Monte Carlo simulations of the hydrophobic effect in aqueous electrolyte solutions

The hydrophobic interaction between two methane molecules in salt-free and high salt-containing aqueous solutions and the structure in such solutions have been investigated using an atomistic model solved by Monte Carlo simulations. Monovalent salt representing NaCl and divalent salt with the same nonelectrostatic properties as the monovalent salt have been used to examine the influence of the valence of the salt species. In salt-free solution the effective interaction between the two methane molecules displayed a global minimum at close contact of the two methane molecules and a solvent-separated secondary minimum. In 3 and 5 M monovalent salt solution the potential of mean force became slightly more attractive, and in a 3 M divalent salt solution the attraction became considerably stronger. The structure of the aqueous solutions was determined by radial distribution functions and angular probability functions. The distortion of the native water structure increased with ion valence. The increase of the hydrophobic attraction was associated with (i) a breakdown of the tetrahedral structure formed by neighboring water molecules and of the hydrogen bonds between them and (i) the concomitant increase of the solution density.     

The free energy of the metastable supersaturated vapor via restricted ensemble simulations. II. Effects of constraints and comparison with molecular dynamics simulations

Extensive restricted canonical ensemble Monte Carlo simulations [D. S. Corti and P. Debenedetti, Chem. Eng. Sci. 49, 2717 (1994)] were performed. Pressure, excess chemical potential, and excess free energy with respect to ideal gas data were obtained at different densities of the supersaturated Lennard-Jones (LJ) vapor at reduced temperatures from 0.7 to 1.0. Among different constraints imposed on the system studied, the one with the local minimum of the excess free energy was taken to be the approximated equilibrium state of the metastable LJ vapor. Also, a comparison of our results with molecular dynamic simulations [A. Linhart et al., J. Chem. Phys. 122, 144506 (2005)] was made.     

Solubility of KF and NaCl in water by molecular simulation

The solubility of two ionic salts, namely, KF and NaCl, in water has been calculated by Monte Carlo molecular simulation. Water has been modeled with the extended simple point charge model (SPC/E), ions with the Tosi-Fumi model and the interaction between water and ions with the Smith-Dang model. The chemical potential of the solute in the solution has been computed as the derivative of the total free energy with respect to the number of solute particles. The chemical potential of the solute in the solid phase has been calculated by thermodynamic integration to an Einstein crystal. The solubility of the salt has been calculated as the concentration at which the chemical potential of the salt in the solution becomes identical to that of the pure solid. The methodology used in this work has been tested by reproducing the results for the solubility of KF determined previously by Ferrario et al. [J. Chem. Phys. 117, 4947 (2002)]. For KF, it was found that the solubility of the model is only in qualitative agreement with experiment. The variation of the solubility with temperature for KF has also been studied. For NaCl, the potential model used predicts a solubility in good agreement with the experimental value. The same is true for the hydration chemical potential at infinite dilution. Given the practical importance of solutions of NaCl in water the model used in this work, whereas simple, can be of interest for future studies.     

聚丙烯酰胺稀溶液的分子模拟

聚丙烯酰胺(PAM)是一类重要的线性水溶性聚合物,具有"百业助剂"之称,因此对其溶液性质的研究意义重大.在溶液质量浓度约为1g·mL-1的基础上,分别构建了含有不同水分子数的溶液模型.采用分子动力学(MD)方法模拟分析了不同温度下非离子型的聚丙烯酰胺(PAM-H)和阴离子型的聚丙烯酰胺(HPAM)在纯水溶液及含不同质量分数NaCl的水溶液中的回旋半径(Rg).结果发现,不同温度下PAM-H和HPAM的抗盐性能的模拟结果与实验数据基本吻合,水分子数不同的溶液模型所得模拟结果趋势没有明显变化,为了提高模拟效率,选取含有2000个水分子的溶液模型分析HPAM链中氧负离子及氧原子的径向分布函数,从微观结构模拟说明了HPAM水溶液粘度随NaCl质量分数增加而减小,且HPAM比PAM-H具有较好的增粘效果及较差的抗盐性能的原因.     

Thermodynamic Properties of Aqueous Glucose–Urea–Salt Systems

In this work, the thermodynamic behavior of aqueous solutions containing the solutes NaCl, glucose, and/or urea is investigated. These substances are vital components for living bodies and further they are main components of blood serum. Osmotic coefficients were determined by cryoscopic measurements in single-solute and multi-solute aqueous solutions containing salts (NaCl, KCl, CaCl₂), glucose, and/or urea. The results show that NaCl determines the osmotic coefficients in the urea/glucose/NaCl/water system. Investigation of the effect of different salts on osmotic coefficients revealed ion-specific effects. At physiologically important solute concentrations in typical blood serum solutions, the osmotic coefficients were found to be in the range of 0.90–0.93. In a second step, the state of water in different glucose/salt/water and urea/salt/water systems was investigated. Depending on the kind of salt, the chemical potential of water in urea/salt/water is either higher or lower than in glucose/salt/water systems at equal nonelectrolyte concentrations. This result was found to be independent of the salt molality. Finally, the investigated systems were modeled with the Pitzer model and the ePC-SAFT equation of state, which allowed predicting of the properties of these multi-solute aqueous solutions.     

Soret coefficients of mixed electrolytes

Practical equations are developed which relate the Soret coefficients of mixed electrolytes to the entropies and enthalpies of transport. The derived equations together with published binary thermal diffusion data can be used to estimate the Soret coefficients of mixed electrolytes. The procedure is illustrated for the systems NaCl+HCl+ water and NaCl+MgCl₂+ water. Aqueous NaCl, like most salts, diffuses to the cold plate in binary Soret experiments. In aqueous HCl solutions, however, NaCl can diffuse to the warm plate, and the magnitude of its Soret coefficient can take values twice as large as those for binary solutions. The thermal diffusion of trace amounts of a salt in a solution containing a large excess of another salt is discussed. Exceptionally large Soret effects are predicted for traces of strong acids in aqueous salt solutions.     

A potential model for methane in water describing correctly the solubility of the gas and the properties of the methane hydrate

We have obtained the excess chemical potential of methane in water, over a broad range of temperatures, from computer simulation. The methane molecules are described as simple Lennard-Jones interaction sites, while water is modeled by the recently proposed TIP4P/2005 model. We have observed that the experimental values of the chemical potential are not reproduced when using the Lorentz-Berthelot combining rules. However, we also noticed that the deviation is systematic, suggesting that this may be corrected. In fact, by introducing positive deviations from the energetic Lorentz-Berthelot rule to account indirectly for the polarization methane-water energy, we are able to describe accurately the excess chemical potential of methane in water. Thus, by using a model capable of describing accurately the density of pure water in a wide range of temperatures and by deviating from the Lorentz-Berthelot combining rules, it is possible to reproduce the properties of methane in water at infinite dilution. In addition, we have applied this methane-water potential to the study of the solid methane hydrate structure, commonly denoted as sI, and find that the model describes the experimental value of the unit cell of the hydrate with an error of about 0.2%. Moreover, we have considered the effect of the amount of methane contained in the hydrate. In doing so, we determine that the presence of methane increases slightly the value of the unit cell and decreases slightly the compressibility of the structure. We also note that the presence of methane increases greatly the range of pressures where the sI hydrate is mechanically stable.     

Molecular simulation of condensation process of Lennard-Jones fluids confined in nanospace with jungle-gym structure

We report grand canonical Monte Carlo simulations for a Lennard-Jones (LJ) fluid modeled on methane confined in nanospace with jungle-gym-like (JG) cubic structure, which is typically found in porous coordination polymers. Pillars composing the cubic structure were modeled as structureless smooth solid rods made of LJ carbon. We examined the effects of pore size, pore geometry, rod thickness, and rod potential onto the condensation phenomena in the JG pore structure. The simulations clarified that the condensation pressure and adsorption amount in the JG structure were influenced by pore size and rod potential, while the transition type was determined by rod thickness. The characteristics of the JG structure lie in the sensitivity to the slight changes in pore size, rod thickness, and rod potential owing to the combination of the packing effect of molecules and the superposition effect of rod potentials.     

Solubility of NaCl in water by molecular simulation revisited

In this paper, the solubility of NaCl in water is evaluated by using computer simulations for three different force fields. The condition of chemical equilibrium (i.e., equal chemical potential of the salt in the solid and in the solution) is obtained at room temperature and pressure to determine the solubility of the salt. We used the same methodology that was described in our previous work [E. Sanz and C. Vega, J. Chem. Phys. 126, 014507 (2007)] although several modifications were introduced to improve the accuracy of the calculations. It is found that the predictions of the solubility are quite sensitive to the details of the force field used. Certain force fields underestimate the experimental solubility of NaCl in water by a factor of four, whereas the predictions of other force fields are within 20% of the experimental value. Direct coexistence molecular dynamic simulations were also performed to determine the solubility of the salt. Reasonable agreement was found between the solubility obtained from free energy calculations and that obtained from direct coexistence simulations. This work shows that the evaluation of the solubility of salts in water can now be performed in computer simulations. The solubility depends on the ion-ion, ion-water, and water-water interactions. For this reason, the prediction of the solubility can be quite useful in future work to develop force fields for ions in water.     

氯盐溶液中甲烷水合物高压分解条件及影响因素

向水合物储层注入盐类溶液是水合物常规开采技术之一,所以必须掌握储层压力条件下盐类溶液中水合物分解条件及其影响因素.本文研究了NaCl、MgCl2、CaCl2氯盐溶液中甲烷水合物分解条件,结果表明NaCl(2.0、1.0、0.5 mol·L-1)、MgCl2 (1.0、0.5 mol·L-1)和CaCl2 (1.0、0.5 mol·L-1)溶液中甲烷水合物的分解温度比纯水中分别降低了(4.8、2.4、1.0 K (NaCl))、(5.3、1.5 K (MgCl2))和(4.3、1.8 K (CaCl2)).以van der Waals 和Platteeuw 热力学模型为基础,结合电解质溶液中水的活度方程(Pitzer-Mayorga 方程),给出了氯盐溶液中水合物分解条件热力学模型,进而比较了模型计算值与实验值,结果显示两者非常吻合.分析表明,氯盐溶液中离子静电作用产生的水分子溶剂化效应和盐析效应降低了水的活度而导致水合物分解温度降低.     

Effect of NaCl on the excess enthalpies of binary liquid systems

The excess molar enthalpies h^E₁₊₂₃ of ethanol+(water+NaCl), benzylalcohol+(water+NaCl), and cyclohexane+(methanol+NaCl) were measured at 298.15 K, those of methanol+(water+NaCl) at 298.15 and 323.15 K. An LKB flow microcalorimeter was used and a special flow-mix cell was developed with regard to the corrosive electrolyte solutions. Knowing the integral enthalpy of solution and the solution enthalpy at infinite dilution for a salt (3) in a solvent (2), the molar excess enthalpy h^E₁₂₃ can be calculated.     

Molecular dynamics simulation of potassium along the liquid-vapor coexistence curve

The applicability of pair potential functions to liquid alkali metals is questionable. On the one hand, some recent reports in the literature suggest the validity of two-parameter pair-wise additive Lennard-Jones (LJ) potentials for liquid alkali metals. On the other hand, there are some reports suggesting the inaccuracy of pair potential functions for liquid metals. In this work, we have performed extensive molecular dynamics simulations of vapor-liquid phase equilibria in potassium to check the validity of the proposed LJ potentials and to improve their accuracy by changing the LJ exponents and taking into account the temperaturedependencies of the potential parameters. We have calculated the orthobaric liquid and vapor densities of potassium using LJ (12–6), LJ (8.5–4) and LJ (5–4), effective pair potential energy functions. The results show that using an LJ (8.5–4) potential energy function with temperature-independent parameters, ε and σ, is inadequate to account for the vapor-liquid coexistence properties of potassium. Taking into account the temperature-dependencies of the LJ parameters, ε(T) and σ(T), we obtained the densities of coexisting liquid and vapor potassium in a much better agreement with experimental data. Changing the magnitude of repulsive and attractive contributions to the potential energy function shows that a two-parameter LJ (5–4) potential can well reproduce the densities of liquid and vapor potassium. The results show that LJ (5–4) potential with temperature-dependent parameters produces the densities of liquid and vapor potassium more accurately, compared to the results obtained using LJ (12–6) and LJ (8.5–4) potential energy functions.     

Modified Protein-Water Interactions in CHARMM36m for Thermodynamics and Kinetics of Proteins in Dilute and Crowded Solutions

Proper balance between protein-protein and protein-water interactions is vital for atomistic molecular dynamics (MD) simulations of globular proteins as well as intrinsically disordered proteins (IDPs). The overestimation of protein-protein interactions tends to make IDPs more compact than those in experiments. Likewise, multiple proteins in crowded solutions are aggregated with each other too strongly. To optimize the balance, Lennard-Jones (LJ) interactions between protein and water are often increased about 10% (with a scaling parameter, λ = 1.1) from the existing force fields. Here, we explore the optimal scaling parameter of protein-water LJ interactions for CHARMM36m in conjunction with the modified TIP3P water model, by performing enhanced sampling MD simulations of several peptides in dilute solutions and conventional MD simulations of globular proteins in dilute and crowded solutions. In our simulations, 10% increase of protein-water LJ interaction for the CHARMM36m cannot maintain stability of a small helical peptide, (AAQAA)₃ in a dilute solution and only a small modification of protein-water LJ interaction up to the 3% increase (λ = 1.03) is allowed. The modified protein-water interactions are applicable to other peptides and globular proteins in dilute solutions without changing thermodynamic properties from the original CHARMM36m. However, it has a great impact on the diffusive properties of proteins in crowded solutions, avoiding the formation of too sticky protein-protein interactions.     

Interface tension of silica hydroxylated nanoparticle with brine: a combined experimental and molecular dynamics study

We have used molecular dynamics simulations to calculate the interfacial tension of hydroxylated SiO(2) nanoparticles under different temperatures and solutions (helium and brine with monovalent and divalent salts). In order to benchmark the atomistic model, quartz SiO(2) interfacial tension was measured based on inverse gas chromatography under He atmosphere. The experimental interfacial tension values for quartz were found between 0.512 and 0.617 N/m. Our calculated results for the interfacial tension of silica nanoparticles within helium atmosphere was 0.676 N/m, which is higher than the value found for the system containing He∕α-quartz (0.478 N/m), but it is similar to the one found for amorphous silica surface. We have also studied the interfacial tension of the nanoparticles in electrolyte aqueous solution for different types and salts concentrations (NaCl, CaCl(2), and MgCl(2)). Our calculations indicate that adsorption properties and salt solutions greatly influence the interfacial tension in an order of CaCl(2) > MgCl(2) > NaCl. This effect is due to the difference in distribution of ions in solution, which modifies the hydration and electrostatic potential of those ions near the nanoparticle.     

Solubility of lysozyme in the presence of aqueous chloride salts: common-ion effect and its role on solubility and crystal thermodynamics

Understanding protein solubility is important for a rational design of the conditions of protein crystallization. We report measurements of lysozyme solubility in aqueous solutions as a function of NaCl, KCl, and NH4Cl concentrations at 25 degrees C and pH 4.5. Our solubility results are directly compared to preferential-interaction coefficients of these ternary solutions determined in the same experimental conditions by ternary diffusion. This comparison has provided new important insight on the dependence of protein solubility on salt concentration. We remark that the dependence of the preferential-interaction coefficient as a function of salt concentration is substantially shaped by the common-ion effect. This effect plays a crucial role also on the observed behavior of lysozyme solubility. We find that the dependence of solubility on salt type and concentration strongly correlates with the corresponding dependence of the preferential-interaction coefficient. Examination of both preferential-interaction coefficients and second virial coefficients has allowed us to demonstrate that the solubility dependence on salt concentration is substantially affected by the corresponding change of protein chemical potential in the crystalline phase. We propose a simple model for the crystalline phase based on salt partitioning between solution and the hydrated protein crystal. A novel solubility equation is reported that quantitatively explains the observed experimental dependence of protein solubility on salt concentration.     

The effect of salts on the conformation and microstructure of poly(N‐isopropylacrylamide) (PNIPA) in aqueous solution

We present an experimental investigation of the conformation and microstructure of Poly(N‐isopropylacrylamide) (PNIPA) in aqueous solution in the presence of salts. As a model, a strong salting–out salt (Na₂SO₄) and a strong salting–in salt (NaSCN) were chosen. Light scattering measurements show that Na₂SO₄ decreases the radius of gyration of PNIPA compared to its value in water, whereas NaSCN increases it. Moreover, the NaSCN solution was found to be a better solvent for PNIPA compared to water, whereas Na₂SO₄ solution is worse. Small‐angle neutron scattering measurements of semidilute PNIPA solutions, at temperatures well below the phase‐transition temperature, exhibit the behavior predicted by the model of dynamic concentration fluctuations characterized by a single correlation length. Excess scattering at low angles is observed in salt solutions at temperatures that are near, yet below, the phase‐transition temperature. This may indicate intrachain heterogeneities on the scale of 6–8 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3713–3720, 2004     

How ions affect the structure of water

We model ion solvation in water. We use the MB model of water, a simple two-dimensional statistical mechanical model in which waters are represented as Lennard-Jones disks having Gaussian hydrogen-bonding arms. We introduce a charge dipole into MB waters. We perform (NPT) Monte Carlo simulations to explore how water molecules are organized around ions and around nonpolar solutes in salt solutions. The model gives good qualitative agreement with experiments, including Jones-Dole viscosity B coefficients, Samoilov and Hirata ion hydration activation energies, ion solvation thermodynamics, and Setschenow coefficients for Hofmeister series ions, which describe the salt concentration dependence of the solubilities of hydrophobic solutes. The two main ideas captured here are (1) that charge densities govern the interactions of ions with water, and (2) that a balance of forces determines water structure: electrostatics (water's dipole interacting with ions) and hydrogen bonding (water interacting with neighboring waters). Small ions (kosmotropes) have high charge densities so they cause strong electrostatic ordering of nearby waters, breaking hydrogen bonds. In contrast, large ions (chaotropes) have low charge densities, and surrounding water molecules are largely hydrogen bonded.     

A novel algorithm for creating coarse-grained, density dependent implicit solvent models

Implicit solvent simulations are those in which solvent molecules are not explicitly simulated, and the solute-solute interaction potential is modified to compensate for the implicit solvent effect. Implicit solvation is well known in Brownian dynamics of dilute solutions but offers promise to speed up many other types of molecular simulations as well, including studies of proteins and colloids where the local density can vary considerably. This work examines implicit solvent potentials within a more general coarse-graining framework. While a pairwise potential between solute sites is relatively simple and ubiquitous, an additional parametrization based on the local solute concentration has the possibility to increase the accuracy of the simulations with only a marginal increase in computational cost. We describe here a method in which the radial distribution function and excess chemical potential of solute insertion for a system of Lennard-Jones particles are first measured in a fully explicit, all-particle simulation, and then reproduced across a range of solute particle densities in an implicit solvent simulation.     

Salting-in/Salting-out Mechanism of Carbon Dioxide in Aqueous Electrolyte Solutions

The solvation of carbon dioxide in sea water plays an important role in the carbon circle and the world climate. The salting-out/salting-in mechanism of CO₂ in electrolyte solutions still remains elusive at molecule level. The ability of ion salting-out/salting-in CO₂ in electrolyte solution follows Hofmeister Series and the change of water mobility induced by salts can be predicted by the viscosity B-coefficients. In this work, the chemical potential of carbon dioxide and the dynamic properties of water in aqueous NaCl, KF and NaClO₄ solutions are calculated and analyzed. According to the viscosity B-coefficients, NaClO₄ (0.012) should salt out the carbon dioxide relative to in pure water, but the opposite effect is observed for it. Our simulation results suggest that the salting-in effect of NaClO₄ is due to the strongly direct anion-CO₂ interaction. The inconsistency between Hofmeister Series and the viscosity B-coefficient suggests that it is not always right to indicate whether a salt belongs to salting-in or salting-out just from these properties of the salt solution in the absence of solute.     

肌醇在碱金属氯化物溶液中的体积性质

使用精密数字密度计测定了298.15和308.15 K肌醇在不同浓度的LiCl-H2O、NaCl-H2O或KCl-H2O溶液中的密度, 计算了肌醇的表观摩尔体积Vφ和极限偏摩尔体积Vθφ , 得到了其由纯水溶剂转移至混合溶剂中的迁移偏摩尔体积⊿trsVθ椎 .结果表明, LiCl, NaCl和KCl在溶液中对肌醇的体积性质影响显著, 极限偏摩尔体积Vθφ和极限迁移偏摩尔体积⊿trsVθφ都随盐浓度的增大而增加;温度对肌醇的极限偏摩尔体积和极限迁移偏摩尔体积只有轻微影响. 从分子-离子间的相互作用角度对实验结果进行了讨论.