Effects of Moisture on the Mechanical Properties of Microcrystalline Cellulose and the Mobility of the Water Molecules as Studied by the Hybrid Molecular Mechanics–Molecular Dynamics Simulation Method

A hybrid molecular mechanics–molecular dynamics simulation method has been performed to study the effects of moisture content on the mechanical properties of microcrystalline cellulose (MCC) and the mobility of the water molecules. The specific volume and diffusion coefficient of the water increase with increasing moisture content in the range studied of 1.8–25.5 w/w%, while the Young's modulus decreases. The simulation results are in close agreement with the published experimental data. Both the bound scission and free‐volume mechanisms contribute to the plasticization of MCC by water. The Voronoi volume increases with increasing moisture content. It is related to the free volume and the increase enhances the mobility of the water molecules and thus increases the coefficient of diffusion of the water. Moreover, with increasing moisture content, the hydrogen bonding per water molecule between MCC–water molecules decreases, thus increasing the water mobility and number of free water molecules. © 2019 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 454–464     

WATER TRANSPORT BY A SPREADING SURFACTANT IN FINE DISPERSE MATERIALS

A surface active substance (surfactant) spreads on the water film lying on the surface of fine disperse materials (clay, oxides), with lower velocity than on the surface of bulk water and on coarse materials (sand).

The spreading surfactant carries the underlying water although the surface is not continuous and water is present as a thin film.

The ratio of the transported water to the spread surfactant decreases with increasing specific surface, being > 10⁴ on sand surface and < 10 on fine disperse materials (clay, oxides).

The amount of transported water increases with increasing specific surface and increasing water film thickness. The driving force for water transport is the surface pressure; the presence of another surfactant is therefore prejudicial for the spreading and transport of underlying water.

The water transport by the spreading surfactant is accompanied by the streaming potential, which is inversely related to the specific surface.     

Fundamental investigation on effect of microencapsulated water on expansion behavior of microcapsules

The microcapsules containing water were prepared with the suspension polymerization method, and the fundamental investigation was performed to make the effect of microencapsulated water on expansion behavior of microcapsules clear. In the experiment, only the volume of water added into styrene monomer was changed to make the effect of microencapsulated water volume clear, and three kinds of water contents were measured: namely, the initial water content for the microcapsules just after preparation, the middle water content for the microcapsules dried at 44°C for 24 hours, and the final water content for the microcapsules dried at 110°C for 1 hours. With increasing the added water volume, the initial water content increased; the middle water content decreased after increasing halfway through, and the final water content gradually decreased. Also, with increasing the added water volume, the drying rate of the microcapsules increased and the expansion ratio decreased. The water volume required to expand the microcapsules, in other words, the critical shell thickness required to prevent evaporation of water and to contribute to expansion of microcapsules is discussed.     

Interfacial composition and structural parameters of water/C12-s-C12 x 2Br/n-hexanol/n-heptane microemulsions studied by the dilution method

The interfacial composition of the stable water/C12-s-C12 x 2Br/n-hexanol/n-heptane microemulsions has been studied in detail by dilution method. The results showed a marked maximum amount of the n-hexanol populating on the surfaces of droplets (represented as a = n(a)i/n(s), where n(a)i and n(s) are respectively the moles of n-hexanol and gemini surfactant on the surface of droplets) with increasing water content. At a constant level of water addition (the molar ratio of water to surfactant W0 = 20), a decreased with increasing the spacer length in the C12-s-C12 x 2Br molecule. The structural parameters of a w/o microemulsion were also estimated by analyzing the data of dilution experiments, and we found that the radius of the water pool was very sensitive to the increment of water content. The radius of the water pool varied from 0.74 to 5.35 nm with increasing W0 from 10 to 50. The variation extent reached 4.61 nm. In the cases of water/CPC/n-butanol/isopropyl myristate and water/CTAB/n-butanol/isopropyl myristate, however, the corresponding variation extents were only 1.22 and 1.68 nm, respectively, when increasing comparable water content. The ratio of N(a)/N(2C), where N(a) and N(2C) are respectively the average numbers of n-hexanol and the total average numbers of alkyl chains of gemini surfactant populating on per droplet surface, decreased obviously with increasing water content at W0 > 15. This indicated that C12-2-C12 x 2Br favored to form large droplets that were suitable to solubilize more water.     

Structure and dynamics of copoly(oxyethylene-oxypropylene-oxyethylene) in o-xylene/water mixtures

Abstract : The structure and dynamics of supramolecules of a triblock copolymer, copoly(oxyethylene-oxypropylene-oxyethylene), also known as PLURONIC L64: PEO₁₃PPO₃₀PEO₁₃, in o-xylene/water mixtures were studied by means of dynamic light scattering, small-angle X-ray scattering and NMR. At low copolymer concentrations, micelles coexisted with unimers and the micellar size increased with increasing amount of water in the mixture. Large aggregates were formed at higher copolymer concentrations. The size and the amount of the large aggregates increased with increasing amount of water in the mixtures, and increasing copolymer concentration. The solubilized water can be classified into free-water(forming hydrogen bond with water) and bound-water(forming hydrogen bond with EO units). The environment of EO units changed with the amount of solubilized water. The conformation of the copolymer remained essentially the same before and after micellization and did not change with the amount of solubilized water.     

Electro-osmotic pumping of sodium chloride solutions

Electro-osmotic pumping (EOP) theory and its characteristics (transport numbers, brine concentration, current density, current efficiency, electro-osmotic coefficients, etc.) of Selemion AMV and CMV ion-exchange membranes were studied. The brine concentration increased with increase in current density and feed water concentration. Current efficiency was nearly constant in a wide range of current densities and feed water concentrations. The water flow through the membranes also increased with increasing current density and feed water concentration. The increase in water flow increased the current efficiency significantly. Consequently, water flow through electrodialysis (ED) membranes had a positive effect on ED. Electro-osmotic coefficients decreased with increasing feed water concentration. Osmotic flow in EOP-ED decreased relative to the total flow with increasing current density while the electro-osmotic flow increased relative to the osmotic flow. Osmotic flow significantly contributes to the total water flow in EOP. Selemion AMV and CMV membranes performed well for salt concentration. A simple membrane potential measurement has been demonstrated to function reasonably satisfactorily to predict membrane performance for salt concentration.     

Roughness and ordering at the interface of oxidized polystyrene and water

For the first time, atomistically detailed molecular dynamics calculations revealed molecular ordering of the water-oxidized atactic polystyrene (aPS) interface. Both ordering of the water molecules and the phenyl rings occur. In addition, the natural roughness of the surface has been simulated and compared to experimental values. The composition of the simulated aPS films is based on spin-coated aPS films that have been oxidized and characterized experimentally. The aPS surfaces are oxidized with ultraviolet-ozone radiation and have been characterized by XPS, AFM, and water contact angle measurements. XPS measurements show that the oxygen content in the sample increases rapidly with exposure and reaches saturation near 24 at. % of oxygen. The molecular dynamics simulations show smoothening of an hydrophobic aPS surface upon transition from vacuum to water. The smoothening decreases with increasing hydrophilicity. The calculations reveal ordering of oxidized phenyl rings for aPS surfaces in water. The order increases with increasing hydrophilicity. Additionally, we investigated the water structure near the aPS-water interface as a function of the surface hydrophilicity. With increasing hydrophilicity, the density of water at the aPS-water interface increases. The water density profile is steeper in the presence of hydrophobic aPS. The water shows an ordered layer near both the hydrophobic and hydrophilic surfaces; the position of this layer shifts toward the interface with increasing hydrophilicity.     

Quantification of partial structures of aquatic humic substances by 1H-NMR under WATR conditions

Aquatic humic substances (HS) isolated from surface water, leakage water and ground water have been investigated by ¹H-NMR. The overlapping HOD signal was eliminated by adding ammonium chloride and applying the multiecho method CPMG (Carr, Purcell, Meiboom, Gill) under WATR conditions (water attenuation by transverse relaxation) permitting quantification of partial structures of HS. The proportion of carbohydrates/alcohols/ethers decreases and the proportion of alkyl moieties increases with increasing water or soil depth and thus microbial diagenesis. Also, increasing deoxygenation of aromatic substituents is observed with increasing water or soil depth. In some cases, elimination of the NMR signal of HOD is accompanied by the appearance of another HOD signal which is slightly shifted and much smaller in intensity; this signal probably results from water strongly bound by hydrogen bonding within the HS macromolecules.     

Calorimetric and relaxation properties of xylitol-water mixtures

We present the first broadband dielectric spectroscopy (BDS) and differential scanning calorimetry study of supercooled xylitol-water mixtures in the whole concentration range and in wide frequency (10(-2)-10(6) Hz) and temperature (120-365 K) ranges. The calorimetric glass transition, T(g), decreases from 247 K for pure xylitol to about 181 K at a water concentration of approximately 37 wt. %. At water concentrations in the range 29-35 wt. % a plentiful calorimetric behaviour is observed. In addition to the glass transition, almost simultaneous crystallization and melting events occurring around 230-240 K. At higher water concentrations ice is formed during cooling and the glass transition temperature increases to a steady value of about 200 K for all higher water concentrations. This T(g) corresponds to an unfrozen xylitol-water solution containing 20 wt. % water. In addition to the true glass transition we also observed a glass transition-like feature at 220 K for all the ice containing samples. However, this feature is more likely due to ice dissolution [A. Inaba and O. Andersson, Thermochim. Acta, 461, 44 (2007)]. In the case of the BDS measurements the presence of water clearly has an effect on both the cooperative α-relaxation and the secondary β-relaxation. The α-relaxation shows a non-Arrhenius temperature dependence and becomes faster with increasing concentration of water. The fragility of the solutions, determined by the temperature dependence of the α-relaxation close to the dynamic glass transition, decreases with increasing water content up to about 26 wt. % water, where ice starts to form. This decrease in fragility with increasing water content is most likely caused by the increasing density of hydrogen bonds, forming a network-like structure in the deeply supercooled regime. The intensity of the secondary β-relaxation of xylitol decreases noticeably already at a water content of 2 wt. %, and at a water content above 5 wt. % it has been replaced by a considerably stronger water (w) relaxation at about the same frequency. However, the similarities in time scale and activation energy between the w-relaxation and the β-relaxation of xylitol at water contents below 13 wt. % suggest that the w-relaxation is governed, in some way, by the β-relaxation of xylitol, since clusters of water molecules are rare at these water concentrations. At higher water concentrations the intensity and relaxation rate of the w-relaxation increase rapidly with increasing water content (up to the concentration where ice starts to form), most likely due to a rapid increase of small water clusters where an increasing number of water molecules interacting with other water molecules.     

Synthesis and characterization of nanoporous polycaprolactone membranes via thermally- and nonsolvent-induced phase separations for biomedical device application

A family of crosslinked poly(ethylene glycol) diacrylate (XLPEGDA) materials was synthesized via free-radical photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) solutions in water. These materials are potential fouling-resistant coatings for ultrafiltration (UF) membranes. PEGDA chain length (n = 10–45, where n is the average number of ethylene oxide units in the PEGDA molecule) and water content in the prepolymerization mixture (0–80 wt.%) were varied, resulting in XLPEGDA materials with water permeability values ranging from 0.5 to 150 L μm/(m² h bar). Generally, water permeability increased with increasing prepolymerization water content and with increasing PEGDA chain length. Moreover, water permeability exhibits a strong correlation with equilibrium water uptake. However, solute rejection, probed using poly(ethylene glycol)s of well defined molar mass, decreased with increasing prepolymerization water content and increasing PEGDA chain length. That is, there is a tradeoff between water permeability and separation properties. Finally, the fouling resistance of XLPEGDA materials was characterized via contact angle measurements and static protein adhesion experiments. From these results, XLPEGDA surfaces are more hydrophilic in samples prepared at higher prepolymerization water content or with longer PEGDA chains, and the more hydrophilic surfaces generally exhibit less BSA accumulation.     

Effect of flexibility on hydrophobic behavior of nanotube water channels

Carbon nanotubes can serve as simple nonpolar water channels. Here we report computer simulations exploring the relationship between the mechanical properties of such channels and their interaction with water. We show that on one hand, increasing the flexibility of the carbon nanotubes increases their apparent hydrophobic character, while on the other hand the presence of water inside the channel makes them more resistant to radial collapse. We quantify the effect of increasing flexibility on the hydrophobicity of the nanotube water channel. We also show that flexibility impedes water transport across the nanotube channel by increasing the free-energy barriers to such motion. Conversely, the presence of water inside the nanotube is shown to affect the energetics of radial collapse in a water nanotube, an ostensibly mechanical property. We quantify the magnitude of the effect and show that it arises from the formation of energetically favorable low-dimensional water structures inside the nanotube such as one-dimensional wires and two-dimensional sheets.     

Effect of ionic strength and type of ions on the structure of water swollen polyelectrolyte multilayers

This study addresses the effect of ionic strength and type of ions on the structure and water content of polyelectrolyte multilayers. Polyelectrolyte multilayers of poly(sodium-4-styrene sulfonate) (PSS) and poly(diallyl dimethyl ammonium chloride) (PDADMAC) prepared at different NaF, NaCl and NaBr concentrations have been investigated by neutron reflectometry against vacuum, H(2)O and D(2)O. Both thickness and water content of the multilayers increase with increasing ionic strength and increasing ion size. Two types of water were identified, "void water" which fills the voids of the multilayers and does not contribute to swelling but to a change in scattering length density and "swelling water" which directly contributes to swelling of the multilayers. The amount of void water decreases with increasing salt concentration and anion radius while the amount of swelling water increases with salt concentration and anion radius. This is interpreted as a denser structure in the dry state and larger ability to swell in water (sponge) for multilayers prepared from high ionic strengths and/or salt solution of large anions. No exchange of hydration water or replacement of H by D was detected even after eight hours incubation time in water of opposing isotopic composition.     

A water-soluble m-phenylene ethynylene foldamer

[reaction: see text] A water-soluble m-phenylene ethynylene (mPE) foldamer was realized by appending hexaethylene glycol side chains to the backbone repeat unit. UV spectra of the oligomer in aqueous solutions were consistent with a helical conformation. The association constant of the oligomer with (-)-alpha-pinene increased dramatically with increasing water composition, peaking at 90% water by volume in acetonitrile. The rate of the host/guest system's approach to equilibrium was found to decrease considerably with increasing water content.     

The Candida antarctica lipase B catalysed kinetic resolution of seudenol in non-aqueous media of controlled water activity

For further investigation of the kinetic resolutions in transesterification reactions with the highly enantioselective Candida antarctica lipase B, an easy to study model reaction with one typical substrate, the Douglas Fir Beetle pheromone 3-methyl-2-cyclohexen-1-ol (Seudenol), was developed. The influence of the nature of the solvent and thermodynamic water activity was studied. Initial rates showed constant or progressively increasing values with increasing water activity. Enantioselectivity depended on the choice of solvent and descended in most cases with increasing water activity. No general correlations of enantioselectivity or activity with physicochemical constants of the solvent were found. However, at a water activity of 0.11 a tendency toward optimum hydrophobicity (i.elog P ≈ for enantioselectivity was observed. Enantiomeric ratios were in the range 8–32.     

小角X衍射和ESR方法研究十二烷基磺酸钠/正戊醇/水三元体系的相结构

测定了十二烷基磺酸钠/正戊醇/水体系的相图, 小角X衍射方法测定相图中液晶区的结构。结果表明: 在一定温度下, 整个液晶区均为层状液晶; 液晶层间距随水含量的增大而增大, 随正戊醇含量的增大而减小; 液相内水的渗透率正比于水含量, 反比于正戊醇含量。ESR研究表明: 自旋标记探针分子5NS在整个液晶相中的结构参数为0.32±0.02; 油包水和水包油胶束区内探针分子运动的各向异性程度分别随着水和油含量的增多而增加。     

DSC study of phase transition of anhydrous phospholipid DHPC and influence of water content

The phase transition behavior of 1,2-di-n-heptadecanoyl phosphatidylcholme (DHPC)with and without water has been studied by use of differential scanning calorimetry It was found by experiment that the glass transition occurred at first during the first heating of a sample of DHPC without water and then the sample underwent melting as an ordinary crystal.Therefore the sample of DHPC without water was a glassy crystal However,the DHPC sample crystallizing from melt was an ordinary crystal From the relationship between the total melting enthalpy Qf of freezable water and the water content h,it was concluded that the water contained in the DHPC samples might exist in three states recognizable thermodynamically.The water in the first state was an unfreezable water It was the water bound directly with the head groups of the phospholipid,i.e.the primary hydration water Every head group might bind seven such molecules of water.The water in the second state was the secondary hydration water,us melt ing point was     

Thickness-dependent ordering of water layers at the NaCl(100) surface

We have determined the ordering properties of water adsorbed at room temperature on the rock salt (100) surface under four different conditions: ultrahigh vacuum, dry nitrogen atmosphere, 45% and 75% relative humidity. Details of the atomic structure are determined for both sides of the solid-liquid interface. The top most layer of NaCl shows a small relaxation that changes from an expansion to a contraction with increasing humidity. Under all measured conditions water monolayers with different ordering properties are present at the interface. Surprisingly, we find that the amount of ordering in the first layer is increasing with increasing thickness of the water film. At a solid-liquid interface, the ordering appears to be correlated with the solubility.     

Origin of the dynamic transition upon pressurization of crystalline proteins

We study the role of hydration water in the dynamic transition of low-hydrated proteins upon pressurization found recently (Meinhold, L.; Smith, J. C. Phys. Rev. E 2005, 72, 061908). Clustering and percolation of water in the hydration shells of protein molecules in crystalline Staphylococcal nuclease are analyzed at various pressures. The number of water molecules in the hydration shell increases and the hydrogen-bonded network of hydration water spans with increasing pressure. The dynamic transition of protein occurs when the spanning water network exists with the probability of about 50% and hydration water shows large density fluctuations. Formation of a spanning water network upon pressurization promotes protein dynamics as in the case of the dynamic transition with increasing hydration. Properties of hydration water in various thermodynamic states and their influence on biological function are discussed.     

Controllable Preparation of Monodisperse Polystyrene Microspheres with Different Sizes by Dispersion Polymerization

Summary: Monodisperse polystyrene (PS) microspheres with different sizes were prepared by dispersion polymerization in dispersion media of ethanol/water and isopropayl alcohol/water, respectively. The effect of polarity of the dispersion medium, stabilizer and initiator concentration on the average sizes and size range were evaluated. The results show that monodisperse PS microspheres with different sizes could be prepared in dispersion media of ethanol and isopropyl alcohol/water when appropriate initiator and stabilizer concentrations were employed, and the latter is a more appropriate medium to prepare uniform PS microspheres. It was found that the microsphere sizes reduced with increasing water content in the dispersion medium. Furthermore, in isopropyl alcohol/water dispersions, the average sizes decreased with increasing stabilizer concentration.     

Formation of FeCl(2)/NaCl-nanoparticles in supercritical water investigated by molecular dynamics simulations: nucleation rates

Nucleation and growth of FeCl(2) in supercritical water containing NaCl at different state points between temperatures of 798 and 873 K and system densities between 0.24 and 0.14 g cm(-3) have been studied by molecular dynamics simulations. The number of NaCl ion pairs was chosen to simulate particle formation in seawater and brine of higher salinity. Rigid SPC/E water was used to model the water molecules while a combination of Coulomb and Lennard-Jones potentials was used for the ions. Two different methods for determination of nucleation rates are applied and their results compared. We find decreasing nucleation rates with both increasing temperature and decreasing system density. Our results are also compared to those we recently obtained in an investigation of pure FeCl(2) from supercritical water. We find both increasing nucleation rates and a decreasing size of the critical cluster with increasing amount of NaCl.