醇类抑制剂对甲烷水合物形成的影响

在本工作中,甲烷水合物的生长动力学是通过甲醇、乙醇、乙二醇三种不同醇类抑制剂存在下的分子动力学模拟研究的.模拟结果发现,三种醇类都可作为甲烷水合物的抑制剂,醇类分子中的亲水性羟基极大地破坏了水合物笼的结构,并且羟基可以与局部的液态水分子形成氢键,从而增加了形成水合物笼型结构的难度,导致甲烷水合物的生长速率降低.对于甲醇分子,甲醇分子的亲水性羟基与水分子形成氢键从而破坏了水分子结构,而亲油性甲基对周围的水分子具有簇效应,两者都会降低水合物生长速率;对于乙二醇和乙醇分子,它们只含有羟基,特别是乙二醇分子含有两个羟基,其对H₂O分子有很强的吸附作用,导致水合物生长速率降低.在抑制效果方面,甲醇分子最优,乙二醇稍微优于乙醇.     

Anomalous slowing down of the vibrational relaxation of liquid water upon nanoscale confinement

We study the vibrational dynamics of nanodroplets of liquid water with femtosecond two-color midinfrared pump-probe spectroscopy. For the smallest nanodroplet, containing 10-15 water molecules, the lifetime T1 of the O-H stretch vibrations is equal to 0.85+/-0.1 ps, which is more than 3 times as long as in bulk liquid water. We find that the truncation of the hydrogen-bond network of water leads to a dramatic change of the relaxation mechanism.     

Chemical potentials of water and organic solutes in imidazolium ionic liquids: a simulation study

The excess chemical potentials of a series of molecules dissolved in the ionic liquid dimethyl imidazolium chloride have been determined by a series of transformations. The molecules are water, methanol, dimethyl ether, acetone and propane. Water and methanol have large negative values of the excess chemical potential (-29kJmol^?1 and — 14kJ mol^?1 respectively); the polar molecules dimethyl ether and acetone have positive values of about 7kJmol^?1 while the value for propane is +26 kJ mol^?1. Hydrogen bonding to the anion plays an important part in the stabilization of water and methanol.     

Short-time microscopic dynamics of aqueous methanol solutions

In this paper we present the picosecond vibrational dynamics of a series of methanol aqueous solutions over a wide concentration range from dense to dilute solutions. We studied the vibrational dephasing and vibrational frequency modulation by calculating the time correlation functions of vibrational relaxation by fits in the frequency domain. This method is applied to aqueous methanol solutions xMeOH–(1???x)H₂O, where x?=?0, 0.2, 0.4, 0.6, 0.8 and 1. The important finding is that the vibrational dynamics of the system become slower with increasing methanol concentration. The removal of many-body effects by having the molecules in less-crowded environments seems to be the key factor. The interpretation of the vibrational correlation function in the context of Kubo theory, which is based on the assumption that the environmental modulation arises from a single relaxation process and applied to simple liquids, is inadequate for all solutions studied. We found that the vibrational correlation functions of the solutions over the whole concentration range comply with the Rothschild approach, assuming that the environmental modulation is described by a stretched exponential decay. The evolution of the dispersion parameter α with dilution indicates the deviation of the solutions from the model simple liquid and the results are discussed in the framework of the current phenomenological status of the field.     

Sine-Gordon Solitons and Breathers in Rod-like Magnetic Liquid Crystals under External Magnetic Field

To study the nonlinear phenomena in rod-like magnetic liquid crystals (RMLCs), this paper establishes the dynamic model of molecular motion when giving a twisting disturbance to the molecules under external magnetic field. We find the twist of the molecules under magnetic field can be propagated in the form of a traveling wave. The dynamic equation of the molecular twisting we derived satisfies the form of Sine-Gordon equation. We obtain two solutions of the Sine-Gordon equation by theoretical calculation: the kink and anti-kink solitons and breathers. The characteristics of those solitons and breathers are discussed.     

X-ray emission spectroscopy of hydrogen bonding and electronic structure of liquid water

We use x-ray emission spectroscopy to examine the influence of the intermolecular interaction on the local electronic structure of liquid water. By comparing x-ray emission spectra of the water molecule and liquid water, we find a strong involvement of the a(1)-symmetry valence-orbital in the hydrogen bonding. The local electronic structure of water molecules, where one hydrogen bond is broken at the hydrogen site, is separately determined. Our results provide an illustration of the important potential of x-ray emission spectroscopy for elucidating basic features of liquids.     

Cooperative origin of low-density domains in liquid water

We study clusters formed by water molecules possessing large enough tetrahedrality with respect to their nearest neighbors. Using Monte Carlo simulation of SPC/E water and Voronoi tessellation, we find that regions of lower density than the bulk are formed by accretion of molecules into clusters exceeding a minimum size. Clusters are predominantly linear objects and become less compact as they grow until they reach a size beyond which further accretion is not accompanied by a density decrease. The results suggest that the formation of "icelike" regions in liquid water is cooperative.     

Selective hydrogenation by polymer-encapsulated platinum nanoparticles prepared by an easy single-step sonochemical synthesis

Polypyrrole-encapsulated platinum nanoparticles (PPy/Pt-NPs) prepared by an easy single-step sonochemical synthesis were used as catalysts for the liquid phase hydrogenation of substituted alkenes in methanol or methanol/water mixtures. Polypyrrole (PPy) coatings on the nanoparticles were able to act as nanoscopic filters for substrates molecules, and consequently substrate selectivity could be controlled in the catalytic processes.     

Liquid order at the interface of KDP crystals with water: evidence for icelike layers

We present a surface x-ray diffraction study on the KDP-water interface in which the structure of both the crystalline and liquid part of the interface has been measured. We have been able to determine the ordering components in the liquid in both the perpendicular and parallel directions. We find interface-induced ordering in the first four layers of water molecules. The first two layers behave icelike and are strongly bound to the surface. The next two layers are more diffuse and show only minor lateral and perpendicular ordering. Subsequent layers are found to behave similar to a bulk liquid.     

Salt effects on water/hydrophobic liquid interfaces: a molecular dynamics study

We investigate structural and dynamical properties of NaCl and KCl solution/n-decane interfaces. We find that K(+) and Cl(-) ions localize close to the interface and modify the orientations of both first-layer and second-layer water molecules in the interfacial region. Na(+) and Cl(-) ions are also localized; however, they do not affect the orientation significantly. NaCl salts cause an increase of the surface tension and the residence time of interfacial water molecules. They also decrease the residence time of interfacial n-decane molecules. KCl salt has similar effects, although to a smaller extent. These findings may help us to better understand biological interfaces in physiological solutions.     

对浸入水或甲醇中的石墨氧化物的理论研究 (cited: 3)

采用密度泛函理论优化了含水和不含水的石墨氧化物的多种结构. 当层间没有水分子时,优化的层间距在6 ?左右,小于6.5～7 ?的实验值. 反之,水石墨氧化物的层间距和实验值符合很好. 基于优化的石墨氧化物结构,用分子动力学方法模拟了水或甲醇中的石墨氧化物. 对于不含水的石墨氧化物,水和甲醇分子不进入其层间. 而对于含水的石墨氧化物,液体分子进入层间,增大了层间距,半定量地重复了实验现象.     

Surfactant-free solution-dispersible Si nanocrystals surface modification by impurity control

Si nanocrystals (Si-NCs) dispersible in polar liquid without surface functionalization by organic molecules have been realized by simultaneously doping n and p type impurities. We show that the codoped Si-NCs are stable in methanol for more than five months, while intrinsic Si-NCs prepared by the same procedure form large agglomerates. The different behavior of the intrinsic and codoped Si-NCs in solutions suggests that doped impurities exist on the surface of Si-NCs and the surface potential is large enough to prevent the agglomeration. The colloidal solution of codoped Si-NCs exhibits broad photoluminescence with the maximum in the near infrared range (1.1-1.3?eV).     

Influence of alcohol on mechanical and electrical properties of thin organic films

Stability of organic materials properties is essential for further applications and was intensely investigated in last few decades. The aim of this study is to detect the structural changes of dipalmitoyl-phosphatidylcholine (DPPC) monolayer as a model system of organic material under influence of alcohols solutions. As subphases of monolayers (Langmuir films), pure water, ethanol and methanol solutions were used. For detection of changes in charge states of the molecules as well as relation with structural and conformational changes, a contactless method employing Maxwell’s displacement currents (MDC) was used. In DPPC monolayer on the subphase of methanol-water, a gradual absorption of methanol molecules into the layer can appear. In DPPC monolayer on the subphase of ethanol-water adsorption of ethanol molecules on the layer can be observed. Influence of alcohols results in a significant change of mechanical and electrical properties as well as in the stability of thin films. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia     

Effect of external electric field on the terahertz transmission characteristics of electrolyte solutions

We fabricated a microfluidic chip with simple structure and good sealing performance, and studied the influence of the electric field on THz absorption intensity of liquid samples treated at different times by using THz time domain spectroscopy system. The tested liquids were deionised water and CuSO₄, CuCl₂, NaHCO₃, Na₂CO₃ and NaCl solutions. The transmission intensity of the THz wave increases as the standing time of the electrolyte solution in the electric field increases. The applied electric field alters the dipole moment of water molecules in the electrolyte solution, which affects the vibration and rotation of the whole water molecules, breaks the hydrogen bonds in the water, increases the number of single water molecules and leads to the enhancement of the THz transmission spectrum.     

Scientific Review: Interactions of PEO with Monovalent Electrolytes in Solvents of Different Hydrogen Bonding Capacities

Small-Angle Neutron Scattering (SANS) has been used in order to investigate the ion binding capacities of PEO in different solvents. Aprotic (acetonitrile) as well as protic (methanol and water) solvents, have been studied where methanol and water form an average two and four tetrahedrally oriented hydrogen bonds per molecule, respectively [1]. Unusual behavior of PEO has been observed in aprotic solvents and solvents with moderate hydrogen bonding where monovalent ions associate to the polymer backbone leading to a polyelectrolyte-like (where a certain fraction of monomers are charged) behavior. This is in marked contrast to behavior in aqueous solutions where water molecules associate via hydrogen bonding to the polymer and the ions are more preferentially coordinated by the solvent than the polymer.     

Ethanol and methanol induced changes in phospholipid monolayer

The main components of cell membranes are phospholipids and proteins. The aim of our study was to examine structural changes of dipalmitoyl-phosphatidylcholine (DPPC) monolayer as a simple model system of a cell membrane in different environments. Pure water, ethanol and methanol solutions were used as subphases of Langmuir films as a membrane models. For detection of changes in charge states of the molecules as well as relation with structural and conformational changes, a contactless method Maxwell's displacement currents (MDC) was used. Behaviour of DPPC molecules on two different subphases is substantialy different. In DPPC monolayer on the subphase of methanol-water, a gradual absorption (incorporation, penetration) of methanol molecules into the layer can appear. In DPPC monolayer on the subphase of ethanol-water adsorption of ethanol molecules on the layer can be observed. The membrane permeability might change. At both subphases (ethanol-water and methanol-water) the elasticity modulus of the monolayer decreases leading to the loss of membrane elasticity.     

Stokes-Einstein relation in supercooled aqueous solutions of glycerol

The diffusion of glycerol molecules decreases with decreasing temperature as its viscosity increases in a manner simply described by the Stokes-Einstein relation. Approaching the glass transition, this relation breaks down as it does with a number of other pure liquid glass formers. We have measured the diffusion coefficient for binary mixtures of glycerol and water and find that the Stokes-Einstein relation is restored with increasing water concentration. Our comparison with theory suggests that adding water postpones the formation of frustration domains.     

Heat and mass transfer at adiabatic evaporation of binary zeotropic solutions

Results of numerical simulation of heat and mass transfer in a laminar flow of three-component gas at adiabatic evaporation of binary solutions from a flat plate are presented. The studies were carried out for the perfect solution of ethanol/methanol and zeotrope solutions of water/acetone, benzene/acetone, and ethanol/acetone. The liquid-vapor equilibrium is described by the Raoult law for the ideal solution and Carlson–Colburn model for real solutions. The effect of gas temperature and liquid composition on the heat and diffusion flows, and temperature of vapor-gas mixture at the interface is analyzed. The formula for calculating the temperature of the evaporation surface for the binary liquid mixtures using the similarity of heat and mass transfer was proposed. Data of numerical simulations are in a good agreement with the results of calculations based on the proposed dependence for all examined liquid mixtures in the considered range of temperatures and pressures.     

Atomic partial charges in condensed phase from an exact sum rule for infrared absorption

A general sum rule for infrared intensities provides a definition of effective partial charges which can be experimentally obtained using isotopic substitutions and is valid in both gas and condensed phases. Of particular interest is the case of molecular liquids. We have, therefore, determined the hydrogen partial charges in liquid methanol and liquid water from the available literature. The resulting charges are 0.63 e and 0.14 e for hydrogen atoms bounded to the methanol oxygen and carbon atoms, respectively, and 0.55 e for hydrogen atoms in liquid water. The effective partial charges in liquid water were also computed from density functional based ab initio molecular dynamics simulations and found in good agreement with experiment.     

The structure of liquid methanol revisited: a neutron diffraction experiment at −80 °C and +25 °C

Pulsed neutron diffraction with isotope substitution on the hydroxyl hydrogens (H) is used to study the structure of pure liquid methanol at ?80 °C and +25 °C. Although this liquid has been studied with neutrons several times in the past this is the first time that the composite partial structure factors, XX, XH and HH, are derived from the diffraction data. Here X represents a weighted sum of correlations from carbon (C), oxygen (O), and methyl hydrogen (M) atoms on the methanol molecule. The data are used in an empirical potential structure refinement (EPSR) computer simulation of the liquid at both temperatures. Model distributions of molecules consistent with these data are used to estimate the individual site—site radial distribution functions, the coefficients of the spherical harmonic expansion of the orientational pair correlation function, and the length of possible chains of methanol molecules formed in the liquid. Although the results are qualitatively similar to those of earlier computer simulation studies of this liquid, they do differ in detail from previous work. In particular, although most molecules in the liquid are found as part of chains up to 10 molecules long, the average chain length is only about 2.7 molecules at both temperatures, there are about 1.3 hydrogen bonds per molecule on average, and the chains are highly nonlinear on average.