Relationships between Molecular Structure of Carbohydrates and Their Dynamic Hydration Shells Revealed by Terahertz Time-Domain Spectroscopy

Despite more than a century of research on the hydration of biomolecules, the hydration of carbohydrates is insufficiently studied. An approach to studying dynamic hydration shells of carbohydrates in aqueous solutions based on terahertz time-domain spectroscopy assay is developed in the current work. Monosaccharides (glucose, galactose, galacturonic acid) and polysaccharides (dextran, amylopectin, polygalacturonic acid) solutions were studied. The contribution of the dissolved carbohydrates was subtracted from the measured dielectric permittivities of aqueous solutions based on the corresponding effective medium models. The obtained dielectric permittivities of the water phase were used to calculate the parameters describing intermolecular relaxation and oscillatory processes in water. It is established that all of the analyzed carbohydrates lead to the increase of the binding degree of water. Hydration shells of monosaccharides are characterized by elevated numbers of hydrogen bonds and their mean energies compared to undisturbed water, as well as by elevated numbers and the lifetime of free water molecules. The axial orientation of the OH(4) group of sugar facilitates a wider distribution of hydrogen bond energies in hydration shells compared to equatorial orientation. The presence of the carboxylic group affects water structure significantly. The hydration of polysaccharides is less apparent than that of monosaccharides, and it depends on the type of glycosidic bonds.     

Molecular Mechanism of the Hydration of Candida antarctica Lipase B in the Gas Phase: Water Adsorption Isotherms and Molecular Dynamics Simulations

Hydration is a major determinant of activity and selectivity of enzymes in organic solvents or in gas phase. The molecular mechanism of the hydration of Candida antarctica lipase B (CALB) and its dependence on the thermodynamic activity of water (a_w) was studied by molecular dynamics simulations and compared to experimentally determined water sorption isotherms. Hydration occurred in two phases. At low water activity, single water molecules bound to specific water binding sites at the protein surface. As the water activity increased, water networks gradually developed. The number of protein‐bound water molecules increased linearly with a_w, until at a_w=0.5 a spanning water network was formed consisting of 311 water molecules, which covered the hydrophilic surface of CALB, with the exception of the hydrophobic substrate‐binding site. At higher water activity, the thickness of the hydration shell increased up to 10 Å close to a_w=1. Above a limit of 1600 protein‐bound water molecules the hydration shell becomes unstable and the formation of pure water droplets occurs in these oversaturated simulation conditions. While the structure and the overall flexibility of CALB was independent of the hydration state, the flexibility of individual loops was sensitive to hydration: some loops, such as those part of the substrate‐binding site, became more flexible, while other parts of the protein became more rigid upon hydration. However, the molecular mechanism of how flexibility is related to activity and selectivity is still elusive.     

Nanopore detection of DNA molecules in magnesium chloride solutions

High translocation speed of a DNA strand through a nanopore is a major bottleneck for nanopore detection of DNA molecules. Here, we choose MgCl₂ electrolyte as salt solution to control DNA mobility. Experimental results demonstrate that the duration time for straight state translocation events in 1 M MgCl₂ solution is about 1.3 ms which is about three times longer than that for the same DNA in 1 M KCl solution. This is because Mg²⁺ ions can effectively reduce the surface charge density of the negative DNA strands and then lead to the decrease of the DNA electrophoretic speed. It is also found that the Mg²⁺ ions can induce the DNA molecules binding together and reduce the probability of straight DNA translocation events. The nanopore with small diameter can break off the bound DNA strands and increase the occurrence probability of straight DNA translocation events.     

FTIR analyses of water in MX-80 bentonite compacted from high salinary salt solution systems

The effect of the exchangeable cations on the infrared (IR) spectra of water in MX-80 bentonite compacted from high salinary salt solution systems was studied using self-supporting film and attenuated total reflection (ATR) techniques. Na-bentonite MX-80 was saturated with homo-cationic (NaCl, KCl, CaCl₂ or MgCl₂) or hetero-cationic (mixtures of Na–, K–, Ca– and Mg–chlorides) solutions. The specimens for IR spectroscopy were prepared as self-supporting films (ssf) or compacted pastes. Differences in the wavenumbers and intensities of the structural OH group vibrations in relation to the type of the interlayer cation were found in the spectra of heated ssf. The most pronounced changes were observed for Mg-ssf, while only negligible changes occurred for K-ssf. The absorptions of water in heated Na- and K-ssf showed displacement of the stretching and bending bands to higher and lower wavenumbers, respectively, which indicates decreasing strength of H-bonding between water molecules. In contrast, for Mg-ssf the position of the stretching band of water substantially decreased on heating up to 90 °C followed by an increase upon further heating above 100 °C. The origin of these differences was discussed in terms of variations in the polarising ability of the interlayer cations influencing their hydration number. The ATR spectra of homo-cationic clay-pastes showed that the interlayer cations modify both the position and the intensity of the complex water band near 3400 cm⁻¹. The position decrease and the intensity increase followed the same order: K⁺, Na⁺, Ca²⁺, Mg²⁺. Good correlation between water band position and polarising power of the cations confirmed their influence on the strength of hydrogen bonds between water molecules. Similarly, a systematic shift of the H₂O-stretching band to lower frequencies with the increasing Mg²⁺ content in the samples was observed in the spectra of clay-pastes saturated with hetero-cationic chloride solutions. The intensity of the stretching band of water of both homo- and hetero-cationic pastes correlated very well with the water content obtained gravimetrically.     

离子水化的分子动力学模拟

采用分子动力学模拟的方法在 2 98 1 5K及无限稀释条件下对Li+、Na+、K+、F- 、Cl- 5种单个离子的水化现象进行研究 模拟得到了离子溶液体系一幅清晰的微观物理图像 ,阳离子周围的水分子以氧来靠近阳离子 ,而阴离子周围的水分子则以其中某一个氢来逼近阴离子 提出了一个“水化因子”的新概念来定量地表征离子水化的强弱 ,阳离子水化的强弱顺序为Li+>Na+>K+ 阴离子水化强弱顺序为F- >Cl- 对于水化作用较强的Li+,其虽有第二配位圈 ,但并无水化 离子的Pauling半径大小是决定离子水化强弱的关键因素 ,这些信息将为建立相应的分子热力学模型提供基础     

Development of Nd (III)-Based Terahertz Absorbers Revealing Temperature Dependent Near-Infrared Luminescence

Molecular vibrations in the solid-state, detectable in the terahertz (THz) region, are the subject of research to further develop THz technologies. To observe such vibrations in terahertz time-domain spectroscopy (THz-TDS) and low-frequency (LF) Raman spectroscopy, two supramolecular assemblies with the formula [Nd^III (phen)₃ (NCX)₃] 0.3EtOH (X = S, 1-S; Se, 1-Se) were designed and prepared. Both compounds show several THz-TDS and LF-Raman peaks in the sub-THz range, with the lowest frequencies of 0.65 and 0.59 THz for 1-S and 1-Se, and 0.75 and 0.61 THz for 1-S and 1-Se, respectively. The peak redshift was observed due to the substitution of SCN⁻ by SeCN⁻. Additionally, temperature-dependent TDS-THz studies showed a thermal blueshift phenomenon, as the peak position shifted to 0.68 THz for 1-S and 0.62 THz for 1-Se at 10 K. Based on ab initio calculations, sub-THz vibrations were ascribed to the swaying of the three thiocyanate/selenocyanate. Moreover, both samples exhibited near-infrared (NIR) emission from Nd (III), and very good thermometric properties in the 300–150 K range, comparable to neodymium (III) oxide-based thermometers and higher than previously reported complexes. Moreover, the temperature dependence of fluorescence and THz spectroscopy analysis showed that the reduction in anharmonic thermal vibrations leads to a significant increase in the intensity and a reduction in the width of the emission and LF absorption peaks. These studies provide the basis for developing new routes to adjust the LF vibrational absorption.     

Preparation of CaO granules using the granulation method

ABSTRACT

Improving the hydration resistance of CaO particle in manufacturing and application of free CaO-containing materials has practical significance. In this study, CaO granules was made from Ca(OH)₂ particles, which were fabricated by the granulation method. The results showed that the hydration resistance of the CaO granules which was prepared under 1700?r?min^?1 was the best, the CaO granules was sintered well in calcination process, the shell of CaO granules was relatively dense, which improves the hydration resistance of CaO granules, and the rate of hydration weight increment was 0.58% after placed in the air for 20 days under a temperature of 10–14°C and a relative humidity of 57–81%.     

Density measurements of poly(acrylic acid) sodium salts

Summary Density measurements of poly(acrylic acid) sodium salts (PANa) with different degrees of neutralization and water contents are presented. The apparent partial molar volumes of polymer, V ₂ ^* , and the partial molar volumes of water, V₁, were calculated from the densities. The values of V ₂ ^* decreased with increasing water content and eventually leveled off. The values of Vj, which at low water contents were much smaller than that of free water increased with increasing water content and reached that of free water, showing consequently the appearance of free water. Before reaching the final value of free water, the data indicated the formation of primary and secondary hydration shells. The structure of primary hydration was suggested to be of octet coordination in which carboxyl oxygen atoms participate.     

Strong effects of counterions on the electrochemistry of poly(N‐methylaniline) thin films

Poly(N‐methylaniline) thin films show different cyclic voltammetric behaviour when cycled in HClO₄, HBF₄, HCl or HNO₃. While in the first two acids the film shows profiles peak potentials similar to those of polyaniline, profiles in HCl and HNO₃ show higher peak potentials for oxidation and a different shape. The free energy for the process, calculated from the oxidation peak potential, shows a linear correlation with the free energy of hydration of the anions present in the test solution. An energy cycle for the oxidation process is proposed to explain the results. The reaction mechanism assumes that anions have to lose their hydration shell to form the polymer salt during electrochemical oxidation of the films. Electropolymerization also depends on the anion present in the solution. While this is possible with low hydration energy anions (ClO₄^?, BF₄^?), it is difficult or impossible when the electrolyte solution contains other anions (Cl^?, NO₃^?) where a higher oxidation potential of the preformed polymer is observed. © 2002 Society of Chemical Industry     

NMR study of temperature-induced phase separation and polymer-solvent interactions in poly(vinyl methyl ether)/D2O/ethanol solutions

The changes in the dynamic structure during temperature-induced phase transition in D₂O/ethanol solutions of poly(vinyl methyl ether) (PVME) were studied using NMR methods. The effect of polymer concentration and ethanol (EtOH) content in D₂O/EtOH mixtures on the appearance and extent of the phase separation was determined. Measurements of ¹H and ¹³C spin-spin and spin-lattice relaxations showed the presence of two kinds of EtOH molecules: besides the free EtOH expelled from the PVME mesoglobules there are also EtOH molecules bound in PVME mesoglobules. The existence of two different types of EtOH molecules at temperatures above the phase transition was in solutions with polymer concentration 20 wt% manifested by two well-resolved NMR signals (corresponding to free and bound EtOH) in ¹³C and ¹H NMR spectra. With time the originally bound EtOH is slowly released from globular-like structures. From the point of view of polymer-solvent interactions in the phase-separated PVME solutions both EtOH and water (HDO) molecules show a similar behaviour so indicating that the decisive factor in this behaviour is a polar character of these molecules and hydrogen bonding.     

Hydration of Simple Model Peptides in Aqueous Osmolyte Solutions

The biology and chemistry of proteins and peptides are inextricably linked with water as the solvent. The reason for the high stability of some proteins or uncontrolled aggregation of others may be hidden in the properties of their hydration water. In this study, we investigated the effect of stabilizing osmolyte–TMAO (trimethylamine N-oxide) and destabilizing osmolyte–urea on hydration shells of two short peptides, NAGMA (N-acetyl-glycine-methylamide) and diglycine, by means of FTIR spectroscopy and molecular dynamics simulations. We isolated the spectroscopic share of water molecules that are simultaneously under the influence of peptide and osmolyte and determined the structural and energetic properties of these water molecules. Our experimental and computational results revealed that the changes in the structure of water around peptides, caused by the presence of stabilizing or destabilizing osmolyte, are significantly different for both NAGMA and diglycine. The main factor determining the influence of osmolytes on peptides is the structural-energetic similarity of their hydration spheres. We showed that the chosen peptides can serve as models for various fragments of the protein surface: NAGMA for the protein backbone and diglycine for the protein surface with polar side chains.     

Theoretical calculations of the structure and UV-vis absorption spectra of hydrated C60 fullerene

A combined Monte Carlo simulation with semiempirical quantum mechanics calculations has been performed to investigate the structure of hydrated fullerene (C₆₀HyFn) and the influence of hydration on its UV-vis spectra. The statistical information of the C₆₀ fullerene aqueous solution (C₆₀FAS) is obtained from NPT ensemble including one C₆₀ fullerene immerses in 898 water molecules. To obtain an efficient ensemble average, the auto-correlation function of the energy has been calculated. The analyzed center-of-mass pair-wise radial distribution function indicates that, on average, there are 65 and 151 water molecules around the first and second hydration shells, respectively, of a single C₆₀ molecule. To calculate the average UV-vis transition energies of C₆₀HyFn, only the statistically uncorrelated configurations are used in the quantum mechanical calculations (INDO/CIS). These involve hundreds of supramolecular structures containing one C₆₀ fullerene surrounded by the first hydration shell. The calculated average transitions at 268 and 350 nm are in very good agreement with the experimental prediction.     

Deep hydration: Poly(ethylene glycol) Mw 2000–8000 Da probed by vibrational spectrometry and small-angle neutron scattering and assignment of ΔG° to individual water layers

Aqueous solutions of poly(ethylene glycol) (PEG) exhibit some remarkable properties, among which is the small changes in water activity compared to the volumes occupied by the PEG: For example, the water in a 20% mass fraction solution of 6000 Da PEG has an activity of 0.9939. We have investigated PEGs with molecular weights 200, 400, 1000, 2000, 4000, and 8000 Da in the concentration range 1% to 17% mass fraction at neutral pH and with added KCl concentrations of 10 mmol L^?1 in aqueous solutions–conditions near those for promoting protein crystallization. These solutions exhibit a structural change at around 6% mass fraction as seen in the solution viscosities, compressibilities, and infrared spectra. Raman spectroscopy shows that the PEGs remain in the same structural form over the concentration range, and the infrared spectra indicate that the change must be due to a local shift in the water structure. Modeling of the results from small-angle neutron scattering (SANS) on the solutions suggests that the structures of the PEGs in the molecular mass range 2000 Da to 8000 Da are paired in the solution, and the separation distance decreases with increasing PEG concentration. From the structure, it becomes clear that the small effect on water activity occurs because of screening by the more weakly bound outer layers. From the bulk measurement of a_w and with reasonable assumptions, a free energy ΔG° can be assigned to each of the fourth, third, and second hydration layers.     

A new process for fuel ethanol dehydration based on modeling the phase equilibria of the anhydrous MgCl2 + ethanol + water system

The use of ethanol as a fuel for motor engines has attracted significant attention because of its possible environmental and economic advantages over fossil fuel. However, the energy demand for the ethanol dehydration process significantly impacts its production cost. A new and energy efficient process is developed on the basis of salt extractive distillation, which uses recycled MgCl₂ granules as a separating agent. Vapor‐liquor‐equilibria (VLE) data for the ternary MgCl₂ + ethanol + water system, and the three constituent binary systems were measured at 30, 60, 90, and 101.3 kPa. A large enhancement of relative volatility of the ethanol + water system in the presence of MgCl₂ is observed throughout the entire ethanol concentration range, which completely broke the azeotrope. The salt effect of MgCl₂ is thought to be the result of energetic interactions and the hydration equilibrium reaction of the Mg²⁺ ion with water molecules. The calculation results by the mixed‐solvent electrolyte model embedded in the OLI platform equipped with new model interaction parameters and equilibrium constant (obtained via the regression of experimental VLE data), provided for a satisfactory means of simulating the MgCl₂ salt extractive distillation process. Finally, the process was proven feasible at the laboratory‐scale resulting in large granules of recovered MgCl₂ and a product of 99.5 wt % ethanol. © 2014 American Institute of Chemical Engineers AIChE J, 61: 664–676, 2015     

Nanostructural characterization of Al(OH)3 formed during the hydration of calcium sulfoaluminate cement

Ye'elimite (Ca₄Al₆SO₁₆) is a main mineral in calcium sulfoaluminate cements. Aluminum hydroxide is one of the products formed by hydration of ye'elimite. To characterize this phase, various aluminum hydroxides were synthesized from their chemical constituents using sol‐gel processing and compared with the aluminum hydroxide formed during the hydration of ye'elimite. The nanostructure of aluminum hydroxide formed during the hydration of ye'elimite was investigated in detail using X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy, inductively coupled plasma optical emission spectroscopy, and ²⁷Al magic angle spinning nuclear magnetic resonance spectroscopy. No evidence was observed that indicated the existence of amorphous aluminum hydroxide in the hydration of ye'elimite. The pH values, thermogravimetric analysis, particle morphology, and Al‐O coordination indicated that the aluminum hydroxide from the hydration of ye'elimite had a crystal‐like structure. The X‐ray diffraction analysis, particle sizes, and ion activity product showed that the aluminum hydroxide from the hydration of ye'elimite had a microcrystalline structure.     

Effect of Ring-Size Variation within Dibenzocrown Ether Resins upon Ion-Pair Sorption of Alkali-Metal Cations from Aqueous and Aqueous Methanol Solutions

Abstract

A batch analysis method has been developed for evaluation of metal salt sorption by crown ether polymers. Selectivity in competitive alkali-metal chloride sorption by a series of formaldehyde condensation polymers of dibenzocrown ethers is influenced by the relationship between the crown ether cavity size and metal ion diameter, as well as the degree of hydration of the metal salt. Effective and selective sorption of KCl from the other alkali-metal chlorides was obtained with a dibenzo-18-crown-6 resin. Excellent sorption selectivity for the monovalent metal chlorides was noted for competitive ion-pair sorption of NaCl, KCl, MgCl₂, and CaCl₂ by this resin. This resin was examined as a stationary phase for selective column separation of KCl from alkali-metal chlorides and of KCl and NaCl from alkali-metal and alkaline-earth chloride mixtures in 80% methanol—20% water.     

Plugging behavior of gellan in porous saline media

In this article, the hydrodynamic behavior of dilute aqueous solutions of a natural polysaccharide—gellan in the porous media under the modeled oilfield conditions is described. The hydrodynamic properties of gellan and poly(acrylamide) solutions in saline porous media are compared. The influence of inorganic salts NaCl, KCl, CaCl₂, MgCl₂, and BaСl₂ on sol–gel and gel–sol transitions of dilute gellan solutions was evaluated. The mechanism of sol–gel transition in the presence of individual alkaline and alkaline‐earth metal salts is described on the basis of literature data. The viscometric measurements revealed that the effectiveness of salts to enhance gelation of gellan changes in the following order: BaСl₂ > CaCl₂ ≈ MgCl₂ > KCl > NaCl. The sol–gel and gel–sol phase transitions of gellan solution were also observed upon addition of oil field water containing 73 g L^?1 of alkaline and alkaline earth metal ions. During the injection of gellan solutions into the porous media saturated by saline water an oscillation of the injection pressure was observed. Such behavior of gellan is explained by either the sol‐to‐gel and the gel‐to‐sol transitions of the polymer taking place in saline water or the step‐by‐step plugging of high permeable channels until all high permeable channels of sand packs are plugged due to gellan invasion. The application of brine‐initiated gelation of gellan for water shutoff operations (WSO) in field conditions was demonstrated. Higher technological effectiveness of gellan injection in comparison with existing gelation systems was shown. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41256.     

Reactivation of partially-sulphated limestone particles from a cfb combustor by hydration

Spent limestone samples from the bed and baghouse of a 22 MWe circulating fluidized bed (CFB) boiler were hydrated and then sulphated in a thermogravimetric analyzer under conditions similar to those found in CFB combustors (850°C, 0.3% SO₂, 9% O₂, 9% CO₂ and 81.7% N₂). Hydration using water gave faster rates and higher levels of conversion of the residual CaO to Ca (OH)₂ than immersion in pure steam at 150 and 200°C. The particles expanded during hydration and their internal volume increased from 0.1 cm³/g Ca before hydration to nearly 0.6 cm³/g Ca after dehydration. Hydration rejuvenated the reactivity of the bed material but not that of the baghouse particles. The conversion of Ca to CaSO₄, in the treated bed particles increased from 32% to over 80% during re-sulphation.     

Hydration of calcium aluminates at 60°C – Development paths of C2AHx in dependence on the content of free water

The influence of water loss during the hydration of calcium aluminates on the phase development is investigated at 60°C. This is relevant for applications in which calcium aluminate cement (CAC) based formulations are exposed to quick drying during hydration. The presented results provide new insights into the well-known conversion processes occurring in CAC pastes. Using in situ XRD two different routes of the development of initially formed C₂AH₈ are determined: (a) transformation to C₃AH₆ + AH₃ in the presence of sufficient free water and (b) dehydration to C₂AH₅ at a lack of free water. Moreover, the influence of precuring of the pastes at 23°C before heating to 60°C is investigated. The increasing loss of free water with increasing precuring time resulting from both, precipitation of hydrate phases and evaporation, causes incomplete hydration of CA or CA₂ as well as dehydration of C₂AH₈ instead of conversion into C₃AH₆. Comparative investigations of sealed samples always revealed complete hydration of CA and CA₂ as well as complete conversion of C₂AH₈.     

H NMR study of thermotropic phase transitions in D2O solutions of poly(N-isopropylmethacrylamide)/poly(vinyl methyl ether) mixtures

¹H NMR spectroscopy was used to investigate thermotropic phase transitions in D₂O solutions of poly(N-isopropylmethacrylamide) (PIPMAm)/poly(vinyl methyl ether) (PVME) mixtures. In all studied solutions (polymer concentrations c=0.1-10 wt%) two phase transitions were detected at temperatures roughly corresponding to different lower critical solution temperatures of PIPMAm and PVME. While the phase transition of PVME component (located at lower temperatures) is not affected by the presence of PIPMAm in the mixture, the phase transition temperatures of PIPMAm component (located at higher temperatures) are affected by the phase separation of the PVME component. Measurements of ¹H spin-spin relaxation of residual water (HDO) molecules revealed that above the phase transition, a certain portion of water molecules is bound to polymer globular structures. A major part of bound water is present in globular structures of predominating polymer component in the mixture.