Synergy between Hofmeister effect and coupled water in proteins: Unusual dilational moduli of BSA at air/solution interface

This study relates interfacial interactions of bovine serum albumin (BSA) molecules in dilute solutions with its dilatational rheology. Dynamic surface tension and the associated dilational elastic modulus and viscosity for BSA and mixtures of BSA with Hofmeister electrolytes—NaCl, NaClO₄, Na₂SO₄, NaF and Na₂HPO₄ have been studied using a sinusoidal surface compression and expansion for frequencies ranging from 0.01 to 0.4 Hz. at solution/air interface. In all the BSA + electrolyte systems, both the elastic modulus and viscosity show unusually high values compared with pure BSA or pure electrolytes. In the presence of NaF and Na₂SO₄ the viscosity of protein increases almost by 50–80-fold and the corresponding elastic modulus also changes by 30–50-fold. Hydrated Hofmeister ions surely influence the measured rheological properties. In addition, the synergistic effect of the hydrated protein and the vicinal hydrated electrolytes possibly contribute to the high viscosity and elasticity due to change in dynamics of these assemblies. Thus the behavior of BSA is effected by salts in different ways, especially due to the dynamics and strength of the water molecules in the assembly.     

Participation of water in conformational change of isotactic poly(2-hydroxyethyl methacrylate) as studied by viscometry in various electrolytic solutions

Conformational properties of isotactic poly(2-hydroxyethyl methacrylate) (PHEMA) have been studied by viscometry in various electrolytic solutions. The intrinsic viscosity of isotactic PHEMA at 0.01M salt solution increases with decreasing the B coefficient in Jones—Dole's equation. In respective to water structures, a polymer chain is more expanded in the salt solution including water structure breaker ions. As the concentration of ions increases, the interactions between polymer segments and ions make a major contribution to conformational changes of isotactic PHEMA. Depending on the kind of ions, a salting-in or out effect is observed at higher concentrations than 0.1M salt solution. We observed that the denaturing effects of various anions in isotactic PHEMA salt solutions are as follows; SO₄^2- < F^? < I^? NO₃^? < SCN^-. This order is similar to the Hofmeister series. To investigate the influences of denaturing agents on solvent structures, we also compared the guanidine hydrochloride effect with the tetrabutylammonium chloride effect in isotactic PHEMA solution.     

Apparent molal volumes and heat capacities of some alkali halides and tetraalkylammonium bromides in aqueoustert-butanol solutions

The densities and volumetric specific heats of hydrochloric acid, alkali chlorides and bromides, and tetraalkylammonium bromides were measured in 0 to 40% by weighttert-butanol (t-BuOH) in water with a flow densimeter and a flow microcalorimeter. The effect of salt concentration was investigated in the case of NaCl. The apparent molal volumes and heat capacities and the derived transfer functions of the electrolytes from water tot-BuOH-water mixtures can be interpreted through solute-solute pair and triplet interactions by analogy with the transfer functions oft-BuOH from water to electrolyte solutions, with the salting-in and salting-out effects, and with the influence of electrolytes on the thermodynamics of micellization. At lowt-BuOH concentrations, the transfer functions seem to be reflecting primarily electrolyte-nonelectrolyte pair interactions. At intermediatet-BuOH concentration, wheret-BuOH associates, the hydrophobic bonding is enhanced by hydrophilic ions through a salting-out effect on monomers and by hydrophobic salts through triplet interaction (mixed association complexes). The Me ₄ NBr and Et ₄ NBr are intermediate electrolytes which do not have much effect on thet-BuOH hydrophobic bonding. At hight-BuOH concentrations the transfer functions tend to the values they would have in puret-BuOH.     

Influence of the Hofmeister anions on self-organization of 1-decyl-3-methylimidazolium chloride in aqueous solutions

Inorganic salts usually influence water structure affecting the hydration of the molecules which lead to a salting-in or a salting-out effect of hydrophobic compounds. Specific conductivity and isothermal titration calorimetry have been used to study the effect of inorganic salts on aggregation of the cationic surfactant 1-decyl-3-methylimidazolium chloride in aqueous solutions. The effect of the concentration, the nature of the anion and temperature on micelle formation were studied. A decreasing critical micelle concentration (CMC) due to the weakening electrostatic repulsion between the headgroups was observed. The salts used in this investigation decreased the CMC and degree of micelle ionization in the order of Cl(-)相似文献   

Chromatographic behaviour of aromatic compounds on gel filtration Media

Summary Highly cross-linked gels utilized as gel filtration media exhibit adsorption effects towards aromatic or apolar compounds. The adsorption is linearly dependent on salt concentration. We investigated the effect of various salts spanning the Hofmeister series on the adsorption of three model compounds, Adenosine 5′-phosphate, ε-dinitrophenyllysine and tryptophan. It was found that salts exhibiting marked salting-out properties, such as potassium phosphate and sodium sulfate, were the most effective in enhancing the adsorption were the most effective in enhancing the adsorption of the aromatic molecules onto the gel. On the contrary, in the presence of salts with marked salting-in properties, such as Kl or KSCN, the linear dependence of elution parameters for the same compounds was negatively correlated and adsorption decreased with salt concentration. However, a number of salts of intermediate character in the Hofmeister series, such as NaCl or NH₄Cl, did not affect the elution behaviour of the chosen model compounds. The different effects observed are probably due to differential hydration of the molecules in the presence of the salts and to the consequent different hydrodynamic behaviour of the solute when interacting with the hydration layers of the gel matrix.     

Distribution constants of lower alcohols,acetone, and ethyl acetate in <Emphasis Type="Italic">n</Emphasis>-hexane-aqueous solutions of inorganic salt systems and the nature of the salting-out effect

The distribution of model oxygen-containing organic nonelectrolytes in n-hexane-aqueous solutions of mineral salts (KF, (NH₄)₂SO₄, K₂CO₃, K₃PO₄) and lower alcohol-saturated aqueous solutions of salt (KF, K₂CO₃, K₃PO₄) systems are studied at a temperature of 20 ± 1°C. Increments of the methylene and functional groups of organic nonelectrolyte of partition constants logarithm are calculated. It is shown that the nature of the salting-out effect primarily involves strengthening of the salt solution’s structure and growth of the methylene group increment. A comparative characteristic of various salts according to the degree of their structuring effect and the effectiveness of the salting-out of organic nonelectrolytes from aqueous solutions is given.     

Hofmeister anion effect on aqueous phase behavior of heptaethylene glycol dodecyl ether

The aqueous phase behavior of heptaethylene glycol dodecyl ether (C12E7) was investigated in the presence of sodium salts of Cl-, I-, and ClO4-. Pseudo binary T-X phase diagrams were constructed for these mixtures by means of differential scanning calorimetry. The salting-out electrolyte NaCl expanded the Lalpha region toward higher temperatures and shrank the H1 region toward lower temperatures compared with the salt-free system. On the contrary, the salting-in electrolytes NaI and NaClO4 induced shrinkage of the Lalpha region and an expansion of the H1 phase. The influence of these salts on the mesophase regions was more pronounced for the Lalpha phase than for the H1 phase, and area of the Lalpha phase region decreased in the sequence of NaCl > none > NaI > NaClO4, consist with the Hofmeister series of the anions. This salt effect on the mesophase stability in aqueous nonionic surfactant mixture would be qualitatively interpreted in terms of the salt effect on the hydration of the polyoxyethylene chain in the surfactant molecules.     

Liquid-to-Solid Phase Transitions of Imidazolium-Based Zwitterionic Polymers Induced by Hofmeister Anions

In this study, we compared the responses of two different types of zwitterionic polymers (ZPs), polyvinylimidzole sulfobetaine (poly(SBVI)) and polymethacrylate sulfobetaine (poly(SBMA)) to Hofmeister anions. Although the anions of the two ZPs were the same as the sulfonate anions and only the types of their cations were different from each other, the aggregation behavior of each in the salt aqueous solution was remarkably different. Consequently, poly(SBVI) exhibited both salting-in and salting-out effects depending on the type and concentration of salt, while poly(SBMA) only exhibited the anti-polyelectrolyte effect. The results of this study provide a deeper understanding of the behavior of zwitterionic polymers in salt solutions and will greatly expand their applications.     

Conductance of 1∶1 electrolytes in methyl acetate

The electrolytic conductances of NaClO₄, NaB(C₆H₅)₄, (n-C₄H₉)₄NClO₄ and (n-C₄H₉)₄NPF₆ have been measured in methyl acetate at 25°C. A dominating feature of these electrolyte solutions is, as expected, strong ion pairing. In addition it is found that the formation of triple ions makes an important contribution to the overall molar conductivities. The data suggest that there are strong ion-solvent interactions leading to structure-enhanced (after Diamond) ion association and triple ion formation which has an exact analogy in the phenomena of salting-in. The effects of increasing solution permittivity and viscosity are discussed, particularly in regard to comparing two models of treating conductivity data. The first model includes ion pairs and triple ions, and the second model ignores triple ion formation ascribing the anomalous increase in molar conductivities to a decrease in the ion association equilibrium constant caused by increasing solution permittivity.     

Salt effect on polymer solutions

The salt effect was investigated by measurements of viscosity, cloud point, and solubility of aqueous solutions of poly(vinyl alcohol—acetate) copolymers, as these copolymers in water are sensitive in various ways to addition of various electrolytes. The major role in the salt effect is played by the anions, and water-structure breaking anions produce salting-in of the copolymers. Tetraalkylammonium halides (bromides and iodides) cause salting-in of the copolymers more effectively with increase of size of the hydrophobic cations. The Setschenow equation does not hold for the polymers except for very dilute polymer concentration. In salts of monoalkyl-substituted anions (R? COONa and R? SO₄Na) and cations (R? NH₃Cl and Br), so long as the alkyl chain is short, the salt effect is also dominated by the anions. With increase of the alkyl chain length, sodium salts of the monoalkyl-substituted anions exert a stronger salting-in effect upon the polymers than chlorides of similar long-chain cations. The significance of the counteranions is suggested for the interaction of nonionic polymers and the long-chain cations. The action of the salts on the copolymers is discussed in terms of medium effects (change of the water structure) and of the binding effect of the single ions to the polymers.     

Electrolytic Double-Layer Supercapacitors Based on Sodium-Ion Systems,with Activated-Carbon Electrodes

1 M solutions of NaClO₄ mixed with ethylene carbonate, dimethyl carbonate, and fluoroethylene carbonate were studied as electrolytes for a double-layer supercapacitor with electrodes made of Norit DLC Supra 30 activated carbon. It was shown that the specific capacity of activated carbon depends on the electrolyte composition, range of cycling voltages, and current density. The maximum specific capacitance of 40 F g^–1 was obtained in 1 M NaClO₄ mixed with ethylene carbonate: dimethyl carbonate: fluoroethylene carbonate (4: 5: 1) at a current density of 36 mA g^–1 in the range 10–2300 mV. The minimum specific capacitance was obtained under the same cycling conditions in the electrolyte with 1 M NaClO₄ + ethylene carbonate: dimethyl carbonate (1: 1). The variation of the specific capacitance with the electrolyte composition and range of cycling voltages is accounted for by the existence of a pseudocapacitance caused by the occurrence of side processes on the surface of activated carbon. The impedance spectroscopy was used to find that the introduction of fluoroethylene carbonate into the electrolyte positively affects the charge-transfer resistance and favors an increase in the specific capacitance of activated carbon.     

Water structure and electron trapping in aqueous ionic solutions

The optical absorption spectra observed by pulse radiolysis of alkaline (NaOH, KOH, RbOH), chloride (LiCl, MgCl₂, CaCl₂, NaCl, KCl) and perchloride (NaClO₄) solutions at temperature 298 K are reported. Some measurements were performed at low temperature with aqueous ionic glasses. With increasing concentration of the above solutes a uniform blue-shift of the maximum of the solvated electron (e¯_sol) absorption band is observed. Near infrared (NIR) spectroscopy was so used to examine the properties of water in several concentrated electrolyte solutions. It is shown that some inorganic electrolytes (e.g. NaOH, NaClO₄) substantially change the water structure whereas some others (e.g. LiCl, CaCl₂) influence water structure insignificantly. The correlation between the ability of excess electron trapping in electrolyte solutions and water structure deduced from NIR spectroscopy is discussed.     

Stereoselectivity ratios in a simple Diels-Alder reaction in aqueous salt solutions of alcohols

This is the first exhaustive report on the variation of stereoselectivity ratios for a simple Diels-Alder reaction between cyclopentadiene and methyl acrylate. The reaction was carried out in aqueous mixtures of methanol, ethanol, propan-1-ol and butan-1-ol in presence of LiClO₄, LiCl, NaCl, KCl, CaCl₂ and MgCl₂. The endo stereoisomer decreases with the increase in carbon chain length of the alcohol. However, LiClO₄, a salting-in agent in water becomes salting-out in aqueous mixtures of alcohols. The solvent properties, thus can be attuned by adjusting the amount of solvents and salts.     

Hydrotrope-induced inversion of salt effects on the cloud point of an extended surfactant

We report on the effects of electrolytes spanning a range of anions (NaOc, NaSCN, NaNO(3), NaBr, NaCl, NaBu, NaOAc, Na(2)SO(4), Na(2)HPO(4), and Na(2)CO(3)) and cations (LiCl, NaCl, KCl, CsCl, and choline chloride) on the aqueous solubility of an extended surfactant. The surfactant is anionic with a long hydrophobic tail as well as a significant fraction of propylene oxide groups and ethylene oxide groups (C(12-14)-PO(16)-EO(2)-SO(4)Na, X-AES). In the absence of electrolytes, X-AES exhibits a cloud-point temperature that decreases with increasing surfactant concentration. After the addition of salts to the surfactant solutions, various shifts in the solubility curves are observed. These shifts follow precisely the same Hofmeister series that is found for salting-in and salting-out effects in protein solutions. In the presence of different concentrations of sodium xylene sulfonate (SXS), the solubility of the surfactant increases. In this context, SXS can be considered to be a salting-in salt. However, when the electrolytes are added to an aqueous solution of X-AES and SXS the Hofmeister series reverses for divalent anions such as Na(2)SO(4), Na(2)HPO(4), and Na(2)CO(3). Studies on the phase behavior and micelle structures using polarization microscopy, freeze-etch TEM, and NMR measurements indicate a dramatic change in the coexisting phases on the addition of SXS.     

The salt effect for the solubilities of metal β-diketonates—II: Beryllium benzoylacetonate

In order to confirm extensively a generalized interpretation for the salt effect in solvent extraction of metal chelates, the solubilities of bis(1-phenyl-1,3-butanedionato) Be(II) (Be(bzac)₂) in aqueous solutions of LiCl, NaClO₄, NaNO₃, KBr, NaBr, KCl, NaCl and Na₂SO₄ were determined at 25°C. The salting coefficients of these salts for Be(bzac)₂ were obtained from the above data, and were found to accord with McDevit-Long equation except for LiCl. The salting-in effect of LiCl is discussed from the aspect of the strong hydration of small Li⁺ ion. The salting coefficients for Be(bzac)₂ are compared with those for the corresponding copper chelate (Cu(bzac)₂) and an influence of the stereochemical configurations of the metal chelates on the salt effect is also discussed.     

Effect of addition of 1-butyl-3-methylimidazolium thiocyanate on conductivity of Na-containing polymer electrolyte

Research in the environmentally friendly energy field has grown rapidly due to severe problems such as global warming and climate change. Sodium-ion technology is one of the most promising alternatives to lithium-ion batteries. Use of ionic liquids containing thiocyanate anion has been considered because of their low cost, low viscosity, and nonhazardous nature. In this work, polyethylene oxide (PEO)–sodium perchlorate (NaClO₄) samples containing different amounts of 1-butyl-3-methylimidazolium thiocyanate ionic liquid were prepared by a solution casting method. Addition of the ionic liquid to the PEO–NaClO₄ electrolyte further increased the ionic conductivity. The electrolyte containing 30 wt% ionic liquid exhibited the maximum ionic conductivity of ~5.0 × 10^?4 S/cm at room temperature. Fourier-transform infrared (FT-IR) spectroscopy revealed the interaction between the polymer chain and salt ion complexes for various sodium salt contents. Differential scanning calorimetry (DSC) demonstrated that the crystallinity was reduced by addition of 1-butyl-3-methylimidazolium thiocyanate ionic liquid.     

Ionic liquid–water mixtures as solvents for poly(N-vinylimidazole)

Ionic liquids extend the Hofmeister series and create a wide range of new possibilities for processes involving salt effects on both soluble and crosslinked systems. This work reports on some mixtures of water with NaCl or an ionic liquid, either 1-ethyl-3-methylimidazolium tosylate or 1-hexyl-3-methylimidazolium chloride, which are better solvents for linear poly(N-vinylimidazole) (L-PVI) than water, i.e., that exhibit a salting-in effect. The intensity of the salt effects was measured on the basis of the polymer solubility, the decrease in polymer–solvent interaction parameter (measured by light scattering), and the increase of coil size (measured through the intrinsic viscosity). It was thus found that the intensity of the salting-in effect of either NaCl or 1-hexyl-3-methylimidazolium chloride on L-PVI is different (larger for the ionic liquid), which denotes that salt effects are not under anion control, and the mechanisms operating in the linear and crosslinked polymers are different. These results are discussed after accounting for the role of ion–polymer interactions.     

Salt effects on the partition coefficients of phenol in two-phase mixtures of water and carbon dioxide at pressures from (8 to 30) MPa at a temperature of 313 K

Partition coefficients K_c of phenol between an aqueous solution containing different salts and a compressed CO₂ phase have been determined at T=313 K. For NaCl and (CH₃)₄NBr a pressure range from 8 MPa to around 30 MPa was investigated, for KCl and NaBr measurements were performed at a pressure of 22 MPa. The salt concentration has been varied between (0.25 and 3.0) mol·dm⁻³. With increasing pressure a rise in K_c is observed which typically is also found in systems free of salt. Salting-out was observed for the alkali salts, salting-in has been found for the ammonium salt, both effects increased with increasing salt concentration. From the concentration dependence of the K_c values Setschenow coefficients k_S have been derived. At p>10 MPa values are obtained as found in two phase mixtures of water with other organic solvents at ambient pressure. This conclusion was confirmed with both literature and own experimental data in the case of salting-out by NaCl as well as for the salting-in by (CH₃)₄NBr from measurements with phenol in (water + cyclohexane) at T=313 K.     

Electrochemical reduction of carbon dioxide with lead cathode and zinc anode in dry acetonitrile solution

The electrochemical reduction of carbon dioxide (CO₂) is investigated in acetonitrile with tetrabutylammonium perchlorate as an electrolyte using a lead cathode and a sacrificial zinc anode, and the product under such a setup is insoluble zinc oxalate at potentials between ?2.2 and ?2.8 V vs. Ag rod electrode. Preelectrolysis is an effective method to remove the water in the electrolyte, which makes a distinct reduction peak of CO₂ appear at ?2.6 V vs. Ag on cyclic voltammogram. Even trace amounts of water in the electrolyte can interfere with the faradaic efficiency of reduction of CO₂ to oxalate, and the product could be β-ZnC₂O₄ (in anhydrous solution) or ZnC₂O₄?·?2H₂O (if water exists). The faradaic efficiency for oxalate production also depends on the cathode potential and the temperature, and the maximum is 96.8 % at ?2.6 V vs. Ag and 5 °C. This is the highest value of CO₂ electrochemical reduction found in the literature under ambient pressure.