agent), each containing a carboxyl group and a hydrophobic moiety, were loaded into the amino-group-containing inner shell by a combination of ionic and hydrophobic interactions. The release rate of the loaded drugs was slow at pH 7.4, mimicking the blood environment, whereas the release rate increased significantly at acidic pH, mimicking the intracellular conditions in the endosome/lysosome. This can be attributed to the disruption of the ionic bond caused by protonation of the carboxylate anion of the drugs and the swelling of the inner shell caused by protonation of the amino groups.

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

PubMed

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

2015-09-01

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

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

PubMed

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

2011-10-01

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

Single-molecule spectroscopy of the unexpected collapse of an unfolded protein at low pH

NASA Astrophysics Data System (ADS)

Hofmann, Hagen; Nettels, Daniel; Schuler, Benjamin

2013-09-01

The dimensions of intrinsically disordered and unfolded proteins critically depend on the solution conditions, such as temperature, pH, ionic strength, and osmolyte or denarurant concentration. However, a quantitative understanding of how the complex combination of chain-chain and chain-solvent interactions is affected by the solvent is still missing. Here, we take a step towards this goal by investigating the combined effect of pH and denaturants on the dimensions of an unfolded protein. We use single-molecule fluorescence spectroscopy to extract the dimensions of unfolded cold shock protein (CspTm) in mixtures of the denaturants urea and guanidinium chloride (GdmCl) at neutral and acidic pH. Surprisingly, even though a change in pH from 7 to 2.9 increases the net charge of CspTm from -3.8 to +10.2, the radius of gyration of the chain is very similar under both conditions, indicating that protonation of acidic side chains at low pH results in additional hydrophobic interactions. We use a simple shared binding site model that describes the joint effect of urea and GdmCl, together with polyampholyte theory and an ion cloud model that includes the chemical free energy of counterion interactions and side chain protonation, to quantify this effect.

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.

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.

Evaluation of biochar-ultrafiltration membrane processes for humic acid removal under various hydrodynamic, pH, ionic strength, and pressure conditions.

PubMed

Shankar, Vaibhavi; Heo, Jiyong; Al-Hamadani, Yasir A J; Park, Chang Min; Chu, Kyoung Hoon; Yoon, Yeomin

2017-07-15

The performance of an ultrafiltration (UF)-biochar process was evaluated in comparison with a UF membrane process for the removal of humic acid (HA). Bench-scale UF experiments were conducted to study the rejection and flux trends under various hydrodynamic, pH, ionic strength, and pressure conditions. The resistance-in-series model was used to evaluate the processes and it showed that unlike stirred conditions, where low fouling resistance was observed (28.7 × 10 12  m -1 to 32.5 × 10 12  m -1 ), higher values and comparable trends were obtained for UF-biochar and UF alone for unstirred conditions (28.7 × 10 12  m -1 to 32.5 × 10 12  m -1 ). Thus, the processes were further evaluated under unstirred conditions. Additionally, total fouling resistance was decreased in the presence of biochar by 6%, indicating that HA adsorption by biochar could diminish adsorption fouling on the UF membrane and thus improve the efficiency of the UF-biochar process. The rejection trends of UF-biochar and UF alone were similar in most cases, whereas UF-biochar showed a noticeable increase in flux of around 18-25% under various experimental conditions due to reduced membrane fouling. Three-cycle filtration tests further demonstrated that UF-biochar showed better membrane recovery and antifouling capability by showing more HA rejection (3-5%) than UF membrane alone with each subsequent cycle of filtration. As a result of these findings, the UF-biochar process may potentially prove be a viable treatment option for the removal of HA from water. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

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

Kani, Yuko; Kamosida, Mamoru; Watanabe, Daisuke

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

Hollow fiber supported ionic liquid membrane microextraction for determination of sulfonamides in environmental water samples by high-performance liquid chromatography.

PubMed

Tao, Yong; Liu, Jing-Fu; Hu, Xia-Lin; Li, Hong-Cheng; Wang, Thanh; Jiang, Gui-Bin

2009-08-28

By using ionic liquid as membrane liquid and tri-n-octylphosphine oxide (TOPO) as additive, hollow fiber supported liquid phase microextraction (HF-LPME) was developed for the determination of five sulfonamides in environmental water samples by high-performance liquid chromatography with ultraviolet detection The extraction solvent and the parameters affecting the extraction enrichment factor such as the type and amount of carrier, pH and volume ratio of donor phase and acceptor phase, extraction time, salt-out effect and matrix effect were optimized. Under the optimal extraction conditions (organic liquid membrane phase: [C(8)MIM][PF(6)] with 14% TOPO (w/v); donor phase: 4mL, pH 4.5 KH(2)PO(4) with 2M Na(2)SO(4); acceptor phase: 25microL, pH 13 NaOH; extraction time: 8 h), low detection limits (0.1-0.4microg/L, RSDor=0.999) were obtained for all the analytes. The presence of humic acid (0-25mg/L dissolved organic carbon) and bovine serum albumin (0-100microg/mL) had no significant effect on the extraction efficiency. Good spike recoveries over the range of 82.2-103.2% were obtained when applying the proposed method on five real environmental water samples. These results indicated that this present method was very sensitive and reliable with good repeatabilities and excellent clean-up in water samples. The proposed method confirmed hollow fiber supported ionic liquid membrane based LPME to be robust to monitoring trace levels of sulfadiazine, sulfamerazine, sulfamethazine, sulfadimethoxine and sulfamethoxazole in aqueous samples.

Preferential adhesion of surface groups of Bacillus subtilis on gibbsite at different ionic strengths and pHs revealed by ATR-FTIR spectroscopy.

PubMed

Hong, Zhi-Neng; Jiang, Jun; Li, Jiu-Yu; Xu, Ren-Kou

2018-05-01

Adhesion of bacteria onto minerals is a ubiquitous process that plays a central role in many biogeochemical, microbiology and environmental processes in soil and sediment. Although bacterial adhesion onto soil minerals such as phyllosilicates and Fe-oxides have been investigated extensively, little is known about the mechanisms for bacterial attachment onto Al-oxides. Here, we explored the adhesion of Bacillus subtilis onto gibbsite (γ-AlOOH) under various ionic strengths (1, 10, 50, and 100 mM NaCl) and pHs (pH 4, 7, and 9) by in-situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The time evolution of the peak intensities of the attached bacteria suggested that the adhesion underwent an initial rapid reaction followed by a slow pseudo-first-order kinetic stage. Spectral comparison between the attached and free cells, together with the interaction energy calculated with the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory and the micro-morphology of bacteria-gibbsite complexes, indicated that both electrostatic and chemical (bacterial groups such as phosphate and carboxyl covalently bind to gibbsite) interactions participated in the adhesion processes. Both solution ionic strength (IS) and pH impacted the spectra of attached bacteria, but the peak intensity of different bands changed differently with these two factors, showing a preferential adhesion of surface groups (phosphate, carboxyl, and amide groups) on gibbsite at different conditions. The diverse responses to IS and pH alteration of the forces (chemical bonds, electrostatic attractions, and the hydrophobic interactions) that essentially govern the adhesion might be responsible for the preferential adhesion. These results may help to better understand how bacteria adhere onto soil oxides at molecular scales. Copyright © 2018 Elsevier B.V. All rights reserved.

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

USGS Publications Warehouse

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

2010-01-01

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

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

PubMed

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

2011-08-30

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

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.

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

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

PubMed

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

2013-10-21

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

Sorption mechanisms of metals to graphene oxide

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

Showalter, Allison R.; Duster, Thomas A.; Szymanowski, Jennifer E. S.

2016-05-01

Environmental toxic metal contamination remediation and prevention is an ongoing issue. Graphene oxide is highly sorptive for many heavy metals over a wide pH range under different ionic strength conditions. We present x-ray absorption fine structure (XAFS) spectroscopy results investigating the binding environment of Pb(II), Cd(II) and U(VI) ions onto multi-layered graphene oxide (MLGO). Analysis indicates that the dominant sorption mechanism of Pb to MLGO changes as a function of pH, with increasing inner sphere contribution as pH increases. In contrast, the sorption mechanism of Cd to MLGO remains constant under the studied pH range. This adsorption mechanism is anmore » electrostatic attraction between the hydrated Cd+2 ion and the MLGO surface. The U(VI), present as the uranyl ion, changes only subtly as a function of pH and is bound to the surface via an inner sphere bond. Knowledge of the binding mechanism for each metal is necessary to help in optimizing environmental remediation or prevention in filtration systems.« less

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

PubMed

Pan, Kang; Zhong, Qixin

2013-09-25

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

Studies on the extraction of nitrogenous and phosphorus-containing materials from the seeds of kidney beans (Phaseolus vulgaris)

PubMed Central

Pusztai, A.

1965-01-01

1. The conditions of extracting nitrogenous, phosphorus-containing and glucosamine-containing components of the seeds of kidney bean have been studied. 2. The dispersing of proteins was incomplete below pH 7, and the exact amount of protein extracted depended on the pH and the ionic strength of the solvent. 3. The extraction of proteins was practically complete in the range pH 7–9, but the relative amounts of the individual proteins obtained still depended on the pH of the extracting media, indicating a pH-dependent association–dissociation reaction between the protein molecules present. 4. The extraction of phosphorus-containing material showed an optimum at pH 6–7, and only a part of this was removed on dialysis. The precipitates obtained with trichloroacetic acid, on the other hand, retained very little phosphorus-containing material. 5. The significance of these findings is discussed. PMID:14340051

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

PubMed

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

2013-04-01

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

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

PubMed

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

2003-07-01

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

pH during non-synaptic epileptiform activity-computational simulations.

PubMed

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

2015-09-02

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

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

USGS Publications Warehouse

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

1992-01-01

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

Rechargeable infection-responsive antifungal denture materials.

PubMed

Cao, Z; Sun, X; Yeh, C-K; Sun, Y

2010-12-01

Candida-associated denture stomatitis (CADS) is a significant clinical concern. We developed rechargeable infection-responsive antifungal denture materials for potentially managing the disease. Polymethacrylic acid (PMAA) was covalently bound onto diurethane dimethacrylate denture resins in the curing step. The PMAA resins bound cationic antifungal drugs such as miconazole and chlorhexidine digluconate (CG) through ionic interactions. The anticandidal activities of the drug-containing PMAA-resin discs were sustained for a prolonged period of time (weeks and months). Drug release was much faster at acidic conditions (pH 5) than at pH 7. Drugs bound to the denture materials could be "washed out" by treatment with EDTA, and the drug-depleted resins could be recharged with the same or a different class of anticandidal drugs. These results suggest clinical potential of the newly developed antifungal denture materials in the management of CADS and other infectious conditions.

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

PubMed

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

2012-12-18

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

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

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

PubMed

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

2009-08-15

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

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.

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.

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

PubMed

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

2017-09-15

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

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.

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

PubMed

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

2017-01-15

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

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.

Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions

NASA Technical Reports Server (NTRS)

Nadarajah, Arunan

1996-01-01

Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.

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.

The Ca(2+)-EDTA chelation as standard reaction to validate Isothermal Titration Calorimeter measurements (ITC).

PubMed

Ràfols, Clara; Bosch, Elisabeth; Barbas, Rafael; Prohens, Rafel

2016-07-01

A study about the suitability of the chelation reaction of Ca(2+)with ethylenediaminetetraacetic acid (EDTA) as a validation standard for Isothermal Titration Calorimeter measurements has been performed exploring the common experimental variables (buffer, pH, ionic strength and temperature). Results obtained in a variety of experimental conditions have been amended according to the side reactions involved in the main process and to the experimental ionic strength and, finally, validated by contrast with the potentiometric reference values. It is demonstrated that the chelation reaction performed in acetate buffer 0.1M and 25°C shows accurate and precise results and it is robust enough to be adopted as a standard calibration process. Copyright © 2016 Elsevier B.V. All rights reserved.

[Effects of simulated acid rain on respiration rate of cropland system with different soil pH].

PubMed

Zhu, Xue-zhu; Zhang, Gao-chuan; Li, Hui

2009-10-15

To evaluate the effects of acid rain on the respiration rate of cropland system, an outdoor pot experiment was conducted with paddy soils of pH 5.48 (S1), pH 6.70 (S1) and pH 8.18 (S3) during the 2005-2007 wheat-growing seasons. The cropland system was exposed to acid rain by spraying the wheat foliage and irrigating the soil with simulated rainwater of T1 (pH 6.0), T2 (pH 6.0, ionic concentration was twice as rainwater T1), and T3 (pH 4.4, ionic concentration was twice as rainwater T1), respectively. The static opaque chamber-gas chromatograph method was used to measure CO2 fluxes from cropland system. The results showed that acid rain affected the respiration rate of cropland system through crop plant, and the cropland system could adapt to acid rain. Acid rainwater significantly increased the average respiration rate in alkaline soil (S3) cropland system, while it had no significant effects on the average respiration rate in neutral soil (S2) and acidic soil (S1) cropland systems. During 2005-2006, after the alkaline soil cropland system was treated with rainwater T3, the average respiration rate was 23.6% and 27.6% higher than that of alkaline soil cropland system treated with rainwater T1 and T2, respectively. During March to April, the respiration rate was enhanced with the increase of rainwater ionic concentration, while it was dropped with the decrease of rainwater pH value in acidic soil cropland system. It was demonstrated that soil pH and crop plant played important roles on the respiration rate of cropland system.

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

PubMed Central

Tebo, Bradley M.

2017-01-01

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

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

PubMed

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

2016-05-01

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

Effect of pH on the rheological and structural properties of gels of water-washed chicken-breast muscle at physiological ionic strength.

PubMed

Feng, Y; Hultin, H O

2001-08-01

Adjustment of pH from 6.4 to neutrality improved gelling ability and water-holding capacity of twice water-washed, minced chicken-breast muscle significantly at physiological ionic strength, at which the majority of the myofibrillar proteins, including myosin, are not soluble. A strain value of 2.2 was obtained at neutral pH. Myofibrils were the main components of the gel network at both pH 6.4 and 7.0; however, the myofibrillar distribution varied with the pH value. At pH 6.4, myofibrils formed a network of localized aggregates leaving large voids between, whereas at neutral pH, an evenly distributed network of myofibrils was formed. In addition, at neutral pH, a network of fine strands was found within the network of myofibrils. The network was much less developed at pH 6.4. The thin and thick filaments within each myofibrillar structure were disorganized at both pH values. The intramyofibrillar spaces were larger at neutral pH than at pH 6.4. It was proposed that adjustment of pH to neutrality increased electrostatic repulsion leading to a more even distribution of the myofibrillar proteins, a key factor responsible for the improved gel strength and water-holding capacity.

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

NASA Technical Reports Server (NTRS)

Sumida, John

2002-01-01

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

Influence of pH and ionic strength on electrostatic properties of ferredoxin, FNR, and hydrogenase and the rate constants of their interaction

NASA Astrophysics Data System (ADS)

Diakonova, A. N.; Khrushchev, S. S.; Kovalenko, I. B.; Riznichenko, G. Yu; Rubin, A. B.

2016-10-01

Ferredoxin (Fd) protein transfers electrons from photosystem I (PSI) to ferredoxin:NADP+-reductase (FNR) in the photosynthetic electron transport chain, as well as other metabolic pathways. In some photosynthetic organisms including cyanobacteria and green unicellular algae under anaerobic conditions Fd transfers electrons not only to FNR but also to hydrogenase—an enzyme which catalyzes reduction of atomic hydrogen to H2. One of the questions posed by this competitive relationship between proteins is which characteristics of thylakoid stroma media allow switching of the electron flow between the linear path PSI-Fd-FNR-NADP+ and the path PSI-Fd-hydrogenase-H2. The study was conducted using direct multiparticle simulation approach. In this method protein molecules are considered as individual objects that experience Brownian motion and electrostatic interaction with the surrounding media and each other. Using the model we studied the effects of pH and ionic strength (I) upon complex formation between ferredoxin and FNR and ferredoxin and hydrogenase. We showed that the rate constant of Fd-FNR complex formation is constant in a wide range of physiologically significant pH values. Therefore it can be argued that regulation of FNR activity doesn’t involve pH changes in stroma. On the other hand, in the model rate constant of Fd-hydrogenase interaction dramatically depends upon pH: in the range 7-9 it increases threefold. It may seem that because hydrogenase reduces protons it should be more active when pH is acidic. Apparently, regulation of hydrogenase’s affinity to both her reaction partners (H+ and Fd) is carried out by changes in its electrostatic properties. In the dark, the protein is inactive and in the light it is activated and starts to interact with both Fd and H+. Therefore, we can conclude that in chloroplasts the rate of hydrogen production is regulated by pH through the changes in the affinity between hydrogenase and ferredoxin.

Evaluation of the LIVE/DEAD BacLight Kit for Detection of Extremophilic Archaea and Visualization of Microorganisms in Environmental Hypersaline Samples

PubMed Central

Leuko, Stefan; Legat, Andrea; Fendrihan, Sergiu; Stan-Lotter, Helga

2004-01-01

Extremophilic archaea were stained with the LIVE/DEAD BacLight kit under conditions of high ionic strength and over a pH range of 2.0 to 9.3. The reliability of the kit was tested with haloarchaea following permeabilization of the cells. Microorganisms in hypersaline environmental samples were detectable with the kit, which suggests its potential application to future extraterrestrial halites. PMID:15528557

Nature of the interaction of chondroitin 4-sulphate and chondroitin sulphate–proteoglycan with collagen

PubMed Central

Öbrink, Björn; Wasteson, Åke

1971-01-01

The electrostatic interaction of chondroitin sulphate and the chondroitin sulphate–proteoglycan with collagen was studied by chromatography of the glycosaminoglycan and the proteoglycan on a collagen gel. The observed binding between the macromolecules increased with decreasing pH and ionic strength, and was significant under physiological conditions. A study of the interaction between chondroitin sulphate and a preparation of soluble collagen, with a partition-equilibrium technique, afforded similar results. PMID:4256063

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.

Interaction of chloroquine and its analogues with heme: An isothermal titration calorimetric study.

PubMed

Bachhawat, K; Thomas, C J; Surolia, N; Surolia, A

2000-10-05

Quinoline-containing drugs such as chloroquine and quinine have had a long and successful history in antimalarial chemotherapy. Identification of ferriprotoporphyrin IX ([Fe(III)PPIX], haematin) as the drug receptors for these antimalarials called for investigations of the binding affinity, mode of interaction, and the conditions affecting the interaction. The parameters obtained are significant in recent times with the emergence of chloroquine resistant strains of the malaria parasites. This has underlined the need to unravel the molecular mechanism of their action so as to meet the requirement of an alternative to the existing antimalarial drugs. The isothermal titration calorimetric studies on the interaction of chloroquine with haematin lead us to propose an altered mode of binding. The initial recognition is ionic in nature mediated by the propionyl group of haematin with the quaternary nitrogen on CQ. This ionic interaction induces a conformational change, such as to favour binding of subsequent CQ molecules. On the contrary, conditions emulating the cytosolic environment (pH 7.4 and 150 mM salt) reveal the hydrophobic force to be the sole contributor driving the interaction. Interaction of a carefully selected panel of quinoline antimalarial drugs with monomeric ferriprotoporphyrin IX has also been investigated at pH 5.6 mimicking the acidic environment prevalent in the food vacuoles of parasite, the center of drug activity, which are consistent with their antimalarial activity. Copyright 2000 Academic Press.

Fluorescence spectroscopy as a specific tool for the interaction study of two surfactants with natural and synthetic organic compounds

NASA Astrophysics Data System (ADS)

Jung, Aude-Valérie; Frochot, Céline; Bersillon, Jean-Luc

2016-04-01

Four different techniques were used to study the binding of cationic cetyltrimethylammonium bromide (CTAB) and non-ionic nonylphenylethoxyl (NPE) surfactants to three synthetic organic components that mimic humic-like aggregates and to two natural aggregated humic substances (HS) extracted from aquatic suspended matter. The composition of synthetic organic components were chosen to be similar to high molecular weight highly processed terrigenous HS and low and high molecular weight less processed terrigenous (or aquatic terrigenous) HS. The natural HS were extracted under two different meteorological conditions (rainy and dry periods). No significant interaction between the non-ionic surfactant and any of the studied compounds was found. Concerning CTAB; pH, conductivity and turbidity measurements, along with fluorescence spectroscopy were combined to provide a better understanding of interactions between organic aggregates and the surfactant. The spectroscopic data show that a "highly processed terrigenous HS" fluorophore interacts in a different way with the cationic surfactant than an "aquatic terrigenous (or less processed terrigenous) HS" fluorophore does. Under similar conditions, some spectral changes in the fluorescence signal are correlated to changes in non-specific physical-chemical parameters (pH, turbidity, conductivity) for the organic compounds tested. The complexation mechanism is essentially governed by charge neutralization, which can be monitored specifically by the fluorescence of the organic moieties.

The effects of environmental conditions on the enrichment of antibiotics on microplastics in simulated natural water column.

PubMed

Shen, Xian-Cheng; Li, De-Chang; Sima, Xiao-Feng; Cheng, Hui-Yuan; Jiang, Hong

2018-06-20

Concerns regarding the release of microplastics (MPs) into the environment led us to explore the relationship between the different environmental factors and physicochemical properties of MPs, as well as the change of interaction between MPs and organic pollutants. In this study, the effects of environmental factors (ageing conditions), such as pH, temperature, ionic strength, ageing time, and humic acid (HA) concentration, on the characteristics of MPs and their adsorption toward tetracycline (TC) were systematically investigated. The results showed that ageing factors such as pH, ionic strength, and temperature were found to have little impact on the adsorptive capacity of MPs for TC. However, MPs aged in HA solution exhibited a significant decreased adsorptive capacity for TC. HA, which has numerous functional groups, can cover the surface of MPs and change their hydrophobicity, thereby reducing the adsorption affinity to TC. The electrostatic repulsion between adsorbed HA and TC molecules may also decrease the adsorption of TC. In addition, the competing effect of HA for adsorption sites on the surface of MPs further reduces the adsorption of TC. The data presented in this work provide useful information for understanding the transfer of antibiotics by aged MPs, which is of fundamental importance to assess the environmental impact of MPs. Copyright © 2018 Elsevier Inc. All rights reserved.

Background electrolytes and pH effects on selenate adsorption using iron-impregnated granular activated carbon and surface binding mechanisms.

PubMed

Zhang, Ning; Gang, Daniel Dianchen; McDonald, Louis; Lin, Lian-Shin

2018-03-01

Iron-impregnated granular activated carbon (Fe-GAC) has been shown effective for selenite adsorptive removal from aqueous solutions, but similar effectiveness was not observed with selenate. This study examined the effects of background electrolytes and pH on selenate adsorption on to Fe-GAC, and surface bindings to elucidate the selenate adsorption mechanisms. The decrease magnitude of selenate adsorption capacity under three background electrolytes followed the order: LiCl > NaCl > KCl, as ionic strength increased from 0.01 to 0.1 M. Larger adsorption capacity differences among the three electrolytes were observed under the higher ionic strengths (0.05 and 0.1 M) than those under 0.01 M. Multiplet peak fittings of high resolution X-ray photoelectron spectra for O1s and Fe2p 3/2 indicated the presence of iron (III) on adsorbent surface. pH variations during the adsorbent preparation within 3-8 in NaCl solutions did not cause appreciable changes in the iron redox state and composition. Raman spectra showed the formation of both monodentate and bidentate inner sphere complexes under pHs <7 and a mixture of outer sphere and inner sphere complexes at pH 8. These results explained the lower selenate adsorption under alkaline conditions. Mechanisms for monodentate and bidentate formations and a stable six-member ring structure were proposed. Two strategies were recommended for modifying Fe-GAC preparation procedure to enhance the selenate adsorption: (1) mixed-metal oxide coatings to increase the point of zero charge (pH zpc ); and (2) ferrous iron coating to initially reduce selenate followed by selenite adsorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of pH on ion current through conical nanopores

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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.

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

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

Direct Ionic Regulation of the Activity of Myo-Inositol Biosynthesis Enzymes in Mozambique Tilapia

PubMed Central

Villarreal, Fernando D.; Kültz, Dietmar

2015-01-01

Myo-inositol (Ins) is a major compatible osmolyte in many cells, including those of Mozambique tilapia (Oreochromis mossambicus). Ins biosynthesis is highly up-regulated in tilapia and other euryhaline fish exposed to hyperosmotic stress. In this study, enzymatic regulation of two enzymes of Ins biosynthesis, Ins phosphate synthase (MIPS) and inositol monophosphatase (IMPase), by direct ionic effects is analyzed. Specific MIPS and IMPase isoforms from Mozambique tilapia (MIPS-160 and IMPase 1) were selected based on experimental, phylogenetic, and structural evidence supporting their role for Ins biosynthesis during hyperosmotic stress. Recombinant tilapia IMPase 1 and MIPS-160 activity was assayed in vitro at ionic conditions that mimic changes in the intracellular milieu during hyperosmotic stress. The in vitro activities of MIPS-160 and IMPase 1 are highest at alkaline pH of 8.8. IMPase 1 catalytic efficiency is strongly increased during hyperosmolality (particularly for the substrate D-Ins-3-phosphate, Ins-3P), mainly as a result of [Na+] elevation. Furthermore, the substrate-specificity of IMPase 1 towards D-Ins-1-phosphate (Ins-1P) is lower than towards Ins-3P. Because MIPS catalysis results in Ins-3P this results represents additional evidence for IMPase 1 being the isoform that mediates Ins biosynthesis in tilapia. Our data collectively demonstrate that the Ins biosynthesis enzymes are activated under ionic conditions that cells are exposed to during hypertonicity, resulting in Ins accumulation, which, in turn, results in restoration of intracellular ion homeostasis. We propose that the unique and direct ionic regulation of the activities of Ins biosynthesis enzymes represents an efficient biochemical feedback loop for regulation of intracellular physiological ion homeostasis during hyperosmotic stress. PMID:26066044

Direct Ionic Regulation of the Activity of Myo-Inositol Biosynthesis Enzymes in Mozambique Tilapia.

PubMed

Villarreal, Fernando D; Kültz, Dietmar

2015-01-01

Myo-inositol (Ins) is a major compatible osmolyte in many cells, including those of Mozambique tilapia (Oreochromis mossambicus). Ins biosynthesis is highly up-regulated in tilapia and other euryhaline fish exposed to hyperosmotic stress. In this study, enzymatic regulation of two enzymes of Ins biosynthesis, Ins phosphate synthase (MIPS) and inositol monophosphatase (IMPase), by direct ionic effects is analyzed. Specific MIPS and IMPase isoforms from Mozambique tilapia (MIPS-160 and IMPase 1) were selected based on experimental, phylogenetic, and structural evidence supporting their role for Ins biosynthesis during hyperosmotic stress. Recombinant tilapia IMPase 1 and MIPS-160 activity was assayed in vitro at ionic conditions that mimic changes in the intracellular milieu during hyperosmotic stress. The in vitro activities of MIPS-160 and IMPase 1 are highest at alkaline pH of 8.8. IMPase 1 catalytic efficiency is strongly increased during hyperosmolality (particularly for the substrate D-Ins-3-phosphate, Ins-3P), mainly as a result of [Na+] elevation. Furthermore, the substrate-specificity of IMPase 1 towards D-Ins-1-phosphate (Ins-1P) is lower than towards Ins-3P. Because MIPS catalysis results in Ins-3P this results represents additional evidence for IMPase 1 being the isoform that mediates Ins biosynthesis in tilapia. Our data collectively demonstrate that the Ins biosynthesis enzymes are activated under ionic conditions that cells are exposed to during hypertonicity, resulting in Ins accumulation, which, in turn, results in restoration of intracellular ion homeostasis. We propose that the unique and direct ionic regulation of the activities of Ins biosynthesis enzymes represents an efficient biochemical feedback loop for regulation of intracellular physiological ion homeostasis during hyperosmotic stress.

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

PubMed Central

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

2012-01-01

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

Effect of pH and ionic strength on exposure and toxicity of encapsulated lambda-cyhalothrin to Daphnia magna.

PubMed

Son, Jino; Hooven, Louisa A; Harper, Bryan; Harper, Stacey L

2015-12-15

Encapsulation of pesticide active ingredients in polymers has been widely employed to control the release of poorly water-soluble active ingredients. Given the high dispersibility of these encapsulated pesticides in water, they are expected to behave differently compared to their active ingredients; however, our current understanding of the fate and effects of encapsulated pesticides is still limited. In this study, we employed a central composite design (CCD) to investigate how pH and ionic strength (IS) affect the hydrodynamic diameter (HDD) and zeta potential of encapsulated λ-cyhalothrin and how those changes affect the exposure and toxicity to Daphnia magna. R(2) values greater than 0.82 and 0.84 for HDD and zeta potential, respectively, irrespective of incubation time suggest those changes could be predicted as a function of pH and IS. For HDD, the linear factor of pH and quadratic factor of pH×pH were found to be the most significant factors affecting the change of HDD at the beginning of incubation, whereas the effects of IS and IS×IS became significant as incubation time increased. For zeta potential, the linear factor of IS and quadratic factor of IS×IS were found to be the most dominant factors affecting the change of zeta potential of encapsulated λ-cyhalothrin, irrespective of incubation time. The toxicity tests with D. magna under exposure conditions in which HDD or zeta potential of encapsulated λ-cyhalothrin was maximized or minimized in the overlying water also clearly showed the worst-case exposure condition to D. magna was when the encapsulated λ-cyhalothrin is either stable or small in the overlying water. Our results show that water quality could modify the fate and toxicity of encapsulated λ-cyhalothrin in aquatic environments, suggesting understanding their aquatic interactions are critical in environmental risk assessment. Herein, we discuss the implications of our findings for risk assessment. Copyright © 2015 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

Sorption of Lincomycin by Manure-Derived Biochars from Water

PubMed Central

Liu, Cheng-Hua; Chuang, Ya-Hui; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.; Gonzalez, Javier M.; Johnston, Cliff T.; Lehmann, Johannes; Zhang, Wei

2018-01-01

The presence of antibiotics in agroecosystems raises concerns about the proliferation of antibiotic-resistant bacteria and adverse effects to human health. Soil amendment with biochars pyrolized from manures may be a win-win strategy for novel manure management and antibiotics abatement. In this study, lincomycin sorption by manure-derived biochars was examined using batch sorption experiments. Lincomycin sorption was characterized by two-stage kinetics with fast sorption reaching quasi-equilibrium in the first 2 d, followed by slow sorption over 180 d. The fast sorption was primarily attributed to surface adsorption, whereas the long-term slow sorption was controlled by slow diffusion of lincomycin into biochar pore structures. Two-day sorption experiments were performed to explore effects of biochar particle size, solid/water ratio, solution pH, and ionic strength. Lincomycin sorption to biochars was greater at solution pH 6.0 to 7.5 below the dissociation constant of lincomycin (7.6) than at pH 9.9 to 10.4 above its dissociation constant. The enhanced lincomycin sorption at lower pH likely resulted from electrostatic attraction between the positively charged lincomycin and the negatively charged biochar surfaces. This was corroborated by the observation that lincomycin sorption decreased with increasing ionic strength at lower pH (6.7) but remained constant at higher pH (10). The long-term lincomycin sequestration by biochars was largely due to pore diffusion plausibly independent of solution pH and ionic composition. Therefore, manure-derived biochars had lasting lincomycin sequestration capacity, implying that biochar soil amendment could significantly affect the distribution, transport, and bioavailability of lincomycin in agroecosystems. PMID:27065399

Sensitive voltammetric determination of chloramphenicol by using single-wall carbon nanotube-gold nanoparticle-ionic liquid composite film modified glassy carbon electrodes.

PubMed

Xiao, Fei; Zhao, Faqiong; Li, Jiangwen; Yan, Rui; Yu, Jingjing; Zeng, Baizhao

2007-07-16

A novel composite film modified glassy carbon electrode has been fabricated and characterized by scanning electron microscope (SEM) and voltammetry. The composite film comprises of single-wall carbon nanotube (SWNT), gold nanoparticle (GNP) and ionic liquid (i.e. 1-octyl-3-methylimidazolium hexafluorophosphate), thus has the characteristics of them. The resulting electrode shows good stability, high accumulation efficiency and strong promotion to electron transfer. On it, chloramphenicol can produce a sensitive cathodic peak at -0.66 V (versus SCE) in pH 7.0 phosphate buffer solutions. Parameters influencing the voltammetric response of chloramphenicol are optimized, which include the composition of the film and the operation conditions. Under the optimized conditions, the peak current is linear to chloramphenicol concentration in the range of 1.0x10(-8)-6.0x10(-6) M, and the detection limit is estimated to be 5.0x10(-9) M after an accumulation for 150 s on open circuit. The electrode is applied to the determination of chloramphenicol in milk samples, and the recoveries for the standards added are 97.0% and 100.3%. In addition, the electrochemical reaction of chloramphenicol and the effect of single-wall carbon nanotube, gold nanoparticle and ionic liquid are discussed.

[Difference in ionic specificity of ATP synthesis in extremely alkalophilic sulfate-reducing and acetogenic bacteria].

PubMed

Pitriuk, A V; Pusheva, M A

2001-01-01

Ionic specificity of oxidative phosphorylation was studied in Natroniella acetigena and Desulfonatronum lacustre, which are new alkaliphilic anaerobes that were isolated from soda lakes and have a pH growth optimum of 9.5-9.7. The ability of their cells to synthesize ATP in response to the imposition of artificial delta pH+ and delta pNa+ gradients was studied. As distinct from other marine and freshwater sulfate reducers and extremely alkaliphilic anaerobes, D. lacustre uses a Na(+)-translocating ATPase for ATP synthesis. The alkaliphilic acetogen N. acetigena, which develops at a much higher Na+ concentration in the medium, generated primary delta pH+ for ATP synthesis. Thus, the high Na+ concentrations and alkaline pH values typical of soda lakes do not predetermine the type of bioenergetics of their inhabitants.

Formulation and characterization of nanoencapsulated curcumin using sodium caseinate and its incorporation in ice cream.

PubMed

Kumar, Deep Diyuti; Mann, Bimlesh; Pothuraju, Ramesh; Sharma, Rajan; Bajaj, Rajesh; Minaxi

2016-01-01

In the present investigation, the preparation and characterization of a curcumin nanoemulsion with milk protein (sodium caseinate) and its incorporation into ice cream were undertaken. Among the different combinations, the most stable formulation was observed using milk fat (8%), medium chain triglycerides (2%), curcumin (0.24%) and sodium caseinate (6%) with a mean particle size of 333.8 ± 7.18 nm, a zeta potential of -44.1 ± 0.72 mV and an encapsulation efficiency of 96.9 ± 0.28%. The effect of different processing conditions (heating, pH and ionic strength) on the particle size distribution and zeta potential of the nanoemulsion was evaluated. During heat treatment, the particle size of the nanoemulsion was increased from 333.8 ± 7.18 to 351.1 ± 4.04 nm. The nanoemulsion was destabilized at pH 4.6 and the particle size increased above and below pH 5.0. However, there was a slight increase in the particle size with a change in the ionic concentration. The release kinetics data suggested that in simulated gastro-intestinal digestion, the nanoemulsion was stable against pepsin digestion (a 5.25% release of curcumin), while pancreatic action led to a 16.12% release of curcumin from the nanoemulsion. Finally, our formulation was successfully incorporated into ice cream and the sensory attributes were evaluated. No significant difference was observed in the scores of the sensory attributes between the control and ice cream prepared with a curcumin nanoemulsion. Moreover, the encapsulation efficiency of the curcumin incorporated into the ice cream was 93.7%, which indicates that it can withstand the processing conditions. The findings suggest that ice cream is a suitable dairy product for the delivery of lipophilic bioactive components (curcumin) which can be used for therapeutic purposes.

The Role of Ionic Interactions in the Adherence of the S. epidermidis Adhesin SdrF to Prosthetic Material

PubMed Central

Toba, Faustino A.; Visai, Livia; Trivedi, Sheetal; Lowy, Franklin D.

2012-01-01

Staphylococcus epidermidis infections are common complications of prosthetic device implantation. SdrF, a surface protein, appears to play a critical role in the initial colonization step by adhering to type I collagen and Dacron™. The role of ionic interactions in S. epidermidis adherence to prosthetic material was examined. SdrF was cloned and expressed in Lactococcus lactis. The effect of pH, cation concentration and detergents on adherence to different types of plastic surfaces was assessed by crystal violet staining and bacterial cell counting. SdrF, in contrast with controls and other S. epidermidis surface proteins, bound to hydrophobic materials such as polystyrene. Binding was an ionic interaction and was affected by surface charge of the plastic, pH and cation concentration. Adherence of the SdrF construct was increased to positively charged plastics and was reduced by increasing concentrations of Ca2+ and Na+. Binding was optimal at pH 7.4. Kinetic studies demonstrated that the SdrF B domain, as well as one of the B subdomains was sufficient to mediate binding. The SdrF construct also bound more avidly to Goretex™ than the lacotococcal control. SdrF is a multifunctional protein that contributes to prosthetic devices infections by ionic, as well as specific receptor-ligand interactions. PMID:23039791

Rechargeable Infection-responsive Antifungal Denture Materials

PubMed Central

Cao, Z.; Sun, X.; Yeh, C.-K.; Sun, Y.

2010-01-01

Candida-associated denture stomatitis (CADS) is a significant clinical concern. We developed rechargeable infection-responsive antifungal denture materials for potentially managing the disease. Polymethacrylic acid (PMAA) was covalently bound onto diurethane dimethacrylate denture resins in the curing step. The PMAA resins bound cationic antifungal drugs such as miconazole and chlorhexidine digluconate (CG) through ionic interactions. The anticandidal activities of the drug-containing PMAA-resin discs were sustained for a prolonged period of time (weeks and months). Drug release was much faster at acidic conditions (pH 5) than at pH 7. Drugs bound to the denture materials could be “washed out” by treatment with EDTA, and the drug-depleted resins could be recharged with the same or a different class of anticandidal drugs. These results suggest clinical potential of the newly developed antifungal denture materials in the management of CADS and other infectious conditions. PMID:20940361

Bone Marrow Stem Cells in Response to Intervertebral Disc-Like Matrix Acidity and Oxygen Concentration: Implications for Cell-based Regenerative Therapy.

PubMed

Naqvi, Syeda M; Buckley, Conor T

2016-05-01

In vitro culture of porcine bone marrow stem cells (BMSCs) in varying pH microenvironments in a three-dimensional hydrogel system. To characterize the response of BMSCs to varying pH environments (blood [pH 7.4], healthy intervertebral disc (IVD) (pH 7.1), mildly degenerated IVD (pH 6.8), and severely degenerated IVD (pH 6.5) in three-dimensional culture under normoxic (20%) and hypoxic (5%) conditions. The IVD is an avascular organ relying on diffusion of essential nutrients through the cartilaginous endplates (CEPs) thereby creating a challenging microenvironment. Within a degenerated IVD, oxygen and glucose concentrations decrease further (<5% oxygen, <5 mmol/L glucose) and matrix acidity (

Assessing the influence of media composition and ionic strength on drug release from commercial immediate-release and enteric-coated aspirin tablets.

PubMed

Karkossa, Frank; Klein, Sandra

2017-10-01

The objective of this test series was to elucidate the importance of selecting the right media composition for a biopredictive in-vitro dissolution screening of enteric-coated dosage forms. Drug release from immediate-release (IR) and enteric-coated (EC) aspirin formulations was assessed in phosphate-based and bicarbonate-based media with different pH, electrolyte composition and ionic strength. Drug release from aspirin IR tablets was unaffected by media composition. In contrast, drug release from EC aspirin formulations was affected by buffer species and ionic strength. In all media, drug release increased with increasing ionic strength, but in bicarbonate-based buffers was delayed when compared with that in phosphate-based buffers. Interestingly, the cation species in the dissolution medium had also a clear impact on drug release. Drug release profiles obtained in Blank CarbSIF, a new medium simulating pH and average ionic composition of small intestinal fluid, were different from those obtained in all other buffer compositions studied. Results from this study in which the impact of various media parameters on drug release of EC aspirin formulations was systematically screened clearly show that when developing predictive dissolution tests, it is important to simulate the ionic composition of intraluminal fluids as closely as possible. © 2017 Royal Pharmaceutical Society.

Extraction of ranitidine and nizatidine with using imidazolium ionic liquids prior spectrophotometric and chromatographic detection.

PubMed

Kiszkiel, Ilona; Starczewska, Barbara; Leśniewska, Barbara; Późniak, Patrycja

2015-03-15

A new extraction medium was proposed for liquid-liquid extraction of the histamine H2 receptor antagonists ranitidine (RNT) and nizatidine (NZT). The ionic liquids with low vapor pressure and favorable solvating properties for a range of compounds such as 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4mim][Tf2N] were tested for isolation of analytes. The extraction parameters of RNT and NZT, namely, amount of ionic liquid, pH of sample solution, shaking and centrifugation time were optimized. The isolation processes were performed with 1 mL of the ionic liquids. The extracted samples (pH values near 4) were shaken at 1750 rpm. The influence of interfering substances on the efficiency of extraction process was also studied. Methods for the histamine H2 receptor antagonists (ranitidine and nizatidine) determination after their separation using imidazolium ionic liquids by high performance liquid chromatography (HPLC) combined with UV spectrophotometry were developed. The application of ionic liquids in extraction step allows for selective isolation of analytes from aqueous matrices and their preconcentration. The above methods were applied to the determination of RNT and NZT in environmental samples (river water and wastewater after treatment). Copyright © 2014 Elsevier B.V. All rights reserved.

SEPARATION OF PLUTONIUM FROM FISSION PRODUCTS BY A COLLOID REMOVAL PROCESS

DOEpatents

Schubert, J.

1960-05-24

A method is given for separating plutonium from uranium fission products. An acidic aqueous solution containing plutonium and uranium fission products is subjected to a process for separating ionic values from colloidal matter suspended therein while the pH of the solution is maintained between 0 and 4. Certain of the fission products, and in particular, zirconium, niobium, lanthanum, and barium are in a colloidal state within this pH range, while plutonium remains in an ionic form, Dialysis, ultracontrifugation, and ultrafiltration are suitable methods of separating plutonium ions from the colloids.

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

Impact of lysozyme on stability mechanism of nanozirconia aqueous suspension

NASA Astrophysics Data System (ADS)

Szewczuk-Karpisz, Katarzyna; Wiśniewska, Małgorzata

2016-08-01

The effect of lysozyme (LSZ) presence on the zirconium(IV) oxide (ZrO2) aqueous suspension stability was examined. The applied zirconia contains mesopores (with a diameter about 30 nm) and its mean particle size is about 100 nm. To determine the stability mechanism of ZrO2 suspension in the biopolymer presence, the adsorption and electrokinetic (surface charge density and zeta potential) measurements were performed in the pH range 3-10. The lysozyme adsorption on the nanozirconia surface proceeds mainly through electrostatic forces. Under solid-polymer repulsion conditions, there is no adsorption of lysozyme (pH < 6, CNaCl 0.01 mol/dm3). The increase of solution ionic strength to 0.2 mol/dm3 causes screening of unfavourable forces and biopolymer adsorption becomes possible. The LSZ addition to the ZrO2 suspension influences its stability. At pH 3, 4.6 and 7.6, slight improvement of the system stability was obtained. In turn, at pH 9 considerable destabilization of nanozirconia particles covered by polymeric layers occurs.

An accurate coarse-grained model for chitosan polysaccharides in aqueous solution.

PubMed

Tsereteli, Levan; Grafmüller, Andrea

2017-01-01

Computational models can provide detailed information about molecular conformations and interactions in solution, which is currently inaccessible by other means in many cases. Here we describe an efficient and precise coarse-grained model for long polysaccharides in aqueous solution at different physico-chemical conditions such as pH and ionic strength. The Model is carefully constructed based on all-atom simulations of small saccharides and metadynamics sampling of the dihedral angles in the glycosidic links, which represent the most flexible degrees of freedom of the polysaccharides. The model is validated against experimental data for Chitosan molecules in solution with various degree of deacetylation, and is shown to closely reproduce the available experimental data. For long polymers, subtle differences of the free energy maps of the glycosidic links are found to significantly affect the measurable polymer properties. Therefore, for titratable monomers the free energy maps of the corresponding links are updated according to the current charge of the monomers. We then characterize the microscopic and mesoscopic structural properties of large chitosan polysaccharides in solution for a wide range of solvent pH and ionic strength, and investigate the effect of polymer length and degree and pattern of deacetylation on the polymer properties.

An accurate coarse-grained model for chitosan polysaccharides in aqueous solution

PubMed Central

Tsereteli, Levan

2017-01-01

Computational models can provide detailed information about molecular conformations and interactions in solution, which is currently inaccessible by other means in many cases. Here we describe an efficient and precise coarse-grained model for long polysaccharides in aqueous solution at different physico-chemical conditions such as pH and ionic strength. The Model is carefully constructed based on all-atom simulations of small saccharides and metadynamics sampling of the dihedral angles in the glycosidic links, which represent the most flexible degrees of freedom of the polysaccharides. The model is validated against experimental data for Chitosan molecules in solution with various degree of deacetylation, and is shown to closely reproduce the available experimental data. For long polymers, subtle differences of the free energy maps of the glycosidic links are found to significantly affect the measurable polymer properties. Therefore, for titratable monomers the free energy maps of the corresponding links are updated according to the current charge of the monomers. We then characterize the microscopic and mesoscopic structural properties of large chitosan polysaccharides in solution for a wide range of solvent pH and ionic strength, and investigate the effect of polymer length and degree and pattern of deacetylation on the polymer properties. PMID:28732036

Teaching light scattering spectroscopy: the dimension and shape of tobacco mosaic virus.

PubMed Central

Santos, N C; Castanho, M A

1996-01-01

The tobacco mosaic virus is used as a model molecular assembly to illustrate the basic potentialities of light scattering techniques (both static and dynamic) to undergraduates. The work has two objectives: a pedagogic one (introducing light scattering to undergraduate students) and a scientific one (stabilization of the virus molecular assembly structure by the nucleic acid). Students are first challenged to confirm the stabilization of the cylindrical shape of the virus by the nucleic acid, at pH and ionic strength conditions where the coat proteins alone do not self-assemble. The experimental intramolecular scattering factor is compared with the theoretical ones for several model geometries. The data clearly suggest that the geometry is, in fact, a rod. Comparing the experimental values of gyration radius and hydrodynamic radius with the theoretical expectations further confirms this conclusion. Moreover, the rod structure is maintained over a wider range of pH and ionic strength than that valid for the coat proteins alone. The experimental values of the diffusion coefficient and radius of gyration are compared with the theoretical expectations assuming the dimensions detected by electron microscopy techniques. In fact, both values are in agreement (length approximately 300 nm, radius approximately 20 nm). PMID:8874039

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

PubMed

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

2014-08-19

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

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

PubMed Central

Hosseinzadeh, Reza; Khorsandi, Khatereh; Hemmaty, Syavash

2013-01-01

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

Photoactive Gel for Assisted Cleaning during Olive Mill Wastewater Membrane Microfiltration

PubMed Central

Han, Yilong

2017-01-01

A photoactive gel has been fabricated on the surface of polyethylene membranes for enhancing the fouling resistance during olive mill wastewater treatment. Light and pH responsive materials have been introduced in the membrane surface through the build up of a layer-by-layer pattern, which is formed by photocatalytic nanoparticles and ionic polyelectrolytes. The best working conditions to contrast foulants adsorption have been explored and identified. Repulsive interfacial forces and assisted transfer of foulants to catalytic sites have been envisaged as crucial factors for contrasting the decline of the flux during microfiltration. Tests in submerged configuration have been implemented for six continuous hours under irradiation at two different pH conditions. As a result, a worthy efficiency of the photoactive gel has been reached when suitable chemical microenvironments have been generated along the shell side of the membranes. No additional chemical reagents or expensive back-flushing procedures have been necessary to further clean the membranes; rather, fast and reversible pH switches have been enough to remove residues, thereby preserving the integrity of the layer-by-layer (LBL) complex onto the membrane surface. PMID:29186819

Interaction of diazepam with surfactants. Spectrophotometric and spectrofluorometric study

NASA Astrophysics Data System (ADS)

De La Guardia, M.; Rodilla, F.

1986-03-01

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

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

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.

Microsphere morphology tuning and photo-luminescence properties of monoclinic Y2WO6

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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

PubMed

Adewoye, L O; Worobec, E A

1999-12-01

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

Stimuli-Responsive Polymer Brushes for Flow Control through Nanopores

PubMed Central

Adiga, Shashishekar P.; Brenner, Donald W.

2012-01-01

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

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

PubMed

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

2013-01-01

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

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

NASA Technical Reports Server (NTRS)

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

1998-01-01

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

Peroxidase-mediated polymerization of 1-naphthol: impact of solution pH and ionic strength.

PubMed

Bhandari, Alok; Xu, Fangxiang; Koch, David E; Hunter, Robert P

2009-01-01

Peroxidase-mediated oxidation has been proposed as a treatment method for naphthol-contaminated water. However, the impact of solution chemistry on naphthol polymerization and removal has not been documented. This research investigated the impact of pH and ionic strength on peroxidase-mediated removal of 1-naphthol in completely mixed batch reactors. The impact of hydrogen peroxide to 1-naphthol ratio and activity of horseradish peroxidase was also studied. Size exclusion chromatography was used to estimate the molecular weight distribution of oligomeric products, and liquid chromatography/mass spectrometry was used to estimate product structure. Naphthol transformation decreased with ionic strength, and substrate removal was lowest at neutral pHs. Solution pH influenced the size and the composition of the oligomeric products. An equimolar ratio of H(2)O(2):naphthol was sufficient for optimal naphthol removal. Polymerization products included naphthoquinones and oligomers derived from two, three, and four naphthol molecules. Our results illustrate the importance of water chemistry when considering a peroxidase-based approach for treatment of naphthol-contaminated waters.

Biocompatible Stimuli-Responsive W/O/W Multiple Emulsions Prepared by One-Step Mixing with a Single Diblock Copolymer Emulsifier.

PubMed

Protat, Marine; Bodin, Noémie; Gobeaux, Frédéric; Malloggi, Florent; Daillant, Jean; Pantoustier, Nadège; Guenoun, Patrick; Perrin, Patrick

2016-09-22

Multiple water-in-oil-in-water (W/O/W) emulsions are promising materials in designing carriers of hydrophilic molecules or drug delivery systems, provided stability issues are solved and biocompatible chemicals can be used. In this work, we designed a biocompatible amphiphilic copolymer, poly(dimethylsiloxane)-b-poly(2-(dimethylamino)ethyl methacrylate) (PDMS-b-PDMAEMA), that can stabilize emulsions made with various biocompatible oils. The hydrophilic/hydrophobic properties of the copolymer can be adjusted using both pH and ionic strength stimuli. Consequently, the making of O/W (oil in water), W/O (water in oil), and W/O/W emulsions can be achieved by sweeping the pH and ionic strength. Of importance, W/O/W emulsions are formulated over a large pH and ionic strength domain in a one-step emulsification process via transitional phase inversion and are stable for several months. Cryo-TEM and interfacial tension studies show that the formation of these W/O/W emulsions is likely to be correlated to the interfacial film curvature and microemulsion morphology.

The missing piece in the puzzle: Prediction of aggregation via the protein-protein interaction parameter A∗2.

PubMed

Koepf, Ellen; Schroeder, Rudolf; Brezesinski, Gerald; Friess, Wolfgang

2018-07-01

The tendency of protein pharmaceuticals to form aggregates is a major challenge during formulation development, as aggregation affects quality and safety of the product. In particular, the formation of large native-like particles in the context of liquid-air interfacial stress is a well-known but not fully understood problem. Focusing on the two most fundamental criteria of protein formulation affecting protein-protein interaction, the impact of pH and ionic strength on the interaction parameter A ∗ 2 and its link to aggregation upon mechanical stress was investigated. A ∗ 2 of two monoclonal antibodies (mABs) and a polyclonal IgG was determined using dynamic light scattering and was correlated to the number of particles formed upon shaking in vials analyzed by visual inspection, turbidity analysis, light obscuration and micro-flow imaging. A good correlation between aggregation induced by interfacial stress and formulation pH was given. It could be shown that A ∗ 2 was highest for mAB 1 and lowest for IgG, what was in good accordance with the number of particles formed. Shaking of IgG resulted in overall higher numbers of particles compared to the two mABs. A ∗ 2 decreased and particle numbers increased with increasing pH. Different to pH, ionic strength only slightly affected A ∗ 2 . Nevertheless, at high ionic (100 mM) strength the samples exhibited more pronounced particle formation, particularly of large particles >25 µm, which was most pronounced at high pH. Protein solutions were identified to form continuous films with an inhomogeneous protein distribution at the liquid-air interface. These areas of agglomerated, native-like protein material can be transferred into the bulk solution by compression-decompression of the interface. Whether or not those clusters lead to the appearance of large protein aggregates or fall apart depends on the attractive or repulsive forces between protein molecules. Thus, protein aggregation due to interfacial stress is correlated with the protein-protein interactions as determined by A ∗ 2 . This enables to differentiate different antibodies according to their propensity to form particles upon mechanical stress and to identify optimum formulation conditions. Copyright © 2018 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.

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

PubMed

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

2001-02-01

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

Ultrasound-assisted temperature-controlled ionic liquid emulsification microextraction coupled with capillary electrophoresis for the determination of parabens in personal care products.

PubMed

Ma, Teng; Li, Zheng; Jia, Qiong; Zhou, Weihong

2016-07-01

We developed a CE and ultrasound-assisted temperature-controlled ionic liquid emulsification microextraction method for the determination of four parabens (methyl paraben, ethyl paraben, propyl paraben, and butyl paraben) in personal care products including mouthwash and toning lotion. In the proposed extraction procedure, ionic liquid (IL, 1-octyl-3-methylimidazolium hexafluorophosphate) was used as extraction solvent, moreover, no disperser solvent was needed. Parameters affecting the extraction efficiency including volume of IL, heating temperature, ultrasonic time, extraction time, sample pH, ionic strength, and centrifugation time were optimized. Under the optimized conditions, the method was found to be linear over the range of 3-500 ng/mL with coefficient of determination (R(2) ) in the range of 0.9990-0.9998. The LODs and LOQs for the four parabens were 0.45-0.72 ng/mL and 1.50-2.40 ng/mL, respectively. Intraday and interday precisions (RSDs, n = 5) were in the range of 5.4-6.8% and 7.0-8.7%, respectively. The recoveries of parabens at different spiked levels ranged from 71.9 to 119.2% with RSDs less than 9.5%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of temperature, pH, and ionic strength on the Henry's law constant of triethylamine

NASA Astrophysics Data System (ADS)

Leng, Chun-Bo; Roberts, Jason E.; Zeng, Guang; Zhang, Yun-Hong; Liu, Yong

2015-05-01

The Henry's law constants (KH) of triethylamine (TEA) in pure water and in 1-octanol were measured for the temperatures pertinent to the lower troposphere (278-298 K) using a bubble column system coupled to a Fourier transform infrared spectrometer. The KH values of TEA in water and 1-octanol at 298 K are 5.75 ± 0.86 mol L-1 atm-1 and 115.62 ± 5.78 mol L-1 atm-1. The KH values display strong dependence on temperature, pH, and ionic strength. The characteristic times for TEA to establish an equilibrium between gas and droplet with a size of 5.6 µm are ~33 s (298 K, pH = 5.6); ~8.9 × 102 s (278 K, pH = 5.6); ~1.3 × 103 s (298 K, pH = 4.0); and 3.6 × 104 s (278 K, pH = 4.0). The evaluation of TEA partitioning between gas phase and condensed phase implies that TEA predominantly resides in rainwater, and TEA loss to organic aerosol is negligible.

Rheology of interfacial protein-polysaccharide composites

NASA Astrophysics Data System (ADS)

Fischer, P.

2013-05-01

The morphology and mechanical properties of protein adsorption layers can significantly be altered by the presence of surfactants, lipids, particles, other proteins, and polysaccharides. In food emulsions, polysaccharides are primarily considered as bulk thickener but can under appropriate environmental conditions stabilize or destabilize the protein adsorption layer and, thus, the entire emulsion system. Despite their ubiquitous usage as stabilization agent, relatively few investigations focus on the interfacial rheology of composite protein/polysaccharide adsorption layers. The manuscript provides a brief review on both main stabilization mechanisms, thermodynamic phase separation and electrostatic interaction and discusses the rheological response in light of the environmental conditions such as ionic strength and pH.

Tuning of protein-surfactant interaction to modify the resultant structure.

PubMed

Mehan, Sumit; Aswal, Vinod K; Kohlbrecher, Joachim

2015-09-01

Small-angle neutron scattering and dynamic light scattering studies have been carried out to examine the interaction of bovine serum albumin (BSA) protein with different surfactants under varying solution conditions. We show that the interaction of anionic BSA protein (pH7) with surfactant and the resultant structure are strongly modified by the charge head group of the surfactant, ionic strength of the solution, and mixed surfactants. The protein-surfactant interaction is maximum when two components are oppositely charged, followed by components being similarly charged through the site-specific binding, and no interaction in the case of a nonionic surfactant. This interaction of protein with ionic surfactants is characterized by the fractal structure representing a bead-necklace structure of micellelike clusters adsorbed along the unfolded protein chain. The interaction is enhanced with ionic strength only in the case of site-specific binding of an anionic surfactant with an anionic protein, whereas it is almost unchanged for other complexes of cationic and nonionic surfactants with anionic proteins. Interestingly, the interaction of BSA protein with ionic surfactants is significantly suppressed in the presence of nonionic surfactant. These results with mixed surfactants thus can be used to fold back the unfolded protein as well as to prevent surfactant-induced protein unfolding. For different solution conditions, the results are interpreted in terms of a change in fractal dimension, the overall size of the protein-surfactant complex, and the number of micelles attached to the protein. The interplay of electrostatic and hydrophobic interactions is found to govern the resultant structure of complexes.

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

NASA Astrophysics Data System (ADS)

Samanta, Anuva; Paul, Bijan Kumar; Guchhait, N.

2011-05-01

In this report we have studied micellization process of anionic, cationic and non-ionic surfactants using N,N-dimethylaminonapthyl-(acrylo)-nitrile (DMANAN) as an external fluorescence probe. Micropolarity, microviscosity, critical micellar concentration of these micelles based on steady state absorption and fluorescence and time resolved emission spectroscopy of the probe DMANAN show that the molecule resides in the micelle-water interface for ionic micelles and in the core for the non-ionic micelle. The effect of variation of pH of the micellar solution as well as fluorescence quenching measurements of DMANAN provide further support for the location of the probe in the micelles.

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 unexpected mechanism underlying the high-valent mono-oxo-rhenium(V) hydride catalyzed hydrosilylation of C=N functionalities: insights from a DFT study.

PubMed

Wang, Jiandi; Wang, Wenmin; Huang, Liangfang; Yang, Xiaodi; Wei, Haiyan

2015-04-07

In this study, we theoretically investigated the mechanism underlying the high-valent mono-oxo-rhenium(V) hydride Re(O)HCl2(PPh3)2 (1) catalyzed hydrosilylation of C=N functionalities. Our results suggest that an ionic S(N)2-Si outer-sphere pathway involving the heterolytic cleavage of the Si-H bond competes with the hydride pathway involving the C=N bond inserted into the Re-H bond for the rhenium hydride (1) catalyzed hydrosilylation of the less steric C=N functionalities (phenylmethanimine, PhCH=NH, and N-phenylbenzylideneimine, PhCH=NPh). The rate-determining free-energy barriers for the ionic outer-sphere pathway are calculated to be ∼28.1 and 27.6 kcal mol(-1), respectively. These values are slightly more favorable than those obtained for the hydride pathway (by ∼1-3 kcal mol(-1)), whereas for the large steric C=N functionality of N,1,1-tri(phenyl)methanimine (PhCPh=NPh), the ionic outer-sphere pathway (33.1 kcal mol(-1)) is more favorable than the hydride pathway by as much as 11.5 kcal mol(-1). Along the ionic outer-sphere pathway, neither the multiply bonded oxo ligand nor the inherent hydride moiety participate in the activation of the Si-H bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physicochemical degradation studies of calcium phosphate glass ceramic in the CaO-P2O5-MgO-TiO2 system.

PubMed

Dias, A G; Gibson, I R; Santos, J D; Lopes, M A

2007-03-01

The aim of this work was to evaluate the in vitro degradation behaviour of a 45CaO-37P(2)O(5)-5MgO-13TiO(2) (mol.%) glass ceramic, under two different simulated physiological conditions: normal physiological pH 7.4, and pH 3.0, which was designed to simulate the acidic conditions produced by osteoclast cells. The in vitro testing was carried out at 37 degrees C for up to 42 days for the pH 7.4 solution and for up to 1 day for the pH 3.0 solution. The incorporation of TiO(2) into the glass structure leads to the precipitation of specific crystalline phases in the glass matrix, namely alpha- and beta-Ca(2)P(2)O(7), TiP(2)O(7) and CaTi(4)(PO(4))(6). The degradation testing at pH 3.0 showed a higher weight loss compared with degradation testing at pH 7.4; the weight loss under the acidic condition after 1 day (24 h) was about 10 times higher than the weight loss after 42 days of immersion at pH 7.4. The ionic release profile of Ca(2+), PO(4)(3-), Mg(2+) and Ti(4+) showed a continuous increase in concentration over all immersion times for both testing solutions. After 1 day of immersion at pH 3.0, the concentration levels of Mg(2+), Ca(2+), PO(4)(3-) were about six times higher than the levels achieved after 42 days of immersion at pH 7.4. The glass ceramic showed similar degradation to hydroxyapatite, and therefore has potential to be used in certain clinical applications where relatively slow resorption of the implant and replacement by bone is required, e.g. cranioplasty.

Effects of pH on transport properties of articular cartilages.

PubMed

Loret, Benjamin; Simões, Fernando M F

2010-02-01

Articular cartilages swell and shrink depending on the ionic strength of the electrolyte they are in contact with. This electro-chemo-mechanical coupling is due to the presence of fixed electrical charges on proteoglycans (PGs). In addition, at nonphysiological pH, collagen fibers become charged. Therefore, variation of the pH of the electrolyte has strong implications on the electrical charge of cartilages and, by the same token, on their transport and mechanical properties. Articular cartilages are viewed as three-phase multi-species porous media. The constitutive framework is phrased in the theory of thermodynamics of porous media. Acid-base reactions, as well as calcium binding, are embedded in this framework. Although macroscopic in nature, the model accounts for a number of biochemical details defining collagen and PGs. The change of the electrical charge is due to the binding of hydrogen ions on specific sites of PGs and collagen. Simulations are performed mimicking laboratory experiments where either the ionic strength or the pH of the bath, the cartilage piece is in contact with, is varied. They provide the evolutions of the chemical compositions of mobile ions, of the sites of acid-base reactions and calcium binding, and of the charges of collagen and glycosaminoglycans, at constant volume fraction of water. Emphasis is laid on the effects of pH, ionic strength and calcium binding on the transport properties of cartilages, and, in particular, on the electrical conductivity and electro-osmotic coefficient.

Interactions between natural organic matter and gold nanoparticles stabilized with different organic capping agents.

PubMed

Stankus, Dylan P; Lohse, Samuel E; Hutchison, James E; Nason, Jeffrey A

2011-04-15

The adsorption of natural organic matter (NOM) to the surfaces of natural colloids and engineered nanoparticles is known to strongly influence, and in some cases control, their surface properties and aggregation behavior. As a result, the understanding of nanoparticle fate, transport, and toxicity in natural systems must include a fundamental framework for predicting such behavior. Using a suite of gold nanoparticles (AuNPs) with different capping agents, the impact of surface functionality, presence of natural organic matter, and aqueous chemical composition (pH, ionic strength, and background electrolytes) on the surface charge and colloidal stability of each AuNP type was investigated. Capping agents used in this study were as follows: anionic (citrate and tannic acid), neutral (2,2,2-[mercaptoethoxy(ethoxy)]ethanol and polyvinylpyrrolidone), and cationic (mercaptopentyl(trimethylammonium)). Each AuNP type appeared to adsorb Suwannee River Humic Acid (SRHA) as evidenced by measurable decreases in zeta potential in the presence of 5 mg C L(-1) SRHA. It was found that 5 mg C L(-1) SRHA provided a stabilizing effect at low ionic strength and in the presence of only monovalent ions while elevated concentrations of divalent cations lead to enhanced aggregation. The colloidal stability of the NPs in the absence of NOM is a function of capping agent, pH, ionic strength, and electrolyte valence. In the presence of NOM at the conditions examined in this study, the capping agent is a less important determinant of stability, and the adsorption of NOM is a controlling factor.

Development of an ionic-liquid-based dispersive liquid-liquid microextraction method for the determination of antichagasic drugs in human breast milk: Optimization by central composite design.

PubMed

Padró, Juan M; Pellegrino Vidal, Rocío B; Echevarria, Romina N; Califano, Alicia N; Reta, Mario R

2015-05-01

Chagas disease constitutes a major public health problem in Latin America. Human breast milk is a biological sample of great importance for the analysis of therapeutic drugs, as unwanted exposure through breast milk could result in pharmacological effects in the nursing infant. Thus, the goal of breast milk drug analysis is to inquire to which extent a neonate may be exposed to a drug during lactation. In this work, we developed an analytical technique to quantify benznidazole and nifurtimox (the two antichagasic drugs currently available for medical treatment) in human breast milk, with a simple sample pretreatment followed by an ionic-liquid-based dispersive liquid-liquid microextraction combined with high-performance liquid chromatography and UV detection. For this technique, the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate has been used as the "extraction solvent." A central composite design was used to find the optimum values for the significant variables affecting the extraction process: volume of ionic liquid, volume of dispersant solvent, ionic strength, and pH. At the optimum working conditions, the average recoveries were 77.5 and 89.7%, the limits of detection were 0.06 and 0.09 μg/mL and the interday reproducibilities were 6.25 and 5.77% for benznidazole and nifurtimox, respectively. The proposed methodology can be considered sensitive, simple, robust, accurate, and green. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic description of Tc(iv) solubility and carbonate complexation in alkaline NaHCO3-Na2CO3-NaCl systems.

PubMed

Baumann, A; Yalçıntaş, E; Gaona, X; Polly, R; Dardenne, K; Prüßmann, T; Rothe, J; Altmaier, M; Geckeis, H

2018-03-28

The solubility of 99 Tc(iv) was investigated in dilute to concentrated carbonate solutions (0.01 M ≤ C tot ≤ 1.0 M, with C tot = [HCO 3 - ] + [CO 3 2- ]) under systematic variation of ionic strength (I = 0.3-5.0 M NaHCO 3 -Na 2 CO 3 -NaCl-NaOH) and pH m (-log[H + ] = 8.5-14.5). Strongly reducing conditions (pe + pH m ≈ 2) were set with Sn(ii). Carbonate enhances the solubility of Tc(iv) in alkaline conditions by up to 3.5 log 10 -units compared to carbonate-free systems. Solvent extraction and XANES confirmed that Tc was kept as +IV during the timeframe of the experiments (≤ 650 days). Solid phase characterization performed by XAFS, XRD, SEM-EDS, chemical analysis and TG-DTA confirmed that TcO 2 ·0.6H 2 O(am) controls the solubility of Tc(iv) under the conditions investigated. Slope analysis of the solubility data in combination with solid/aqueous phase characterization and DFT calculations indicate the predominance of the species Tc(OH) 3 CO 3 - at pH m ≤ 11 and C tot ≥ 0.01 M, for which thermodynamic and activity models are derived. Solubility data obtained above pH m ≈ 11 indicates the formation of previously unreported Tc(iv)-carbonate species, possibly Tc(OH) 4 CO 3 2- , although the likely formation of additional complexes prevents deriving a thermodynamic model valid for this pH m -region. This work provides the most comprehensive thermodynamic dataset available for the system Tc 4+ -Na + -Cl - -OH - -HCO 3 - -CO 3 2- -H 2 O(l) valid under a range of conditions relevant for nuclear waste disposal.

Kinetics of binding of chicken cystatin to papain.

PubMed

Björk, I; Alriksson, E; Ylinenjärvi, K

1989-02-21

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

Acid-base behavior of the gaspeite (NiCO3(s)) surface in NaCl solutions.

PubMed

Villegas-Jiménez, Adrián; Mucci, Alfonso; Pokrovsky, Oleg S; Schott, Jacques

2010-08-03

Gaspeite is a low reactivity, rhombohedral carbonate mineral and a suitable surrogate to investigate the surface properties of other more ubiquitous carbonate minerals, such as calcite, in aqueous solutions. In this study, the acid-base properties of the gaspeite surface were investigated over a pH range of 5 to 10 in NaCl solutions (0.001, 0.01, and 0.1 M) at near ambient conditions (25 +/- 3 degrees C and 1 atm) by means of conventional acidimetric and alkalimetric titration techniques and microelectrophoresis. Over the entire experimental pH range, surface protonation and electrokinetic mobility are strongly affected by the background electrolyte, leading to a significant decrease of the pH of zero net proton charge (PZNPC) and the pH of isoelectric point (pH(iep)) at increasing NaCl concentrations. This challenges the conventional idea that carbonate mineral surfaces are chemically inert to background electrolyte ions. Multiple sets of surface complexation reactions (i.e., ionization and ion adsorption) were formulated within the framework of three electrostatic models (CCM, BSM, and TLM) and their ability to simulate proton adsorption and electrokinetic data was evaluated. A one-site, 3-pK, constant capacitance surface complexation model (SCM) reproduces the proton adsorption data at all ionic strengths and qualitatively predicts the electrokinetic behavior of gaspeite suspensions. Nevertheless, the strong ionic strength dependence exhibited by the optimized SCM parameters reveals that the influence of the background electrolyte on the surface reactivity of gaspeite is not fully accounted for by conventional electrostatic and surface complexation models and suggests that future refinements to the underlying theories are warranted.

Production of Isolated Giant Unilamellar Vesicles under High Salt Concentrations

PubMed Central

Stein, Hannah; Spindler, Susann; Bonakdar, Navid; Wang, Chun; Sandoghdar, Vahid

2017-01-01

The cell membrane forms a dynamic and complex barrier between the living cell and its environment. However, its in vivo studies are difficult because it consists of a high variety of lipids and proteins and is continuously reorganized by the cell. Therefore, membrane model systems with precisely controlled composition are used to investigate fundamental interactions of membrane components under well-defined conditions. Giant unilamellar vesicles (GUVs) offer a powerful model system for the cell membrane, but many previous studies have been performed in unphysiologically low ionic strength solutions which might lead to altered membrane properties, protein stability and lipid-protein interaction. In the present work, we give an overview of the existing methods for GUV production and present our efforts on forming single, free floating vesicles up to several tens of μm in diameter and at high yield in various buffer solutions with physiological ionic strength and pH. PMID:28243205

Reducing agent-free synthesis of curcumin-loaded albumin nanoparticles by self-assembly at room temperature.

PubMed

Safavi, Maryam Sadat; Shojaosadati, Seyed Abbas; Yang, Hye Gyeong; Kim, Yejin; Park, Eun Ji; Lee, Kang Choon; Na, Dong Hee

2017-08-30

The purpose of this study was to prepare curcumin-loaded bovine serum albumin nanoparticles (CCM-BSA-NPs) by reducing agent-free self-assembly at room temperature. A 2 4 factorial design approach was used to investigate the CCM-BSA-NP preparation process at different pH values, temperatures, dithiothreitol amounts, and CCM/BSA mass ratios. Increasing the ionic strength enabled preparation of CCM-BSA-NPs at 25°C without reducing agent. CCM-BSA-NPs prepared under the optimized conditions at 25°C showed a particle size of 110±6nm, yield of 88.5%, and drug loading of 7.1%. The CCM-BSA-NPs showed strong antioxidant activity and neuroprotective effects in glutamate-induced mouse hippocampal neuronal HT22 cells. This study suggests that ionic strength can be a key parameter affecting the preparation of albumin-based NPs. Copyright © 2017 Elsevier B.V. All rights reserved.

A study in the adsorption of Fe(2+) and NO(3)(-) on pine needles based hydrogels.

PubMed

Chauhan, Ghanshyam S; Chauhan, Sandeep; Kumar, Sunil; Kumari, Anita

2008-09-01

Novel supports for use as cation and anion adsorbents were prepared from lignocellulosics using pine needles and their carboxymethylated forms by network/hydrogel formation with acrylamide and N,N-methylene bisacrylamide. The hydrogels thus prepared were further functionalized by partial alkaline hydrolysis with 0.5 N NaOH and were characterized by FTIR, SEM and nitrogen analysis. Adsorption of Fe(2+) on these hydrogels was carried as a function of time, temperature, pH and ionic strength. The hydrogel having the maximum adsorption capacity was loaded with Fe(2+) at the conditions those afforded maximum uptake and was used as novel anionic adsorbent for NO(3)(-). The water uptake capacities and biodegradability of the hydrogels before and after the ion loading was studied to evaluate the possible end-uses of these hydrogels as alternate materials in the removal of ionic species from water.

Development of a novel naphthoic acid ionic liquid and its application in "no-organic solvent microextraction" for determination of triclosan and methyltriclosan in human fluids and the method optimization by central composite design.

PubMed

Wang, Hui; Gao, Jiajia; Yu, Nana; Qu, Jingang; Fang, Fang; Wang, Huili; Wang, Mei; Wang, Xuedong

2016-07-01

In traditional ionic liquids (ILs)-based microextraction, the hydrophobic and hydrophilic ILs are often used as extractant and disperser, respectively. However, the functional effects of ILs are not utilized in microextraction procedures. Herein, we introduced 1-naphthoic acid into imidazolium ring to synthesize a novel ionic liquid 1-butyl-3-methylimidazolium naphthoic acid salt ([C4MIM][NPA]), and its structure was characterized by IR, (1)H NMR and MS. On the basis of its acidic property and lower solubility than common [CnMIM][BF4], it was used as a mixing dispersive solvent with [C4MIM][BF4] in "functionalized ionic liquid-based no organic solvent microextraction (FIL-NOSM)". Utilization of [C4MIM][NPA] in FIL-NOSM procedures has two obvious advantages: (1) it promoted the non-polar environment, increased volume of the sedimented phase, and thus could enhance the extraction recoveries of triclosan (TCS) and methyltriclosan (MTCS) by more than 10%; and (2) because of the acidic property, it can act as a pH modifier, avoiding extra pH adjustment step. By combining single factor optimization and central composite design, the main factors in the FIL-NOSM method were optimized. Under the optimal conditions, the relative recoveries of TCS and MTCS reached up to 98.60-106.09%, and the LODs of them were as low as 0.12-0.15µgL(-1) in plasma and urine samples. In total, this [C4MIM][NPA]-based FIL-NOSM method provided high extraction efficiency, and required less pretreatment time and unutilized any organic solvent. To the best of our knowledge, this is the first application of [C4mim][NPA]-based microextraction method for the simultaneous quantification of trace TCS and MTCS in human fluids. Copyright © 2016 Elsevier B.V. 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.

Cation effects on phosphatidic acid monolayers at various pH conditions.

PubMed

Zhang, Ting; Cathcart, Matthew G; Vidalis, Andrew S; Allen, Heather C

2016-10-01

The impact of pH and cations on phase behavior, stability, and surface morphology for dipalmitoylphosphatidic acid (DPPA) monolayers was investigated. At pH<10, DPPA monolayers on water are predominantly populated by neutral species and display the highest packing density. Cations are found to expand and stabilize the monolayer in the following order of increasing magnitude at pH 5.6: Na + >K + ∼Mg 2+ >Ca 2+ . Additionally, cation complexation is tied to the pH and protonation state of DPPA, which are the primary factors controlling the monolayer surface behavior. The binding affinity of cations to the headgroup and thus deprotonation capability of the cation, ranked in the order of Ca 2+ >Mg 2+ >Na + >K + , is found to be well explained by the law of matching water affinities. Nucleation of surface 3D lipid structures is observed from Ca 2+ , Mg 2+ , and Na + , but not from K + , consistent with the lowest binding affinity of K + . Unraveling cation and pH effects on DPPA monolayers is useful in further understanding the surface properties of complex systems such as organic-coated marine aerosols where organic films are directly influenced by the pH and ionic composition of the underlying aqueous phase. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Cesium migration in saturated silica sand and Hanford sediments as impacted by ionic strength.

PubMed

Flury, Markus; Czigány, Szabolcs; Chen, Gang; Harsh, James B

2004-07-01

Large amounts of 137Cs have been accidentally released to the subsurface from the Hanford nuclear site in the state of Washington, USA. The cesium-containing liquids varied in ionic strengths, and often had high electrolyte contents, mainly in the form of NaNO3 and NaOH, reaching concentrations up to several moles per liter. In this study, we investigated the effect of ionic strengths on Cs migration through two types of porous media: silica sand and Hanford sediments. Cesium sorption and transport was studied in 1, 10, 100, and 1000 mM NaCl electrolyte solutions at pH 10. Sorption isotherms were constructed from batch equilibrium experiments and the batch-derived sorption parameters were compared with column breakthrough curves. Column transport experiments were analyzed with a two-site equilibrium-nonequilibrium model. Cesium sorption to the silica sand in batch experiments showed a linear sorption isotherm for all ionic strengths, which matched well with the results from the column experiments at 100 and 1000 mM ionic strength; however, the column experiments at 1 and 10 mM ionic strength indicated a nonlinear sorption behavior of Cs to the silica sand. Transport through silica sand occurred under one-site sorption and equilibrium conditions. Cesium sorption to Hanford sediments in both batch and column experiments was best described with a nonlinear Freundlich isotherm. The column experiments indicated that Cs transport in Hanford sediments occurred under two-site equilibrium and nonequilibrium sorption. The effect of ionic strength on Cs transport was much more pronounced in Hanford sediments than in silica sands. Effective retardation factors of Cs during transport through Hanford sediments were reduced by a factor of 10 when the ionic strength increased from 100 to 1000 mM; for silica sand, the effective retardation was reduced by a factor of 10 when ionic strength increased from 1 to 1000 mM. A two order of magnitude change in ionic strength was needed in the silica sand to observe the same change in Cs retardation as in Hanford sediments. Copyright 2003 Elsevier B.V.

Harnessing Poly(ionic liquid)s for Sensing Applications.

PubMed

Guterman, Ryan; Ambrogi, Martina; Yuan, Jiayin

2016-07-01

The interest in poly(ionic liquid)s for sensing applications is derived from their strong interactions to a variety of analytes. By combining the desirable mechanical properties of polymers with the physical and chemical properties of ILs, new materials can be created. The tunable nature of both ionic liquids and polymers allows for incredible diversity, which is exemplified in their broad applicability. In this article we examine the new field of poly(ionic liquid) sensors by providing a detailed look at the current state-of-the-art sensing devices for solvents, gases, biomolecules, pH, and anions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Salt- and pH-Triggered Helix-Coil Transition of Ionic Polypeptides under Physiology Conditions.

PubMed

Yuan, Jingsong; Zhang, Yi; Sun, Yue; Cai, Zhicheng; Yang, Lijiang; Lu, Hua

2018-06-11

Controlling the helix-coil transition of polypeptides under physiological conditions is an attractive way toward smart functional materials. Here, we report the synthesis of a series of tertiary amine-functionalized ethylene glycol (EG x )-linked polypeptide electrolytes with their secondary structures tunable under physiological conditions. The resultant polymers, denoted as P(EG x DMA-Glu) ( x = 1, 2, and 3), show excellent aqueous solubility (>20 mg/mL) regardless of their charge states. Unlike poly-l-lysine that can form a helix only at pH above 10, P(EG x DMA-Glu) undergo a pH-dependent helix-coil switch with their transition points within the physiological range (pH ∼5.3-6.5). Meanwhile, P(EG x DMA-Glu) exhibit an unusual salt-induced helical conformation presumably owing to the unique properties of EG x linkers. Together, the current work highlights the importance of fine-tuning the linker chemistry in achieving conformation-switchable polypeptides and represents a facile approach toward stimuli-responsive biopolymers for advanced biological applications.

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

PubMed

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

2014-08-01

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

The history and character of acid precipitation in eastern North America

Treesearch

Charles V. Cogbill

1976-01-01

The history and present distribution of precipitation acidity in eastern North America is reviewed. Precipitation chemistry from the 1920's indicates heavy ionic deposition, but low acidity (calculated) in Tennessee (pH 7.4) and New York (pH 6.15). However, high acidity was apparently widespread over northeast North America by 1955-56 and measured pH's below...

Stability and Transport of Cerium Oxide Nanoparticles in Aqueous Environment: Effect of pH, Ionic Strength, and Organic Matter.

EPA Science Inventory

This study investigated the stability and transport of CeO2 NPs under the influence of pH, natural/manmade organic matter, and electrolyte (NaCl) concentrations. In column test, effluent concentration of CeO2 NPs was close to the influent at pH 10, while most NPs deposited on san...

Physicochemical parameters influencing coaggregation between the freshwater bacteria Sphingomonas natatoria 2.1 and Micrococcus luteus 2.13.

PubMed

Min, K R; Zimmer, M N; Rickard, A H

2010-11-01

The aim of this study was to explore the physicochemical parameters that influence coaggregation between the freshwater bacteria Sphingomonas natatoria 2.1 and Micrococcus luteus 2.13. Using visual coaggregation assays, the effect of different buffers, solutions of differing ionic strength, pH, temperature, and viscosity on the degree of coaggregation was assessed. Coaggregation occurred maximally in distilled water but was inhibited when coaggregates were suspended in a commonly-used oral bacterial coaggregation buffer, saline solutions, and Tris-Cl buffers. Coaggregation was weakly expressed in standard laboratory buffers. The ionic strength of inorganic salt solutions required to inhibit coaggregation depended upon the inorganic salt being tested. Coaggregation occurred at a pH of 3-10, between 5 and 80°C and was inhibited in solutions with a viscosity of 22.5 centipoises at 20°C. Inhibition of coaggregation with NaCl impaired biofilm development. When developing buffers to test for coaggregation, the natural liquid environment should be considered. Coaggregation between S. natatoria 2.1 and M. luteus 2.13 is only affected by physicochemical conditions beyond those typically found in natural freshwater ecosystems. Such a robust ability to coaggregate may enhance the ability of S. natatoria 2.1 and M. luteus 2.13 to develop a niche in freshwater biofilms.

Highly Efficient Extraction of Phenolic Compounds by Use of Magnetic Room Temperature Ionic Liquids for Environmental Remediation

PubMed Central

Deng, Ning; Li, Min; Zhao, Lijie; Lu, Chengfei; de Rooy, Sergio L.; Warner, Isiah M.

2011-01-01

A hydrophobic magnetic room temperature ionic liquid (MRTIL), trihexyltetradecylphosphonium tetrachloroferrate(III) ([3C6PC14][FeCl4]), was synthesized from trihexyltetradecylphosphonium chloride and FeCl3·6H2O. This MRTIL was investigated as a possible separation agent for solvent extraction of phenolic compounds from aqueous solution. Due to its strong paramagnetism, [3C6PC14][FeCl4] responds to an external neodymium magnet, which was employed in the design of a novel magnetic extraction technique. The conditions for extraction, including extraction time, volume ratio between MRTIL and aqueous phase, pH of aqueous solution, and structures of phenolic compounds were investigated and optimized. The magnetic extraction of phenols achieved equilibrium in 20 min and the phenolic compounds were found to have higher distribution ratios under acidic conditions. In addition, it was observed that phenols containing a greater number of chlorine or nitro substitutents exhibited higher distribution ratios. For example, the distribution ratio of phenol (DPh) was 107. In contrast, 3,5-dichlorophenol distribution ratio (D3,5-DCP) had a much higher value of 6372 under identical extraction conditions. When compared with four selected traditional non-magnetic room temperature ionic liquids, our [3C6PC14][FeCl4] exhibited significantly higher extraction efficiency under the same experimental conditions used in this work. Pentachlorophenol, a major component in the contaminated soil sample obtained from a superfund site, was successfully extracted and removed by use of [3C6PC14][FeCl4] with high extraction efficiency. Pentachlorophenol concentration was dramatically reduced from 7.8 μg.mL−1 to 0.2 μg.mL−1 after the magnetic extraction by use of [3C6PC14][FeCl4]. PMID:21783320

Novel self-powered pH indicator using ionic polymeric gel muscles

NASA Astrophysics Data System (ADS)

Shahinpoor, Mohsen

1994-05-01

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

Solvent-free direct reductive amination by catalytic use of an organotin reagent incorporated on an ionic liquid.

PubMed

Pham, Phuoc Dien; Bertus, Philippe; Legoupy, Stéphanie

2009-11-07

An organotin reagent supported on an ionic liquid was used as a highly effective catalyst (down to 0.1 mol%) for the direct reductive amination of aldehydes and ketones using PhSiH3; this solvent-free method facilitates purification of the products, thus minimizing the contamination by tin.

pH-Driven Ordering Transitions in Liquid Crystal Induced by Conformational Changes of Cardiolipin.

PubMed

Sidiq, Sumyra; Verma, Indu; Pal, Santanu Kumar

2015-04-28

We report an investigation of interfacial phenomena occurring at aqueous-liquid crystal (LC) interfaces that triggers an orientational ordering transition of the LC in the presence of cardiolipin (CL) by varying pH, salt concentration and valence. In particular, the effects of three different conformational isomeric forms of the CL are observed to cause the response of the LC ordering to vary significantly from one to another at those interfaces. An ordering transition of the LC was observed when the CL is mostly in undissociated (at pH 2) and/or in bicyclic (at pH 4) conformation in which LC shows changes in the optical appearance from bright to dark. By contrast, no change in the optical appearance of the LC was observed when the pH of the system increases to 8 or higher in which the CL mostly exists in the open conformation. Fluorescence microscopy measurements further suggest that pH-dependent conformational forms of the CL have different ability to self-assemble (thus different packing efficiency) at aqueous-LC interfaces leading to dissimilar orientational behavior of the LC. Specifically, we found that change in headgroup-headgroup repulsion of the central phosphatidyl groups of the CL plays a key role in tuning the lipid packing efficiency and thus responses to interfacial phenomena. Orientational ordering transition of the LC was also observed as a function of increasing the ionic strength (buffer capacity) and strongly influenced in the presence of mono and divalent cations. Langmuir-Blodgett (LB) and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) measurements provide further insight in modulation of the lipid packing efficiency and alkyl chain conformation of the CL at different pH and ionic conditions. Overall, the results presented in this paper establish that LCs offer a promising approach to differentiate different conformations (label free detection) of the CL through ordering transition of the LC at aqueous-LC interfaces.

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

PubMed

Chango, Gabriela; Palacio, Edwin; Cerdà, Víctor

2018-08-15

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

Sorption influenced transport of ionizable pharmaceuticals onto a natural sandy aquifer sediment at different pH.

PubMed

Schaffer, Mario; Boxberger, Norman; Börnick, Hilmar; Licha, Tobias; Worch, Eckhard

2012-04-01

The pH-dependent transport of eight selected ionizable pharmaceuticals was investigated by using saturated column experiments. Seventy-eight different breakthrough curves on a natural sandy aquifer material were produced and compared for three different pH levels at otherwise constant conditions. The experimentally obtained K(OC) data were compared with calculated K(OC) values derived from two different logK(OW)-logK(OC) correlation approaches. A significant pH-dependence on sorption was observed for all compounds with pK(a) in the considered pH range. Strong retardation was measured for several compounds despite their hydrophilic character. Besides an overall underestimation of K(OC), the comparison between calculated and measured values only yields meaningful results for the acidic and neutral compounds. Basic compounds retarded much stronger than expected, particularly at low pH when their cationic species dominated. This is caused by additional ionic interactions, such as cation exchange processes, which are insufficiently considered in the applied K(OC) correlations. Copyright © 2011 Elsevier Ltd. All rights reserved.

Immobilization of an L-aminoacylase-producing strain of Aspergillus oryzae into gelatin pellets and its application in the resolution of D,L-methionine.

PubMed

Yuan Yj, Ying-jin; Wang Sh, Shu-hao; Song Zx, Zheng-xiao; Gao Rc, Rui-chang

2002-04-01

The conditions for immobilization of an l-aminoacylase-producing strain of Aspergillus oryzae in gelatin and the enzymic characteristics of the immobilized pellets were studied. The optimal concentrations of gelatin, glutaraldehyde and ethyldiamine and time of immobilization were determined. Scanning electron micrographs reveal the cross-linked structure differences between the native and immobilized pellets. Optimum pH and temperature of the native and immobilized pellets were determined. Effects of ionic strength and substrate concentration on relative activity of the native and immobilized pellets were investigated in detail. The immobilized pellets were more stable over broader temperature and pH ranges. In addition, the immobilized pellets showed stable activity under operational and storage conditions. The immobilized pellets lost about 20% of their initial activity after five cycles of reuse. The results reported in this paper show the potential for using the immobilized A. oryzae pellets to resolve d,l-methionine.

Improvement of chemical monitoring of water-chemistry conditions at thermal power stations based on electric conductivity and pH measurements

NASA Astrophysics Data System (ADS)

Larin, A. B.; Larin, B. M.

2016-05-01

The increased requirements to the quality of the water heat conductor for working superhigh (SHP) and supercritical (SCP) pressure power plants and promising units, including combined-cycle gas turbine (CCGT) units and power plants with ultrasupercritical parameters (USCPs), can largely be satisfied through specific electric conductivity and pH measurements for cooled heat conductor samples combined with calculations of ionic equilibria and indirect measurements of several specified and diagnostic parameters. The possibility of calculating the ammonia and chloride concentrations and the total concentration of hardness and sodium cations in the feed water of drum-type boilers and the phosphate and salt contents in boiler water was demonstrated. An equation for evaluating the content of potentially acid substances in the feed water of monotube boilers was suggested. The potential of the developed procedure for evaluating the state of waterchemistry conditions (WCCs) in power plants with CCGT units was shown.

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

PubMed

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

2015-01-09

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

Ionic pH and glucose sensors fabricated using hydrothermal ZnO nanostructures

NASA Astrophysics Data System (ADS)

Wang, Jyh-Liang; Yang, Po-Yu; Hsieh, Tsang-Yen; Juan, Pi-Chun

2016-01-01

Hydrothermally synthesized aluminum-doped ZnO (AZO) nanostructures have been adopted in extended-gate field-effect transistor (EGFET) sensors to demonstrate the sensitive and stable pH and glucose sensing characteristics of AZO-nanostructured EGFET sensors. The AZO-nanostructured EGFET sensors exhibited the following superior pH sensing characteristics: a high current sensitivity of 0.96 µA1/2/pH, a high linearity of 0.9999, less distortion of output waveforms, a small hysteresis width of 4.83 mV, good long-term repeatability, and a wide sensing range from pHs 1 to 13. The glucose sensing characteristics of AZO-nanostructured biosensors exhibited the desired sensitivity of 60.5 µA·cm-2·mM-1 and a linearity of 0.9996 up to 13.9 mM. The attractive characteristics of high sensitivity, high linearity, and repeatability of using ionic AZO-nanostructured EGFET sensors indicate their potential use as electrochemical and disposable biosensors.

Structure evolution of gelatin particles induced by pH and ionic strength.

PubMed

Xu, Jing; Li, Tianduo; Tao, Furong; Cui, Yuezhi; Xia, Yongmei

2013-03-01

Microstructure of gelatin particles played a key role in determining the physicochemical properties of gelatin. Ionic strength and pH as systematic manners were considered to affect gelatin particles structure on the micrometer scale. Scanning electron microscopy was used for depicting the morphologies of gelatin particles. Increasing pH to 10.0 or decreasing pH to 4.0, spherical, spindle, and irregular aggregates of gelatin particles at 2, 6, 10, and 14% solution (w/w) were all transformed to spindle aggregates. When NaCl was added to the system, the molecular chains of gelatin possibly rearranged themselves in a stretched state, and the ribbon aggregates was observed. The structural transitions of gelatin aggregates were strongly depended on the electrostatic repulsion. In the gelatin-sodium dodecyl sulfate (SDS) case, the micrometer scale of aggregates was larger and the different degrees of cross-links were induced through hydrophobic interaction and electrostatic repulsion. Copyright © 2012 Wiley Periodicals, Inc.

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.

Ionic liquid and aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of seven rare ginsenosides in Xue-Sai-Tong injection.

PubMed

Li, Lan-Jie; Jin, Yong-Ri; Wang, Xiao-Zhong; Liu, Ying; Wu, Qian; Shi, Xiao-Lei; Li, Xu-Wen

2015-09-01

A method of ionic liquid salt aqueous two-phase extraction coupled with high-performance liquid chromatography has been developed for the analysis of seven rare ginsenosides including Rg6 , F4 , 20(S)-Rg3 , 20(R)-Rg3 , Rk3 , Rk1 , and Rg5 in Xue-Sai-Tong injection. The injection was mixed with ionic liquid 1-butyl-3-methylimidazolium bromide aqueous solution, and a mixture was obtained. With the addition of sodium dodecyl sulfate and dipotassium phosphate into the mixture, the aqueous two-phase mixture was formed after ultrasonic treatment and centrifuged. Rare ginsenosides were extracted into the upper phase. To obtain a high extraction factors, various influences were considered systematically, such as the volume of ionic liquid, the category and amount of salts, the amount of sodium dodecyl sulfate, the pH value of system, and the time of ultrasonic treatment. Under the optimal condition, rare ginsenosides in Xue-Sai-Tong injection were enriched and detected, the recoveries of seven rare ginsenosides ranged from 90.05 to 112.55%, while relative standard deviations were lower than 2.50%. The developed method was reliable, rapid and sensitive for the determination of seven rare ginsenosides in the injections. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calcium-calmodulin does not alter the anion permeability of the mouse TMEM16A calcium-activated chloride channel

PubMed Central

Yu, Yawei; Kuan, Ai-Seon

2014-01-01

The transmembrane protein TMEM16A forms a Ca2+-activated Cl− channel that is permeable to many anions, including SCN−, I−, Br−, Cl−, and HCO3−, and has been implicated in various physiological functions. Indeed, controlling anion permeation through the TMEM16A channel pore may be critical in regulating the pH of exocrine fluids such as the pancreatic juice. The anion permeability of the TMEM16A channel pore has recently been reported to be modulated by Ca2+-calmodulin (CaCaM), such that the pore of the CaCaM-bound channel shows a reduced ability to discriminate between anions as measured by a shift of the reversal potential under bi-ionic conditions. Here, using a mouse TMEM16A clone that contains the two previously identified putative CaM-binding motifs, we were unable to demonstrate such CaCaM-dependent changes in the bi-ionic potential. We confirmed the activity of CaCaM used in our study by showing CaCaM modulation of the olfactory cyclic nucleotide–gated channel. We suspect that the different bi-ionic potentials that were obtained previously from whole-cell recordings in low and high intracellular [Ca2+] may result from different degrees of bi-ionic potential shift secondary to a series resistance problem, an ion accumulation effect, or both. PMID:24981232

Ionic Liquid Dispersive Liquid-Liquid Microextraction Method for the Determination of Irinotecan, an Anticancer Drug, in Water and Urine Samples Using UV-Vis Spectrophotometry.

PubMed

Uysal, Deniz; Karadaş, Cennet; Kara, Derya

2017-05-01

A new, simple, efficient, and environmentally friendly ionic liquid dispersive liquid-liquid microextraction method was developed for the determination of irinotecan, an anticancer drug, in water and urine samples using UV-Vis spectrophotometry. The ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate was used as the extraction solvent, and ethanol was used as the disperser solvent. The main parameters affecting the extraction efficiency, including sample pH, volume of the ionic liquid, choice of the dispersive solvent and its volume, concentration of NaCl, and extraction and centrifugation times, were investigated and optimized. The effect of interfering species on the recovery of irinotecan was also examined. Under optimal conditions, the LOD (3σ) was 48.7 μg/L without any preconcentration. Because the urine sample was diluted 10-fold, the LOD for urine would be 487 μg/L. However, this could be improved 16-fold if preconcentration using a 40 mL aliquot of the sample is used. The proposed method was successfully applied to the determination of irinotecan in tap water, river water, and urine samples spiked with 10.20 mg/L for the water samples and 8.32 mg/L for the urine sample. The average recovery values of irinotecan determined were 99.1% for tap water, 109.4% for river water, and 96.1% for urine.

Quasi-simultaneous Measurements of Ionic Currents by Vibrating Probe and pH Distribution by Ion-selective Microelectrode

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

Isaacs, H.S.; Lamaka, S.V.; Taryba, M.

2011-01-01

This work reports a new methodology to measure quasi-simultaneously the local electric fields and the distribution of specific ions in a solution via selective microelectrodes. The field produced by the net electric current was detected using the scanning vibrating electrode technique (SVET) with quasi-simultaneous measurements of pH with an ion-selective microelectrode (pH-SME). The measurements were performed in a validation cell providing a 48 ?m diameter Pt wire cross section as a source of electric current. A time lag between acquiring each current density and pH data-point was 1.5 s due to the response time of pH-SME. The quasi-simultaneous SVET-pH measurementsmore » that correlate electrochemical oxidation-reduction processes with acid-base chemical equilibria are reported for the first time. No cross-talk between the vibrating microelectrode and the ion-selective microelectrode could be detected under given experimental conditions.« less

Effects of pH and Carbon Source on Synechococcus PCC 7002 Cultivation: Biomass and Carbohydrate Production with Different Strategies for pH Control.

PubMed

De Farias Silva, Carlos Eduardo; Sforza, Eleonora; Bertucco, Alberto

2017-02-01

Synechococcus PCC 7002 is an interesting species in view of industrial production of carbohydrates. The cultivation performances of this species are strongly affected by the pH of the medium, which also influences the carbohydrate accumulation. In this work, different methods of pH control were analyzed, in order to obtain a higher production of both Synechococcus biomass and carbohydrates. To better understand the influence of pH on growth and carbohydrate productivity, manual and automatic pH regulation in CO 2 and bicarbonate system were applied. The pH value of 8.5 resulted the best to achieve both of these goals. From an industrial point of view, an alternative way to maintain the pH practically constant during the entire period of cultivation is the exploitation of the bicarbonate-CO 2 buffer system, with the double aim to maintain the pH in the viability range and also to provide the amount of carbon required by growth. In this condition, a high concentration of biomass (6 g L -1 ) and carbohydrate content (around 60 %) were obtained, which are promising in view of a potential use for bioethanol production. The chemical equilibrium of C-N-P species was also evaluated by applying the ionic balance equations, and a relation between the sodium bicarbonate added in the medium and the equilibrium value of pH was discussed.

The Final Frontier of pH and the Undiscovered Country Beyond

PubMed Central

Bal, Wojciech; Kurowska, Ewa; Maret, Wolfgang

2012-01-01

The comparison of volumes of cells and subcellular structures with the pH values reported for them leads to a conflict with the definition of the pH scale. The pH scale is based on the ionic product of water, K w = [H+]×[OH−].We used K w [in a reversed way] to calculate the number of undissociated H2O molecules required by this equilibrium constant to yield at least one of its daughter ions, H+ or OH− at a given pH. In this way we obtained a formula that relates pH to the minimal volume VpH required to provide a physical meaning to K w, (where N A is Avogadro’s number). For example, at pH 7 (neutral at 25°C) VpH = 16.6 aL. Any deviation from neutral pH results in a larger VpH value. Our results indicate that many subcellular structures, including coated vesicles and lysosomes, are too small to contain free H+ ions at equilibrium, thus the definition of pH based on K w is no longer valid. Larger subcellular structures, such as mitochondria, apparently contain only a few free H+ ions. These results indicate that pH fails to describe intracellular conditions, and that water appears to be dissociated too weakly to provide free H+ ions as a general source for biochemical reactions. Consequences of this finding are discussed. PMID:23049874

Structural Insight into and Mutational Analysis of Family 11 Xylanases: Implications for Mechanisms of Higher pH Catalytic Adaptation.

PubMed

Bai, Wenqin; Zhou, Cheng; Zhao, Yueju; Wang, Qinhong; Ma, Yanhe

2015-01-01

To understand the molecular basis of higher pH catalytic adaptation of family 11 xylanases, we compared the structures of alkaline, neutral, and acidic active xylanases and analyzed mutants of xylanase Xyn11A-LC from alkalophilic Bacillus sp. SN5. It was revealed that alkaline active xylanases have increased charged residue content, an increased ratio of negatively to positively charged residues, and decreased Ser, Thr, and Tyr residue content relative to non-alkaline active counterparts. Between strands β6 and β7, alkaline xylanases substitute an α-helix for a coil or turn found in their non-alkaline counterparts. Compared with non-alkaline xylanases, alkaline active enzymes have an inserted stretch of seven amino acids rich in charged residues, which may be beneficial for xylanase function in alkaline conditions. Positively charged residues on the molecular surface and ionic bonds may play important roles in higher pH catalytic adaptation of family 11 xylanases. By structure comparison, sequence alignment and mutational analysis, six amino acids (Glu16, Trp18, Asn44, Leu46, Arg48, and Ser187, numbering based on Xyn11A-LC) adjacent to the acid/base catalyst were found to be responsible for xylanase function in higher pH conditions. Our results will contribute to understanding the molecular mechanisms of higher pH catalytic adaptation in family 11 xylanases and engineering xylanases to suit industrial applications.

Structural Insight into and Mutational Analysis of Family 11 Xylanases: Implications for Mechanisms of Higher pH Catalytic Adaptation

PubMed Central

Bai, Wenqin; Zhou, Cheng; Zhao, Yueju; Wang, Qinhong; Ma, Yanhe

2015-01-01

To understand the molecular basis of higher pH catalytic adaptation of family 11 xylanases, we compared the structures of alkaline, neutral, and acidic active xylanases and analyzed mutants of xylanase Xyn11A-LC from alkalophilic Bacillus sp. SN5. It was revealed that alkaline active xylanases have increased charged residue content, an increased ratio of negatively to positively charged residues, and decreased Ser, Thr, and Tyr residue content relative to non-alkaline active counterparts. Between strands β6 and β7, alkaline xylanases substitute an α-helix for a coil or turn found in their non-alkaline counterparts. Compared with non-alkaline xylanases, alkaline active enzymes have an inserted stretch of seven amino acids rich in charged residues, which may be beneficial for xylanase function in alkaline conditions. Positively charged residues on the molecular surface and ionic bonds may play important roles in higher pH catalytic adaptation of family 11 xylanases. By structure comparison, sequence alignment and mutational analysis, six amino acids (Glu16, Trp18, Asn44, Leu46, Arg48, and Ser187, numbering based on Xyn11A-LC) adjacent to the acid/base catalyst were found to be responsible for xylanase function in higher pH conditions. Our results will contribute to understanding the molecular mechanisms of higher pH catalytic adaptation in family 11 xylanases and engineering xylanases to suit industrial applications. PMID:26161643

Enhanced production of polygalacturonase in solid-state fermentation: selection of the process conditions, isolation and partial characterization of the enzyme.

PubMed

Zaslona, Halina; Trusek-Holownia, Anna

2015-01-01

Polygalacturonase (PG) production by Penicillium chrysogenum during solid-state fermentation was accompanied by decomposition of orange peels. A leaching procedure was developed through the selection of solvent, time and intensity of stirring. A maximum PG activity was observed after 48 h peel inoculation. Further cultivation decreased the enzyme activity significantly, up to 60% of the maximum PG activity. During fermentation, a rapid acidification of the solid medium which inhibited the pectinolytic enzyme, was observed. Buffering agents with different pH values and different ionic strengths were examined to identify the most suitable medium to avoid this problem. Buffer addition counteracted acidification and enhanced active protein production, which was observed for all of the applied pH values (6.5-8.0) of the buffering agent. The most satisfactory results were obtained when using the highest pH at 8.0. The protein content and PG activity increased from 3.5 mg/g and 1.09 U/g to 7.7 mg/g and 7.11 U/g during cultivation, with uncontrolled and pH-controlled medium, respectively. Measurements at wide pH and temperature ranges indicated an optimum for PG activity at pH 5.0 and 43°C; however, high thermal stability corresponded to lower temperatures, and a temperature of 37°C is thus recommended. Under these conditions, the operational stability was determined to be t1/2=570 h.

The evaporation study of silicon-containing ionic liquid

NASA Astrophysics Data System (ADS)

Chilingarov, Norbert S.; Medvedev, Artem A.; Deyko, Grigoriy S.; Kustov, Leonid M.; Chernikova, Elena A.; Glukhov, Lev M.; Polyakova, Marina V.; Ioutsi, Vitaliy A.; Markov, Vitaliy Yu.; Sidorov, Lev N.

2016-07-01

1,2-Dimethyl-3-(1‧,1‧,3‧,3‧-tetramethyl-3‧-phenyldisiloxanyl)methylimidazolium bis(trifluoromethanesulfonyl)amide ([PhC5OSi2MMIm+][Tf2N-]) is the first silicon-containing ionic liquid which was characterized with the vaporization enthalpy, (138.5 ± 1.8) kJ mol-1, and saturated vapor pressure, ln(p/Pa) = -(16656 ± 219)/(T/K) + (30.69 ± 0.92). This compound is a unique ionic liquid giving ions, retaining both cationic and anionic portions, in the electron impact ionization (EI) mass spectrum.

Molecular interactions in self-assembled nano-structures of chitosan-sodium alginate based polyelectrolyte complexes.

PubMed

Wasupalli, Geeta Kumari; Verma, Devendra

2018-03-16

We report here the self-assembled structures of polyelectrolyte complexes (PECs) of polyanionic sodium alginate with the polycationic chitosan at room temperature. The PECs prepared at different pH values exhibited two distinct morphologies. The chitosan-alginate PECs self-assembled into the fibrous structure in a low pH range of pH3 to 7. The PECs obtained at high pH series around pH8 and above resulted in the formation of colloidal nanoparticles in the range of 120±9.48nm to 46.02±16.66nm. The zeta potential measurement showed that PECs prepared at lower pH (pH<6) exhibited nearly neutral surface charge, whereas PECs prepared at higher pH than 6 exhibited highly negative surface charge. The molecular interactions in nano-colloids and fibers were evaluated using FTIR analysis. The results attest that the ionic state of the chitosan and alginate plays an important role controlling the morphologies of the PECS. The present study has identified the enormous potential of the polyelectrolytes complexes to exploit shape by the alteration of ionic strength. These findings might be useful in the development of novel biomaterial. The produced fibers and nanocolloids could be applied as a biomaterial for tissue engineering and drug delivery. Copyright © 2017. Published by Elsevier B.V.

Sensitive SERS-pH sensing in biological media using metal carbonyl functionalized planar substrates.

PubMed

Kong, Kien Voon; Dinish, U S; Lau, Weber Kam On; Olivo, Malini

2014-04-15

Conventional nanoparticle based Surface enhanced Raman scattering (SERS) technique for pH sensing often fails due to the aggregation of particles when detecting in acidic medium or biosamples having high ionic strength. Here, We develop SERS based pH sensing using a novel Raman reporter, arene chromium tricarbonyl linked aminothiophenol (Cr(CO)3-ATP), functionalized onto a nano-roughened planar substrates coated with gold. Unlike the SERS spectrum of the ATP molecule that dominates in the 400-1700 cm(-1) region, which is highly interfered by bio-molecules signals, metal carbonyl-ATP (Cr(CO)3)-ATP) offers the advantage of monitoring the pH dependent strong CO stretching vibrations in the mid-IR (1800-2200 cm(-1)) range. Raman signal of the CO stretching vibrations at ~1820 cm(-1) has strong dependency on the pH value of the environment, where its peak undergo noticeable shift as the pH of the medium is varied from 3.0 to 9.0. The sensor showed better sensitivity in the acidic range of the pH. We also demonstrate the pH sensing in a urine sample, which has high ionic strength and our data closely correlate to the value obtained from conventional sensor. In future, this study may lead to a sensitive chip based pH sensing platform in bio-fluids for the early diagnosis of diseases. © 2013 Published by Elsevier B.V.

Packaging of Polyelectrolytes in Viral Capsids: The Interplay Between Polymer Length and Capsid Size

NASA Astrophysics Data System (ADS)

Knobler, Charles

2008-03-01

Each particle of the Cowpea Chlorotic Mottle Virus (CCMV) has a very small ``parts list,'' consisting of two components: a molecule of single-stranded RNA and a 190-residue protein that makes up the 28-nm diameter icosahedral capsid. When purified viral RNA and capsid protein are mixed in solution at an appropriate pH and ionic strength, infectious wild-type viruses form spontaneously. Virus-like particles (VLPs) are formed when the protein self assembles around other anionic polymers such as poly(styrene sulfonate) (PSS). Under different pH and ionic strength conditions the capsid protein can assemble by itself into empty capsids, multishell structures, tubes and sheets. To explore the effect on virion size of the competition between the preferred curvature of the protein and the size of the packaged cargo we have examined the formation of VLPs around PSS polymers with molecular weights ranging from 400 kDa to 3.4 MDa. Two distinct sizes are observed -- 22 nm for the lower molecular weights, jumping to 27 nm at 2 MDa. While under given conditions the size of PSS in solution is directly determined by its molecular weight, the self-complementarity of RNA makes its solution structure dependent on the nucleotide sequence as well. We have therefore employed Small-Angle X-ray Scattering and Fluorescence Correlation Spectroscopy to examine the sizes of viral and non-viral RNAs of identical lengths. A model for the assembly that includes both the self-interactions of the polyelectrolyte and the capsid proteins and the interactions between them provides insight into the experimental results.

Capillary electrophoresis for aluminum ion speciation: Optimized separation conditions for complex polycation mixtures.

PubMed

Ouadah, Nesrine; Moire, Claudine; Brothier, Fabien; Kuntz, Jean-François; Deschaume, Olivier; Bartic, Carmen; Cottet, Hervé

2018-06-01

Aluminum chlorohydrates (ACH) are used in numerous applications and commercial products on a global scale including water treatment, catalysis or antiperspirants. They are complex mixtures of water soluble aluminum polycations of different degrees of polymerization, that are difficult to separate and quantify due to their susceptibility to depolymerize in solution when placed out of equilibrium, which is inherent to any separation process. We recently achieved the first capillary electrophoresis separation and characterization of ACH oligomers using 4-morpholineethanesulfonic acid (MES) as background electrolyte counter-ion. MES stabilizes the separated ACH oligomers during the electrophoretic process leading to highly repeatable and fast separations. In this work, the separation of ACH oligomers was further studied and perfected by varying the ionic strength, MES concentration and pH of the background electrolyte. Complex electrophoretic behavior is reported for the separation of Al 13 , Al 30 and Na + ions according to these experimental parameters. The transformation of the electropherograms in effective mobility scale and the use of the slope-plot approach are used to better understand the observed changes in selectivity/resolution. Optimal conditions (700 mM MES at 25 mM ionic strength containing 0.1 mM didodecyldimethylammonium bromide for dynamic capillary coating, pH 4.8) obtained for the separation of ACH oligomers are used for the baseline separation of samples difficult to analyze with other methods, including different molecular, aggregated and colloidal forms of aluminum from the Al 13 , Al 30 and Na + mixture, validating the rationale of the approach. Copyright © 2018. Published by Elsevier B.V.

Sodium alginate/graphene oxide hydrogel beads as permeable reactive barrier material for the remediation of ciprofloxacin-contaminated groundwater.

PubMed

Zhao, Pingping; Yu, Fei; Wang, Ruoyu; Ma, Yao; Wu, Yanqing

2018-06-01

The wide occurrence of antibiotics in groundwater has raised serious concerns due to their impacts on humans and the ecosystem. Most of the research in groundwater remediation focuses on the exploitation of nano-materials. However, nano-materials have several disadvantages such as high production cost, rapid reduction in permeability, disposal problems, and high sensitivity to environmental conditions. To solve these issues, novel sodium alginate/graphene oxide hydrogel beads (GSA) were synthesised and their effectiveness as permeable reactive barrier (PRB) backfill material in the remediation of ciprofloxacin (CPX)-contaminated groundwater was tested. The adsorption of CPX onto GSA followed the pseudo-second-order kinetic model. The isotherm data followed the Freundlich model. The maximum adsorption capacity was 100 mg g -1 at pH 7.0. The adsorption process was sensitive to contact time, initial CPX concentration and ionic strength. However, it was not pH sensitive. Hydrophobic interaction, electrostatic interaction, ion exchange, H-bonding, and pore filling were proposed to be the main adsorption mechanisms. The effects of flow rate, influent CPX concentration, and ionic strength on the performance of PRB were confirmed through flow-through column experiments and by using a chemical non-equilibrium two-site model. Accordingly, a proper PRB was designed based on hydrogeological conditions. Finally, the lifetime and cost of the PRBs were calculated. The results obtained provided concrete evidence that GSA is a promising adsorbent material for PRBs applications in the remediation of CPX-contaminated groundwater. Copyright © 2018 Elsevier Ltd. All rights reserved.

The role of groundwater chemistry in the transport of bacteria to water-supply wells

USGS Publications Warehouse

Harvey, R.W.; Metge, D.W.

1999-01-01

Static mini-columns and in situ injection and recovery tests were used to assess the effects of modest changes in groundwater chemistry upon the pH-dependence of bacterial attachment, a primary determinant of bacterial mobility in drinking water aquifers. In uncontaminated groundwater (<1 mg l-1 dissolved organic carbon, DOC), bacterial attachment to aquifer grain surfaces declined steadily from 93 to 20% in response to an increase in pH from 5.8 to 7.8. However, bacterial attachment in modestly-contaminated groundwater (4 mg l-1 DOC) was relatively insensitive to pH change from pH 3.5 to pH 8, as was bacterial attachment in uncontaminated groundwater amended with only ~3 mg l-1 of purified humic acid. Destruction by UV-oxidation of the DOC in contaminated groundwater partially restored the pH-dependence of bacterial attachment. Results from static column tests and from a small-scale (3.6 m) natural-gradient injection and recovery study suggest that low concentrations of surfactants can also substantively alter the attraction of groundwater bacteria for grain surfaces and, therefore can alter the transport of bacteria to water-supply wells. This phenomenon was pH-sensitive and dependent upon the nature of the surfactant. At pH 7.6, 200 mg l-1 of the non-ionic surfactant, Imbentin, caused a doubling of fractional bacterial attachment in aquifer-sediment columns, but had little effect under slightly acidic conditions (e.g. at pH 5.8). In contrast, 1 mg l-1 of linear alkylbenzene sulphonate (LAS) surfactant, a common sewage-derived contaminant, decreased the fractional bacterial attachment by more than 30% at pH 5.8, but had little effect at pH 7.3.Static mini-columns and in situ injection and recovery tests were used to assess the effects of modest changes in groundwater chemistry upon the pH-dependence of bacterial attachment, a primary determinant of bacterial mobility in drinking water aquifers. In uncontaminated groundwater (<1 mg l-1 dissolved organic carbon, DOC), bacterial attachment to aquifer grain surfaces declined steadily from 93 to 20% in response to an increase in pH from 5.8 to 7.8. However, bacterial attachment in modestly-contaminated groundwater (4 mg l-1 DOC) was relatively insensitive to pH change from pH 3.5 to pH 8, as was bacterial attachment in uncontaminated groundwater amended with only approx. 3 mg l-1 of purified humic acid. Destruction of UV-oxidation of the DOC in contaminated groundwater partially restored the pH-dependence of bacterial attachment. Results from the static column tests and from a small-scale (3.6 m) natural-gradient injection and recovery study suggest that low concentrations of surfactants can also substantively alter the attraction of groundwater bacteria for grain surfaces and, therefore can alter the transport of bacteria to water-supply wells. This phenomenon was pH-sensitive and dependent upon the nature of the surfactant. At pH 7.6, 200 mg l-1 of the non-ionic surfactant, Imbentin, caused a doubling of fractional bacterial attachment in aquifer-sediment columns, but had little effect under slightly acidic conditions (e.g. at pH 5.8). In contrast, 1 mg l-1 of linear alkylbenzene sulphonate (LAS) surfactant, a common sewage-derived contaminant, decreased the fractional bacterial attachment by more than 30% at pH 5.8, but had little effect at pH 7.3.

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%.

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 %.

On the Preparation of Buffer Solutions.

ERIC Educational Resources Information Center

Thomson, Bruce M.; Kessick, Michael A.

1981-01-01

Presents a method, suitable for use on programmable calculators, which allows calculation of the pH and ionic strength (I) of a mixed solution of salts of an acid or amounts necessary to produce a solution of a particular pH and I. Includes limitations when using the calculations described. (SK)

Macroscopic experimental and modeling evaluation of selenite and selenate adsorption mechanisms on gibbsite

USDA-ARS?s Scientific Manuscript database

Selenite Se(IV) and selenate Se(VI) selenium adsorption behavior was investigated on gibbsite as a function of solution pH and solution ionic strength. Adsorption of both Se redox states decreased with increasing solution pH. Electrophoretic mobility measurements showed downward shifts in point of...

Morphological and immunohistochemical reactions of the larval epidermis in the Italian newt (Lissotriton italicus) after exposure to low pH.

PubMed

Brunelli, Elvira

2018-02-01

Mounting evidence suggests that amphibians are globally and currently the most threatened group of vertebrates and different causes might be responsible for this phenomenon. Acidification of water bodies is a global environmental issue that has been proposed as a possible cause for amphibian populations decline. Indeed, it has been widely demonstrated that low pH may exert harmful effects on amphibians, either directly or by increasing the adverse effects of other stressors. Surprisingly only few studies documented the response of amphibian integument to acidic pH conditions and no data are available on the effects of a non-lethal level of pH onto the amphibian larval epidermis. The present study showed that acidic pH (4.5) condition has severe effects on the epidermis of the Italian newt (Lissotriton italicus, formerly Triturus italicus) inducing both morphological and functional alterations. The increase of mucus is the first evident effect of acid injury, followed by the flattening of the epithelium and the appearance of a keratinized shedding layer. The immunolabeling of cytokeratins substantially changes acquiring an adult-like pattern. Also aquaporin 3 and iNOS expression modify their distribution according to a change of the histological features of the epidermis. These results clearly indicate that a short-term exposure to a sub-lethal pH disrupts the epidermis morphology and function in L. italicus larvae. Since the skin exerts a prominent role in both respiration and osmoregulation, the described alterations may adversely affect the overall ionic balance, with a long chain of cascading effects significantly decreasing newts survival probabilities when environmental pH lowering occurs. Copyright © 2018 Elsevier GmbH. All rights reserved.

A novel membrane-based process to isolate peroxidase from horseradish roots: optimization of operating parameters.

PubMed

Liu, Jianguo; Yang, Bo; Chen, Changzhen

2013-02-01

The optimization of operating parameters for the isolation of peroxidase from horseradish (Armoracia rusticana) roots with ultrafiltration (UF) technology was systemically studied. The effects of UF operating conditions on the transmission of proteins were quantified using the parameter scanning UF. These conditions included solution pH, ionic strength, stirring speed and permeate flux. Under optimized conditions, the purity of horseradish peroxidase (HRP) obtained was greater than 84 % after a two-stage UF process and the recovery of HRP from the feedstock was close to 90 %. The resulting peroxidase product was then analysed by isoelectric focusing, SDS-PAGE and circular dichroism, to confirm its isoelectric point, molecular weight and molecular secondary structure. The effects of calcium ion on HRP specific activities were also experimentally determined.

A novel membrane based process to isolate photosystem-I membrane complex from spinach.

PubMed

Liu, Jianguo; Yin, Mengmeng; Wang, Meng; Zhang, Xuefang; Ge, Baosheng; Liu, Shuang; Lu, Jianren; Cui, Zhanfeng

2011-02-01

The isolation of photosystem-I (PS-I) from spinach has been conducted using ultrafiltration with 300 kDa molecular weight cut-off polyethersulfone membranes. The effects of ultrafiltration operating conditions on PS-I activity were optimized using parameter scanning ultrafiltration. These conditions included solution pH, ionic strength, stirring speed, and permeate flux. The effects of detergent (Triton X-100 and n-dodecyl-beta-D-maltoside) concentration on time dependent activity of PS-I were also studied using an O(2) electrode. Under optimized conditions, the PS-I purity obtained in the retentate was about 84% and the activity recovery was greater than 94% after ultrafiltration. To our knowledge, this is the first report of the isolation of a membrane protein using ultrafiltration alone.

A temperature, pH and sugar triple-stimuli-responsive nanofluidic diode.

PubMed

Zheng, Yu-Bin; Zhao, Shuang; Cao, Shuo-Hui; Cai, Sheng-Lin; Cai, Xiu-Hong; Li, Yao-Qun

2017-01-07

In this article, we have demonstrated for the first time a triple stimuli-responsive nanofluidic diode that can rectify ionic current under multiple external stimuli including temperature, pH, and sugar. This diode was fabricated by immobilizing poly[2-(dimethylamino)ethyl methacrylate]-co-[4-vinyl phenylboronic acid] (P(DMAEMA-co-VPBA)) onto the wall of a single glass conical nanopore channel via surface-initiator atom transfer radical polymerization (SI-ATRP). The copolymer brushes contain functional groups sensitive to pH, temperature and sugar that can induce charge and configuration change to affect the status of the pore wall. The experimental results confirmed that the P(DMAEMA-co-VPBA) brush modified nanochannel regulated the ionic current rectification successfully under three different external stimuli. This biomimetically inspired research simulates the complex biological multi-functions of ion channels and promotes the development of "smart" biomimetic nanochannel systems for actuating and sensing applications.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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

PubMed

Nir, Oded; Marvin, Esra; Lahav, Ori

2014-11-01

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

An artificial-intelligence technique for qualitatively deriving enzyme kinetic mechanisms from initial-velocity measurements and its application to hexokinase.

PubMed Central

Garfinkel, L; Cohen, D M; Soo, V W; Garfinkel, D; Kulikowski, C A

1989-01-01

We have developed a computer method based on artificial-intelligence techniques for qualitatively analysing steady-state initial-velocity enzyme kinetic data. We have applied our system to experiments on hexokinase from a variety of sources: yeast, ascites and muscle. Our system accepts qualitative stylized descriptions of experimental data, infers constraints from the observed data behaviour and then compares the experimentally inferred constraints with corresponding theoretical model-based constraints. It is desirable to have large data sets which include the results of a variety of experiments. Human intervention is needed to interpret non-kinetic information, differences in conditions, etc. Different strategies were used by the several experimenters whose data was studied to formulate mechanisms for their enzyme preparations, including different methods (product inhibitors or alternate substrates), different experimental protocols (monitoring enzyme activity differently), or different experimental conditions (temperature, pH or ionic strength). The different ordered and rapid-equilibrium mechanisms proposed by these experimenters were generally consistent with their data. On comparing the constraints derived from the several experimental data sets, they are found to be in much less disagreement than the mechanisms published, and some of the disagreement can be ascribed to different experimental conditions (especially ionic strength). PMID:2690819

Iron species determination by task-specific ionic liquid-based in situ solvent formation dispersive liquid-liquid microextraction combined with flame atomic absorption spectrometry.

PubMed

Sadeghi, Susan; Ashoori, Vahid

2017-10-01

The task-specific ionic liquid (TSIL) of 1-ethyl-3-methylimidazolium bromide functionalized with 8-hydroxyquinoline was used as a chelating agent and extracting solvent for dispersive liquid-liquid microextraction and subsequent determination of Fe(III) by flame atomic absorption spectrometry. The in situ solvent formation of TSIL using KPF 6 provided the desired water-immiscible ionic liquid. The total Fe concentration could be determined after pre-oxidation of Fe(II) to Fe(III). Various factors affecting the proposed extraction procedure were optimized. The proposed analytical conditions were: sample pH 5, TSIL amount 0.3% (w/v), KPF 6 amount 0.15% (w/v), anti-sticking 0.1% (w/v) and salt concentration 5% (w/v). Under optimal conditions, the linear dynamic ranges for Fe(III) and total Fe were 20-80 and 20-110 ng mL -1 , respectively, with a detection limit of 6.9 ng mL -1 for Fe(III) and relative standard deviation of 2.2%. The proposed method was successfully applied to the determination of trace Fe(III) in water (underground, tap, refined water and artificial sea water) and beverage (apple, tomato, and tea) samples. The developed method offers advantages such as simplicity, ease of operation, and extraction of Fe(III) from aqueous solutions without the use of organic solvent. It was successfully applied for iron speciation in different real samples. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Nanofiltration of Mine Water: Impact of Feed pH and Membrane Charge on Resource Recovery and Water Discharge

PubMed Central

Mullett, Mark; Fornarelli, Roberta; Ralph, David

2014-01-01

Two nanofiltration membranes, a Dow NF 270 polyamide thin film and a TriSep TS 80 polyamide thin film, were investigated for their retention of ionic species when filtering mine influenced water streams at a range of acidic pH values. The functional iso-electric point of the membranes, characterized by changes in retention over a small pH range, were examined by filtering solutions of sodium sulphate. Both membranes showed changes in retention at pH 3, suggesting a zero net charge on the membranes at this pH. Copper mine drainage and synthetic solutions of mine influenced water were filtered using the same membranes. These solutions were characterized by pH values within 2 and 5, thus crossing the iso-electric point of both membranes. Retention of cations was maximized when the feed solution pH was less than the iso-electric point of the membrane. In these conditions, the membrane has a net positive charge, reducing the transmission rate of cations. From the recoveries of a range of cations, the suitability of nanofiltration was discussed relative to the compliance with mine water discharge criteria and the recovery of valuable commodity metals. The nanofiltration process was demonstrated to offer advantages in metal recovery from mine waste streams, concomitantly enabling discharge criteria for the filtrate disposal to be met. PMID:24957170

A newly high alkaline lipase: an ideal choice for application in detergent formulations

PubMed Central

2011-01-01

Background Bacterial lipases received much attention for their substrate specificity and their ability to function in extreme environments (pH, temperature...). Many staphylococci produced lipases which were released into the culture medium. Reports of thermostable lipases from Staphylococcus sp. and active in alkaline conditions are not previously described. Results A newly soil-isolated Staphylococcus sp. strain ESW secretes an induced lipase in the culture medium. The effects of temperature, pH and various components in a detergent on the activity and stability of Staphylococcus sp. lipase (SL1) were studied in a preliminary evaluation for use in detergent formulation solutions. The enzyme was highly active over a wide range of pH from 9.0 to 13.0, with an optimum at pH 12.0. The relative activity at pH 13.0 was about 60% of that obtained at pH 12.0. It exhibited maximal activity at 60°C. This novel lipase, showed extreme stability towards non-ionic and anionic surfactants after pre-incubation for 1 h at 40°C, and relative stability towards oxidizing agents. Additionally, the crude enzyme showed excellent stability and compatibility with various commercial solid and liquid detergents. Conclusions These properties added to the high activity in high alkaline pH make this novel lipase an ideal choice for application in detergent formulations. PMID:22123072

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.

Desorption of Lipases Immobilized on Octyl-Agarose Beads and Coated with Ionic Polymers after Thermal Inactivation. Stronger Adsorption of Polymers/Unfolded Protein Composites.

PubMed

Virgen-Ortíz, Jose J; Pedrero, Sara G; Fernandez-Lopez, Laura; Lopez-Carrobles, Nerea; Gorines, Beatriz C; Otero, Cristina; Fernandez-Lafuente, Roberto

2017-01-05

Lipases from Candida antarctica (isoform B) and Rhizomucor miehei (CALB and RML) have been immobilized on octyl-agarose (OC) and further coated with polyethylenimine (PEI) and dextran sulfate (DS). The enzymes just immobilized on OC supports could be easily released from the support using 2% SDS at pH 7, both intact or after thermal inactivation (in fact, after inactivation most enzyme molecules were already desorbed). The coating with PEI and DS greatly reduced the enzyme release during thermal inactivation and improved enzyme stability. However, using OC-CALB/RML-PEI-DS, the full release of the immobilized enzyme to reuse the support required more drastic conditions: a pH value of 3, a buffer concentration over 2 M, and temperatures above 45 °C. However, even these conditions were not able to fully release the thermally inactivated enzyme molecules from the support, being necessary to increase the buffer concentration to 4 M sodium phosphate and decrease the pH to 2.5. The formation of unfolded protein/polymers composites seems to be responsible for this strong interaction between the octyl and some anionic groups of OC supports. The support could be reused five cycles using these conditions with similar loading capacity of the support and stability of the immobilized enzyme.

Factors influencing sorption of ciprofloxacin onto activated sludge: experimental assessment and modelling implications.

PubMed

Polesel, Fabio; Lehnberg, Kai; Dott, Wolfgang; Trapp, Stefan; Thomas, Kevin V; Plósz, Benedek Gy

2015-01-01

Many of the pharmaceuticals and personal care products occurring in municipal sewage are ionizing substances, and their partitioning behaviour is affected by ionic interactions with solid matrices. In activated sludge systems, such interactions have currently not been adequately understood and described, particularly for zwitterionic chemicals. Here we present an assessment of the effects of pH and iron salt dosing on the sorption of ciprofloxacin onto activated sludge using laboratory experiments and full-scale fate modelling. Experimental results were described with Freundlich isotherms and showed that non-linear sorption occurred under all the conditions tested. The greatest sorption potential was measured at pH=7.4, at which ciprofloxacin is speciated mostly as zwitterion. Iron salt dosing increased sorption under aerobic and, to a lesser extent, anoxic conditions, whereas no effect was registered under anaerobic conditions. The activated sludge model for xenobiotics (ASM-X) was extended with Freundlich-based sorption kinetics and used to predict the fate of ciprofloxacin in a wastewater treatment plant (WWTP). Scenario simulations, using experimental Freundlich parameters, were used to identify whether the assessed factors caused a significant increase of aqueous ciprofloxacin concentration in full-scale bioreactors. Simulation results suggest that a pH increase, rather than a reduction in iron salt dosing, could be responsible for a systematic deterioration of sorption of ciprofloxacin in the WWTP. Copyright © 2014 Elsevier Ltd. All rights reserved.

Anisotropic amplification of proton transport in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Thimmappa, Ravikumar; Fawaz, Mohammed; Devendrachari, Mruthyunjayachari Chattanahalli; Gautam, Manu; Kottaichamy, Alagar Raja; Shafi, Shahid Pottachola; Thotiyl, Musthafa Ottakam

2017-07-01

Though graphene oxide (GO) membrane shuttles protons under humid conditions, it suffer severe disintegration and anhydrous conditions lead to abysmal ionic conductivity. The trade-off between mechanical integrity and ionic conductivity challenge the amplification of GO's ionic transport under anhydrous conditions. We show anisotropic amplification of GO's ionic transport with a selective amplification of in plane contribution under anhydrous conditions by doping it with a plant extract, phytic acid (PA). The hygroscopic nature of PA stabilized interlayer water molecules and peculiar geometry of sbnd OH functionalities around saturated hydrocarbon ring anisotropically enhanced ionic transport amplifying the fuel cell performance metrics.

Time course of the establishment of uterine seawater conditions in late-term pregnant spiny dogfish (Squalus acanthias).

PubMed

Kormanik, G A

1988-07-01

The gestation period for embryos of the spiny dogfish, Squalus acanthias (L.) lasts for nearly 2 years. During the latter part of this period the pups remain in the uterus and the fluid surrounding the embryos resembles sea water with respect to the major ions, but is low in pH (approx. 6), high in partial pressure of carbon dioxide (approx. 3 mmHg; 1 mmHg = 133.3 Pa), low in total carbon dioxide content (approx. 0.2 mmol l-1), and may have a total ammonia concentration of up to 22 mmol l-1. Thus the conditions under which the pups complete their development in utero is quite remarkable. The derivation of these conditions was examined in late-term pregnant females, from whose uterine horns the pups had been removed, by monitoring changes that occurred in instilled uterine sea water. The mother is responsible for reducing the pH, reducing the total carbon dioxide content and elevating the partial pressure of carbon dioxide to the levels observed in fresh-caught females, in less than 24 h. The ammonia concentration is also elevated, but this takes rather longer. The decreased pH is responsible for the accumulation of ammonia in the uterine sea water, and it also serves to protect the pups from the toxic effects of NH3, by converting it to the relatively non-toxic ionic form, NH4+. The reasons for the establishment of these uterine seawater conditions are still not evident.

Removal of trace metal contaminants from potable water by electrocoagulation.

PubMed

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

2016-06-21

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

Removal of trace metal contaminants from potable water by electrocoagulation

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Ionic liquid ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of the aqueous phase for preconcentration of heavy metals ions prior to determination by LC-UV.

PubMed

Werner, Justyna

2018-05-15

Ionic liquid ultrasound-assisted dispersive liquid-liquid microextraction based on solidification of the aqueous phase was used for preconcentration of Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ , Pb 2+ in natural water samples prior to liquid chromatography with UV detection. In the proposed method, the ammonium pyrrolidinedithiocarbamate was used as a complexing agent and the phosphonium ionic liquid trihexyl(tetradecyl)phosphonium bis[(2,4,4-trimethyl)pentyl]phosphinate (Cyphos IL 104) was used as an extractant. Ultrasound energy was used to disperse the extractant in the aqueous phase. After microextraction, the ionic liquid and aqueous phases were separated by centrifugation. Then the aqueous phase was frozen and the lighter than water ionic liquid phase containing metal ions complexes with pyrrolidinedithiocarbamate was separated and dissolved in a small volume of methanol prior to injection into the liquid chromatograph. Several parameters including the volume of extractant, the pH of the sample, the concentration of complexing agent, the time of ultrasound energy treatment, the time and speed of centrifugation and the effect of ionic strength were optimized. Under the optimized conditions (10 µL of Cyphos IL 104, pH = 5, 0.3% w/v ammonium pyrrolidinedithiocarbamate, 60 s of ultrasound use, 5 min/5000 rpm (2516×g) of centrifugation, 2.0 mg of NaCl), preconcentration factors were 211, 210, 209, 207 and 211 for Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ and Pb 2+ respectively. Linearity was observed in the ranges 0.2-75.0 µg L -1 for Pb 2+ , Cd 2+ , Co 2+ and 0.5-100.0 µg L -1 for Cu 2+ , Ni 2+ . The limits of detection were 0.03 µg L -1 for Ni 2+ , 0.03 µg L -1 for Co 2+ , 0.03 µg L -1 for Cd 2+ , 0.02 µg L -1 for Cu 2+ , 0.02 µg L -1 for Pb 2+ , respectively. The accuracy of this method was evaluated by preconcentration and determination of Ni 2+ , Co 2+ , Cd 2+ , Cu 2+ , Pb 2+ in certified reference materials (TMRAIN-04 and NIST 1643e) with the recovery values in the range of 97-102%. The presented method has been successfully applied for the determination of analytes in natural water samples (river and lake waters). Copyright © 2018 Elsevier B.V. All rights reserved.

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.

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

PubMed

Hjörleifsson, Jens G; Ásgeirsson, Bjarni

2017-09-26

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

Aggregation of asbestos fibers in water: role of solution chemistry

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Fermentation pH influences the physiological-state dynamics of Lactobacillus bulgaricus CFL1 during pH-controlled culture.

PubMed

Rault, Aline; Bouix, Marielle; Béal, Catherine

2009-07-01

This study aims at better understanding the effects of fermentation pH and harvesting time on Lactobacillus bulgaricus CFL1 cellular state in order to improve knowledge of the dynamics of the physiological state and to better manage starter production. The Cinac system and multiparametric flow cytometry were used to characterize and compare the progress of the physiological events that occurred during pH 6 and pH 5 controlled cultures. Acidification activity, membrane damage, enzymatic activity, cellular depolarization, intracellular pH, and pH gradient were determined and compared during growing conditions. Strong differences in the time course of viability, membrane integrity, and acidification activity were displayed between pH 6 and pH 5 cultures. As a main result, the pH 5 control during fermentation allowed the cells to maintain a more robust physiological state, with high viability and stable acidification activity throughout growth, in opposition to a viability decrease and fluctuation of activity at pH 6. This result was mainly explained by differences in lactate concentration in the culture medium and in pH gradient value. The elevated content of the ionic lactate form at high pH values damaged membrane integrity that led to a viability decrease. In contrast, the high pH gradient observed throughout pH 5 cultures was associated with an increased energetic level that helped the cells maintain their physiological state. Such results may benefit industrial starter producers and fermented-product manufacturers by allowing them to better control the quality of their starters, before freezing or before using them for food fermentation.

Determination of the parameters controlling swelling of chemically cross-linked pH-sensitive poly(N-vinylimidazole) hydrogels.

PubMed

Molina, M Jesús; Gómez-Antón, M Rosa; Piérola, Inés F

2007-10-25

The number of variables controlling the behavior of ionic gels is large and very often some of them are unknown. The aim of this work is to interpret quantitatively the swelling behavior of pH sensitive gels, with the minimum number of simplifying assumptions. With this purpose, the equilibrium degree of swelling (S) and protonation (alpha) of chemically cross-linked poly(N-vinylimidazole) (PVI) immersed in aqueous salt solutions were measured as a function of the ionic strength (mu), in the whole range of pH. In acid solutions with pH in the range 0 to 4, imidazole moieties become protonated, and PVI behaves as a polyelectrolyte gel: S decreases upon increasing mu both for NaCl and for CaCl(2), with HCl as protonating acid. In aqueous solutions with larger pH, between 4 and 12, the hydrogel is practically neutral, and S increases as mu rises, showing a salting-in effect. From the quantitative analysis of these results, the following facts emerged. Protonation induces chain stiffness (as measured by the non-Gaussian factor) and worsening of the solvent quality of the aqueous media (as measured by the polymer-solvent interaction parameter). For alpha below 33%, swelling seems to be governed by the excess of mobile counterions inside the gel with respect to the bath, with a minor but still significantly negative contribution of the osmotic swelling pressure due to polymer-solvent mixing. Above 33% protonation, it is necessary to consider Manning counterion condensation to get parameters with physical meaning. The crossover between polyelectrolyte and salting-in effects corresponds to alpha and mu values with the same ionic and mixing contributions to the osmotic swelling pressure. The formation of ionic nonpermanent cross-links, with H(2)SO(4) as the protonating acid, was discarded.

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.

Fouling of nanofiltration, reverse osmosis, and ultrafiltration membranes by protein mixtures: the role of inter-foulant-species interaction.

PubMed

Wang, Yi-Ning; Tang, Chuyang Y

2011-08-01

Protein fouling of nanofiltration (NF), reverse osmosis (RO), and ultrafiltration (UF) membranes by bovine serum albumin (BSA), lysozyme (LYS), and their mixture was investigated under cross-flow conditions. The effect of solution chemistry, membrane properties, and permeate flux level was systematically studied. When the solution pH was within the isoelectric points (IEPs) of the two proteins (i.e., pH 4.7-10.4), the mixed protein system experienced more severe flux decline compared to the respective single protein systems, which may be attributed to the electrostatic attraction between the negatively charged BSA and positively charged LYS molecules. Unlike a typical single protein system, membrane fouling by BSA-LYS mixture was only weakly dependent on solution pH within this pH range, and increased ionic strength was found to enhance the membrane flux as a result of the suppressed BSA-LYS electrostatic attraction. Membrane fouling was likely controlled by foulant-fouled-membrane interaction under severe fouling conditions (elevated flux level and unfavorable solution chemistry that promotes fouling), whereas it was likely dominated by foulant-clean-membrane interaction under mild fouling conditions. Compared to nonporous NF and RO membranes, the porous UF membrane was more susceptible to dramatic flux decline due to the increased risk of membrane pore plugging. This study reveals that membrane fouling by mixed macromolecules may behave very differently from that by typical single foulant system, especially when the inter-foulant-species interaction dominates over the intra-species interaction in the mixed foulant system.

Direct observation and determination of the mechanisms governing mobility of asbestos in porous media

NASA Astrophysics Data System (ADS)

Seiphoori, A.; Ortiz, C. P.; Jerolmack, D. J.

2017-12-01

Transport of asbestos through soil by groundwater is typically considered to be negligible. There are indications, however, that under some conditions of pore-water/soil chemistry asbestos may become mobile, implying that buried contaminants could migrate from a disposal site and surface elsewhere. Shape, size and surface charge may influence the physical and chemical interactions of colloids with the soil matrix, and asbestos consists of elongated particles with different size and unique surface charge properties. Although chemical factors such as pH and ionic strength of pore water may affect the transport properties, the presence of dissolved organic carbon (DOC) has been identified to remarkably enhance the mobility of colloids including asbestos. To date, there is no explanation for how the presence of DOC may facilitate the mobilization of asbestos in soil - mainly because the soil medium has been treated as a black box without the possibility of observing particles within the matrix. Here, we investigated the mobility of chrysotile asbestos particles ( 10 um long) in porous media by developing a flow cell with an optically-transparent porous medium composed of granules of a refractive-index matched material. This enabled us to observe and track the particles within the water-saturated porous medium using in situ microscopy. The aqueous suspension of asbestos fibers was passed through this artificial soil, while the physical and chemical interaction of asbestos particles with the medium and their pore-scale distribution were analyzed. We studied the effects of changing solution chemistry (e.g., ionic strength, pH, and DOC content) on transport, attachment and aggregation of chrysotile particles. Experiments revealed a novel mechanism where the DOC-associated nanoparticles attach to chrysotile fibers by an electrostatic attraction, which facilitates their mobilization through the porous medium while modulating aggregation among fibers. Although pH and ionic strength also influenced aggregation and the attachment rate of particles to the substrate, the effect of DOC was more pronounced. This work may lead to enhanced predictions for the fate and transport of asbestos (as well as other contaminants) in the environment, and has implications for the mobility of asbestos particles in the human body.

Effect of pH on the Electrophoretic Mobility of Spores of Bacillus anthracis and Its Surrogates in Aqueous Solutions

EPA Science Inventory

Electrophoretic mobility (EPM) of endospores of Bacillus anthracis and surrogates were measured in aqueous solution across a broad pH range and several ionic strengths. EPM values trended around phylogenetic clustering based on the 16S rRNA gene. Measurements reported here prov...

Macroscopic experimental and modeling evaluation of selenite and selenate adsorption mechanisms on gibbsite

USDA-ARS?s Scientific Manuscript database

Selenite Se(IV) and selenate Se(VI) adsorption behavior was investigated on gibbsite as a function of solution pH and solution ionic strength. Adsorption of both Se redox states decreased with increasing solution pH. Electrophoretic mobility measurements showed downward shifts in point of zero cha...

A dynamic system for the simulation of fasting luminal pH-gradients using hydrogen carbonate buffers for dissolution testing of ionisable compounds.

PubMed

Garbacz, Grzegorz; Kołodziej, Bartosz; Koziolek, Mirko; Weitschies, Werner; Klein, Sandra

2014-01-23

The hydrogen carbonate buffer is considered as the most biorelevant buffer system for the simulation of intestinal conditions and covers the physiological pH range of the luminal fluids from pH 5.5 to about pH 8.4. The pH value of a hydrogen carbonate buffer is the result of a complex and dynamic interplay of the concentration of hydrogen carbonate ions, carbonic acid, the concentration of dissolved and solvated carbon dioxide and its partial pressure above the solution. The complex equilibrium between the different ions results in a thermodynamic instability of hydrogen carbonate solutions. In order to use hydrogen carbonate buffers with pH gradients in the physiological range and with the dynamics observed in vivo without changing the ionic strength of the solution, we developed a device (pHysio-grad®) that provides both acidification of the dissolution medium by microcomputer controlled carbon dioxide influx and alkalisation by degassing. This enables a continuous pH control and adjustment during dissolution of ionisable compounds. The results of the pH adjustment indicate that the system can compensate even rapid pH changes after addition of a basic or acidic moiety in amounts corresponding up to 90% of the overall buffer capacity. The results of the dissolution tests performed for a model formulation containing ionizable compounds (Nexium 20mg mups) indicate that both the simulated fasting intraluminal pH-profiles and the buffer species can significantly affect the dissolution process by changing the lag time prior to initial drug release and the release rate of the model compound. A prediction of the in vivo release behaviour of this formulation is thus most likely strongly related to the test conditions such as pH and buffer species. Copyright © 2013 Elsevier B.V. All rights reserved.

Human fibrinogen adsorption on positively charged latex particles.

PubMed

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

2014-09-23

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

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

PubMed

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

2017-09-25

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

Textile dye removal from aqueous solutions by malt bagasse: Isotherm, kinetic and thermodynamic studies.

PubMed

Fontana, Klaiani B; Chaves, Eduardo S; Sanchez, Jefferson D S; Watanabe, Erica R L R; Pietrobelli, Juliana M T A; Lenzi, Giane G

2016-02-01

The biosorption of orange solimax TGL 182% (OS-TGL) textile dye onto new and low cost biossorbent (malt bagasse) in aqueous solutions was investigated. The malt bagasse was characterized by Fourier transform infrared spectroscopy and specific surface area (BET method).Batch biosorption experiments were conducted in order to determine the following parameters: particles size, pH, agitation speed, temperature, contact time, biomass dosage, influence of the ionic strength and, finally, the influence of other textile dye on the OS-TGL biosorption. The optimum conditions for OS-TGL removal were obtained at pH 1.5, agitation speed of 150rpm, contact time of 180min and biomass dosage 2, 8gL(-1). The results show that the kinetics of biosorption followed a pseudo-second-order model and by increasing the temperature from 293 up to 313K, the biosorption capacity was improved. The Langmuir model showed better fit and the estimated biosorption capacity was 23.2mgg(-1). The negative values of Gibbs free energy, ΔG°, and positive value of enthalpy, ΔH°, confirm the spontaneous nature and endothermic character of the biosorption process. The results of the ionic strength effect indicated that the biosorption process under study had a strong tolerance in high salt concentrations. The removal capacity (>95%) was not affected with the presence of other textile dyes. Copyright © 2015 Elsevier Inc. All rights reserved.

Optimization, purification and characterization of novel thermostable, haloalkaline, solvent stable protease from Bacillus halodurans CAS6 using marine shellfish wastes: a potential additive for detergent and antioxidant synthesis.

PubMed

Annamalai, Neelamegam; Rajeswari, Mayavan Veeramuthu; Thavasi, Rengathavasi; Vijayalakshmi, Shanmugam; Balasubramanian, Thangavel

2013-07-01

A protease producing marine bacterium, Bacillus halodurans CAS6 isolated from marine sediments, was found to produce higher enzyme by utilizing shrimp shell powder. Optimum culture conditions for protease production were 50 °C, pH 9.0, 30 % NaCl and 1 % shrimp shell powder (SSP) and the protease purified with a specific activity of 509.84 U/mg. The enzyme retained 100 % of its original activity even at 70 °C, pH 10.0 and 30 % NaCl for 1 h. The purified protease exhibited higher stability when treated with ionic, non-ionic (72-94 %) and commercial detergents (76-88 %), and organic solvents (88-126 %). Significant blood stain removal activity was found with the enzyme in washing experiments. The culture supernatant supplemented with 1 % SSP showed 93.67 ± 2.52 % scavenging activity and FT-IR analysis of the reaction mixture confirmed the presence of antioxidants such as cyclohexane and cyclic depsipeptide with aliphatic amino groups. These remarkable qualities found with this enzyme produced by Bacillus halodurans CAS6 could make this as an ideal candidate to develop the industrial process for bioconversion of marine wastes and antioxidant synthesis.

Ammonium pyrrolidine dithiocarbamate anchored Symphoricarpus albus biomass for lead(II) removal: batch and column biosorption study.

PubMed

Akar, Sibel Tunali; Arslan, Derya; Alp, Tugba

2012-08-15

The biosorption properties of APDC modified S. albus were tested in batch and column conditions. Effective experimental parameters such as pH, biosorbent dosage, contact time, temperature, initial lead(II) ion concentration, flow rate and bed height were investigated. The biosorption capacity of modified biosorbent was at maximum when lead(II) solution pH and biosorbent dosage were 5.5 and 2.0 g L(-1), respectively. The biosorption equilibrium was established in 20 min. Langmuir isotherm fitted well to the equilibrium data and kinetics is found to fit pseudo-second-order model. Increase in ionic strength of lead(II) solutions caused a slight decrease in the biosorption yield of APDC-modified biosorbent. Co-ions affected the biosorption performance of modified biomass up to maximum 20.81% reduction. Column biosorption of lead(II) showed higher biosorption yields at lower flow rates. Required time of breakthrough point was found to be 200 min. The recommended mechanism was found to depend mainly on electrostatic interaction, ion-exchange and complex formation. The ion-exchange mechanism for lead(II) biosorption onto the modified biosorbent is verified from the ionic strength effect and EDX analysis. Carbonyl, phosphate and CN groups on the modified surface of S. albus were found to responsible for complexation with lead(II). Copyright © 2012 Elsevier B.V. All rights reserved.

Pyridinium ionic liquid-based liquid-solid extraction of inorganic and organic iodine from Laminaria.

PubMed

Peng, Li-Qing; Yu, Wen-Yan; Xu, Jing-Jing; Cao, Jun

2018-01-15

A simple, green and effective extraction method, namely, pyridinium ionic liquid- (IL) based liquid-solid extraction (LSE), was first designed to extract the main inorganic and organic iodine compounds (I - , monoiodo-tyrosine (MIT) and diiodo-tyrosine (DIT)). The optimal extraction conditions were as follows: ultrasonic intensity 100W, IL ([EPy]Br) concentration 200mM, extraction time 30min, liquid/solid ratio 10mL/g, and pH value 6.5. The morphologies of Laminaria were studied by scanning electron microscopy and transmission electron microscopy. The recovery values of I - , MIT and DIT from Laminaria were in the range of 88% to 94%, and limits of detection were in the range of 59.40 to 283.6ng/g. The proposed method was applied to the extraction and determination of iodine compounds in three Laminaria. The results showed that IL-based LSE could be a promising method for rapid extraction of bioactive iodine from complex food matrices. Copyright © 2017 Elsevier Ltd. All rights reserved.

The final frontier of pH and the undiscovered country beyond.

PubMed

Bal, Wojciech; Kurowska, Ewa; Maret, Wolfgang

2012-01-01

The comparison of volumes of cells and subcellular structures with the pH values reported for them leads to a conflict with the definition of the pH scale. The pH scale is based on the ionic product of water, K(w) = [H(+)]×[OH(-)].We used K(w) [in a reversed way] to calculate the number of undissociated H(2)O molecules required by this equilibrium constant to yield at least one of its daughter ions, H(+) or OH(-) at a given pH. In this way we obtained a formula that relates pH to the minimal volume V(pH) required to provide a physical meaning to K(w), V(pH)=10(pH-pK(w/2) x 10(pK(w/2)/N(A) (where N(A) is Avogadro's number). For example, at pH 7 (neutral at 25°C) V(pH) =16.6 aL. Any deviation from neutral pH results in a larger V(pH) value. Our results indicate that many subcellular structures, including coated vesicles and lysosomes, are too small to contain free H(+) ions at equilibrium, thus the definition of pH based on K(w) is no longer valid. Larger subcellular structures, such as mitochondria, apparently contain only a few free H(+) ions. These results indicate that pH fails to describe intracellular conditions, and that water appears to be dissociated too weakly to provide free H(+) ions as a general source for biochemical reactions. Consequences of this finding are discussed.

Extraction of triazole fungicides in environmental waters utilizing poly (ionic liquid)-functionalized magnetic adsorbent.

PubMed

Liu, Cheng; Liao, Yingmin; Huang, Xiaojia

2017-11-17

This work prepared a new poly (ionic liquid)-functionalized magnetic adsorbent (PFMA) for the extraction of triazole fungicides (TFs) in environmental waters prior to determination by high performance liquid chromatography/diode array detection (HPLC-DAD). A polymerizable ionic liquid, 1-methyl-3-allylimidazolium bis(trifluoromethylsulfonyl)imide was employed to copolymerize with divinylbenzene on the surface of modified magnetite to fabricate the PFMA. The morphology, spectroscopic and magnetic properties of the new adsorbent were investigated by different techniques. A series of key parameters that influence the extraction performance including the amount of PFMA, desorption solvent, adsorption and desorption time, sample pH value and ionic strength were optimized in detail. Under the optimum conditions, the prepared PFMA could extract targeted TFs effectively and quickly under the format of magnetic solid-phase extraction (MSPE). Satisfactory linearities were achieved in the range of 0.1-200.0μg/L for triadimenol and 0.05-200.0μg/L for other TFs with good coefficients of determination above 0.99 for all analytes. The limits of detection (S/N=3) and limits of quantification (S/N=10) for TFs were in the range of 0.0050-0.0078μg/L and 0.017-0.026μg/L, respectively. Environmental waters including lake, river and well waters were used to demonstrate the applicability of developed MSPE-HPLC-DAD method, and satisfactory recoveries and repeatability were obtained. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

Wang, Xiangke; Chen, Yixue; Wu, Yican

2004-06-01

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

Retention and release of oil-in-water emulsions from filled hydrogel beads composed of calcium alginate: impact of emulsifier type and pH.

PubMed

Zeeb, Benjamin; Saberi, Amir Hossein; Weiss, Jochen; McClements, David Julian

2015-03-21

Delivery systems based on filled hydrogel particles (microgels) can be fabricated from natural food-grade lipids and biopolymers. The potential for controlling release characteristics by modulating the electrostatic interactions between emulsifier-coated lipid droplets and the biopolymer matrix within hydrogel particles was investigated. A multistage procedure was used to fabricate calcium alginate beads filled with lipid droplets stabilized by non-ionic, cationic, anionic, or zwitterionic emulsifiers. Oil-in-water emulsions stabilized by Tween 60, DTAB, SDS, or whey protein were prepared by microfluidization, mixed with various alginate solutions, and then microgels were formed by simple extrusion into calcium solutions. The microgels were placed into a series of buffer solutions with different pH values (2 to 11). Lipid droplets remained encapsulated under acidic and neutral conditions, but were released under highly basic conditions (pH 11) due to hydrogel swelling when the alginate concentration was sufficiently high. Lipid droplet release increased with decreasing alginate concentration, which could be attributed to an increase in the pore size of the hydrogel matrix. These results have important implications for the design of delivery systems to entrap and control the release of lipophilic bioactive components within filled hydrogel particles.

Modulating β-lactoglobulin nanofibril self-assembly at pH 2 using glycerol and sorbitol.

PubMed

Dave, Anant C; Loveday, Simon M; Anema, Skelte G; Jameson, Geoffrey B; Singh, Harjinder

2014-01-13

β-Lactoglobulin (β-lg) forms fibrils when heated at 80 °C, pH 2, and low ionic strength (<0.015 mM). When formed at protein concentrations <3%, these fibrils are made up of peptides produced from the acid hydrolysis of the β-lg monomer. The present study investigated the effects of the polyhydroxy alcohols (polyols) glycerol and sorbitol (0-50% w/v) on β-lg self-assembly at pH 2. Glycerol and sorbitol stabilize native protein structure and modulate protein functionality by preferential exclusion. In our study, both polyols decreased the rate of β-lg self-assembly but had no effect on the morphology of fibrils. The mechanism of these effects was studied using circular dichroism spectroscopy and SDS-PAGE. Sorbitol inhibited self-assembly by stabilizing β-lg against unfolding and hydrolysis, resulting in fewer fibrillogenic species, whereas glycerol inhibited nucleation without inhibiting hydrolysis. Both polyols increased the viscosity of the solutions, but viscosity appeared to have little effect on fibril assembly, and we believe that self-assembly was not diffusion-limited under these conditions. This is in agreement with previous reports for other proteins assembling under different conditions. The phenomenon of peptide self-assembly can be decoupled from protein hydrolysis using glycerol.

Laser Raman spectra of mono-, oligo- and polysaccharides in solution

NASA Astrophysics Data System (ADS)

Barrett, T. W.

We examined the Raman spectra of thirteen sugars—seven monosaccharides, two disaccharides, one trisaccharide and three polysaccharides—in the wavelength range 200—1700 cm -1 and (i) varied the phosphate buffered solution from pH 6.0 to 8.5 at constant ionic strength of 0.1 and (ii) varied HCl solutions from pH 0.8 to 5.0. As is to be expected with molecules containing COH groupings, all the molecular spectra are distinct. Of the thirteen sugars examined, only D-fructose 1,6-diphosphate (FDP) demonstrated spectral changes for the pH range 6.0—8.5 in phosphate buffer; but all exhibited band intensity enhancement in HCl at the lower pHs, but not band wavenumber changes. The results indicate that: (i) changes in the pH of the major intracellular buffer, phosphate, toward acidity, are able to hydrolyze the 1-phosphate group of FDP and the relative concentration of fructose 1-phosphate to fructose 6-phosphate is indicated by the intensity ratio of the 982 and 1080 cm -1 bands; (ii) it appears that all phosphate groups of FDP are hydrolyzed at pH 0.8 in HCl; and (iii) although conditions of extreme acidity are able to hydrolyze other sugars examined, there is no major degradation.

Development of a P((MAA-co-NVP)-g-EG) Hydrogel Platform for Oral Protein Delivery: Effects of Hydrogel Composition on Environmental Response and Protein Partitioning.

PubMed

Steichen, Stephanie; O'Connor, Colleen; Peppas, Nicholas A

2017-01-01

Hydrogels based upon terpolymers of methacrylic acid, N-vinyl pyrrolidone, and poly(ethylene glycol) are developed and characterized for their ability to respond to changes in environmental pH and to partition protein therapeutics of varying molecular weights and isoelectric points. P((MAA-co-NVP)-g-EG) hydrogels are synthesized with PEG-based cross-linking agents of varying length and incorporation densities. The composition is confirmed using FT-IR spectroscopy and shows peak shifts indicating hydrogen bonding. Scanning electron microscopy reveals microparticles with an irregular, planar morphology. The pH-responsive behavior of the hydrogels is confirmed under equilibrium and dynamic conditions, with the hydrogel collapsed at acidic pH and swollen at neutral pH. The ability of the hydrogels to partition model protein therapeutics at varying pH and ionic strength is evaluated using three model proteins: insulin, porcine growth hormone, and ovalbumin. Finally, the microparticles are evaluated for adverse interactions with two model intestinal cell lines and show minimal cytotoxicity at concentrations below 5 mg mL -1 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Arginine inactivates human herpesvirus 2 and inhibits genital herpesvirus infection.

PubMed

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

2012-12-01

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

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.

Inner-Helmholtz potential development at the hematite (α-Fe 2O 3) (0 0 1) surface

NASA Astrophysics Data System (ADS)

Boily, Jean-François; Chatman, Shawn; Rosso, Kevin M.

2011-08-01

Electric potentials of the (0 0 1) surface of hematite were measured as a function of pH and ionic strength in solutions of sodium nitrate and oxalic acid using the single-crystal electrode approach. The surface is predominantly charge-neutral in the pH 4-14 range, and develops a positive surface potential below pH 4 due to protonation of μ-OH 0 sites (p K1,1,0,int = -1.32). This site is resilient to deprotonation up to at least pH 14 (-p K-1,1,0,int ≫ 19). The associated Stern layer capacitance of 0.31-0.73 F/m 2 is smaller than typical values of powders, and possibly arises from a lower degree of surface solvation. Acid-promoted dissolution under elevated concentrations of HNO 3 etches the (0 0 1) surface, yielding a convoluted surface populated by -OH20.5+ sites. The resulting surface potential was therefore larger under these conditions than in the absence of dissolution. Oxalate ions also promoted (0 0 1) dissolution. Associated electric potentials were strongly negative, with values as large as -0.5 V, possibly from metal-bonded interactions with oxalate. The hematite surface can also acquire negative potentials in the pH 7-11 range due to surface complexation and/or precipitation of iron species (0.0038 Fe/nm 2) produced from acidic conditions. Oxalate-bearing systems also result in negative potentials in the same pH range, and may include ferric-oxalate surface complexes and/or surface precipitates. All measurements can be modeled by a thermodynamic model that can be used to predict inner-Helmholtz potentials of hematite surfaces.

Mobile colloid generation induced by a cementitious plume: mineral surface-charge controls on mobilization.

PubMed

Li, Dien; Kaplan, Daniel I; Roberts, Kimberly A; Seaman, John C

2012-03-06

Cementitious materials are increasingly used as engineered barriers and waste forms for radiological waste disposal. Yet their potential effect on mobile colloid generation is not well-known, especially as it may influence colloid-facilitated contaminant transport. Whereas previous papers have studied the introduction of cement colloids into sediments, this study examined the influence of cement leachate chemistry on the mobilization of colloids from a subsurface sediment collected from the Savannah River Site, USA. A sharp mobile colloid plume formed with the introduction of a cement leachate simulant. Colloid concentrations decreased to background concentrations even though the aqueous chemical conditions (pH and ionic strength) remained unchanged. Mobile colloids were mainly goethite and to a lesser extent kaolinite. The released colloids had negative surface charges and the mean particle sizes ranged primarily from 200 to 470 nm. Inherent mineralogical electrostatic forces appeared to be the controlling colloid removal mechanism in this system. In the background pH of ~6.0, goethite had a positive surface charge, whereas quartz (the dominant mineral in the immobile sediment) and kaolinite had negative surface charges. Goethite acted as a cementing agent, holding kaolinite and itself onto the quartz surfaces due to the electrostatic attraction. Once the pH of the system was elevated, as in the cementitious high pH plume front, the goethite reversed to a negative charge, along with quartz and kaolinite, then goethite and kaolinite colloids were mobilized and a sharp spike in turbidity was observed. Simulating conditions away from the cementitious source, essentially no colloids were mobilized at 1:1000 dilution of the cement leachate or when the leachate pH was ≤ 8. Extreme alkaline pH environments of cementitious leachate may change mineral surface charges, temporarily promoting the formation of mobile colloids.

Bayesian belief network modelling of chlorine disinfection for human pathogenic viruses in municipal wastewater.

PubMed

Carvajal, Guido; Roser, David J; Sisson, Scott A; Keegan, Alexandra; Khan, Stuart J

2017-02-01

Chlorine disinfection of biologically treated wastewater is practiced in many locations prior to environmental discharge or beneficial reuse. The effectiveness of chlorine disinfection processes may be influenced by several factors, such as pH, temperature, ionic strength, organic carbon concentration, and suspended solids. We investigated the use of Bayesian multilayer perceptron (BMLP) models as efficient and practical tools for compiling and analysing free chlorine and monochloramine virus disinfection performance as a multivariate problem. Corresponding to their relative susceptibility, Adenovirus 2 was used to assess disinfection by monochloramine and Coxsackievirus B5 was used for free chlorine. A BMLP model was constructed to relate key disinfection conditions (CT, pH, turbidity) to observed Log Reduction Values (LRVs) for these viruses at constant temperature. The models proved to be valuable for incorporating uncertainty in the chlor(am)ination performance estimation and interpolating between operating conditions. Various types of queries could be performed with this model including the identification of target CT for a particular combination of LRV, pH and turbidity. Similarly, it was possible to derive achievable LRVs for combinations of CT, pH and turbidity. These queries yielded probability density functions for the target variable reflecting the uncertainty in the model parameters and variability of the input variables. The disinfection efficacy was greatly impacted by pH and to a lesser extent by turbidity for both types of disinfections. Non-linear relationships were observed between pH and target CT, and turbidity and target CT, with compound effects on target CT also evidenced. This work demonstrated that the use of BMLP models had considerable ability to improve the resolution and understanding of the multivariate relationships between operational parameters and disinfection outcomes for wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Al(I) molecule, Ph2COAl and its anion

NASA Astrophysics Data System (ADS)

Zhang, Xinxing; Eichhorn, Bryan; Schnöckel, Hansgeorg; Bowen, Kit

2016-08-01

We have formed the Al(I)-containing molecule, benzophenone-aluminum, i.e., Ph2COAl, and studied it by conducting density functional theory calculations on both its neutral and anionic forms and by measuring the photoelectron spectrum of its anion. Our calculations identified two nearly iso-energetic anion isomers, (Ph2COAl)-, the vertical detachment energies (VDE) of which are in excellent agreement with our photoelectron spectrum. Natural population analysis (NPA) of Ph2COAl found the Al moiety to be positively charged by +0.81 e, indicating a strongly ionic bond between Al and Ph2CO, i.e., Ph2CO-Al+.

Ionic liquid-based single-drop microextraction followed by liquid chromatography-ultraviolet spectrophotometry detection to determine typical UV filters in surface water samples.

PubMed

Vidal, Lorena; Chisvert, Alberto; Canals, Antonio; Salvador, Amparo

2010-04-15

A user-friendly and inexpensive ionic liquid-based single-drop microextraction (IL-SDME) procedure has been developed to preconcentrate trace amounts of six typical UV filters extensively used in cosmetic products (i.e., 2-hydroxy-4-methoxybenzophenone, isoamyl 4-methoxycinnamate, 3-(4'-methylbenzylidene)camphor, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-methoxycinnamate) from surface water samples prior to analysis by liquid chromatography-ultraviolet spectrophotometry detection (LC-UV). A two-stage multivariate optimization approach was developed by means of a Plackett-Burman design for screening and selecting the significant variables involved in the SDME procedure, which were later optimized by means of a circumscribed central composite design. The studied variables were drop volume, sample volume, agitation speed, ionic strength, extraction time and ethanol quantity. Owing to particularities, ionic liquid type and pH of the sample were optimized separately. Under optimized experimental conditions (i.e., 10 microL of 1-hexyl-3-methylimidazolium hexafluorophosphate, 20 mL of sample containing 1% (v/v) ethanol and NaCl free adjusted to pH 2, 37 min extraction time and 1300 rpm agitation speed) enrichment factors up to ca. 100-fold were obtained depending on the target analyte. The method gave good levels of repeatability with relative standard deviations varying between 2.8 and 8.8% (n=6). Limits of detection were found in the low microg L(-1) range, varying between 0.06 and 3.0 microg L(-1) depending on the target analyte. Recovery studies from different types of surface water samples collected during the winter period, which were analysed and confirmed free of all target analytes, ranged between 92 and 115%, showing that the matrix had a negligible effect upon extraction. Finally, the proposed method was applied to the analysis of different water samples (taken from two beaches, two swimming pools and a river) collected during the summer period. (c) 2009 Elsevier B.V. All rights reserved.

Evidence for co-operativity in coenzyme binding to tetrameric Sulfolobus solfataricus alcohol dehydrogenase and its structural basis: fluorescence, kinetic and structural studies of the wild-type enzyme and non-co-operative N249Y mutant.

PubMed

Giordano, Antonietta; Febbraio, Ferdinando; Russo, Consiglia; Rossi, Mosè; Raia, Carlo A

2005-06-01

The interaction of coenzyme with thermostable homotetrameric NAD(H)-dependent alcohol dehydrogenase from the thermoacidophilic sulphur-dependent crenarchaeon Sulfolobus solfataricus (SsADH) and its N249Y (Asn-249-->Tyr) mutant was studied using the high fluorescence sensitivity of its tryptophan residues Trp-95 and Trp-117 to the binding of coenzyme moieties. Fluorescence quenching studies performed at 25 degrees C show that SsADH exhibits linearity in the NAD(H) binding [the Hill coefficient (h) approximately 1) at pH 9.8 and at moderate ionic strength, in addition to positive co-operativity (h=2.0-2.4) at pH 7.8 and 6.8, and at pH 9.8 in the presence of salt. Furthermore, NADH binding is positively co-operative below 20 degrees C (h approximately 3) and negatively co-operative at 40-50 degrees C (h approximately 0.7), as determined at moderate ionic strength and pH 9.8. Steady-state kinetic measurements show that SsADH displays standard Michaelis-Menten kinetics between 35 and 45 degrees C, but exhibits positive and negative co-operativity for NADH oxidation below (h=3.3 at 20 degrees C) and above (h=0.7 at 70-80 degrees C) this range of temperatures respectively. However, N249Y SsADH displays non-co-operative behaviour in coenzyme binding under the same experimental conditions used for the wild-type enzyme. In loop 270-275 of the coenzyme domain and segments at the interface of dimer A-B, analyses of the wild-type and mutant SsADH structures identified the structural elements involved in the intersubunit communication and suggested a possible structural basis for co-operativity. This is the first report of co-operativity in a tetrameric ADH and of temperature-induced co-operativity in a thermophilic enzyme.

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

PubMed

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

2015-02-03

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

Influence of pH on the transport of silver nanoparticles in saturated porous media: laboratory experiments and modeling

NASA Astrophysics Data System (ADS)

Flory, Jason; Kanel, Sushil R.; Racz, LeeAnn; Impellitteri, Christopher A.; Silva, Rendahandi G.; Goltz, Mark N.

2013-03-01

Given the ubiquity of silver nanoparticles (AgNPs) and their potential for toxic effects on both humans and the environment, it is important to understand their environmental fate and transport. The purpose of this study is to gain information on the transport properties of commercial AgNP suspensions in a glass bead-packed column under saturated flow conditions at different solution pH levels. Commercial AgNPs were characterized using high-resolution transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, ultraviolet visible spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. Transport data were collected at different pH levels (4, 6.5, 9, and 11) at fixed ionic strength. Capture of AgNPs increased as the pH of the solution increased from 4 to 6.5. Further increase in pH to 9 and 11 decreased the attachment of AgNPs to the glass beads. AgNP concentration versus time breakthrough data were simulated using an advection-dispersion model incorporating both irreversible and reversible attachment. In particular, a reversible attachment model is required to simulate breakthrough curve tailing at near neutral pH, when attachment is most significant. The laboratory and modeling study reveals that for natural groundwaters, AgNP transport in porous media may be retarded due to capture; but ultimately, most of the mass may be slowly released over time.

Development of a polymeric ionic liquid coating for direct-immersion solid-phase microextraction using polyhedral oligomeric silsesquioxane as cross-linker.

PubMed

Chen, Chunyan; Liang, Xiaotong; Wang, Jianping; Zou, Ying; Hu, Huiping; Cai, Qingyun; Yao, Shouzhuo

2014-06-27

A novel solid-phase microextraction (SPME) fiber was developed by chemical binding of a crosslinked polymeric ionic liquid (PIL) on the surface of an anodized Ti wire, and was applied in direct-immersion mode for the extraction of perfluorinated compounds (PFCs) from water samples coupled with high performance liquid chromatography-tandem mass spectrometry analysis. The PIL coatings were synthesized by using 1-vinyl-3-hexylimidazolium hexafluorophosphate as monomer and methylacryloyl-substituted polyhedral oligomeric silsesquioxane (POSS) as cross-linker via free radical reaction. The proposed fiber coating exhibited high mechanical stability due to the chemical bonding between the coating and the Ti wire surface. The integration of POSS reagent enhanced the organic solvent resistance of the coating. The parameters affecting the extraction performance of the fiber coating including extraction time, pH of solution, ionic strength and desorption conditions were optimized. The developed PIL-POSS fiber showed good linearity (R<0.998) between 0.1 and 50ngmL(-1) with method detection limits ranging from 0.005 to 0.08ngmL(-1) depending on the analyte, and with relative standard deviation for single-fiber repeatability and fiber-to-fiber reproducibility less than 8.6% and 9.5%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

A novel polythiophene - ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis.

PubMed

Pelit, Füsun Okçu; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E E; Türkmen, Hayati; Ertaş, F N

2015-02-15

This report comprises the novel usage of polythiophene - ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett-Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box-Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002-0.667ng mL(-1). Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues. Copyright © 2014 Elsevier B.V. All rights reserved.

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

PubMed

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

2008-03-18

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

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

PubMed

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

2017-02-01

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

Highly efficient and selective adsorption of In{sup 3+} on pristine Zn/Al layered double hydroxide (Zn/Al-LDH) from aqueous solutions

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

Barnabas, Mary Jenisha; Parambadath, Surendran; Mathew, Aneesh

2016-01-15

A pristine Zn/Al-layered double hydroxide (Zn/Al-LDH) showed excellent adsorption ability and selectivity towards In{sup 3+} ions from aqueous solutions. The adsorption behaviour as a function of the contact time, solution pH, ionic strength, and amount of adsorbent under ambient conditions revealed a strong dependency on the pH and ionic strength over In{sup 3+} intake. The structure and properties of Zn/Al-LDH and In{sup 3+} adsorbed Zn/Al-LDH (In–Zn/Al-LDH) were examined carefully by X-ray diffraction, Fourier transform infrared spectroscopy, N{sub 2}-sorption/desorption, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent had a sufficient number of active sites that were responsible for the In{sup 3+}more » adsorption and quite stable even after the adsorption process. The selective adsorption of In{sup 3+} on Zn/Al-LDH was also observed even from a mixture containing competing ions, such as Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+}. The adsorption experiments showed that Zn/Al-LDH is a promising material for the pre-concentration and selective removal of In{sup 3+} from large volumes of aqueous solutions. - Highlights: • A pristine Zn/Al-layered double hydroxide showed good selectivity for In{sup 3+} ions. • The material exhibited a maximum In{sup 3+} intake of 205 mg g{sup −1} at pH 6. • The materials showed good affinity of In{sup 3+} over Cu{sup 2+} and Pb{sup 2+} from ion mixtures.« less

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

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

Hassett, J.M.

1988-01-01

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

The copper complexation ability of a synthetic humic-like acid formed by an abiotic humification process and the effect of experimental factors on its copper complexation ability.

PubMed

Yang, Ting; Hodson, Mark E

2018-03-26

Humic acids have an important impact on the distribution, toxicity, and bioavailability of hazardous metals in the environment. In this study, a synthetic humic-like acid (SHLA) was prepared by an abiotic humification process using catechol and glycine as humic precursors and a MnO 2 catalyst. The effect of physico-chemical conditions (ionic strength from 0.01 to 0.5 M NaNO 3 , pH from 4 to 8, temperature from 25 to 45 °C, and humic acid concentration from 5 to 100 mg/L) on the complexation ability of SHLA for Cu 2+ were investigated. A commercial humic acid (CHA, CAS: 1415-93-6) from Sigma-Aldrich was also studied for comparison. The results showed that for pH 4 to 8, the conditional stability constants (log K) of SHLA and CHA were in the range 5.63-8.62 and 4.87-6.23, respectively, and complexation capacities (CC) were 1.34-2.61 and 1.42-2.31 mmol/g, respectively. The Cu complexation ability of SHLA was higher than that of the CHA due to its higher number of acidic functional groups (SHLA 19.19 mmol/g; CHA 3.87 mmol/g), extent of humification and aromaticity (AL/AR: 0.333 (SHLA); 1.554 (CHA)), and O-alkyl functional groups (SHLA 15.56%; CHA 3.45%). The log K and complexation efficiency (fraction of metal bound to SHLA) of SHLA were higher at higher pH, lower ionic strength, higher temperature, and higher SHLA concentration. Overall, SHLA was a good and promising complexation agent for copper in both soil washing of copper contaminated soil and the treatment of copper-containing wastewater.

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

EPA Science Inventory

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

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

PubMed

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

2014-07-15

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

Sorption of Eu(III) on attapulgite studied by batch, XPS, and EXAFS techniques.

PubMed

Fan, Q H; Tan, X L; Li, J X; Wang, X K; Wu, W S; Montavon, G

2009-08-01

The effects of pH, ionic strength, and temperature on sorption of Eu(III) on attapulgite were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The results indicated that the sorption of Eu(III) on attapulgite was strongly dependent on pH and ionic strength, and independent of temperature. In the presence of FA/HA, Eu(III) sorption was enhanced at pH < 4, decreased at pH range of 4-6, and then increased again at pH > 7. The X-ray photoelectron spectroscopy (XPS) analysis suggested that the sorption of Eu(III) might be expressed as is identical to X3Eu0, is identical to S(w)OHEu3+, and is identical to SOEu-OOC-/HA in the ternary Eu/HN/attapulgite system. The extended X-ray absorption fine structure (EXAFS) analysis of Eu-HA complexes indicated that the distances of d(Eu-O) decreased from 2.415 to 2.360 angstroms with increasing pH from 1.76 to 9.50, whereas the coordination number (N) decreased from approximately 9.94 to approximately 8.56. Different complexation species were also found for the different addition sequences of HA and Eu(III) to attapulgite suspension. The results are important to understand the influence of humic substances on Eu(III) behavior in the natural environment.

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

PubMed

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

2007-04-01

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

Removal of trace metal contaminants from potable water by electrocoagulation

PubMed Central

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

2016-01-01

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

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)

Effect of Detergent on Electrical Properties of Squid Axon Membrane

PubMed Central

Kishimoto, Uichiro; Adelman, William J.

1964-01-01

The effects of detergents on squid giant axon action and resting potentials as well as membrane conductances in the voltage clamp have been studied. Anionic detergents (sodium lauryl sulfate, 0.1 to 1.0 mM; dimethyl benzene sulfonate, 1 to 20 mM, pH 7.6) cause a temporary increase and a later decrease of action potential height and the value of the resting potential. Cationic detergent (cetyl trimethyl ammonium chloride, 6 x 10-5 M or more, pH 7.6) generally brings about immediate and irreversible decreases in the action and resting potentials. Non-ionic detergent (tween 80, 0.1 M, pH 7.6) causes a slight reversible reduction of action potential height without affecting the value of the resting potential. Both anionic and cationic detergents generally decrease the sodium and potassium conductances irreversibly. The effect of non-ionic detergent is to decrease the sodium conductance reversibly, leaving the potassium conductance almost unchanged. PMID:14158665

Effect of pH on ionic liquid mediated synthesis of gold nanoparticle using elaiseguineensis (palm oil) kernel extract

NASA Astrophysics Data System (ADS)

Irfan, Muhammad; Ahmad, Tausif; Moniruzzaman, Muhammad; Abdullah, Bawadi

2017-05-01

This study was conducted for microwave assisted synthesis of stable gold nanoparticles (AuNPs) by reduction of chloroauric acid with Elaeis Guineensis (palm oil) kernel (POK) extract which was prepared in aqueous solution of ionic liquid, [EMIM][OAc], 1-Ethyl-3-methylimidazolium acetate. Effect of initial pH of reaction mixture (3.5 - 8.5) was observed on SPR absorbance, maximum wavelength (λmax ) and size distribution of AuNPs. Change of pH of reaction mixture from acidic to basic region resulted in appearance of strong SPR absorption peaks and blue shifting of λmax from 533 nm to 522 nm. TEM analysis revealed the formation of predominantly spherical AuNPs with mean diameter of 8.51 nm. Presence of reducing moieties such as flavonoids, phenolic and carboxylic groups in POK extract was confirmed by FTIR analysis. Colloidal solution of AuNPs was remained stable at room temperature and insignificant difference in zeta value was recorded within experimental tenure of 4 months.

Liquid Crystalline Properties of Amyloid Protein Fibers in Water

NASA Astrophysics Data System (ADS)

Mezzenga, Raffaele; Jung, Jin-Mi

2010-03-01

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

Nanopore Analysis of the 5-Guanidinohydantoin to Iminoallantoin Isomerization in Duplex DNA.

PubMed

Zeng, Tao; Fleming, Aaron M; Ding, Yun; Ren, Hang; White, Henry S; Burrows, Cynthia J

2018-04-06

In DNA, guanine oxidation yields diastereomers of 5-guanidinohydantoin (Gh) as one of the major products. In nucleosides and single-stranded DNA, Gh is in a pH-dependent equilibrium with its constitutional isomer iminoallantoin (Ia). Herein, the isomerization reaction between Gh and Ia was monitored in duplex DNA using a protein nanopore by measuring the ionic current when duplex DNA interacts with the pore under an electrophoretic force. Monitoring current levels in this single-molecule method proved to be superior for analysis of population distributions in an equilibrating mixture of four isomers in duplex DNA as a function of pH. The results identified Gh as a major isomer observed when base paired with A, C, or G at pH 6.4-8.4, and Ia was a minor isomer of the reaction mixture that was only observed when the pH was >7.4 in the duplex DNA context. The present results suggest that Gh will be the dominant isomer in duplex DNA under physiological conditions regardless of the base-pairing partner in the duplex.

Effects of pH on nano-bubble stability and transport in saturated porous media

NASA Astrophysics Data System (ADS)

Hamamoto, Shoichiro; Takemura, Takato; Suzuki, Kenichiro; Nishimura, Taku

2018-01-01

An understanding of nano-scale bubble (NB) transport in porous media is important for potential application of NBs in soil/groundwater remediation. It is expected that the solution chemistry of NB water highly influences the surface characteristics of NBs and porous media and the interaction between them, thus affecting the stability and transport characteristics of NB. In this study, in addition to stability experiments, one-dimensional column transport experiments using glass beads were conducted to investigate the effects of pH on the NB transport behavior. The results showed that the NBs were more stable under higher pH. Column transport experiments revealed that entrapment of NBs, especially larger ones, was enhanced in lower-pH water, likely suggesting pH-dependent NB attachment and physical straining, both of which are also probably influenced by bubble size. Although relatively smaller NBs were released after switching the eluting fluid to one with lower ionic strength, most of the NBs in lower-pH water were still retained in the porous media even altering the chemical condition.

Facile synthesis of magnetic Fe3O4/graphene composites for enhanced U(VI) sorption

NASA Astrophysics Data System (ADS)

Zhao, Donglin; Zhu, Hongyu; Wu, Changnian; Feng, Shaojie; Alsaedi, Ahmed; Hayat, Tasawar; Chen, Changlun

2018-06-01

A novel magnetic Fe3O4/graphene composite (FGC) was fabricated by a facile one-step reaction route and shown to be effective for sorbing U(VI) from aqueous solution. The structure, properties and application of the prepared FGC composite were well evaluated. The high saturation magnetization (45.6 emu/g) made FGC easier to be separated from the media within several seconds under an external magnetic. Effects of different ambient conditions (i.e., pH and ionic strength, contact time, temperatures) on sorption behaviors of U(VI) on FGC were carried out by batch experiments. According to the calculation of Langmuir model, the maximum sorption capacity of U(VI) on the FGC at pH 5.5 and 298 K was 176.47 mg/g. The sorption was correlated with the effects of pH, contact time, and temperature. X-ray photoelectron spectroscopy analysis revealed that U(VI) was sorbed on FGC via oxygen-containing functional groups. This work demonstrated that FGC could be recycled and used as an effective recyclable sorbent for sorption of U(VI).

Effects of pH on nano-bubble stability and transport in saturated porous media.

PubMed

Hamamoto, Shoichiro; Takemura, Takato; Suzuki, Kenichiro; Nishimura, Taku

2018-01-01

An understanding of nano-scale bubble (NB) transport in porous media is important for potential application of NBs in soil/groundwater remediation. It is expected that the solution chemistry of NB water highly influences the surface characteristics of NBs and porous media and the interaction between them, thus affecting the stability and transport characteristics of NB. In this study, in addition to stability experiments, one-dimensional column transport experiments using glass beads were conducted to investigate the effects of pH on the NB transport behavior. The results showed that the NBs were more stable under higher pH. Column transport experiments revealed that entrapment of NBs, especially larger ones, was enhanced in lower-pH water, likely suggesting pH-dependent NB attachment and physical straining, both of which are also probably influenced by bubble size. Although relatively smaller NBs were released after switching the eluting fluid to one with lower ionic strength, most of the NBs in lower-pH water were still retained in the porous media even altering the chemical condition. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparison of microelectrode, DMO, and methylamine methods for measuring intracellular pH.

PubMed

Boron, W F; Roos, A

1976-09-01

The intracellular pH (pHi) of giant barnacle muscle fibers was measured with glass microelectrodes and also calculated from the distribution of 5,5-dimethyl-2,4-oxazolidinedione (DMO) and methylamine (MA). Simultaneously applying any two of these methods to muscle fibers of the same barnacle, we found the pH measured with an intracellular electrode (pH-Elec) to be about 0.06 higher than the DMO-derived pH (pH-DMO), and pH-DMO to be about 0.10 higher than the MA-derived pH (p-ma). in studies on the pHi of squid giant axons, we found that pH-Elec (7.35) and pH-DMO (7.36) were not significantly different. In the barnacle experiments, DMO required about 30 min to reach a steady-state distribution, while MA required more than 5 h. The deviations of pH-DMO and pH-MA from pH-Elec for the barnacle can be explained by a) an error in the assumed intracellular pKa' of DMO or MA, b) membrane permeability to the ionic form of DMO or MA, or c) intracellular compartmentalization. Included is a detailed study of the apparent dissociation constant of DMO as affected by temperature, and ionic strength and composition.

Hydroxyl/bile acid exchange. A new mechanism for the uphill transport of cholate by basolateral liver plasma membrane vesicles.

PubMed

Blitzer, B L; Terzakis, C; Scott, K A

1986-09-15

In order to characterize the driving forces for the concentrative uptake of unconjugated bile acids by the hepatocyte, the effects of pH gradients on the uptake of [3H]cholate by rat basolateral liver plasma membrane vesicles were studied. In the presence of an outwardly directed hydroxyl gradient (pH 6.0 outside and pH 7.5 inside the vesicle), cholate uptake was markedly stimulated and the bile acid was transiently accumulated at a concentration 1.5- to 2-fold higher than at equilibrium ("overshoot"). In the absence of a pH gradient (pH 6.0 or 7.5 both inside and outside the vesicle), uptake was relatively slower and no overshoot was seen. Reductions in the magnitude of the transmembrane pH gradient were associated with slower initial uptake rates and smaller overshoots. Cholate uptake under pH gradient conditions was inhibited by furosemide and bumetanide but not by 4, 4'-diisothiocyano-2,2'-disulfonic stilbene (SITS), 4-acetamido-4'-isothiocyanostilbene-2,2'-disulfonic acid (DIDS), or probenecid. In the absence of a pH gradient, an inside-positive valinomycin-induced K+ diffusion potential caused a slight increase in cholate uptake which was insensitive to furosemide. Moreover, in the presence of an outwardly directed hydroxyl gradient, uphill cholate transport was observed even under voltage clamped conditions. These findings suggest that pH gradient-driven cholate uptake was not due to associated electrical potentials. Despite an identical pKa to that of cholate, an outwardly directed hydroxyl gradient did not drive uphill transport of three other unconjugated bile acids (deoxycholate, chenodeoxycholate, ursodeoxycholate), suggesting that a non-ionic diffusion mechanism cannot account for uphill cholate transport. In canalicular vesicles, although cholate uptake was relatively faster in the presence of a pH gradient than in the absence of a gradient, peak uptake was only slightly above that found at equilibrium under voltage clamped conditions. These findings suggest a specific carrier on the basolateral membrane of the hepatocyte which mediates hydroxyl/cholate exchange (or H+-cholate co-transport). A model for uphill cholate transport is discussed in which the Na+ pump would ultimately drive Na+/H+ exchange which in turn would drive hydroxyl/cholate exchange.

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.

Structural modifications of the salivary conditioning film upon exposure to sodium bicarbonate: implications for oral lubrication and mouthfeel.

PubMed

Ash, A; Wilde, P J; Bradshaw, D J; King, S P; Pratten, J R

2016-03-14

The salivary conditioning film (SCF) that forms on all surfaces in the mouth plays a key role in lubricating the oral cavity. As this film acts as an interface between tongue, enamel and oral mucosa, it is likely that any perturbations to its structure could potentially lead to a change in mouthfeel perception. This is often experienced after exposure to oral hygiene products. For example, consumers that use dentifrice that contain a high concentration of sodium bicarbonate (SB) often report a clean mouth feel after use; an attribute that is clearly desirable for oral hygiene products. However, the mechanisms by which SB interacts with the SCF to alter lubrication in the mouth is unknown. Therefore, saliva and the SCF was exposed to high ionic strength and alkaline solutions to elucidate whether the interactions observed were a direct result of SB, its high alkalinity or its ionic strength. Characteristics including bulk viscosity of saliva and the viscoelasticity of the interfacial salivary films that form at both the air/saliva and hydroxyapatite/saliva interfaces were tested. It was hypothesised that SB interacts with the SCF in two ways. Firstly, the ionic strength of SB shields electrostatic charges of salivary proteins, thus preventing protein crosslinking within the film and secondly; the alkaline pH (≈8.3) of SB reduces the gel-like structure of mucins present in the pellicle by disrupting disulphide bridging of the mucins via the ionization of their cysteine's thiol group, which has an isoelectric point of ≈8.3.

UV-vis, IR and 1H NMR spectroscopic studies and characterization of ionic-pair crystal violet-oxytetracycline

NASA Astrophysics Data System (ADS)

Orellana, Sandra; Soto, César; Toral, M. Inés

2010-01-01

The present study shows the formation and characterization of the ionic-pair between the antibiotic oxytetracycline and the dye crystal violet in ammonia solution pH 9.0 ± 0.2 extracted into chloroform. The characterization was demonstrated using UV-vis spectrophotometry, 1H NMR, measurement of relaxation times T1 and IR spectroscopy, using a comparison between the signals of individual pure compounds with the signals with the mixture CV-OTC in different alkaline media. The formation of ionic-pair was also corroborated by new signals and chemical shifts. (2D) NMR spectroscopy experiments show that the interaction is electrostatic.

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.

[Influencing Factors of Assimilable Organic Carbon (AOC) Formation in Drinking Water During Ozonation Process].

PubMed

Dong, Bing-zhi; Zhang, Jia-li; He, Chang

2016-05-15

The influences of ozone dosage, pH and ionic strength on the formation of Assimilable Organic Carbon (AOC) during ozonation were investigated. The result demonstrated that within the range of 1-5 mg · L⁻¹ O₃, the formation of AOC increased with increasing ozone dosage, but higher ozone dosage (9 mg · L⁻¹) resulted in reduction of AOC formation. AOC formation increased with higher pH but decreased with increasing ionic strength. The result also showed that AOC formation with hydrophobic fraction (HPO) was the most, followed by transphilic fraction (TPI), and charged hydrophilic fraction (CHPI), while neutral hydrophilic fraction (NHPI) was the least. It was found that AOC formation related closely with SUVA of small molecular weight organics, and the lower SUVA produced more AOC.

Disintegration-controllable stimuli-responsive polyelectrolyte multilayer microcapsules via covalent layer-by-layer assembly.

PubMed

Mu, Bin; Lu, Chunyin; Liu, Peng

2011-02-01

The disintegration-controllable stimuli-responsive polyelectrolyte multilayer microcapsules have been fabricated via the covalent layer-by-layer assembly between the amino groups of chitosan (CS) and the aldehyde groups of the oxidized sodium alginate (OSA) onto the sacrificial templates (polystyrene sulfonate, PSS) which was removed by dialysis subsequently. The covalent crosslinking bonds of the multilayer microcapsules were confirmed by FTIR analysis. The TEM analysis showed that the diameter of the multilayer microcapsules was <200nm. The diameter of the multilayer microcapsules decreased with the increasing of the pH values or the ionic strength. The pH and ionic strength dual-responsive multilayer microcapsules were stable in acidic and neutral media while they could disintegrate only at strong basic media. Copyright © 2010 Elsevier B.V. All rights reserved.

Effects of acid rain on plant microbial associations in California. Research report (final)

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

Harris, D.; Paul, E.A.

1984-04-13

The effects of simulated acid rain of pH 5.6 to 3.0, with ionic composition similar to that found in California, on Trifolium repens, Lupinus densiflorus and L. benthamii grown in two soils were tested. The interactions of treatment intensity, soil type, phosphorus uptake and mycorrhizal influences on growth, carbon fixation and allocation and nitrogen fixation were determined. Acidic treatments generally decreased plant growth, nodulation and nitrogenase activity. The exposure of plants to a large number of simulated rainfall conditions of shorter duration did not result in the negative growth effects. Plants adequately supplied with P, either as fertilizer or bymore » mycorrhizal fungi, were much more resistant to conditions caused by acidic precipitation and in some cases growth increases were found.« less

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

EPA Science Inventory

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

Separation of both fibrous and globular proteins on the basis of molecular weight using high-performance size exclusion chromatography.

PubMed

Barden, J A

1983-11-01

A high-performance size exclusion liquid chromatographic system has been used to separate proteins with different shapes solely on the basis of their molecular weights. After the effects of ionic and hydrophobic interactions with the stationary phase have been overcome, protein elution is normally governed by their effective size in solution. Conditions are described under which proteins, with isoelectric points within the normal operating pH range of the columns, are eluted independent of their Stokes' radii. Even fibrous proteins with axial ratios of 50 elute according to their known molecular weights over the range 2000-2,000,000.

Development of ochratoxin a in cereal by chemiluminescence enzyme immunoassay

NASA Astrophysics Data System (ADS)

Li, Min; Liu, Renrong; Zhu, Lixin; Chen, Zhenzhen

2017-11-01

A rapid, simple and sensitive chemiluminescence enzyme immunoassay method (CLEIA) was established to detect ochratoxin A (OTA) in cereal. Optimal conditions including antibody dilution ratio and enzyme conjugate, ionic strength, pH value and organic solvent. Established indirect competition inhibition curve to determine the linear working range, detection limit and recovery rate. Results: The 50% inhibitory concentration and the detection limit of the CLEIA were78.8pg/mL and 14.86 pg/mL, respectively, with a linear range of 0.015-0.4ng/mL. At 1∼4μpg/kg fortified levels in wheat, mean recoveries ranged from 67.47% to100.35%.

Effects of Gold Salt Speciation and Structure of Human and Bovine Serum Albumins on the Synthesis and Stability of Gold Nanostructures

PubMed Central

Miranda, Érica G. A.; Tofanello, Aryane; Brito, Adrianne M. M.; Lopes, David M.; Albuquerque, Lindomar J. C.; de Castro, Carlos E.; Costa, Fanny N.; Giacomelli, Fernando C.; Ferreira, Fabio F.; Araújo-Chaves, Juliana C.; Nantes, Iseli L.

2016-01-01

The present study aimed to investigate the influence of albumin structure and gold speciation on the synthesis of gold nanoparticles (GNPs). The strategy of synthesis was the addition of HAuCl4 solutions at different pH values (3–12) to solutions of human and bovine serum albumins (HSA and BSA) at the same corresponding pH values. Different pH values influence the GNP synthesis due to gold speciation. Besides the inherent effect of pH on the native structure of albumins, the use N-ethylmaleimide (NEM)-treated and heat-denaturated forms of HSA and BSA provided additional insights about the influence of protein structure, net charge, and thiol group approachability on the GNP synthesis. NEM treatment, heating, and the extreme values of pH promoted loss of the native albumin structure. The formation of GNPs indicated by the appearance of surface plasmon resonance (SPR) bands became detectable from 15 days of the synthesis processes that were carried out with native, NEM-treated and heat-denaturated forms of HSA and BSA, exclusively at pH 6 and 7. After 2 months of incubation, SPR band was also detected for all synthesis carried out at pH 8.0. The mean values of the hydrodynamic radius (RH) were 24 and 34 nm for GNPs synthesized with native HSA and BSA, respectively. X-ray diffraction (XRD) revealed crystallites of 13 nm. RH, XRD, and zeta potential values were consistent with GNP capping by the albumins. However, the GNPs produced with NEM-treated and heat-denaturated albumins exhibited loss of protein capping by lowering the ionic strength. This result suggests a significant contribution of non-electrostatic interactions of albumins with the GNP surface, in these conditions. The denaturation of proteins exposes hydrophobic groups to the solvent, and these groups could interact with the gold surface. In these conditions, the thiol blockage or oxidation, the latter probably favored upon heating, impaired the formation of a stable capping by thiol coordination with the gold surface. Therefore, the cysteine side chain of albumins is important for the colloidal stabilization of GNPs rather than as the reducing agent for the synthesis. Despite the presence of more reactive gold species at more acidic pH values, i.e., below 6.0, in these conditions the loss of native albumin structure impaired GNP synthesis. Alkaline pH values (9–12) combined the unfavorable conditions of denaturated protein structure with less reactive gold species. Therefore, an optimal condition for the synthesis of GNPs using serum albumins involves more reactive gold salt species combined with a reducing and negatively charged form of the protein, all favored at pH 6–7. PMID:27066476

Soil pH effects on the interactions between dissolved zinc, non-nano- and nano-ZnO with soil bacterial communities.

PubMed

Read, Daniel S; Matzke, Marianne; Gweon, Hyun S; Newbold, Lindsay K; Heggelund, Laura; Ortiz, Maria Diez; Lahive, Elma; Spurgeon, David; Svendsen, Claus

2016-03-01

Zinc oxide nanoparticles (ZnO NPs) are used in an array of products and processes, ranging from personal care products to antifouling paints, textiles, food additives, antibacterial agents and environmental remediation processes. Soils are an environment likely to be exposed to manmade nanoparticles due to the practice of applying sewage sludge as a fertiliser or as an organic soil improver. However, understanding on the interactions between soil properties, nanoparticles and the organisms that live within soil is lacking, especially with regards to soil bacterial communities. We studied the effects of nanoparticulate, non-nanoparticulate and ionic zinc (in the form of zinc chloride) on the composition of bacterial communities in soil with a modified pH range (from pH 4.5 to pH 7.2). We observed strong pH-dependent effects on the interaction between bacterial communities and all forms of zinc, with the largest changes in bacterial community composition occurring in soils with low and medium pH levels (pH 4.8 and 5.9). The high pH soil (pH 7.2) was less susceptible to the effects of zinc exposure. At the highest doses of zinc (2500 mg/kg dw soil), both nano and non-nano particulate zinc applications elicited a similar response in the soil bacterial community, and this differed significantly to the ionic zinc salt treatment. The results highlight the importance of considering soil pH in nanotoxicology studies, although further work is needed to determine the exact mechanisms controlling the toxicity and fate and interactions of nanoparticles with soil microbial communities.

Deposition mechanisms of TiO2 nanoparticles in a parallel plate system.

PubMed

Chowdhury, Indranil; Walker, Sharon L

2012-03-01

In this study, a microscope-based technique was utilized to understand the fundamental mechanisms involved in deposition of TiO(2) nanoparticles (TNPs). Transport and deposition studies were conducted in a parallel plate (PP) flow chamber with TNP labeled with fluorescein isothiocyanate (FITC) for visualization. Attachment of FITC-labeled TNPs on surfaces is a function of a combination of parameters, including ionic strength (IS), pH and flowrate. Significantly higher deposition rates were observed at pH 5 versus pH 7. This is attributed to the conditions being chemically favorable for deposition at pH 5 as compared to pH 7, as predicted by DLVO theory. Additionally, deposition rates at pH 5 were reduced with IS below 10 mM due to the decrease in range of electrostatic attractive forces. Above 10 mM, aggregate size increased, resulting in higher deposition rates. At pH 7, no deposition was observed below 10 mM and above this concentration, deposition increased with IS. The impact of flowrate was also observed, with decreasing flowrate leading to greater deposition due to the reduction in drag force acting on the aggregate (regardless of pH). Comparisons between experimental and theoretical approximations indicate that non-DLVO type forces also play a significant role. This combination of observations suggest that the deposition of these model nanoparticles on glass surfaces was controlled by a combination of DLVO and non-DLVO-type forces, shear rate, aggregation state, and gravitational force acting on TNPs. Copyright © 2011 Elsevier Inc. All rights reserved.

Performance of Carbon/Polytetrafluoroethylene (PTFE) Air Cathodes from pH 0 to 14 for Li-Air Batteries

DTIC Science & Technology

2007-12-01

aqueous and aqueous electrolytes are kept separate by a non-electronically conducting ceramic membrane impervious to water, but with a high ionic...thought of as being solvated by the ceramic membrane as it passes from non-aqueous to aqueous electrolyte. The half-cell reaction at the lithium...overall charge in the reaction, positive lithium ions flow through an ionically conducting ceramic membrane from the non-aqueous anode compartment to

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

PubMed

Sheikhian, Leila; Bina, Sedigheh

2016-01-15

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

High-Speed Lateral Flow Strategy for a Fast Biosensing with an Improved Selectivity and Binding Affinity.

PubMed

Cho, Dong Guk; Yoo, Haneul; Lee, Haein; Choi, Yeol Kyo; Lee, Minju; Ahn, Dong June; Hong, Seunghun

2018-05-10

We report a high-speed lateral flow strategy for a fast biosensing with an improved selectivity and binding affinity even under harsh conditions. In this strategy, biosensors were fixed at a location away from the center of a round shape disk, and the disk was rotated to create the lateral flow of a target solution on the biosensors during the sensing measurements. Experimental results using the strategy showed high reaction speeds, high binding affinity, and low nonspecific adsorptions of target molecules to biosensors. Furthermore, binding affinity between target molecules and sensing molecules was enhanced even in harsh conditions such as low pH and low ionic strength conditions. These results show that the strategy can improve the performance of conventional biosensors by generating high-speed lateral flows on a biosensor surface. Therefore, our strategy can be utilized as a simple but powerful tool for versatile bio and medical applications.

Analysis of polycyclic aromatic hydrocarbons in water and beverages using membrane-assisted solvent extraction in combination with large volume injection-gas chromatography-mass spectrometric detection.

PubMed

Rodil, Rosario; Schellin, Manuela; Popp, Peter

2007-09-07

Membrane-assisted solvent extraction (MASE) in combination with large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) was applied for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. The MASE conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of extraction conditions (shaking speed, extraction temperature and time), extraction solvent and composition (ionic strength, sample pH and presence of organic solvent). Parameters like linearity and reproducibility of the procedure were determined. The extraction efficiency was above 65% for all the analytes and the relative standard deviation (RSD) for five consecutive extractions ranged from 6 to 18%. At optimized conditions detection limits at the ng/L level were achieved. The effectiveness of the method was tested by analyzing real samples, such as river water, apple juice, red wine and milk.

Magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction of selenium for speciation in foods and beverages.

PubMed

Wang, Xiaojun; Wu, Long; Cao, Jiaqi; Hong, Xincheng; Ye, Rui; Chen, Weiji; Yuan, Ting

2016-07-01

A novel, simple and rapid method based on magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction (MEA-IL-DLLME) followed by graphite furnace atomic absorption spectrometry (GFAAS) determination was established for the speciation of selenium in various food and beverage samples. In the procedure, a special magnetic effervescent tablet containing CO2 sources (sodium carbonate and sodium dihydrogenphosphate), ionic liquids and Fe3O4 magnetic nanoparticles (MNPs) was used to combine extractant dispersion and magnetic recovery procedures into a single step. The parameters influencing the microextraction efficiency, such as pH of the sample solution, volume of ionic liquid, amount of MNPs, concentration of the chelating agent, salt effect and matrix effect were investigated and optimised. Under the optimised conditions, the limits of detection (LODs) for Se(IV) were 0.021 μg l(-)(1) and the linear dynamic range was 0.05-5.0 μg l(-)(1). The relative standard deviation for seven replicate measurements of 1.0 μg l(-)(1) of Se(IV) was 2.9%. The accuracy of the developed method was evaluated by analysis of the standard reference materials (GBW10016 tea, GBW10017 milk powder, GBW10043 Liaoning rice, GBW10046 Henan wheat, GBW10048 celery). The proposed method was successfully applied to food and beverage samples including black tea, milk powder, mushroom, soybean, bamboo shoots, energy drink, bottled water, carbonated drink and mineral water for the speciation of Se(IV) and Se(VI) with satisfactory relative recoveries (92.0-108.1%).

Microwave-assisted ionic liquid homogeneous liquid-liquid microextraction coupled with high performance liquid chromatography for the determination of anthraquinones in Rheum palmatum L.

PubMed

Wang, Zhibing; Hu, Jianxue; Du, Hongxia; He, Shuang; Li, Qing; Zhang, Hanqi

2016-06-05

The microwave-assisted ionic liquid homogeneous liquid-liquid microextraction (MA-IL-HLLME) coupled with high performance liquid chromatography with diode array detection (HPLC-DAD) was developed for the determination of anthraquinones, including aloe-emodin, emodin, chrysophanol and physcion in root of Rheum palmatum L. Several experimental parameters influencing the extraction efficiency, including amount of sample, type and volume of ionic liquid, volume and pH value of extraction medium, microwave power and extraction time, concentration of NH4PF6 as well as centrifugal condition were optimized. When 140μL of ionic liquid ([C8MIM][BF4]) was used as an extraction solvent, target analytes can be extracted from sample matrix in one minute with the help of microwave irradiation. The MA-IL-HLLME is simple and quick. The calibration curves exhibited good linear relationship (r>0.9984). The limits of detection and quantification were in the range of 0.015-0.026 and 0.051-0.088μgmL(-1), respectively. The spiked recovery for each analyte was in the range of 81.13-93.07% with relative standard deviations lower than 6.89%. The present method is free of volatile organic solvents, and represents lower expenditures of sample, extraction time and solvent, compared with ultrasonic and heat reflux extraction. The results indicated that the present method can be successfully applied to the determination of anthraquinones in medicinal plant. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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

2004-12-01

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

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

NASA Astrophysics Data System (ADS)

Leung, Cheuk Yui Curtis

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

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

Tarasevich, Barbara J.; Philo, John S.; Maluf, Nasib Karl

Amelogenin proteins are critical to the formation of enamel in teeth and may have roles in promoting nucleation, controlling growth, and regulating microstructures of the intricately woven hydroxyapatite (HAP). Leucine-rich amelogenin protein (LRAP) is a 59-residue splice variant of amelogenin and contains the N- and C-terminal charged regions of the full-length protein thought to control crystal growth. Although the quaternary structure of full-length amelogenin in solution has been well studied and can consist of self-assemblies of monomers called nanospheres, the quaternary structure of LRAP is not as well studied. Here, analytical ultracentrifugation sedimentation velocity (SV) and small angle neutron scatteringmore » (SANS) were used to study the tertiary and quaternary structure of LRAP over a range of pH values, ionic strengths, and concentrations. SV has advantages over other techniques in accurately quantifying protein speciation in polydisperse solutions. We found that the monomer was the dominant species of phosphorylated LRAP (LRAP(+P)) over a range of solution conditions (pH 2.7 to 4.1, pH 4.5 to 8, 50 mmol/L( mM) to 200 mM NaCl, 0.065 to 2 mg/mL). The monomer was also the dominant species for unphosphorylated LRAP (LRAP(-P)) at pH 7.4 and LRAP(+P) in the presence of 2.5 mM calcium at pH 7.4. LRAP aggregated in a narrow pH range near the isoelectric point (pH 4.1). We conclude that LRAP does not form nanospheres under physiological solution conditions. Both SV and SANS showed that the LRAP monomer has a radius of ~2.0 nm and adopts an extended structure which solution NMR studies show is intrinsically disordered. This work provides new insights into the tertiary and quaternary structure of LRAP and further evidence that the monomeric species is an important functional form of amelogenins« less

The leucine-rich amelogenin protein (LRAP) is primarily monomeric and unstructured in physiological solution

DOE PAGES

Tarasevich, Barbara J.; Philo, John S.; Maluf, Nasib Karl; ...

2014-10-25

Amelogenin proteins are critical to the formation of enamel in teeth and may have roles in promoting nucleation, controlling growth, and regulating microstructures of the intricately woven hydroxyapatite (HAP). Leucine-rich amelogenin protein (LRAP) is a 59-residue splice variant of amelogenin and contains the N- and C-terminal charged regions of the full-length protein thought to control crystal growth. Although the quaternary structure of full-length amelogenin in solution has been well studied and can consist of self-assemblies of monomers called nanospheres, the quaternary structure of LRAP is not as well studied. Here, analytical ultracentrifugation sedimentation velocity (SV) and small angle neutron scatteringmore » (SANS) were used to study the tertiary and quaternary structure of LRAP over a range of pH values, ionic strengths, and concentrations. SV has advantages over other techniques in accurately quantifying protein speciation in polydisperse solutions. We found that the monomer was the dominant species of phosphorylated LRAP (LRAP(+P)) over a range of solution conditions (pH 2.7 to 4.1, pH 4.5 to 8, 50 mmol/L( mM) to 200 mM NaCl, 0.065 to 2 mg/mL). The monomer was also the dominant species for unphosphorylated LRAP (LRAP(-P)) at pH 7.4 and LRAP(+P) in the presence of 2.5 mM calcium at pH 7.4. LRAP aggregated in a narrow pH range near the isoelectric point (pH 4.1). We conclude that LRAP does not form nanospheres under physiological solution conditions. Both SV and SANS showed that the LRAP monomer has a radius of ~2.0 nm and adopts an extended structure which solution NMR studies show is intrinsically disordered. This work provides new insights into the tertiary and quaternary structure of LRAP and further evidence that the monomeric species is an important functional form of amelogenins« less

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

NASA Astrophysics Data System (ADS)

Christl, Iso; Kretzschmar, Ruben

2001-10-01

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

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

PubMed

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

2007-09-19

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

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

PubMed Central

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

2010-01-01

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

Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography.

PubMed

Yu, Honglian; Merib, Josias; Anderson, Jared L

2016-03-18

Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

An etched stainless steel wire/ionic liquid-solid phase microextraction technique for the determination of alkylphenols in river water.

PubMed

Cui, Meiyu; Qiu, Jinxue; Li, Zhenghua; He, Miao; Jin, Mingshi; Kim, Jiman; Quinto, Maurizio; Li, Donghao

2015-01-01

In this study, a stainless steel wire/ionic liquid-solid phase microextraction technique was developed for the direct extraction of APs from water samples. Some parameters were optimised, such as selection of the substrate and ILs, extraction time, extraction temperature, stirring rate and sample pH, etc. The experimental data demonstrated that the etched stainless steel wire was a suitable substrate for IL-coated SPME. The coating was prepared by directly depositing the ILs onto the surface of the etched stainless steel wire, which exhibited a porous structure and a high surface area. The [C8MIM][PF6] IL exhibited maximum efficiency with an extraction time of 30 min, and the aqueous sample was maintained at 40 °C and adjusted to pH 2 under stirring conditions. The enrichment factor of the IL coating for the four APs ranged from 1382 to 4779, the detection limits (LOD, S/N=3) of the four APs ranged from 0.01 to 0.04 ng mL(-1) and the RSD values for purified water spiked with APs ranged from 4.0 to 11.8% (n=3). The calibration graphs were linear in the concentration range from 0.5 to 200 ng mL(-1) (R(2)>0.9569). The optimised method was successfully applied for the analysis of real water samples, and the method was suitable for the extraction of APs from water samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Sorption and transport of acetaminophen, 17alpha-ethynyl estradiol, nalidixic acid with low organic content aquifer sand.

PubMed

Lorphensri, Oranuj; Sabatini, David A; Kibbey, Tohren C G; Osathaphan, Khemarath; Saiwan, Chintana

2007-05-01

The sorption and transport of three pharmaceutical compounds (acetaminophen, an analgesic; nalidixic acid, an antibiotic; and 17alpha-ethynyl estradiol, a synthetic hormone) were examined by batch sorption experiments and solute displacement in columns of silica, alumina, and low organic carbon aquifer sand at neutral pH. Silica and alumina were used to represent negatively-charged and positively-charged fractions of subsurface media. Column transport experiments were also conducted at pH values of 4.3, 6.2, and 8.2 for the ionizable nalidixic acid. The computer program UFBTC was used to fit the breakthrough data under equilibrium and nonequilibrium conditions with linear/nonlinear sorption. Good agreement was observed between the retardation factors derived from column model studies and estimated from equilibrium batch sorption studies. The sorption and transport of nalidixic acid was observed to be highly pH dependent, especially when the pH was near the pK(a) of nalidixic acid (5.95). Thus, near a compound's pK(a) it is especially important that the batch studies be performed at the same pH as the column experiment. While for ionic pharmaceuticals, ion exchange to oppositely-charged surfaces, appears to be the dominant adsorption mechanism, for neutral pharmaceuticals (i.e., acetaminophen, 17alpha-ethynyl estradiol) the sorption correlated well with the K(ow) of the pharmaceuticals, suggesting hydrophobically motivated sorption as the dominant mechanism.

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

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

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

2012-01-01

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

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

PubMed

Sheng, Guodong; Dong, Huaping; Li, Yimin

2012-11-01

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

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.

Corrosion inhibition performance of imidazolium ionic liquids and their influence on surface ferrous carbonate layer formation

NASA Astrophysics Data System (ADS)

Yang, Dongrui

Corrosion inhibitors as effective anti-corrosion applications were widely studied and drawn much attention in both academe and industrial area. In this work, a systematic work, including inhibitors selection, anti-corrosion property and characterization, influence on scale formation, testing system design and so on, were reported. The corrosion inhibition performance of four imidazolium ionic liquids in carbon dioxide saturated NaCl solution was investigated by using electrochemical and surface analysis technologies. The four compounds are 1-ethyl-3-methylimidazolium chloride (a), 1-butyl-3-methylimidazolium chloride (b), 1-hexyl-3-methylimidazolium chloride (c), 1-decyl-3-methylimidazolium chloride (d). Under the testing conditions, compound d showed the highest inhibition efficiency and selected as the main object of further study. As a selected representative formula, 1-decyl-3-methylimidazolium chloride was studied in detail about its corrosion inhibition performance on mild steel in carbon dioxide saturated NaCl brine at pH 3.8 and 6.8. Electrochemical and surface analysis techniques were used to characterize the specimen corrosion process during the immersion in the blank and inhibiting solutions. The precorrosion of specimen surface showed significant and different influences on the anti-corrosion property of DMICL at pH 3.8 and 6.8. The corrosion inhibition efficiency (IE) was calculated based on parameters obtained from electrochemical techniques; the achieved IE was higher than 98% at the 25th hour for the steel with a well-polished surface at pH 3.8. The fitting parameters obtained from electrochemical data helped to account for the interfacial changes. As proved in previous research, 1-decyl-3-methylimidazolium chloride could be used as good corrosion inhibitors under certain conditions. However, under other conditions, such chemicals, as well as other species in oil transporting system, could be a factor influencing the evolution of protective surface inorganic layer. In this part, the FeCO3 layer evolution process for API 5L X52 carbon steel in CO2-saturated NaCl brine in the absence and in the presence of 1-decyl-3-methylimidazolium chloride ionic liquid was characterized using electrochemical techniques. Two models were developed to account for the interfacial evolution: the first model considered the balance of positive and negative charges at the interface of the metal and electrolyte in blank solution, while the second one considered the layer coverage and evolution with the imidazolium compound. The corrosion testing system is scientifically and practically critical for corrosion testing and simulations. In this part, a flowing fluid loop cell (FFLC) system was constructed to simulate the corrosion environment in the pipeline. Main content of this work include the construction of the flowing fluid cell loop (FFLC) system, as well as FFLC-based corrosion/anticorrosion tests under simulated acid conditions. Electrochemical Impedance Spectroscopy (EIS) and Linear Polarization Resistance (LPR) were used as prime techniques to quantify and characterize the corrosion behaviors of carbon steel specimen. The Eff vs. Reynolds number (Re) plots for the specimen located in the chamber and in the loop branch were provided.

Iron oxide functionalized graphene nano-composite for dispersive solid phase extraction of chemical warfare agents from aqueous samples.

PubMed

Chinthakindi, Sridhar; Purohit, Ajay; Singh, Varoon; Tak, Vijay; Goud, D Raghavender; Dubey, D K; Pardasani, Deepak

2015-05-15

Present study deals with the preparation and evaluation of graphene based magnetic nano-composite for dispersive solid phase extraction of Chemical Weapons Convention (CWC) relevant chemicals from aqueous samples. Nano-composite, Fe3O4@SiO2-G was synthesized by covalently bonding silica coated Fe3O4 onto the graphene sheets. Nerve agents (NA), Sulfur mustard (SM) and their non-toxic environmental markers were the target analytes. Extraction parameters like amount of sorbent, extraction time and desorption conditions were optimized. Dispersion of 20 milligram of sorbent in 200mL of water sample for 20min. followed by methanol/chloroform extraction produced average to good recoveries (27-94%) of targeted analytes. Recoveries of real agents exhibited great dependency upon sample pH and ionic strength. Sarin produced maximum recovery under mild acidic conditions (56% at pH 5) while VX demanded alkaline media (83% at pH 9). Salts presence in the aqueous samples was found to be advantageous, raising the recoveries to as high as 94% for SM. Excellent limits of detection (LOD) for sulphur mustard and VX (0.11ngmL(-1) and 0.19ngmL(-1) respectively) proved the utility of the developed method for the off-site analysis of CWC relevant chemicals. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of ionic strength on barium transport in porous media

NASA Astrophysics Data System (ADS)

Ye, Zi; Prigiobbe, Valentina

2018-02-01

Hydraulic fracturing (or fracking) is a well stimulation technique used to extract resources from a low permeability formation. Currently, the most common application of fracking is for the extraction of oil and gas from shale. During the operation, a large volume of brine, rich in hazardous chemicals, is produced. Spills of brine from wells or pits might negatively impact underground water resources and, in particular, one of the major concerns is the migration of radionuclides, such as radium (Ra2+), into the shallow subsurface. However, the transport behaviour of Ra2+ through a reactive porous medium under conditions typical of a brine, i.e., high salinity, is not well understood, yet. Here, a study on the transport behaviour of barium (Ba2+, congener of radium) through a porous medium containing a common mineral such as goethite (FeO(OH)) is presented. Batch and column flood tests were carried out at conditions resembling the produced brine, i.e., large values of ionic strength (I), namely, 1 to 3 mol/kg. The measurements were described with the triple layer surface complexation model coupled with the Pitzer activity coefficient method and a reactive transport model, in the case of the transport tests. The experimental results show that the adsorption of Ba2+ onto FeO(OH) increases with pH but decreases with I and it becomes negligible at the brine conditions. Moreover, even if isotherms show adsorption at large I, at the same conditions during transport, Ba2+ travels without retardation through the FeO(OH) porous medium. The triple layer model agrees very well with all batch data but it does not describe well the transport tests in all cases. In particular, the model cannot match the pH measurements at large I values. This suggests that the chemical reactions at the solid-liquid interface do not capture the mechanism of Ba2+ adsorption onto FeO(OH) at large salinity. Finally, this study suggests that barium, and potentially its congeners, namely, radium, calcium, magnesium, and strontium, may travel at the average flow velocity through a soil where the dominant reactive mineral is goethite.

Up-scaling mineral-aqueous interfacial processes that govern isotope and trace element partitioning during calcite growth

NASA Astrophysics Data System (ADS)

Lammers, L. N.

2014-12-01

The dependence of the isotopic and trace element composition of calcium carbonate minerals on growth conditions including temperature, pH, and salinity is widely used to infer paleoclimate conditions. These inferences rely heavily on phenomenological observations of biogenic and inorganic precipitation both in and ex situ, where only limited variability in solution conditions can be explored. Ionic fluxes between the mineral surface and aqueous growth solution govern the net uptake of both stoichiometric and trace species during calcification, so developing a mechanistic understanding of the reactions governing these fluxes is critical to refine existing proxies and to develop new ones. The micro-scale mechanisms of calcite precipitation from aqueous solution have been extensively studied, and net ionic uptake post-nucleation is known to occur primarily at monomolecular kink sites along step edges at the mineral surface. In this talk, I will present a theoretical framework that uses the quasi-elementary ion attachment and detachment reactions governing ion uptake at kink sites to simultaneously model bulk mineral growth kinetics and tracer partitioning during calcite precipitation. Several distinct processes occur during ion uptake at kink sites that can influence the distribution of trace species, directly impacting the composition of various carbonate paleoproxies including δ44Ca, δ18O, Sr/Ca and Mg/Ca. The distribution of these trace species will be shown to depend on (1) the relative rates of ion desolvation during attachment to kink sites, (2) the relative rates of bond breaking during detachment from kink sites, and (3) the equilibrium partitioning of trace aqueous species. This model accounts for the impact of solution conditions on net ion fluxes and surface speciation, which in turn controls the population of kink sites available for direct ion exchange with the aqueous phase. The impacts of solution variables including pH, temperature and salinity can be treated independently, which unlike traditional partitioning studies allows the impacts of these parameters to be deconvolved. The type of theoretical framework discussed here can be readily extended to explicitly account for each of the major solution composition variables that are implicated in paleoproxy composition.

Nucleobase recognition at alkaline pH and apparent pKa of single DNA bases immobilised within a biological nanopore.

PubMed

Franceschini, Lorenzo; Mikhailova, Ellina; Bayley, Hagan; Maglia, Giovanni

2012-02-01

The four DNA bases are recognized in immobilized DNA strands at high alkaline pH by nanopore current recordings. Ionic currents through the biological nanopores are also employed to measure the apparent pK(a) values of single nucleobases within the immobilised DNA strands. This journal is © The Royal Society of Chemistry 2012

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.

Structural origins of pH and ionic strength effects on protein stability. Acid denaturation of sperm whale apomyoglobin.

PubMed

Yang, A S; Honig, B

1994-04-15

A recently developed approach to calculate the pH dependence of protein stability from three-dimensional structure information is applied to the analysis of acid denaturation of sperm whale apomyoglobin. The finite difference Poisson-Boltzmann method is used to calculate pKa values and these are used to obtain titration curves for the folded protein as well as for compact intermediates. The total electrostatic free energy change involved in apomyoglobin unfolding is then evaluated. Calculations are carried out of the unfolding free energy of the native (N) and the compact intermediate (I) of apomyoglobin relative to the unfolded state (U) over a range of pH at various ionic strengths. The contributions from key ionizable groups to the unfolding process are discussed. For the acid-induced partial unfolding of apomyoglobin near pH 5, the transition from N to I is found to be driven by three histidines that are exposed when the B, C, D and E helices unfold. Similarly, the unfolding of the compact intermediate I consisting of the A, G and H helices is driven primarily by a few carboxylic acids with low pKa values in the compact state. This picture is in contrast to the view which attributes acid denaturation to electrostatic repulsion resulting from the build up of positive charge. In fact, charge-charge interactions in myoglobin are found to be attractive at all pH values where the protein unfolds. pH-dependent changes in these interactions contribute to acid denaturation but other electrostatic effects, such as hydrogen bonding and solvation, are important as well. The effect of increasing ionic strength on unfolding is attributed to the decrease of attractive charge-charge interactions which destabilize the N state relative to I, but stabilize the I state relative to U by reducing the pKa shifts of a few critical carboxylic acids. The I state is found to be more stable than U at neutral pH thus accounting for its presence as an intermediate on the protein folding pathway. Our results have implications for the origins of compact intermediates or "molten globule" states.

Serpentinite and the dawn of life

PubMed Central

Sleep, Norman H.; Bird, Dennis K.; Pope, Emily C.

2011-01-01

Submarine hydrothermal vents above serpentinite produce chemical potential gradients of aqueous and ionic hydrogen, thus providing a very attractive venue for the origin of life. This environment was most favourable before Earth's massive CO2 atmosphere was subducted into the mantle, which occurred tens to approximately 100 Myr after the moon-forming impact; thermophile to clement conditions persisted for several million years while atmospheric pCO2 dropped from approximately 25 bar to below 1 bar. The ocean was weakly acid (pH ∼ 6), and a large pH gradient existed for nascent life with pH 9–11 fluids venting from serpentinite on the seafloor. Total CO2 in water was significant so the vent environment was not carbon limited. Biologically important phosphate and Fe(II) were somewhat soluble during this period, which occurred well before the earliest record of preserved surface rocks approximately 3.8 billion years ago (Ga) when photosynthetic life teemed on the Earth and the oceanic pH was the modern value of approximately 8. Serpentinite existed by 3.9 Ga, but older rocks that might retain evidence of its presence have not been found. Earth's sequesters extensive evidence of Archaean and younger subducted biological material, but has yet to be exploited for the Hadean record. PMID:21930576

Molecular Insights into the Effects of Media-Drug and Carrier-Drug Interactions on pH-Responsive Drug Carriers.

PubMed

Katiyar, Ratna S; Jha, Prateek K

2018-05-10

We have performed two sets of all atom molecular dynamics (MD) simulations of poly(acrylic acid) (PAA) oligomers, considered as a model pH-responsive drug carrier. In the first set, multiple oligomers of PAA are simulated in model gastric and intestinal fluids, where the degree of deprotonation of PAA oligomers is varied with the medium pH. Since the gastric fluid has a pH substantially lower than that of intestinal fluid, PAA is relatively lesser ionized in gastric fluid and forms aggregates. In the second set, we simulated multiple oligomers of PAA with multiple molecules of a cationic anticancer drug, doxorubicin (DOX), for a range of pH values representative of various physiological conditions. The diffusion coefficient of DOX decreases with an increase in pH due to an increase in the ionic complexation of PAA with DOX, despite a decrease in PAA aggregation. Our findings are in agreement with recent experimental reports on pH-triggered targeting of tumor cells by the PAA-DOX system. Results of these two sets of studies establish that both carrier aggregation and carrier-drug interactions are competing influences that together determine the drug release from pH-responsive polymers.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

A comparative study on the effect of Curcumin and Chlorin-p6 on the transport of the LDS cation across a negatively charged POPG bilayer: Effect of pH

NASA Astrophysics Data System (ADS)

Varshney, G. K.; Kintali, S. R.; Gupta, P. K.; Das, K.

2017-02-01

We report the use of interface selective Second Harmonic generation technique to investigate the transport of the LDS cation across POPG liposomes in the pH range of 4.0 to 8.0 in the presence and absence of two amphiphilic drugs, Curcumin and Chlorin-p6 (Cp6). Our results show that bilayer permeability of liposomes is significantly affected by the presence of the drugs and pH of the medium as evidenced by significant changes in the transport kinetics of the LDS. Studies carried out in the pH range 4.0-8.0 show that while Cp6 significantly enhanced the transport of LDS at pH 4.0, the transport of the cation was seen to increase with increasing pH, with maximum effect at pH 7.4 for Curcumin. The pH dependent bilayer localization of both the drugs was investigated by conducting steady state FRET studies using DPH labeled lipids as donors. The FRET results and the relative population of the various ionic/nonionic species of the drugs at different pH suggest that distance dependent interaction between the various ionic species of the drugs and polar head groups of the lipid is responsible for the observed pH dependence enhancement of the drug induced membrane permeability. Another interesting observation was that the stability of Curcumin in presence of POPG liposomes was observed to degrade significantly near physiological pH (7.4 and 8.0). Although this degradation did not affect the liposome integrity, interestingly this was observed to enhance the transport of the LDS cation across the bilayer. That the degradation products of Curcumin are equally effective as the drug itself in enhancing the membrane permeability lends additional support to the current opinion that the bioactive degradation products of the drug may have a significant contribution to its observed pharmacological effects.

Manipulating energy transfer in copolymer-based nanocomposites by their controlled nanocaging and release of an ionic styryl dye: a case of an ultrasensitive pH sensor.

PubMed

Manna, Anamika; Sahoo, Dibakar; Chakravorti, Sankar

2012-03-01

We report an interesting pH-tunable energy transfer between an acceptor ionic styryl dye 2-(4-(dimethylamino)styryl)-1-methylpyridinium iodide and a donor charge-transfer dye 1,8-naphthalimide in a vesicular medium. The polyethylene-b-polyethylene glycol block copolymer intercalates with the sodium dodecyl sulfate anionic surfactant to form self-aggregated nanocomposites. These nanocomposites interact with the donor molecules in aqueous solution to form "vesicles", and the donor molecules become attached on the outer wall by hydrogen bonding. The acceptor molecules are observed to be loaded in the vesicular interior. By controlling the spectral overlap of the donor and acceptor molecules by changing the pH of the medium, the energy-transfer efficiency in vesicles has been studied. The efficiency of energy transfer in vesicular media (55%) is found to be less compared to that in aqueous media (80%) at pH 7. The fall in efficiency has been attributed to the perturbation imparted by the vesicular wall due to the good matching of the donor-acceptor distance with the wall thickness. At low pH, the efficiency shows an abrupt increase (95%) due to the release of the acceptor molecules from the vesicular medium causing subsequent reduction of donor-acceptor separation and an increase of the spectral overlap at that pH.

Electrochemistry and electrocatalysis of hemoglobin in Nafion/nano-CaCO3 film on a new ionic liquid BPPF6 modified carbon paste electrode.

PubMed

Sun, Wei; Gao, Ruifang; Jiao, Kui

2007-05-03

Room temperature ionic liquid N-butylpyridinium hexafluorophosphate (BPPF6) was used as a binder to construct a new carbon ionic liquid electrode (CILE), which exhibited enhanced electrochemical behavior as compared with the traditional carbon paste electrode with paraffin. By using the CILE as the basal electrode, hemoglobin (Hb) was immobilized on the surface of the CILE with nano-CaCO3 and Nafion film step by step. The Hb molecule in the film kept its native structure and showed good electrochemical behavior. In pH 7.0 Britton-Robinson (B-R) buffer solution, a pair of well-defined, quasi-reversible cyclic voltammetric peaks appeared with cathodic and anodic peak potentials located at -0.444 and -0.285 V (vs SCE), respectively, and the formal potential (E degrees') was at -0.365 V, which was the characteristic of Hb Fe(III)/Fe(II) redox couples. The formal potential of Hb shifted linearly to the increase of buffer pH with a slope of -50.6 mV pH-1, indicating that one electron transferred was accompanied with one proton transportation. Ultraviolet-visible (UV-vis) and Fourier transform infrared (FT-IR) spectroscopy studies showed that Hb immobilized in the Nafion/nano-CaCO3 film still remained its native arrangement. The Hb modified electrode showed an excellent electrocatalytic behavior to the reduction of H2O2, trichloroacetic acid (TCA), and NaNO2.

Surfactant-based ionic liquids for extraction of phenolic compounds combined with rapid quantification using capillary electrophoresis.

PubMed

Huang, Fangzhi; Berton, Paula; Lu, Chengfei; Siraj, Noureen; Wang, Chun; Magut, Paul K S; Warner, Isiah M

2014-09-01

A rapid liquid phase extraction employing a novel hydrophobic surfactant-based room temperature ionic liquid (RTIL), tetrabutylphosphonium dioctyl sulfosuccinate ([4C4 P][AOT]), coupled with capillary electrophoretic-UV (CE-UV) detection is developed for removal and determination of phenolic compounds. The long-carbon-chain RTIL used is sparingly soluble in most solvents and can be used to replace volatile organic solvents. This fact, in combination with functional-surfactant-anions, is proposed to reduce the interfacial energy of the two immiscible liquid phases, resulting in highly efficient extraction of analytes. Several parameters that influence the extraction efficiencies, such as extraction time, RTIL type, pH value, and ionic strength of aqueous solutions, were investigated. It was found that, under acidic conditions, most of the investigated phenols were extracted from aqueous solution into the RTIL phase within 12 min. Good linearity was observed over the concentration range of 0.1-80.0 μg/mL for all phenols investigated. The precision of this method, expressed as RSD, was determined to be within 3.4-5.3% range. The LODs (S/N = 3) of the method were in the range of 0.047-0.257 μg/mL. The proposed methodology was successfully applied to determination of phenols in real water samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2016-07-01

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

Inorganic selenium speciation analysis in Allium and Brassica vegetables by ionic liquid assisted liquid-liquid microextraction with multivariate optimization.

PubMed

Castro Grijalba, Alexander; Martinis, Estefanía M; Wuilloud, Rodolfo G

2017-03-15

A highly sensitive vortex assisted liquid-liquid microextraction (VA-LLME) method was developed for inorganic Se [Se(IV) and Se(VI)] speciation analysis in Allium and Brassica vegetables. Trihexyl(tetradecyl)phosphonium decanoate phosphonium ionic liquid (IL) was applied for the extraction of Se(IV)-ammonium pyrrolidine dithiocarbamate (APDC) complex followed by Se determination with electrothermal atomic absorption spectrometry. A complete optimization of the graphite furnace temperature program was developed for accurate determination of Se in the IL-enriched extracts and multivariate statistical optimization was performed to define the conditions for the highest extraction efficiency. Significant factors of IL-VA-LLME method were sample volume, extraction pH, extraction time and APDC concentration. High extraction efficiency (90%), a 100-fold preconcentration factor and a detection limit of 5.0ng/L were achieved. The high sensitivity obtained with preconcentration and the non-chromatographic separation of inorganic Se species in complex matrix samples such as garlic, onion, leek, broccoli and cauliflower, are the main advantages of IL-VA-LLME. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analysis of phenolic acids by ionic liquid-in-water microemulsion liquid chromatography coupled with ultraviolet and electrochemical detector.

PubMed

Peng, Li-Qing; Cao, Jun; Du, Li-Jing; Zhang, Qi-Dong; Shi, Yu-Tin; Xu, Jing-Jing

2017-05-26

An environmentally friendly ionic liquid-in-water (IL/W) microemulsion was established and applied as mobile phase in microemulsion liquid chromatography (MELC) with ultraviolet (UV) detection or electrochemical detector (ECD) for analysis of phenolic compounds in real samples. The optimal condition of the method was using the best composition of microemulsion (0.2% w/v [HMIM]PF 6 , 1.0% w/v SDS, 3.0% w/v n-butanol, 95.8% v/v water, pH 2.5) with UV detection. The validation results indicated that the method provided high degree of sensitivity, precision and accuracy with the low limit of detections ranged from 17.9-238ng/mL, satisfactory mean recovery values in the range of 80.1-105% and good linearity (r 2 >0.9994). Additionally, this method exhibited high selectivity and resolution for the analytes and was more eco-friendly compared with traditional MELC method. Consequently, the established IL/W MELC method was successfully applied to simultaneously separate and determine target compounds in Danshen sample and its preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

Hormetic effect of ionic liquid 1-ethyl-3-methylimidazolium acetate on bacteria

DOE PAGES

Nancharaiah, Y. V.; Francis, A. J.

2015-02-19

The biological effect of ionic liquids (ILs) is one of the highly debated topics as they are being contemplated for various industrial applications. 1-ethyl-2-methylimidazolium acetate ([EMIM][Ac]) showed remarkable hormesis on anaerobic Clostridium sp. and aerobic Psueudomonas putida. Bacterial growth was stimulated at up to 2.5 g L -1 and inhibited at > 2.5 g L -1 of ([EMIM][Ac]). The growth of Clostridium sp. and P. putida were higher by 0.4 and 4-fold respectively, in the presense of 0.5 g L -1 of ([EMIM][Ac]). Assessment of the effect of [EMIM][Ac] under different growth conditions showed that the hormesis of [EMIM][Ac] wasmore » mediated via regulation of medium pH. Hormetic effect of [EMIM][Ac] was evident only in medium with poor buffering capacity and in the presence of a fermentable substrate as the carbon source. The hormetic effect of [EMIM][Ac] on bacterial growth is most likely associated with the buffering capacity of acetate anion. These observations have implications in ILs toxicity studies and ecological risk assessment.« less

Interactions between Silicon Oxide Nanoparticles (SONPs) and U(VI) Contaminations: Effects of pH, Temperature and Natural Organic Matters

PubMed Central

Wu, Hanyu; Li, Ping; Pan, Duoqiang; Yin, Zhuoxin; Fan, Qiaohui; Wu, Wangsuo

2016-01-01

The interactions between contaminations of U(VI) and silicon oxide nanoparticles (SONPs), both of which have been widely used in modern industry and induced serious environmental challenge due to their high mobility, bioavailability, and toxicity, were studied under different environmental conditions such as pH, temperature, and natural organic matters (NOMs) by using both batch and spectroscopic approaches. The results showed that the accumulation process, i.e., sorption, of U(VI) on SONPs was strongly dependent on pH and ionic strength, demonstrating that possible outer- and/or inner-sphere complexes were controlling the sorption process of U(VI) on SONPs in the observed pH range. Humic acid (HA), one dominated component of NOMs, bounded SONPs can enhance U(VI) sorption below pH~4.5, whereas restrain at high pH range. The reversible sorption of U(VI) on SONPs possibly indicated that the outer-sphere complexes were prevalent at pH 5. However, an irreversible interaction of U(VI) was observed in the presence of HA (Fig 1). It was mainly due to the ternary SONPs-HA-U(VI) complexes (Type A Complexes). After SONPs adsorbed U(VI), the particle size in suspension was apparently increased from ~240 nm to ~350 nm. These results showed that toxicity of both SONPs and U(VI) will decrease to some extent after the interaction in the environment. These findings are key for providing useful information on the possible mutual interactions among different contaminants in the environment. PMID:26930197

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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.

Ionic imbalance induced self-propulsion of liquid metals

PubMed Central

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

2016-01-01

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

Ionic imbalance induced self-propulsion of liquid metals.

PubMed

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

2016-08-04

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

Ionic imbalance induced self-propulsion of liquid metals

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Epinigericin toxicity towards Tetrahymena pyriformis GL; changes in cell volume and intracellular pH.

PubMed

Bamdad, M; David, L; Grolière, C A

1995-12-01

A study of the toxicity of epinigericin, an antibiotic ionophor, towards the ciliate Tetrahymena pyriformis showed that this molecule stopped cell division, increased cell volume and led to a more basic intracellular pH. The action of epinigericin was probably linked to its function as an ionophor. The ionic selectivity of this molecule is still not known. The raising of the intracellular pH of ciliates by this antibiotic may be linked to its toxic action and its iontransport mechanism in Tetrahymena.

Effects of temperature, pH, and ionic strength on the adsorption of nanoparticles at liquid-liquid interfaces

NASA Astrophysics Data System (ADS)

Ferdous, Sultana; Ioannidis, Marios A.; Henneke, Dale E.

2012-05-01

The effects of temperature, pH and sodium chloride (NaCl) concentration on the equilibrium and dynamic interfacial tension (IFT) of 4.4-nm gold nanoparticles capped with n-dodecanethiol at hydrocarbon-water interfaces was studied. The pendant drop technique was used to study the adsorption properties of these nanoparticles at the hexane-water and nonane-water interfaces. The physical size of the gold nanoparticles was determined by TEM image analysis. The interfacial properties of mixtures of these nanoparticles, having different sizes and capping agents, were then studied. The addition of NaCl was found to cause a decrease of the equilibrium and dynamic IFT greater than that which accompanies the adsorption of nanoparticles at the interface in the absence of NaCl. Although IFT values for acidic and neutral conditions were found to be similar, a noticeable decrease in the IFT was found for more basic conditions. Increasing the temperature of the system was found to cause an increase in both dynamic and equilibrium IFT values. These findings have implications for the self-assembly of functionalized gold nanoparticles at liquid-liquid interfaces.

Microwave assisted synthesis of metal-organic framework MIL-101 nanocrystals as sorbent and pseudostationary phase in capillary electrophoresis for the separation of anthraquinones in environmental water samples.

PubMed

Liu, Yue; Hu, Jia; Li, Yan; Shang, Yun-Tao; Wang, Jia-Qi; Zhang, Ye; Wang, Zhong-Liang

2017-10-01

In this work, a CE method was developed to separate five anthraquinones: aloe-emodin, rhein, emodin, chrysophanol, and physcion. The CE method used a nano-sized metal organic framework MIL-101 (nMIL-101) as pseudostationary phase (PSP) and sorbent for dispersed particle extraction (DPE). The nMIL-101 was synthesized by microwave technique and was characterized by UV-vis, TEM, Zeta potential, X-ray diffraction spectrometry and micropore physisorption. In this method, anthraquinones were adsorbed by nMIL-101 of a fast kinetics within 10 min and then separated by CE. The CE conditions were optimized considering time, pH, buffer ionic strength, and nanoparticles concentration. The optimal CE condition is using 20 mM sodium borate buffer (pH 9.1) containing 15% methanol (v/v) and 400 mg/L nMIL-101 as additives within 8 min. The LODs varied from 24 to 57 μg/L, which were lower than those previously reported. Our method has been successfully applied to determine trace anthraquinones in environmental water samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of phthalic acid esters in water samples by hollow fiber liquid-phase microextraction prior to gas chromatography tandem mass spectrometry.

PubMed

González-Sálamo, Javier; González-Curbelo, Miguel Ángel; Socas-Rodríguez, Bárbara; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Ángel

2018-06-01

A new hollow fiber liquid-phase microextraction (HF-LPME) method has been developed for the extraction of a group of phthalic acid esters (PAEs) of interest from different water samples prior to gas chromatography tandem mass spectrometry analysis. HF-LPME was carried out using 1-octanol as extraction solvent followed by a back extraction step with cyclohexane. The different parameters that affect HF-LPME such as sample pH, ionic strength, extraction time, stirring rate, extraction temperature and back extraction conditions were investigated. The optimized conditions involved the extraction of 10 mL of sample without pH adjustment or addition of salt during 75 min under a stirring of 850 rpm at 60 °C and subsequent desorption with 200 μL of cyclohexane for 10 min in an ultrasonic bath. The method was validated in terms of calibration and recovery studies using dibutyl phthalate-d 4 as internal standard. The developed procedure gave satisfactory recovery (74-120%) and relative standard deviation values (<20%) for the studied PAEs in mineral, tap, pond and waste water samples. Copyright © 2018 Elsevier Ltd. All rights reserved.

Colloidal stability of CeO2 nanoparticles coated with either natural organic matter or organic polymers under various hydrochemical conditions

NASA Astrophysics Data System (ADS)

Dippon, Urs; Pabst, Silke; Klitzke, Sondra

2016-04-01

The worldwide marked for engineered nanoparticles (ENPs) is growing and concerns on the environmental fate- and toxicity of ENPs are rising. Understanding the transport of ENPs within and between environmental compartments such as surface water and groundwater is crucial for exposition modeling, risk assessment and ultimately the protection of drinking water resources. The transport of ENPs is strongly influenced by the surface properties and aggregation behavior of the particles, which is strongly controlled by synthetic and natural organic coatings. Both, surface properties and aggregation characteristics are also key properties for the industrial application of ENPs, which leads to the development and commercialization of an increasing number of surface-functionalized ENPs. These include metals and oxides such as Cerium dioxide (CeO2) with various organic coatings. Therefore, we investigate CeO2 ENPs with different surface coatings such as weakly anionic polyvinyl alcohol (PVA) or strongly anionic poly acrylic acid (PAA) with respect to their colloidal stability in aqueous matrix under various hydrochemical conditions (pH, ionic strength) and their transport behavior in sand filter columns. Furthermore, we investigate the interaction of naturally occurring organic matter (NOM) with CeO2 ENPs and its effect on surface charge (zeta potential), colloidal stability and transport. While uncoated CeO2 ENPs aggregate at pH > 4 in aqueous matrix, our results show that PAA and PVA surface coatings as well as NOM sorbed to CeO2-NP surfaces can stabilize CeO2 ENPs under neutral and alkaline pH conditions in 1 mM KCl solution. Under slightly acidic conditions, differences between the three particle types were observed. PVA can stabilize particle suspensions in presence of 1 mM KCl at pH > 4.3, PAA at pH >4.0 and NOM at >3.2. While the presence of KCl did not influence particle size of NOM-CeO2 ENPs, CaCl2 at >2 mM lead to aggregation. Further results on the influence of KCl and CaCl2 on aggregation of coated CeO2 ENPs and transport in sand filter columns will be presented.

CADDIS Volume 2. Sources, Stressors and Responses: Simple and Detailed Conceptual Model Diagram Downloads

EPA Pesticide Factsheets

Simple and detailed conceptual model diagram and associated narrative for ammonia, dissolved oxygen, flow alteration, herbicides, insecticides, ionic strength, metals, nutrients, ph, physical habitat, sediments, temperature, unspecified toxic chemicals.

The rate of sulfide oxidation by δMnO 2 in seawater

NASA Astrophysics Data System (ADS)

Yao, Wensheng; Millero, Frank J.

1993-07-01

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

The effect of a local source on the composition of precipitation in south-central Maine

Treesearch

Scott D. Boyce; Samuel S. Butcher

1976-01-01

Bulk precipitation samples were collected from ten sites in south-central Maine during the period 18 June to 30 September 1974. Data from the chemical analyses of the precipitation were used to determine regional deposition patterns of the ionic constituents. Acidic pH values ranging from 3.8 to 5.0 are characteristic of the region, but relatively alkaline pH values of...

Prediction of purification of biopharmeceuticals with molecular dynamics

NASA Astrophysics Data System (ADS)

Ustach, Vincent; Faller, Roland

Purification of biopharmeceuticals remains the most expensive part of protein-based drug production. In ion exchange chromatography (IEX), prediction of the elution ionic strength of host cell and target proteins has the potential to reduce the parameter space for scale-up of protein production. The complex shape and charge distribution of proteins and pores complicates predictions of the interactions in these systems. All-atom molecular dynamics methods are beyond the scope of computational limits for mass transport regimes. We present a coarse-grained model for proteins for prediction of elution pH and ionic strength. By extending the raspberry model for colloid particles to surface shapes and charge distributions of proteins, we can reproduce the behavior of proteins in IEX. The average charge states of titratatable amino acid residues at relevant pH values are determined by extrapolation from all-atom molecular dynamics at pH 7. The pH specific all-atom electrostatic field is then mapped onto the coarse-grained surface beads of the raspberry particle. The hydrodynamics are reproduced with the lattice-Boltzmann scheme. This combination of methods allows very long simulation times. The model is being validated for known elution procedures by comparing the data with experiments. Defense Threat Reduction Agency (Grant Number HDTRA1-15-1-0054).

Phosphate Removal by Anion Binding on Functionalized Nanoporous Sorbents

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

Chouyyok, Wilaiwan; Wiacek, Robert J.; Pattamakomsan, Kanda

2010-03-26

Phosphate was captured from aqueous solutions by cationic metal-EDA complexes anchored inside mesoporous silica MCM-41 supports (Cu(II)-EDA-SAMMS and Fe(III)-EDA-SAMMS). Fe-EDA-SAMMS was more effective at capturing phosphate than the Cu-EDA-SAMMS and was further studied for matrix effects (e.g., pH, ionic strength, and competing anions) and sorption performance (e.g., capacity and rate). The adsorption of phosphate was highly pH dependent; it increased with increasing pH from 1.0 to 6.5, and decreased above pH 6.5. The adsorption was affected by high ionic strength (0.1 M of NaCl). In the presence of 1000-fold molar excess of chloride and nitrate anions, phosphate removal by Fe-EDA-SAMMSmore » was not affected. Slight, moderate and large impacts were seen with bicarbonate, sulfate and citrate anions, respectively. The phosphate adsorption data on Fe-EDA-SAMMS agreed well with the Langmuir model with the estimated maximum capacity of 43.3 mg/g. The material displayed rapid sorption rate (99% of phosphate removal within 1 min) and lowering the phosphate content to ~ 10 µg/L of phosphorus, which is lower than the EPA’s established freshwater contaminant level for phosphorous (20 µg/L).« less

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

PubMed

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

2007-10-01

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

Evaluation of Vapor Pressure and Ultra-High Vacuum Tribological Properties of Ionic Liquids (2) Mixtures and Additives

NASA Technical Reports Server (NTRS)

Morales, Wilfredo; Koch, Victor R.; Street, Kenneth W., Jr.; Richard, Ryan M.

2008-01-01

Ionic liquids are salts, many of which are typically viscous fluids at room temperature. The fluids are characterized by negligible vapor pressures under ambient conditions. These properties have led us to study the effectiveness of ionic liquids containing both organic cations and anions for use as space lubricants. In the previous paper we have measured the vapor pressure and some tribological properties of two distinct ionic liquids under simulated space conditions. In this paper we will present vapor pressure measurements for two new ionic liquids and friction coefficient data for boundary lubrication conditions in a spiral orbit tribometer using stainless steel tribocouples. In addition we present the first tribological data on mixed ionic liquids and an ionic liquid additive. Post mortem infrared and Raman analysis of the balls and races indicates the major degradation pathway for these two organic ionic liquids is similar to those of other carbon based lubricants, i.e. deterioration of the organic structure into amorphous graphitic carbon. The coefficients of friction and lifetimes of these lubricants are comparable to or exceed these properties for several commonly used space oils.

β-cyclodextrin-ionic liquid polymer based dynamically coating for simultaneous determination of tetracyclines by capillary electrophoresis.

PubMed

Zhou, Chunyan; Deng, Jingjing; Shi, Guoyue; Zhou, Tianshu

2017-04-01

Tetracyclines are a group of broad spectrum antibiotics widely used in animal husbandry to prevent and treat diseases. However, the improper use of tetracyclines may result in the presence of their residues in animal tissues or waste. Recently, great attention has been drawn towards the green solvents ionic liquids. Ionic liquids have been employed as a coating material to modify the electroosmotic flow in capillary electrophoresis. In this study, a functionalized ionic liquid, mono-6-deoxy-6-(3-methylimidazolium)-β-cyclodextrin tosylate, was synthesized and used for the simultaneous separation and quantification of tetracyclines by capillary electrophoresis. Good separation efficiency could be achieved due to the multiple functions of β-cyclodextrin derived ionic liquid, including the electrostatic interaction, the hydrogen bonding, and the cavity structure in β-cyclodextrin ionic liquid which can entrap the tetracyclines to form inclusion complex. After optimization, baseline separation achieved in 25 min with the running buffer consisted of 10 mmol/L, pH 7.2 phosphate buffer and 20 mmol/L β-cyclodextrin ionic liquid. The satisfied result demonstrated that the β-cyclodextrin ionic liquid is an ideal background electrolyte modifier in the separation of tetracyclines with high stability and good reproducibility. And it is an effective strategy to design and synthesize specific ILs as additive applied in separation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polyelectrolyte Complex Inclusive Biohybrid Microgels for Tailoring Delivery of Copigmented Anthocyanins.

PubMed

Tan, Chen; B Celli, Giovana; Lee, Michelle; Licker, Jonathan; Abbaspourrad, Alireza

2018-05-14

This study fabricated a novel biohybrid microgel containing polysaccharide-based polyelectrolyte complexes (PECs) for anthocyanins. Herein, anthocyanins were encapsulated into PECs composed of chondroitin sulfate and chitosan, followed by incorporation into alginate microgels using emulsification/internal gelation method. We demonstrated that PECs incorporation strongly affected the properties of microgels, dependent on the polysaccharide concentration and pH in which they were fabricated. The dense internal network surrounded by an alginate shell was clearly visualized in cross-sectioned PECs-microgels. Stability studies carried out under varying ionic strength and pH conditions demonstrated the stimuli-responsiveness of the PECs-microgels. Additionally, the presence of PECs conferred microgels with high rigidity during freeze-drying and excellent reconstitution capacity upon rehydration. These observations were attributed to the modulation of electrostatic and hydrogen-bonding cross-linking between PECs and the alginate gel matrix and suggest the PECs inclusive microgels hold promise as delivery vehicles for the controlled release of hydrophilic bioactive compounds.

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

Preparation of a Sepia Melanin and Poly(ethylene-alt-maleic Anhydride) Hybrid Material as an Adsorbent for Water Purification.

PubMed

Panzarasa, Guido; Osypova, Alina; Consolati, Giovanni; Quasso, Fiorenza; Soliveri, Guido; Ribera, Javier; Schwarze, Francis W M R

2018-01-23

Meeting the increasing demand of clean water requires the development of novel efficient adsorbent materials for the removal of organic pollutants. In this context the use of natural, renewable sources is of special relevance and sepia melanin, thanks to its ability to bind a variety of organic and inorganic species, has already attracted interest for water purification. Here we describe the synthesis of a material obtained by the combination of sepia melanin and poly(ethylene- alt -maleic anhydride) (P(E- alt -MA)). Compared to sepia melanin, the resulting hybrid displays a high and fast adsorption efficiency towards methylene blue (a common industrial dye) for a wide pH range (from pH 2 to 12) and under high ionic strength conditions. It is easily recovered after use and can be reused up to three times. Given the wide availability of sepia melanin and P(E- alt -MA), the synthesis of our hybrid is simple and affordable, making it suitable for industrial water purification purposes.

In vitro degradation of multisubstituted hydroxyapatite and fluorapatite in the physiological condition

NASA Astrophysics Data System (ADS)

Sumathi, Shanmugam; Gopal, Buvaneswari

2015-07-01

Structure of hydroxyapatite (HAP) is more flexible towards ionic substitutions. Properties such as solubility, antimicrobial property can be tailored by substitutions. Substituted hydroxyapatite and fluorapatite of formulae BiNaCa3(PO4)3OH, Bi0.5M0.5Ca4(PO4)3OH (M=K, Ag), Ca10-xCux(PO4)6(OH/F)2 d(x=0.05-0.25) and Bi0.5Na0.5Ca4(PO4)3F were synthesized and characterized by powder XRD, FT-IR, SEM-EDAX and TGA. In vitro solubility of the synthesized compounds was studied in the phosphate buffered medium of pH 7.4 at 37 °C. Based on the release of calcium and phosphorus ion concentration and pH, the solubility of these compounds is discussed. Bismuth and sodium co-substituted hydroxyapatite are found to be more soluble compared with other substituted apatite compounds and unsubstituted hydroxyapatite.

Removal of oxytetracycline and determining its biosorption properties on aerobic granular sludge.

PubMed

Mihciokur, Hamdi; Oguz, Merve

2016-09-01

This study investigates biosorption of Oxytetracycline, a broad-spectrum antibiotic, using aerobic granular sludge as an adsorbent in aqueous solutions. A sequencing batch reactor fed by a synthetic wastewater was operated to create aerobic granular sludge. Primarily, the pore structure and surface area of granular sludge, the chemical structure and the molecular sizes of the pharmaceutical, operating conditions, such as pH, stirring rate, initial concentration of Oxytetracycline, during adsorption process was verified. Subsequently, thermodynamic and kinetic aspects of the adsorption were examined and adsorption isotherm studies were carried out. It was shown that the aerobic granular sludge was a good alternative for biosorption of this pharmaceutical. The pharmaceutical was adsorbed better at pH values of 6-8. The adsorption efficiency increased with rising ionic strength. Also, it was seen that the adsorption process was an exothermic process in terms of thermodynamics. The adsorption can be well explained by Langmuir isotherm model. Copyright © 2016 Elsevier B.V. All rights reserved.

Chromatography of Penicillins, Penicilloates, and Penicilloylamides on Dextran Gels

PubMed Central

Hyslop, Newton E.; Milligan, Richard J.

1974-01-01

The factors influencing the chromatographic behavior on dextran gels of penicillins and their derivatives were investigated by comparing elution profiles and partition coefficients (KD and KAV) of penicillins differing in side-chain structure and among penicillin derivatives of identical side-chain but different nuclear structure. Under the conditions of pH and ionic strength employed (pH 7.4, 0.145 M NaCl, 0.05 M PO4), side-chain adsorptive effects best explained the anomalous behavior of benzylpenicillin and of oxacillin and its chlorine-substituted analogues. Polar side-chain substituents, such as the amino group of ampicillin and the carboxyl group of carbenicillin, and cleavage of the β-lactam ring, exemplified by penicilloates and penicilloylamines, both appeared to interfere with side-chain-directed adsorption. The differential adsorption of penicillins and their derivatives to dextran gels is not only of theoretical interest relative to the mechanism of chromatography but of practical application to analytical and preparative procedures in penicillin chemistry. PMID:15825415

Control of electrochemical signals from quantum dots conjugated to organic materials by using DNA structure in an analog logic gate.

PubMed

Chen, Qi; Yoo, Si-Youl; Chung, Yong-Ho; Lee, Ji-Young; Min, Junhong; Choi, Jeong-Woo

2016-10-01

Various bio-logic gates have been studied intensively to overcome the rigidity of single-function silicon-based logic devices arising from combinations of various gates. Here, a simple control tool using electrochemical signals from quantum dots (QDs) was constructed using DNA and organic materials for multiple logic functions. The electrochemical redox current generated from QDs was controlled by the DNA structure. DNA structure, in turn, was dependent on the components (organic materials) and the input signal (pH). Independent electrochemical signals from two different logic units containing QDs were merged into a single analog-type logic gate, which was controlled by two inputs. We applied this electrochemical biodevice to a simple logic system and achieved various logic functions from the controlled pH input sets. This could be further improved by choosing QDs, ionic conditions, or DNA sequences. This research provides a feasible method for fabricating an artificial intelligence system. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of sodium lauryl sulfate in dissolution media on dissolution of hard gelatin capsule shells.

PubMed

Zhao, Fang; Malayev, Vyacheslav; Rao, Venkatramana; Hussain, Munir

2004-01-01

Sodium lauryl sulfate (SLS) is a commonly used surfactant in dissolution media for poorly water soluble drugs. However, it has occasionally been observed that SLS negatively impacts the dissolution of drug products formulated in gelatin capsules. This study investigated the effect of SLS on the dissolution of hard gelatin capsule shells. The USP paddle method was used with online UV monitoring at 214 nm (peptide bond). Empty size #0 capsule shells were held to the bottom of the dissolution vessel by magnetic three-prong sinkers. SLS significantly slowed down the dissolution of gelatin shells at pH < 5. Visually, the gelatin shells transformed into some less-soluble precipitate under these conditions. This precipitate was found to contain a higher sulfur content than the gelatin control sample by elemental analysis, indicating that SLS is part of the precipitate. Additionally, the slowdown of capsule shell dissolution was shown to be dependent on the SLS concentration and the ionic strength of the media. SLS interacts with gelatin to form a less-soluble precipitate at pH < 5. The use of SLS in dissolution media at acidic pH should be carefully evaluated for gelatin capsule products.

Adsorption of nucleotides onto Fe-Mg-Al rich swelling clays

NASA Astrophysics Data System (ADS)

Feuillie, Cécile; Daniel, Isabelle; Michot, Laurent J.; Pedreira-Segade, Ulysse

2013-11-01

Mineral surfaces may have played a role in the origin of the first biopolymers, by concentrating organic monomers from a dilute ocean. Swelling clays provide a high surface area for the concentration of prebiotic monomers, and have therefore been the subject of numerous investigations. In that context, montmorillonite, the most abundant swelling clay in modern environments, has been extensively studied with regard to adsorption and polymerization of nucleic acids. However, montmorillonite was probably rather marginal on the primitive ocean floor compared to iron-magnesium rich phyllosilicates such as nontronite that results from the hydrothermal alteration of a mafic or ultramafic oceanic crust. In the present paper, we study the adsorption of nucleotides on montmorillonite and nontronite, at various pH and ionic strength conditions plausible for Archean sea-water. A thorough characterization of the mineral surfaces shows that nucleotide adsorb mainly on the edge faces of the smectites by ligand exchange between the phosphate groups of the nucleotides and the -OH groups from the edge sites over a wide pH range (4-10). Nontronite is more reactive than montmorillonite. At low pH, additional ion exchange may play a role as the nucleotides become positively charged.

A mathematical model of the volume, pH, and ion content regulation in reticulocytes. Application to the pathophysiology of sickle cell dehydration.

PubMed Central

Lew, V L; Freeman, C J; Ortiz, O E; Bookchin, R M

1991-01-01

We developed a mathematical model of the reticulocyte, seeking to explain how a cell with similar volume but much higher ionic traffic than the mature red cell (RBC) regulates its volume, pH, and ion content in physiological and abnormal conditions. Analysis of the fluxbalance required by reticulocytes to conserve volume and composition predicted the existence of previously unsuspected Na(+)-dependent Cl- entry mechanisms. Unlike mature RBCs, reticulocytes did not tend to return to their original state after brief perturbations. The model predicted hysteresis and drift in cell pH, volume, and ion contents after transient alterations in membrane permeability or medium composition; irreversible cell dehydration could thus occur by brief K+ permeabilization, transient medium acidification, or the replacement of external Na+ with an impermeant cation. Both the hysteresis and drift after perturbations were shown to depend on the pHi dependence of the K:Cl cotransport, a major reticulocyte transporter. This behavior suggested a novel mechanism for the generation of irreversibly sickled cells directly from reticulocytes, rather than in a stepwise, progressive manner from discocytes. Experimental tests of the model's predictions and the hypothesis are described in the following paper. PMID:1985088

Biomimetic heterogeneous multiple ion channels: a honeycomb structure composite film generated by breath figures

NASA Astrophysics Data System (ADS)

Han, Keyu; Heng, Liping; Wen, Liping; Jiang, Lei

2016-06-01

We design a novel type of artificial multiple nanochannel system with remarkable ion rectification behavior via a facile breath figure (BF) method. Notably, even though the charge polarity in the channel wall reverses under different pH values, this nanofluidic device displays the same ionic rectification direction. Compared with traditional nanochannels, this composite multiple ion channel device can be more easily obtained and has directional ionic rectification advantages, which can be applied in many fields.We design a novel type of artificial multiple nanochannel system with remarkable ion rectification behavior via a facile breath figure (BF) method. Notably, even though the charge polarity in the channel wall reverses under different pH values, this nanofluidic device displays the same ionic rectification direction. Compared with traditional nanochannels, this composite multiple ion channel device can be more easily obtained and has directional ionic rectification advantages, which can be applied in many fields. Electronic supplementary information (ESI) available: Pore size distribution histograms of the AAO substrates; SEM images of the side view of pure AAO membranes and top view of the flat PI/AAO composite film; the current-time curves of the flat composite film; the current-voltage characteristics curves of pure AAO nanochannels with different mean pore diameters; CA of the two surfaces of the composite PI/AAO film, the structural formula of the polymer polyimide resin (PI), and solid surface zeta potential. See DOI: 10.1039/c6nr02506d

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

PubMed

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

2018-06-18

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

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

PubMed

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

2017-04-01

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

Simultaneous determination of Ca, Cu, Ni, Zn and Cd binding strengths with fulvic acid fractions by Schubert's method

USGS Publications Warehouse

Brown, G.K.; MacCarthy, P.; Leenheer, J.A.

1999-01-01

The equilibrium binding of Ca2+, Ni2+, Cd2+, Cu2+ and Zn2+ with unfractionated Suwannee river fulvic acid (SRFA) and an enhanced metal binding subfraction of SRFA was measured using Schubert's ion-exchange method at pH 6.0 and at an ionic strength (??) of 0.1 (NaNO3). The fractionation and subfractionation were directed towards obtaining an isolate with an elevated metal binding capacity or binding strength as estimated by Cu2+ potentiometry (ISE). Fractions were obtained by stepwise eluting an XAD-8 column loaded with SRFA with water eluents of pH 1.0 to pH 12.0. Subfractions were obtained by loading the fraction eluted from XAD-8 at pH 5.0 onto a silica gel column and eluting with solvents of increasing polarity. Schuberts ion exchange method was rigorously tested by measuring simultaneously the conditional stability constants (K) of citric acid complexed with the five metals at pH 3.5 and 6.0. The logK of SRFA with Ca2+, Ni2+, Cd2+, Cu2+ and Zn2+ determined simultaneously at pH 6.0 follow the sequence of Cu2+>Cd2+>Ni2+>Zn2+>Ca2+ while all logK values increased for the enhanced metal binding subfraction and followed a different sequence of Cu2+>Cd2+>Ca2+>Ni2+>Zn2+. Both fulvic acid samples and citric acid exhibited a 1:1 metal to ligand stochiometry under the relatively low metal loading conditions used here. Quantitative 13C nuclear magnetic resonance spectroscopy showed increases in aromaticity and ketone content and decreases in aliphatic carbon for the elevated metal binding fraction while the carboxyl carbon, and elemental nitrogen, phosphorus, and sulfur content did not change. The more polar, elevated metal binding fraction did show a significant increase in molecular weight over the unfractionated SRFA. Copyright (C) 1999 Elsevier Science B.V.

Potentiation of TRPM7 Inward Currents by Protons

PubMed Central

Jiang, Jianmin; Li, Mingjiang; Yue, Lixia

2005-01-01

TRPM7 is unique in being both an ion channel and a protein kinase. It conducts a large outward current at +100 mV but a small inward current at voltages ranging from −100 to −40 mV under physiological ionic conditions. Here we show that the small inward current of TRPM7 was dramatically enhanced by a decrease in extracellular pH, with an ∼10-fold increase at pH 4.0 and 1–2-fold increase at pH 6.0. Several lines of evidence suggest that protons enhance TRPM7 inward currents by competing with Ca2+ and Mg2+ for binding sites, thereby releasing blockade of divalent cations on inward monovalent currents. First, extracellular protons significantly increased monovalent cation permeability. Second, higher proton concentrations were required to induce 50% of maximal increase in TRPM7 currents when the external Ca2+ and Mg2+ concentrations were increased. Third, the apparent affinity for Ca2+ and Mg2+ was significantly diminished at elevated external H+ concentrations. Fourth, the anomalous-mole fraction behavior of H+ permeation further suggests that protons compete with divalent cations for binding sites in the TRPM7 pore. Taken together, it appears that at physiological pH (7.4), Ca2+ and Mg2+ bind to TRPM7 and inhibit the monovalent cationic currents; whereas at high H+ concentrations, the affinity of TRPM7 for Ca2+ and Mg2+ is decreased, thereby allowing monovalent cations to pass through TRPM7. Furthermore, we showed that the endogenous TRPM7-like current, which is known as Mg2+-inhibitable cation current (MIC) or Mg nucleotide–regulated metal ion current (MagNuM) in rat basophilic leukemia (RBL) cells was also significantly potentiated by acidic pH, suggesting that MIC/MagNuM is encoded by TRPM7. The pH sensitivity represents a novel feature of TRPM7 and implies that TRPM7 may play a role under acidic pathological conditions. PMID:16009728

Effects of wastewater sludge and its detergents on the stability of rotavirus

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

Ward, R.L.; Ashley, C.S.

1980-06-01

Wastewater sludge reduced the heat required to inactivate rotavirus SA-11, and ionic detergents were identified as the sludge components responsible for this effect. A similar result was found previously with reovirus. The quantitative effects of individual ionic detergents on rotavirus and reovirus were very different, and rotavirus was found to be extremely sensitive to several of these detergents. However, neither virus was destabilized by nonionic detergents. On the contrary, rotavirus was stabilized by a nonionic detergent against the potent destabilizing effects of the ionic detergent sodium dodecyl sulfate. The destabilizing effects of both cationic and anionic detergents on rotavirus weremore » greatly altered by changes in the pH of the medium.« less

Application of non-ionic surfactant as a developed method for the enhancement of two-phase solvent bar microextraction for the simultaneous determination of three phthalate esters from water samples.

PubMed

Bandforuzi, Samereh Ranjbar; Hadjmohammadi, Mohammad Reza

2018-08-03

The extraction of phthalate esters (PEs) from aqueous matrices using two-phase solvent bar microextraction by organic micellar phase was investigated. A short hollow fiber immobilized with reverse micelles of Brij 35 surfactant in 1-octanol was served as the solvent bar for microextraction. Experimental results show that the extraction efficiency were much higher using two-phase solvent bar microextraction based on non-ionic surfactant than conventional two-phase solvent bar microextraction because of a positive effect of surfactant-containing extraction phase in promoting the partition process by non-ionic intermolecular forces such as polar and hydrophobicity interactions. The nature of the extraction solvent, type and concentration of non-ionic surfactant, extraction time, sample pH, temperature, stirring rate and ionic strength were the effecting parameters which optimized to obtain the highest extraction recovery. Analysis of recovered analytes was carried out with high performance liquid chromatography coupled with ultraviolet detection (HPLC-UV). Under the optimum conditions, linearity was observed in the range of 1-800 ng mL -1 for dimethylphthalate (DMP) and 0.5-800 ng mL -1 for diethylphthalate (DEP) and di-n-butyl phthalate (DBP) with correlation determination values above 0.99 for them. The limits of detection and quantification were ranged from 0.012 to 0.03 ng mL -1 and 0.04-0.1 ng mL -1 , respectively. The ranges of intra-day and inter-day RSD (n = 3) at 20 ng mL -1 of PEs were 1.8-2.1% and 2.1-2.6%, respectively. Results showed that developed method can be a very powerful, innovative and promising sample preparation technique in PEs analysis from environmental and drinking water samples. Copyright © 2018. Published by Elsevier B.V.

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

PubMed

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

2013-12-01

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

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

pH-Dependent Solubility and Dissolution Behavior of Carvedilol--Case Example of a Weakly Basic BCS Class II Drug.

PubMed

Hamed, Rania; Awadallah, Areeg; Sunoqrot, Suhair; Tarawneh, Ola; Nazzal, Sami; AlBaraghthi, Tamadur; Al Sayyad, Jihan; Abbas, Aiman

2016-04-01

The objective of this study was to investigate the pH-dependent solubility and dissolution of weakly basic Biopharmaceutical Classification Systems (BCS) class II drugs, characterized by low solubility and high permeability, using carvedilol, a weak base with a pK a value of 7.8, as a model drug. A series of solubility and in vitro dissolution studies was carried out using media that simulate the gastric and intestinal fluids and cover the physiological pH range of the GI from 1.2 to 7.8. The effect of ionic strength, buffer capacity, and buffer species of the dissolution media on the solubility and dissolution behavior of carvedilol was also investigated. The study revealed that carvedilol exhibited a typical weak base pH-dependent solubility profile with a high solubility at low pH (545.1-2591.4 μg/mL within the pH range 1.2-5.0) and low solubility at high pH (5.8-51.9 μg/mL within the pH range 6.5-7.8). The dissolution behavior of carvedilol was consistent with the solubility results, where carvedilol release was complete (95.8-98.2% released within 60 min) in media simulating the gastric fluid (pH 1.2-5.0) and relatively low (15.9-86.2% released within 240 min) in media simulating the intestinal fluid (pH 6.5-7.8). It was found that the buffer species of the dissolution media may influence the solubility and consequently the percentage of carvedilol released by forming carvedilol salts of varying solubilities. Carvedilol solubility and dissolution decreased with increasing ionic strength, while lowering the buffer capacity resulted in a decrease in carvedilol solubility and dissolution rate.

A new dispersive liquid-liquid microextraction using ionic liquid based microemulsion coupled with cloud point extraction for determination of copper in serum and water samples.

PubMed

Arain, Salma Aslam; Kazi, Tasneem Gul; Afridi, Hassan Imran; Arain, Mariam Shahzadi; Panhwar, Abdul Haleem; Khan, Naeemullah; Baig, Jameel Ahmed; Shah, Faheem

2016-04-01

A simple and rapid dispersive liquid-liquid microextraction procedure based on ionic liquid assisted microemulsion (IL-µE-DLLME) combined with cloud point extraction has been developed for preconcentration copper (Cu(2+)) in drinking water and serum samples of adolescent female hepatitits C (HCV) patients. In this method a ternary system was developed to form microemulsion (µE) by phase inversion method (PIM), using ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and nonionic surfactant, TX-100 (as a stabilizer in aqueous media). The Ionic liquid microemulsion (IL-µE) was evaluated through visual assessment, optical light microscope and spectrophotometrically. The Cu(2+) in real water and aqueous acid digested serum samples were complexed with 8-hydroxyquinoline (oxine) and extracted into IL-µE medium. The phase separation of stable IL-µE was carried out by the micellar cloud point extraction approach. The influence of of different parameters such as pH, oxine concentration, centrifugation time and rate were investigated. At optimized experimental conditions, the limit of detection and enhancement factor were found to be 0.132 µg/L and 70 respectively, with relative standard deviation <5%. In order to validate the developed method, certified reference materials (SLRS-4 Riverine water) and human serum (Sero-M10181) were analyzed. The resulting data indicated a non-significant difference in obtained and certified values of Cu(2+). The developed procedure was successfully applied for the preconcentration and determination of trace levels of Cu(2+) in environmental and biological samples. Copyright © 2015 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

PubMed

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

2018-05-15

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

Food grade microemulsion systems: canola oil/lecithin:n-propanol/water.

PubMed

Abbasi, Soleiman; Radi, Mohsen

2016-03-01

In this study, the capability of a natural surfactant, lecithin, and the influence of ionic strength, pH, and temperature on some properties of a food grade microemulsion system were evaluated. For this purpose, the pseudoternary phase diagrams of canola oil/lecithin:n-propanol/water microemulsions in the presence of different salts (NaCl and CaCl2), ionic strengths, pHs, and temperatures were constructed. Our findings showed that the presence of salts slightly increased the W/O areas on the phase diagrams, whereas pH variation was not effective on the microemulsion formation. The expansion of microemulsion areas with temperature indicated the greater triglycerides solubilization capacity of lecithin based microemulsions at higher temperatures. These findings revealed the efficiency of lecithin-based microemulsion system for solubilization of triglycerides which can potentially be used for extraction of edible vegetable oils particularly canola oil. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed

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

2004-11-01

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

The formation of RCCCO and CCC(O)R (R = Me, Ph) neutral radicals from ionic precursors in the gas phase: the rearrangement of CCC(O)Ph.

PubMed

Peppe, Salvatore; McAnoy, Andrew M; Dua, Suresh; Bowie, John H

2004-01-01

Neutrals MeCCCO, CCC(O)Me, PhCCCO and CCC(O)Ph have been made by neutralisation of [MeCCCO](+), [CCC(O)Me](-), [PhCCCO](+) and [CC(CO)Ph](-). Neutrals MeCCCO, CCC(O)Me and PhCCCO are stable for the microsecond duration of the neutralisation experiment. A joint experimental and theoretical study (energies calculated at the B3LYP/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory) suggests that the neutral radical CCC(O)Ph rearranges via a four-centred ipso radical cyclisation/ring opening to form the isomer PhCCCO in an exothermic reaction. (13)C labelling confirms that the rearrangement does not involve O migration. Some of the PhCCCO radicals formed in this reaction are sufficiently energised to effect decomposition to give PhCC and CO. Copyright 2004 John Wiley & Sons, Ltd.

Rapid analysis of ultraviolet filters using dispersive liquid-liquid microextraction coupled to headspace gas chromatography and mass spectrometry.

PubMed

Pierson, Stephen A; Trujillo-Rodríguez, María J; Anderson, Jared L

2018-05-29

An ionic-liquid-based in situ dispersive liquid-liquid microextraction method coupled to headspace gas chromatography and mass spectrometry was developed for the rapid analysis of ultraviolet filters. The chemical structures of five ionic liquids were specifically designed to incorporate various functional groups for the favorable extraction of the target analytes. Extraction parameters including ionic liquid mass, molar ratio of ionic liquid to metathesis reagent, vortex time, ionic strength, pH, and total sample volume were studied and optimized. The effect of the headspace temperature and volume during the headspace sampling step was also evaluated to increase the sensitivity of the method. The optimized procedure is fast as it only required ∼7-10 min per extraction and allowed for multiple extractions to be performed simultaneously. In addition, the method exhibited high precision, good linearity, and low limits of detection for six ultraviolet filters in aqueous samples. The developed method was applied to both pool and lake water samples attaining acceptable relative recovery values. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2016-02-15

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

How reliable are thermodynamic feasibility statements of biochemical pathways?

PubMed

Maskow, Thomas; von Stockar, Urs

2005-10-20

The driving force for organo- or lithotrophic growth as well as for each step in the metabolic network is the Gibbs reaction energy. For each enzymatic step it must be negative. Thermodynamics contributes therefore to the in-silico description of living systems. It may be used for assessing the feasibility of a given pathway because it provides a further constraint for those pathways which are feasible from the point of view of mass balance calculations (metabolic flux analysis) and the genetic potential of an organism. However, when this constraint was applied to lactic acid fermentation according to a method proposed by Mavrovouniotis (1993a, ISMB 93:273-283) it turned out that an unrealistically wide metabolite concentration range had to be assumed to make this well-known glycolytic pathway thermodynamically feasible. During a search for the reasons of this surprising result the insufficient consideration of the activity coefficients was identified as main cause. However, it is shown in the present contribution that the influence of the activity coefficients on Gibbs reaction energy can be easily taken into account based on the intracellular ionic strength. The uncertainty of the tabulated equilibrium constants and of the apparent standard Gibbs energies derived from them was found to be the second most important reason for the erroneous result of the feasibility analysis. Deviations of intracellular pH from the standard value and bad estimations of currency metabolites, e.g., NAD(+) and NADH, were found to be of lesser importance but not negligible. The pH dependency of Gibbs reaction enthalpy was proved to be easily taken into account. Therefore, the application of thermodynamics for a better in-silico prediction of the behavior of living cell factories calls predominantly for better equilibrium data determined under well defined conditions and also for a more detailed knowledge about the intracellular ionic strength and pH value. Copyright 2005 Wiley Periodicals, Inc.

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.

Ammonia Movement in the Small Intestine: Preferential Transport by the Ileum *

PubMed Central

Mossberg, Sanford M.; Ross, George

1967-01-01

Isolated, surviving sacs of everted small intestine were used to characterize ammonia transport in the golden hamster. Jejunal and ileal sacs incubated aerobically in ammonia-free test solution liberated the same quantity of ammonia as did sacs that were filled and immediately emptied of their contents, indicating no significant evolution of metabolic ammonia. Under aerobic conditions, ileal sacs transferred a solution of high ammonia content from the mucosal surface to the serosal surface against a concentration gradient. This transport was not glucose dependent and exhibited first-order Michaelis-Menten kinetics. Inhibition of absorption occurred with anaerobiosis, 2,4-dinitrophenol, and sodium cyanide. In jejunal segments ammonia was not transported against an adverse chemical gradient. Ileal ammonia absorption was accompanied by bicarbonate secretion and acidification of the serosal solution. Both bicarbonate movement and pH gradients were abolished by inhibitors of ammonia transport. In the jejunum, the absence of ammonia movement occurred in association with minimal bicarbonate secretion and no appreciable change in serosal pH. Despite the creation of hydrogen ion gradients tending to augment or to retard ammonia absorption by nonionic diffusion, ammonia movement was unaffected, i.e., relative acidification of serosal contents did not augment ammonia absorption, and relative alkalinization of serosal fluid caused no inhibition of ammonia transport. In the absence of bicarbonate ion, ammonia transport did not occur. The significance of these findings is discussed with consideration of both ionic and nonionic mechanisms of ammonia movement. It is suggested that ammonia is absorbed in the ileum by active ionic transport. PMID:6021202

Metal Complexation in Xylem Fluid 1

PubMed Central

White, Michael C.; Decker, A. Morris; Chaney, Rufus L.

1981-01-01

Xylem fluid was analyzed for numerous solutes to characterize chemically the sap as a medium for forming and transporting metal complexes. The stem exudate was collected hourly for 8 hours from topped 31-day-old soybean (Glycine max L. Merr.) and 46-day-old tomato (Lycopersicon esculentum Mill.) plants grown in normal (0.5 micromolar) and Za-phytotoxic nutrient solutions. Soybean plants were grown in the normal and high-Zn solutions for 24 days; tomato plants were grown for 32 days. The exudate was analyzed for seven organic acids, 22 amino acids, eight inorganic solutes, apparent ionic strength, and pH. Significant changes in many solutes occurred over the 8-hour sampling period. These fluctuations depended on plant species, individual solute, and Zn treatment, and demonstrated that extrapolation of xylem-fluid analyses to whole-plant xylem sap is valid only for sap samples collected shortly after topping a plant. Exudate pH decreased over the 8-hour period for both species; exudate ionic strength increased for tomato and decreased for soybean. At the normal-Zn treatment (0 to 1 hour), the highest acid micromolar concentrations in soybean exudate were: asparagine, 2,583; citric, 1,706; malic, 890; and malonic, 264. Under the same conditions, the highest acid micromolar concentrations in tomato exudate were: maleic, 1,206; malic, 628; glutamine, 522; citric, 301; and asparagine, 242. Cysteine and methionine were above detection limits only in soybean exudate. Zinc phytotoxicity caused significant changes in many solutes. The analyses reported here provide a comprehensive data base for further studies on metal-complex equilibria in xylem fluid. PMID:16661664

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.