Efficient solutions of self-consistent mean field equations for dewetting and electrostatics in nonuniform liquids

We use a new configuration-based version of linear response theory to efficiently solve self-consistent mean field equations relating an effective single particle potential to the induced density. The versatility and accuracy of the method is illustrated by applications to dewetting of a hard sphere solute in a Lennard-Jones fluid, the interplay between local hydrogen bond structure and electrostatics for water confined between two hydrophobic walls, and to ion pairing in ionic solutions. Simulation time has been reduced by more than an order of magnitude over previous methods.     

电场诱导水的太赫兹透射特性研究

许多生物分子自身的转动、振动或分子团的整体振动模式都位于太赫兹波段内,因此可以利用太赫兹光谱技术对生物分子进行检测。同时又由于太赫兹波的光子能量仅为毫电子伏量级,不会对分子的内部结构造成破坏,所以太赫兹时域光谱技术在生物检测方面具有良好的应用前景。众所周知,绝大多数的生物分子只有在液体条件下才能发挥其生物活性,所以研究液体环境下生物分子之间的相互作用就非常必要。然而水分子的转动模式、振动模式以及和氢键有关的能量均处于太赫兹波段,从而对其产生强烈的吸收;另外,水分子为极性分子,而极性分子对太赫兹波有强烈的共振吸收,这就使利用太赫兹技术对生物分子活性进行动态表征产生了困难。因此在研究溶液中的生物分子与太赫兹波的相互作用时,最大限度地减小水分子对太赫兹波的吸收就成为近年来的研究热点。目前,减少水对太赫兹波吸收的主要方法有：在溶液样品中加入抑制氢键缔合的离子来减小水对太赫兹的吸收;通过改变溶液的温度来调节水对太赫兹的吸收;利用微流控芯片技术,通过减小被测样品与太赫兹波的作用距离来减小水对太赫兹波的吸收。另外,激光的激励、电场或磁场的处理,也能改变水对太赫兹波的吸收,将盛有去离子水的微流控芯片放于电场中,研究经电场处理不同时间的去离子水对太赫兹吸收强度的影响。结果发现,太赫兹波的透射强度随着去离子水在电场当中静置时间的增加而增强,当在电场中静置60 min时,太赫兹的频谱强度达到最大,与空气的频谱强度接近。由此可以推断外加电场使水分子的偶极矩发生了变化,从而对整体水分子的振动和转动产生了影响,并且改变了水中的氢键结构,导致了太赫兹透射光谱强度的增强。     

Bound water: Evidence from and implications for the dielectric properties of aqueous solutions

Broadband dielectric spectra of a variety of aqueous solutions are evaluated as to indications of water that may be considered bound. Static permittivity decrements due to depolarizing internal electric fields, from kinetic depolarization, as well as from dielectric saturation are discussed. The latter effect reflects the preferential orientation of water permanent dipole orientations within strong Coulombic field of small ions, especially multivalent cations. Such water may be considered bound even though rapid rotations around the orientation of the electric dipole moment are definitely possible and also a fast exchange of water molecules between the hydration region and the bulk may take place. Water exhibiting large dielectric relaxation times, as typical for regions with large local concentration of foreign matter, may also be named bound. However, no clear evidence for interaction energies exceeding the hydrogen bond energy of pure water has been found. Rather enhanced relaxation times at low water content reflect the small concentration of hydrogen bonding sites and thus low probability density for the formation of a new hydrogen bond. Potential interferences of the water relaxation with relaxations from other molecules or from ionic structures are mentioned briefly.     

Water behavior in the neighborhood of hydrophilic and hydrophobic membranes: Lessons from molecular dynamics simulations

The study of properties of water in the vicinity of surfaces poses a fascinating challenge. In this article we studied the behavior of water molecules in the neighborhood of membranes. We addressed the question of how these water molecules are influenced by the membranes’ hydrophilicity. Three systems were studied through molecular dynamics simulations: water in the presence of a hydrophilic membrane (PL), water in the presence of a hydrophobic (PB) one and water in the absence of membranes (BULK). Additionally, in order to study the dependence of the effect of the membrane on the behavior of neighboring water molecules with temperature, each system was simulated at three different temperatures (K): 250, 300 and 350. For each condition, kinetic and structural features were studied. The first feature involved the calculation of diffusion coefficients and activation energy. The second feature was evaluated through the study of water density and hydrogen bond distribution. From the present study we concluded that: (1) density studies underestimate the influence of both hydrophilic and hydrophobic membranes on the neighboring water molecules; (2) the hydrophilic and hydrophobic membranes disturb the hydrogen bond network within distances ranging from 1 to 8 nm, depending on the nature of the membrane and the temperature conditions; (3) the presence of a hydrophobic surface results in an enhancement of the natural hydrogen bond network present in liquid water, to a greater extent than what even an ordered Ih ice structure is able to achieve (i.e. PL membrane); (4) the structural enhancement due to the presence of a hydrophobic surface involves roughly 18 to 24 water hydration layers, for ambient and above temperature conditions.     

Water wettability in nanoconfined environment

Water confined in nanoscale space behaves quite differently from that in the bulk.For example,in biological aquaporins and in carbon nanotubes,the traversing water molecules form a single file configuration.Water would stay in vapor state in extremely hydrophobic narrow nanopores owing to the physicochemical interactions between the water molecules and the surface of the nanopore.A spontaneous wet-dry transition has been identified in both biological and artificial nanopores.The nanopore is either fulfilled with liquid water or completely empty.Based on this mechanism,the wetting and dewetting processes inside nanopores have been further developed into highly efficient nanofluidic gates that can be switched by external stimuli,such as light irradiation,electric potential,temperature,and mechanical pressure.This review briefly covers the recent progress in the special wettability in nanoconfined environment,water transportation through biological or artificial nanochannels,as well as the smart nanofluidic gating system controlled by the water wettability.     

Anomalous phase sequences in lyotropic liquid crystals

We present a coarse-grained model in order to describe the unusual sequence of mesophases observed in aqueous solutions of nonionic lipids, such as monoolein. The lipid molecules are modeled as a rigid head and a flexible Gaussian tail, and water is treated explicitly. A key component of the model is thermally reversible hydrogen bonding between the lipid head and water resulting in changes in both head volume and the interactions of the hydrated head with its surroundings. Phase diagrams obtained from unit-cell self-consistent field simulations capture the qualitative thermotropic and lyotropic phase behavior of the monoolein-water system. The unusual phase sequences result from a competition between hydrogen bond formation, changes in head volume and interactions, lipid tail entropy, and the hydrophobic effect.     

Modulation of structure and dynamics of water under alternating electric field and the role of hydrogen bonding

Using Molecular Dynamics simulations, we investigate the effect of alternating (AC) electric field on static and dynamic properties of water. The central question we address is how hydrogen bonds respond to perpetual field-induced dipole reorientations. We assess structural perturbations of water network and changes of hydrogen bond dynamics in a range of alternating electric field strengths and frequencies using a non-polarisable water model, SPC/E, and two distinct polarisable models: SWM4-NDP and BK3. We confirm that AC field causes only moderate structural perturbations. Dynamic properties, including the rates of bond breaking, switching of hydrogen-bonding partners, and diffusion, accelerate with the strength of AC fields. All models reveal a nonmonotonic frequency dependence with fastest dynamics at frequencies around 200?GHz where the period of the field oscillation is commensurate with the average time it takes a typical proton to switch from one acceptor to another. Higher frequencies result in smaller amplitudes of angle oscillations and in reduced probability to complete the switch to another acceptor before the field reversal restores the original configuration. As frequency increases, these effects gradually weaken the influence of the field on the kinetics of hydrogen bonding and the associated rates of translational and rotational diffusion in water.     

Water molecules migration at oil–paper interface under the coupling fields of electric and temperature: a molecular dynamics study

Moisture is an important factor affecting the insulation properties of transformers. Due to the limitations of macroscopic experimental methods, the diffusion of water at oil–paper interface cannot be accurately measured. Therefore, molecular dynamics method was used in this work to establish oil–paper layer model of 10⁵ atoms. Through jointly analysing the aggregation degree, diffusion coefficient, free volume as well as radial distribution function of water molecules, the diffusion mechanism of water molecules at oil–paper interface was studied. The results show that when the initial water content in paper was high, water molecules would accumulate at oil–paper interface to form the local high-water region during heating. The polarisation of the electric field strengthened the hydrogen bonding interaction between water molecules and increased the probability of occurrence of the high-water region. Meanwhile, electric field reduced the free volume and diffusion coefficient of water molecules and rendered its diffusion coefficient anisotropic. What’s more, when the electric field was combined with the temperature field, the electric field played a leading role in the diffusion of water molecules while the temperature field was less affected. Diffusion coefficients of water molecules at different temperatures from molecular dynamics simulations were well consistent with experimental results, which verified the rationality of the model.     

The role of water in the design of glycosidic linkage flexibility

In this paper we show how a variety of computational methods are used to understand the role that water plays in the solution conformational dynamics of carbohydrates. A comparison is made between maltose and a designed disaccharide (α-D-Glc-NAc-(1→4)-β-D-Glc-3-NH₂) in which the cross glycosidic linkage hydrogen bonds have been significantly strengthened. However, despite the stronger intramolecular hydrogen bonds in the maltose derivative, the correlation times for glycosidic dihedral angle fluctuations are approximately the same for the two sugars. Upon investigation of the water in the first hydration shells for the two disaccharides, high water probability densities were found between the functional groups straddling the glycosidic linkage that bonds the two monosaccharides together. This probability density corresponds to single water molecules forming bridging hydrogen bonds between the functional groups on either side of the linkage for periods of 3.66 ps in the case of maltose and 8.36 ps in the case of the amine derivative. Ab initio studies of saccharide structure interaction with single water molecules reveal that these intermolecular (sugar-solvent) hydrogen bonds are of similar strength to the intramolecular (sugar-sugar) hydrogen bonds. This combination of molecular dynamics and ab initio computational methods demonstrates that increasing the internal hydrogen bond strength in oligosaccharides does not lead to significantly slower internal molecular motion of these sugars in solution. The intermolecular hydrogen bonds formed with water compete equally with the intramolecular hydrogen bonds in the sugar. This result has important implications when considering hydrophobic versus hydrophilic effects in glycoproteins.     

Water in contact with extended hydrophobic surfaces: direct evidence of weak dewetting

X-ray reflectivity measurements reveal a significant dewetting of a large hydrophobic paraffin surface floating on water. The dewetting phenomenon extends less than 15 A into the bulk water phase and results in an integrated density deficit of about one water molecule per 25-30 A(2) of water in contact with the paraffin surface. The results are supported by molecular dynamics simulations and related to the hydrophobic effect.     

Selective interaction water-hydrophilic/hydrophobic impurities observed by four-photon Brillouin spectroscopy

The four-photon scattering spectra of water in the aqueous solution/suspension of various hydrophilic/hydrophobic impurities in the range ±3 cm^?1 (±90 GHz) have been observed. We have found the strong dependence of the Brillouin resonance frequency upon the connectivity of the impurities and water molecules. The Brillouin shift is attributed to the local restructuring of the hydrogen bond network in water inside the interface layer that is sensitive to the hydrophilic/hydrophobic properties. In fact, it results in variations in the isothermal compressibility and sound velocity.     

Interface water-induced hydrophobic carbon chain unfolding in water

The folding and unfolding of the carbon chain, which is the basic constitutional unit of polymers,are important to the performance of the material. However, it is difficult to regulate conformational transition of the carbon chain, especially in an aqueous environment. In this paper, we propose a strategy to regulate the conformational transition of the carbon chain in water based on the all-atom molecular dynamics simulations. It is shown that the unfolded carbon chain will spontaneously collapse into the folded state, while the folded carbon chain will unfold with an external electric field. The regulation ability of the electric field is attributed to the electric field-induced redistribution of interface water molecules near the carbon chain. The demonstrated method of regulating conformational transition of the carbon chain in water in this study provides an insight into regulating hydrophobic molecules in water, and has great potential in drug molecule design and new polymer material development.     

Hydrophobicity-induced drying transition in alkanethiol self-assembled monolayer—water interface

During the course of our investigation of the electron transfer properties of some redox species through highly hydrophobic long chain alkanethiol molecules on gold in aqueous and non-aqueous solvents, we obtained some intriguing results such as unusually low interfacial capacitance, very high values of impedance and film resistance, all of which pointed to the possible existence of a nanometer size interfacial gap between the hydrophobic monolayer and aqueous electrolyte. We explain this phenomenon by a model for the alkanethiol monolayer—aqueous electrolyte interface, in which the extremely hydrophobic alkanethiol film repels water molecules adjacent to it and in the process creates a shield between the monolayer film and water. This effectively increases the overall thickness of the dielectric layer that is manifested as an abnormally low value of interfacial capacitance. This behaviour is very much akin to the ‘drying transition’ proposed by Lum, Chandler and Weeks in their theory of length scale dependent hydrophobicity. For small hydrophobic units consisting of apolar solutes, the water molecules can reorganize around them without sacrificing their hydrogen bonds. Since for an extended hydrophobic unit, the existence of hydrogen bonded water structure close to it is geometrically unfavourable, there is a net depletion of water molecules in the vicinity leading to the possible creation of a hydrophobic interfacial gap.     

Observation of Simplest Water Chains on Surface Stabilized by a Hydroxyl Group at One End

The key to fully understanding water-solid interfaces relies on the microscopic nature of hydrogen bond networks,including their atomic structures, interfacial interactions, and dynamic behaviors. Here, we report the observation of two types of simplest water chains on Au(111) surface which is expected unstable according to the rules of hydrogen network on noble metal surfaces. A common feature at the end of chain structures is revealed in high resolution scanning tunneling microscopy images. To explain the stability in observed hydrogen bond networks,we propose a structure model of the water chains terminated with a hydroxyl group. The model is consistent with detailed image analysis and molecular manipulation. The observation of simplest water chains suggests a new platform for exploring fundamental physics in hydrogen bond networks on surfaces.     

Analysis of water molecules around GTP in Hras-GTP complex and GDP in Hras-GDP complex by molecular dynamics simulations

We investigate the structures of the Hras-GTP and the Hras-GDP complexes in water solvents in order to understand the mechanism of GTP hydrolysis in the Hras-GTP complex. We performed MD simulations of these complexes in order to study the positions and the orientations of water molecules around the guanosine nucleotides. Using trajectories we calculated the angular distribution of water molecules around the most distant phosphorus from guanosine in our previous work. It was shown that water molecules are distributed evenly in GTP, although unevenly in GDP. This suggests that the trigger of GTP hydrolysis is possibly the attack of water molecule to γ?phosphate from the appropriate direction. In this paper, in order to investigate the role of water molecules in GTP hydrolysis in detail, we calculate the orientation of water molecules. The distribution of the orientation is different between GTP and GDP. In order to investigate the cause of this difference, we examine the hydrogen bonds between water molecules and oxygen atom of the most distant phosphate from guanosine. We find that these hydrogen bonds are formed. We also find that the oxygen atom of hydrogen bond is determined by the position of the water molecule of hydrogen bond.     

Hydrogen bond lifetimes in supercritical methanol–water mixtures via MD simulation

Dynamical features of hydrogen bonds in methanol–water mixtures have been analysed in terms of lifetime in the wide range of conditions, including supercritical states, using a molecular dynamics simulation with flexible potential models. Hydrogen bond characteristics in methanol–water mixtures were investigated by considering the combination of molecular species and donor–acceptor of hydrogen-bonded molecules. The hydrogen bond lifetimes mainly depend on temperature, and those in supercritical condition were about 1/10th of that at ambient condition. Focusing on the composition dependence of the hydrogen bond lifetime, the unique behaviour of that resulting from hydration structure was observed. Moreover, the molecular combination, which showed the largest hydrogen bond lifetime, was different for ambient and high temperature and high pressure conditions. The relationship between hydrogen bond lifetime and molar volume was also calculated to discuss the hydrogen bond lifetime in terms of the collision frequency of molecules and the intermolecular distance.     

电场中MgO分子吸附H2的理论研究

研究电场中MgO分子与H2的相互作用是探索MgO材料储氢性能的基础。在B3LYP/6-31G**水平上研究了电场中H2在MgO分子上的吸附行为。结果给出电场中单个H2在Mg/O上的吸附能由无电场时-0.021/-0.099eV提高到场强为0.005a.u.时的-0.037/-0.139 eV。H2吸附在O离子上时,电场效应更显著。电场中MgO分子最多能吸附10个H2,相应的质量密度达33wt%。表明电场诱导MgO材料吸附H2是一种具有潜力的储氢方法。通过电子结构分析讨论了电场中MgO分子储氢的机理。     

三氯甲烷在外电场中的物理性质研究

三氯甲烷是挥发性卤代烃,可通过皮肤接触、呼吸或饮水进入人体,危害人体健康,其物理性质的进一步研究对于保护环境与人体健康十分重要.本文采用DFT(密度泛函理论)计算方法,在B3PW91/6-311G+(2d, p)基组水平下对三氯甲烷分子进行优化,从分子结构角度研究了不同外电场作用下,三氯甲烷分子的总能量,键长,电偶极矩,解离势能面,隧穿电离和红外光谱.计算结果表明,随着外加电场的增大,分子键长逐渐增长,偶极矩也随之增加,然而分子的总能量却逐渐减小.分子的最低空轨道能量与最高占据轨道能量之间的能隙也随着外加电场的增大而降低.分子的解离能在增加的电场条件下逐渐降低,吸收光谱的IR强度也有明显的变化.上述的计算结果为利用电场降解三氯甲烷提供重要的理论参考.     

BeO分子在不同方向外电场中的能量和光谱

用密度泛函理论,选用B3LYP/6-311g方法优化,研究了不同方向外电场(0.0—0.05a.u.)对聚变堆第一壁材料中BeO分子的键长、总能量、电荷分布、能级、能隙和红外光谱的影响.计算结果表明,随着外电场从0.0增加到0.05a.u.,BeO分子的键长逐渐增长,总能量E逐渐降低,但能隙EG不断增大.能隙的增大表明了BeO分子在外电场中化学反应的活性减弱,分子结构在外电场中相对稳定,因此随着外电场的增加,BeO分子中的O原子与从反应堆中逃逸出来的H原子结合更困难,这对ITER中的聚变反应是有利的.