Water Aqueous Solutions Research Articles

Phase stability conditions of clathrate hydrates for methane + aqueous solution of water soluble organic promoter system: Modeling using a thermodynamic framework

A thermodynamic model is presented for predicting the phase stability conditions of clathrate hydrates for methane+water-soluble organic promoter aqueous solution. A new equation is then proposed to estimate the enthalpy of hydrate dissociation for methane+aqueous solution of water-soluble organic promoter using Genetic Programming (GP) and Teaching–Learning-Based Optimization (TLBO) evolutionary algorithm. The model reliably predicts the hydrate dissociation conditions for methane+aqueous solutions of tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane and acetone. The van Laar model is used to calculate the activity coefficient of water in aqueous solution of water-soluble organic promoter. About 30% of the reported experimental data were used for finding the empirical relationships to estimate the enthalpy of hydrate dissociation and the remaining 70% was used to test the accuracy and the predictive capability of the correlation. The average absolute error for methane hydrate dissociation temperatures was found to be 0.33K, which indicates the accuracy of the model.

One-Step Transformation from Hierarchical-Structured Superhydrophilic NF Membrane into Superhydrophobic OSN Membrane with Improved Antifouling Effect.

The hierarchical-structured superhydrophilic poly(ethylenimine)/poly(acrylic acid) (PEI/PAA)calcium silicate hydrate (CSH) multilayered membranes (PEI/PAA-CSH)n were prepared as aqueous nanofiltration (NF) membrane, and then they were transformed into superhydrophobic organic solvent nanofiltration (OSN) membranes by one-step modification of trimethylperfluorinatedsilane (PFTS). Investigation on surface structures and properties of these multilayered membranes (PEI/PAA-CSH)n indicated that the hierarchical-structured (PEI/PAA-CSH)n multilayered membrane produced by in situ incorporation of CSH aggregates into PEI/PAA multilayers facilitated its one-step transformation from superhydrophilicity into superhydrophobicity. Both of the superwetting membranes showed better nanofiltration performances for retention of dyes of water and ethanol solution, respectively. Moreover, the long-term performance and antifouling behaviors, investigated by retention of methyl blue (MB), bovine serum albumin (BSA), and humic acid (HA) aqueous water solution and nonaqueous ethanol solution indicated that both of the superhydrophilic and superhydrophobic membrane showed higher stability and excellent antifouling property.

Recrystallization of freezable bound water in aqueous solutions of medium concentration**Project supported by the Knowledge Innovation Project of Chinese Academy of Sciences on Water Science Research (Grant No. KJZD-EW-M03) and the National Natural Science Foundation of China (Grant Nos. 11474325 and 11290161).

For aqueous solutions with freezable bound water, vitrification and recrystallization are mingled, which brings difficulty to application and misleads the interpretation of relevant experiments. Here, we report a quantification scheme for the freezable bound water based on the water-content dependence of glass transition temperature, by which also the concentration range for the solutions that may undergo recrystallization finds a clear definition. Furthermore, we find that depending on the amount of the freezable bound water, different temperature protocols should be devised to achieve a complete recrystallization. Our results may be helpful for understanding the dynamics of supercooled aqueous solutions and for improving their manipulation in various industries.

Proteins Take up Water Before Unfolding.

Proteins perform specific biological functions that strongly depend on their three-dimensional structure. This three-dimensional structure, i.e. the way the protein folds, is strongly determined by the interaction between the protein and the water solvent. We study the dynamics of water in aqueous solutions of several globular proteins at different degrees of urea-induced unfolding, using polarization-resolved femtosecond infrared spectroscopy. We observe that a fraction of the water molecules is strongly slowed down by their interaction with the protein surface. By monitoring the slow water fraction we can directly probe the amount of water-exposed protein surface. We find that at mild denaturing conditions, the water-exposed surface increases by almost 50%, while the secondary structure is still intact. This finding indicates that protein unfolding starts with the protein structure becoming less tight, thereby allowing water to enter.

Effects of osmolytes on solvent features of water in aqueous solutions

The solvatochromic solvent features of water (dipolarity/polarizability, π*, hydrogen bond donor acidity, α, and hydrogen bond acceptor basicity, β) of water have been determined in aqueous solutions of erythritol, glucose, inositol, sarcosine, xylitol and urea with concentrations from 0 to ~3 M and higher. The concentration effects of the osmolytes on the solvent features of water were characterized and compared with those reported previously for sorbitol, sucrose, trimethylamine N-oxide (TMAO), and trehalose. The solvent features of water in solutions of all osmolytes except TMAO and sarcosine were established to be linearly interrelated. It is shown that the concentration effects of essentially all nonionic osmolytes depend on osmolytes’ lipophilicity, molecular polarizability, and polar surface area. It is demonstrated that solubility of various compounds in aqueous solutions of glucose, sucrose, sorbitol, and urea of varied concentrations may be described in terms of solvent dipolarity/polarizability of water in these solutions. Surface tension of aqueous solutions of sucrose and sorbitol may also be described in the same terms. The relative permittivity of aqueous solutions of glucose and sucrose may be described in terms of the solvent hydrogen bond donor acidity of water. It is suggested that the effects of nonionic osmolytes on behavior of proteins and nucleic acids in aqueous media may be considered in terms of the altered solvent features of water instead of “nano-molecular crowding” effect.

Nizkochastotnaya induktivnaya diel'kometriya — informativnyy metod dlya izucheniya strukturirovaniya vody v vodnych rastvorach

Nizkochastotnaya induktivnaya diel'kometriya — informativnyy metod dlya izucheniya strukturirovaniya vody v vodnych rastvorach

Molecular Anion Hydrogen Bonding Dynamics in Aqueous Solution.

The dynamic nature of hydrogen bonding between a molecular anion, selenocyanate (SeCN(-)), and water in aqueous solution (D2O) is addressed using FT-IR spectroscopy, two-dimensional infrared (2D IR) vibrational echo spectroscopy, and polarization selective IR pump-probe (PSPP) experiments performed on the CN stretching mode. The CN absorption spectrum is asymmetric with a wing on the low frequency (red) side of the line in contrast to the spectrum in the absence of hydrogen bonding. It is shown that the red wing is the result of an increase in the CN stretch transition dipole moment due to the effect of hydrogen bonding (non-Condon effect). This non-Condon effect is similar in nature to observations on pure water and other nonionic systems where hydrogen bonding enhances the extinction coefficient. The 2D IR measurements of spectral diffusion (solvent structural evolution) yield a time constant of 1.5 ps, which is within error the same as that of the OH stretch of HOD in D2O (1.4 ps). The orientational relaxation of SeCN(-) measured by PSPP experiments is long (4.04 ps) compared to the spectral diffusion time. The population decay at or near the absorption line center is a single-exponential decay of 37.4 ± 0.3 ps, the vibrational lifetime. However, on the red side of the line the decay is biexponential with a low amplitude, fast component; on the blue side of the line there is a low amplitude, fast growth followed by the lifetime decay. Both of the fast components have 1.5 ps time constants, which is the spectral diffusion time. The fast components of the population decays are the results of the non-Condon effect that causes the red side of the line to be over pumped by the pump pulse. Spectral diffusion then produces the fast decay component on the red side of the line and the growth on the blue side of the line as the excess initial population on the red side produces a net population flow from red to blue.

Characterization of an exopolysaccharide produced by Lactobacillus plantarum YW11 isolated from Tibet Kefir

An exopolysaccharide (EPS)-producing strain YW11 isolated from Tibet Kefir was identified as Lactobacillus plantarum, and the strain was shown to produce 90mgL−1 of EPS when grown in a semi-defined medium. The molecular mass of the EPS was 1.1×105Da. The EPS was composed of glucose and galactose in a molar ratio of 2.71:1, with possible presence of N-acetylated sugar residues in the polysaccharide as confirmed by NMR spectroscopy. Rheological studies showed that the EPS had higher viscosity in skim milk, at lower temperature, or at acidic pH. The viscous nature of the EPS was confirmed by observation with scanning electron microscopy that demonstrated a highly branched and porous structure of the polysaccharide. The atomic force microscopy of the EPS further revealed presence of many spherical lumps, facilitating binding with water in aqueous solution. The EPS had a higher degradation temperature (287.7°C), suggesting high thermal stability of the EPS.

Analyzing the effects of protecting osmolytes on solute–water interactions by solvatochromic comparison method: I. Small organic compounds

Solvent properties of water in aqueous solutions of osmolytes (sorbitol, sucrose, trehalose, and trimethylamine N-oxide (TMAO)) were studied at different concentrations using the solvatochromic comparison method.

Investigation of Solvent Effects on the Reaction of 1-Fluoro-2,4-Dinitrobenzene with Aniline in Molecular-Molecular and Ionic Liquid–Molecular Solvent Mixtures

The solvent effects on the reaction of 1-fluoro-2,4-dinitrobenzene with aniline was studied in various compositions of molecular-molecular solvent mixtures and molecular solvent-2-hydroxyethylammonium formate mixtures as media containing an ionic liquid. A mounting trend with the mole fraction of water in aqueous solution of alcohols up to a maximum at a mole fraction of 0.9 with respect to water was found, but a mild decrease with the mole fraction of ethyl acetate in methanol–ethyl acetate mixtures. A similar increasing trend was observed with increasing methanol, ethanol, 2-propanol and dimethylsulfoxide content in the mixtures containing the ionic liquid. Solvent effect investigations based on linear free energy relationship confirm that polarity has a major effect in molecular-molecular solvent mixtures, whereas polarity and hydrogen–bond acceptor ability were the dominant factors on reaction rate in molecular-ionic solvent mixtures. A nonlinear free energy relationship based on the preferential solvation hypothesis showed differences between the microsphere solvation of the solute and the bulk composition of the solvents. In these mixtures, the intermediate of the reaction was preferentially solvated by the ionic liquid.

The effect of salinity and temperature on electromagnetic wave attenuation in brine

Ice slurries are typically formed from an aqueous solution of water and salt (NaCl) at 5% salinity. Ice pigs, used in many industry areas, are taken from a bulk ice slurry and used to clear waste or recover product from pipes. Ice fraction is a key property of an ice slurry, since it determines it's ‘thickness’ and therefore cleaning capacity. Electromagnetic wave interrogation has been shown to accurately predict an ice fraction to within an error of ±1.2%. The largest remaining process error comes from inherent salinity variation, which affects the electromagnetic wave attenuation significantly. Increasing electromagnetic wave attenuation with increasing salinity and the effect of temperature, shown to also increase attenuation, is quantified. Calibration methods are proposed, aiming to eliminate the unwanted effect of varying salinity. Analysis on multiple samples showed a 16% reduction in average error, and 9% reduction in maximum error when the calibration method was applied.

A GMDH-type neural network for prediction of water activity in glycol and Poly(ethylene glycol) solutions

The objective of current work is to predict the activities of water in aqueous solution of glycols and polyethylene glycols (PEGs) by means of a group method of data handling (GMDH). The proposed model considers temperature, molecular weight of the polymer as well as weight fraction of water for input variables. A 387 experimental data set of activities of water in aqueous binary solution of different glycols and polyethylene glycols is used. Mean absolute error percent (MAE %) of the training and testing obtained were 2.45 and 2.46 respectively; the results when compared to those of an artificial neural network (ANN) model show a weaker correlation. However, a noticeably reduced runtime and more importantly an explicit general correlation function, typical of GMDH networks, offer superior advantages over an ANN model.

Acidity and Hydrogen Exchange Dynamics of Iron(II)‐Bound Nitroxyl in Aqueous Solution

AbstractNitroxyl‐iron(II) (HNO‐FeII) complexes are often unstable in aqueous solution, thus making them very difficult to study. Consequently, many fundamental chemical properties of FeII‐bound HNO have remained unknown. Using a comprehensive multinuclear (1H, 15N, 17O) NMR approach, the acidity of the FeII‐bound HNO in [Fe(CN)5(HNO)]3− was investigated and its pKa value was determined to be greater than 11. Additionally, HNO undergoes rapid hydrogen exchange with water in aqueous solution and this exchange process is catalyzed by both acid and base. The hydrogen exchange dynamics for the FeII‐bound HNO have been characterized and the obtained benchmark values, when combined with the literature data on proteins, reveal that the rate of hydrogen exchange for the FeII‐bound HNO in the interior of globin proteins is reduced by a factor of 106.

Acidity and hydrogen exchange dynamics of iron(II)-bound nitroxyl in aqueous solution.

Nitroxyl-iron(II) (HNO-Fe(II)) complexes are often unstable in aqueous solution, thus making them very difficult to study. Consequently, many fundamental chemical properties of Fe(II)-bound HNO have remained unknown. Using a comprehensive multinuclear ((1)H, (15)N, (17)O) NMR approach, the acidity of the Fe(II)-bound HNO in [Fe(CN)5(HNO)](3-) was investigated and its pK(a) value was determined to be greater than 11. Additionally, HNO undergoes rapid hydrogen exchange with water in aqueous solution and this exchange process is catalyzed by both acid and base. The hydrogen exchange dynamics for the Fe(II)-bound HNO have been characterized and the obtained benchmark values, when combined with the literature data on proteins, reveal that the rate of hydrogen exchange for the Fe(II)-bound HNO in the interior of globin proteins is reduced by a factor of 10(6).

Ice fraction measurement of ice slurries through electromagnetic attenuation

Ice pigging is a process used by many industries for pipe cleaning and product recovery. Ice slurries, used to form an ice pig, are generated using an aqueous solution of water and a freezing point depressant, typically salt (NaCl) at 5% salinity. The ‘thickness’ of an ice slurry is key to the ice pig's performance, and this paper investigates a new non-invasive method of ice fraction measurement. Electromagnetic (EM) waves, with a frequency of 2.5 GHz, are absorbed rapidly by water molecules, but pass through ice with little drop in intensity, due to key differences in the materials' atomic structures. This phenomenon is exploited, and results show ice fraction can be approximated to within ±1.2% using a VNA spectrum analyser, then mathematical manipulation and analysis. This rivals the error in calorimetry, ±1.3%, which currently seen as the ‘gold standard’ in ice fraction measurement across the industry.

Hydration dynamics of aqueous glucose probed with polarization-resolved fs-IR spectroscopy.

The dynamics of water in aqueous solutions of glucose have been investigated using polarization-resolved femtosecond infrared spectroscopy of the hydroxyl stretch vibrations of water and glucose. Using reference measurements on solutions of glucose in dimethylsulfoxide and a spectral decomposition model, we are able to distinguish the reorientation dynamics of the glucose and water hydroxyl groups. We find that the water reorientation dynamics strongly slow down in the presence of glucose.

Structural changes at the interface between polycrystalline Ag and electrolyte solutions containing surfactants as probe molecules

Structural changes are detected at the interface between polycrystalline Ag electrodes and electrolyte solutions containing surfactants as probe molecules. Capacitance and impedance measurements indicate that in aqueous solutions water and 1-butanol molecules change their position on the electrode due to dipole-field interaction. In methanolic solutions such a change is indicated to occur only for triphenyphosphine oxide molecules. The above changes in both solvents are taking place along with the transition of the adsorbed layer from a dense liquid state to a thinner one with increasing negative potentials.

An insight into the kinetics and interface sensitivity for catalytic ozonation: the case of nano-sized NiFe2O4

In this paper, the kinetics and interface sensitivity of nano-sized magnetic NiFe2O4 in incomplete catalytic ozonation were investigated in detail. By analyzing the kinetics of heterogeneous reactions, it was found that both the degradation of phenol and the decomposition of molecular ozone appeared to follow a first order kinetics model and the presence of nano-NiFe2O4 significantly enhanced these processes. The kinetics equations and reaction rate constants were determined according to experimental results. In light of the IR spectra, the Lewis acid sites were further confirmed as reactive centers for catalytic ozonation in the aqueous phase, and the reason for deactivation of the NiFe2O4 nanocatalyst during incomplete ozonation of organic compounds was determined. The catalytic activity of the NiFe2O4 nanocatalyst could be completely recovered by calcination and ozonation methods, which makes it an attractive nanomaterial with prospective applications in water treatment. According to the interface sensitivity of ozone in water, a strong interaction between ozone and NiFe2O4 was observed and the role of water was revisited. Water molecules were clarified as two different types: one is chemisorbed water on the catalyst surface and the other is bulk water in aqueous solution. Both bulk and chemisorbed water molecules should be weak competitors compared with ozone, and the chemisorbed water on the catalyst surface was proposed not as an inhibitor but an accelerator for catalytic activity.

Dynamics of supercooled water in a biological model system of the amino acid L-lysine.

The dynamics of supercooled water in aqueous solutions of the single amino acid L-lysine has been studied by broadband dielectric spectroscopy. The chosen biological system is unique in the sense that the water content is high enough to fully dissolve the amino acid, but low enough to avoid crystallisation to ice at any temperature. This is not possible to achieve for proteins or other larger biomolecules, where either hydrated samples without ice or solutions with large quantities of ice, or a cryoprotectant sugar, have to be studied at low temperatures. Thus, it is a key finding to be able to study water and biomolecular dynamics in a non-crystallized and biologically realistic solution at supercooled temperatures. Here, we focus on the water dynamics in this unique biological solution of L-lysine and water. We show that this unique system also gives rise to unique water dynamics, since, for the first time, a continuation of a cooperative (α-like) water relaxation is observed after a crossover to a more local β-like water relaxation has occurred with decreasing temperature. This implies that the supercooled water in the biological solution shows a twofold relaxation behaviour, with one relaxation identical to the main relaxation of water in hard confinements and one relaxation almost identical to the main water relaxation in ordinary aqueous solutions.

Changes in the structure of water in aqueous solutions of acetic acid, depending on concentration and temperature according to densitometry, viscosimetry, and IR spectroscopy data

The structural features of aqueous solutions of acetic acid are studied by means of viscosimetry, densimetry, and IR spectroscopy within the temperature range of 283.15–333.15 K and a concentration range of 0–80%. The results from our experiments are used to calculate the parameters of viscous flow activation, the structural temperature, the partial molar volume of acetic acid in the solution, the thermal expansion coefficient, and the energies and lengths of the hydrogen bonds between water molecules. The concentration dependences of these parameters are analyzed. Based on the obtained results, we conclude that acetic acid disrupts the structure of water.