Dielectric friction and solvation dynamics: Novel results on relaxation in dipolar liquids

In this article we present a new, general but simple, microscopic expression for time-dependent solvation energy of an ion. This expression is surprisingly similar to the expression for the time-dependent dielectric friction on a moving ion. We show that both the Chandra-Bagchi and the Fried-Mukamel formulations of solvation dynamics can be easily derived from this expression. This expression leads to an almost perfect agreement of the theory with all the available computer simulation results. Second, we show here for the first time that the mobility of a light solute ion can significantly accelerate its own solvation, specially in the underdamped limit. The latter result is also in excellent agreement with the computer simulations.     

Dynamics of solvation of an ion in a dense dipolar liquid

A molecular theory of the dynamics of solvation of an ion in a dense dipolar liquid is presented. The theory is based on an extended hydrodynamic approach that properly includes the interparticle correlations that are present at molecular length scales. The effects of the solvent inertial and viscoelastic responses are also included consistently. Numerical studies reveal rich relaxation behaviour such as short-time oscillations followed by a slow long-time decay. The results are in semi-quantitative agreement with recent computer simulation studies.     

计算离子液体溶液汽液相平衡的分子热力学模型

用平均球近似理论、微扰理论和UNIFAC基团贡献方法分别考虑离子之间的长程静电作用、离子与溶剂之间的中程静电作用以及所有粒子之间的短程作用,本文提出了一种新的分子热力学模型,可用于离子液体溶液中溶剂活度系数的计算.通过对含烷基咪唑磷酸酯类离子液体与水、甲醇或乙醇组成的9个二元体系的饱和蒸汽压数据进行关联,获得了相关的模型参数,即溶剂的分子直径和基团之间的交互作用能参数.溶剂活度系数及饱和蒸汽压的计算结果与实验值的平均偏差为1.40%,符合良好,因此本模型可望用于含离子液体体系汽液相平衡的预测.     

Molecular dynamics studies show solvation structure of type III antifreeze protein is disrupted at low pH

Antifreeze proteins are a class of biological molecules of interest in many research and industrial applications due to their highly specialized function, but there is little information of their stability and properties under varied pH derived from computational studies. To gain novel insights in this area, we conducted molecular dynamics (MD) simulations with the antifreeze protein 1KDF at varied temperatures and pH. Water solvation and H-bond formation around specific residues – ASN14, THR18 and GLN44 – involved in its antifreeze activity were extensively studied. We found that at pH1 there was a disruption in water solvation around the basal and the ice binding surfaces of the molecule. This was induced by a small change in the secondary structure propensities of some titrable residues, particularly GLU35. This change explains the experimentally observed reduction in antifreeze activity previously reported for this protein at pH1. We also found that THR18 showed extremely low H-bond formation, and that the three antifreeze residues all had very low average H-bond lifetimes. Our results confirm long-standing assumptions that these small, compact molecules can maintain their antifreeze activity in a wide range of pH, while demonstrating the mechanism that may reduce antifreeze activity at low pH. This aspect is useful when considering industrial and commercial use of antifreeze proteins subject to extreme pH environments, in particular in food industrial applications.     

Al3+ solvation in solutions of aluminum nitrate in a protic ionic liquid: Nuclear magnetic resonance verification of the solvation shell composition

The closest environment of Al³⁺ cations was analyzed in detail in solutions of aluminum nitrate in the prototypical protic ionic liquid ethyl ammonium nitrate (EAN) using ¹H and ¹⁴N nuclear magnetic resonance (NMR) spectra. For Al (NO₃)₃–EAN mixtures with different water content, a quantitative analysis of the integral intensities of the ¹H and ¹⁴N signals was carried out and the composition of the first solvation shell of the aluminum cation was refined.     

Ionic Association of the Ionic Liquids [C4mim][BF4], [C4mim][PF6], and [Cnmim]Br in Molecular Solvents

Considering the ionic nature of ionic liquids (ILs), ionic association is expected to be essential in solutions of ILs and to have an important influence on their applications. Although numerous studies have been reported for the ionic association behavior of ILs in solution, quantitative results are quite scarce. Herein, the conductivities of the ILs [C_nmim]Br (n=4, 6, 8, 10, 12), [C₄mim][BF₄], and [C₄mim][PF₆] in various molecular solvents (water, methanol, 1‐propanol, 1‐pentanol, acetonitrile, and acetone) are determined at 298.15 K as a function of IL concentration. The conductance data are analyzed by the Lee–Wheaton conductivity equation in terms of the ionic association constant (K_A) and the limiting molar conductance (Λ_m⁰). Combined with the values for the Br^? anion reported in the literature, the limiting molar conductivities and the transference numbers of the cations and [BF₄]^? and [PF₆]^? anions are calculated in the molecular solvents. It is shown that the alkyl chain length of the cations and type of anion affect the ionic association constants and limiting molar conductivities of the ILs. For a given anion (Br^?), the Λ_m⁰ values decrease with increasing alkyl chain length of the cations in all the molecular solvents, whereas the K_A values of the ILs decrease in organic solvents but increase in water as the alkyl chain length of the cations increases. For the [C₄mim]⁺ cation, the limiting molar conductivities of the ILs decrease in the order Br^?>[BF₄]^?>[PF₆]^?, and their ionic association constants follow the order [BF₄]^?>[PF₆]^?>Br^? in water, acetone, and acetonitrile. Furthermore, and similar to the classical electrolytes, a linear relationship is observed between ln K_A of the ILs and the reciprocal of the dielectric constants of the molecular solvents. The ILs are solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation. This information is expected to be useful for the modulation of the IL conductance by the alkyl chain length of the cations, type of anion, and physical properties of the molecular solvents.     

Solvation Structure of Uracil in Ionic Liquids

The local solvation environment of uracil dissolved in the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate has been studied using neutron diffraction techniques. At solvent:solute (ionic liquid:uracil) ratios of 3:1 and 2:1, little perturbation of the ion–ion correlations compared to those of the neat ionic liquid are observed. We find that solvation of the uracil is driven predominantly by the acetate anion of the solvent. While short distance correlations exist between uracil and the imidazolium cation, the geometry of these contacts suggest that they cannot be considered as hydrogen bonds, in contrast to other studies by Araújo et al. (J. M. Araújo, A. B. Pereiro, J. N. Canongia‐Lopes, L. P. Rebelo, I. M. Marrucho, J. Phys. Chem. B 2013, 117, 4109–4120 ). Nevertheless, this combination of interactions of the solute with both the cation and anion components of the solvents helps explain the high solubility of the nucleobase in this media. In addition, favourable uracil–uracil contacts are observed, of similar magnitude to those between cation and uracil, and are also likely to aid dissolution.     

Ionic solvation from conductivity data: Application and extension of the Chen-Adelman model

The most popular current theories representing the conductivity of a moving ion in an electric field are surveyed. The Chen-Adelman model of a partially solvated ion gives a good representation of literature data for alkaline and R₄N⁺ cations in five dipolar aprotic solvents. For multivalent cations however, one must introduce an extension of the Chen-Adelman model to a two-shell solvation model. Most of these results may be interpreted in terms of hard and soft acid-base interactions.This work is an amplification of a part of a Doctorate Thesis, University of Limoges, 1983.     

Solute-solvent interactions. VII. Proton magnetic resonance and infrared study of ion solvation in dipolar aprotic solvents

The solvation of a variety of ions by the dipolar aprotic solvents acetonitrile, sulfolane, and dimethylsulfoxide was studied through the influence of salts on the proton magnetic resonance chemical shifts of the solvents. In the case of acetonitrile the results were supplemented with infrared measurements, which showed that in general anions affect only the C–H and cations both the C–C and particularly the CN stretching frequencies of acetonitrile. The results are discussed in conjunction with transport and other data already in the literature. Current views on the structure of these solvents are summarized.From the Ph.D. thesis of this author, University of Pittsburgh, 1972.     

On the origin of the anomalous ultraslow solvation dynamics in heterogeneous environments

Many recent experimental studies have reported a surprising ultraslow component (even >10 ns) in the solvation dynamics of a polar probe in an organized assembly, the origin of which is not understood at present. Here we propose two molecular mechanisms in explanation. The first one involves the motion of the ‘buried water’ molecules (both translation and rotation), accompanied by cooperative relaxation (‘local melting’) of several surfactant chains. An estimate of the time is obtained by using an effective Rouse chain model of chain dynamics, coupled with a mean first passage time calculation. The second explanation invokes self-diffusion of the (di)polar probe itself from a less polar to a more polar region. This may also involve cooperative motion of the surfactant chains in the hydrophobic core, if the probe has a sizeable distribution inside the core prior to excitation, or escape of the probe to the bulk from the surface of the self-assembly. The second mechanism should result in the narrowing of the full width of the emission spectrum with time, which has indeed been observed in recent experiments. It is argued that both the mechanisms may give rise to an ultraslow time constant and may be applicable to different experimental situations. The effectiveness of solvation as a dynamical probe in such complex systems has been discussed.     

Ionic liquid modification of zeolite and its removal of chromate from water

This study focused on using imidazolium of different chain lengths to modify the negatively charged zeolite. The modification involves a cation exchange process of the organic cations of ionic liquids (ILs) for the alkali and alkaline earth elements on zeolite surfaces. X-ray diffraction analyses revealed that the uptake of ILs was on the external surfaces. Fourier transform infrared analyses showed that different mechanisms were attributed to IL uptake on zeolite at below and above the external cation exchange capacity. After modification, the zeolite reversed its surface charge to positive, thus enhancing adsorptive removal of anionic contaminants such as chromate from water. At the same time, the modified zeolite increased their total organic carbon content, and thus could promote better adsorptive removal of hydrophobic organic contaminants from water, too. These features enable IL-modified zeolite to be used as inexpensive sorbents for the removal of multi-types of contaminants from water simultaneously.     

A comparative theoretical study of dipeptide solvation in water

Molecular dynamics studies have been performed on the zwitterionic form of the dipeptide glycine-alanine in water, with focus on the solvation and electrostatic properties using a range of theoretical methods, from purely classical force fields, through mixed quantum mechanical/molecular mechanical simulations, to fully quantum mechanical Car-Parrinello calculations. The results of these studies show that the solvation pattern is similar for all methods used for most atoms in the dipeptide, but can differ substantially for some groups; namely the carboxy and aminoterminii, and the backbone amid NH group. This might have implications in other theoretical studies of peptides and proteins with charged -NH(3) (+) and -CO(2) (-) side chains solvated in water. Hybrid quantum mechanical/molecular mechanical simulations successfully reproduce the solvation patterns from the fully quantum mechanical simulations (PACS numbers: 87.14.Ee, 87.15.Aa, 87.15.He, 71.15.Pd).     

Continuous medium theory for nonequilibrium solvation: III. Solvation shift by monopole approximation and multipole expansion in spherical cavity

According to the classical electrodynamics, a new and reasonable method about electrostatic energy decomposition of the solute-solvent system has been proposed in this work by introducing the concept of spring energy. This decomposition in equilibrium solvation gives the clear comprehension for different parts of total electrostatic free energy. Logically extending this cognition to nonequilibrium leads to the new formula of electrostatic free energy of nonequilibrium state. Furthermore, the general solvation shift for light absorption/emission has been reformulated and applied to the ideal sphere case with the monopole approximation and multipole expansion. Solvation shifts in vertical ionizations of atomic ions of some series of main group elements have been investigated with monopole approximation, and the variation tendency of the solvation shift versus atomic number has been discussed. Moreover, the solvation shift in photoionization of nitrate anion in glycol has been investigated by the multipole expansion method.     

Explicit ion, implicit water solvation for molecular dynamics of nucleic acids and highly charged molecules

An explicit ion, implicit water solvent model for molecular dynamics was developed and tested with DNA and RNA simulations. The implicit water model uses the finite difference Poisson (FDP) model with the smooth permittivity method implemented in the OpenEye ZAP libraries. Explicit counter-ions, co-ions, and nucleic acid were treated with a Langevin dynamics molecular dynamics algorithm. Ion electrostatics is treated within the FDP model when close to the solute, and by the Coulombic model when far from the solute. The two zone model reduces computation time, but retains an accurate treatment of the ion atmosphere electrostatics near the solute. Ion compositions can be set to reproduce specific ionic strengths. The entire ion/water treatment is interfaced with the molecular dynamics package CHARMM. Using the CHARMM-ZAPI software combination, the implicit solvent model was tested on A and B form duplex DNA, and tetraloop RNA, producing stable simulations with structures remaining close to experiment. The model also reproduced the A to B duplex DNA transition. The effect of ionic strength, and the structure of the counterion atmosphere around B form duplex DNA were also examined.     

Preferential solvation of lysozyme by dimethyl sulfoxide in binary solutions of water and dimethyl sulfoxide

To reveal the denaturation mechanism of lysozyme by dimethyl sulfoxide (DMSO), thermal stability of lysozyme and its preferential solvation by DMSO in binary solutions of water and DMSO was studied by differential scanning calorimetry (DSC) and using densities of ternary solutions of water (1), DMSO (2) and lysozyme (3) at 298.15 K. A significant endothermic peak was observed in binary solutions of water and DMSO except for a solution with a mole fraction of DMSO (x ₂) of 0.4. As x ₂ was increased, the thermal denaturation temperature T _m decreased, but significant increases in changes in enthalpy and heat capacity for denaturation, ΔH _cal and ΔC _p, were observed at low x ₂ before decreasing. The obtained amount of preferential solvation of lysozyme by DMSO (∂g ₂/∂g ₃) was about 0.09 g g⁻¹ at low x ₂, indicating that DMSO molecules preferentially solvate lysozyme at low x ₂. In solutions with high x ₂, the amount of preferential solvation (∂g ₂/∂g ₃) decreased to negative values when lysozyme was denatured. These results indicated that DMSO molecules do not interact directly with lysozyme as denaturants such as guanidine hydrochloride and urea do. The DMSO molecules interact indirectly with lysozyme leading to denaturation, probably due to a strong interaction between water and DMSO molecules.     

Ab-initio molecular dynamics and hybrid explicit-implicit solvation model for aqueous and nonaqueous solvents: GFP chromophore in water and methanol solution as case study

Solute–solvent interactions are proxies for understanding how the electronic density of a chromophore interacts with the environment in a more exhaustive way. The subtle balance between polarization, electrostatic, and non-bonded interactions need to be accurately described to obtain good agreement between simulations and experiments. First principles approaches providing accurate configurational sampling through molecular dynamics may be a suitable choice to describe solvent effects on solute chemical–physical properties and spectroscopic features, such as optical absorption of dyes. In this context, accurate energy potentials, obtained by hybrid implicit/explicit solvation methods along with employing nonperiodic boundary conditions, are required to represent bulk solvent around a large solute–solvent cluster. In this work, a novel strategy to simulate methanol solutions is proposed combining ab initio molecular dynamics, a hybrid implicit/explicit flexible solvent model, nonperiodic boundary conditions, and time dependent density functional theory. As case study, the robustness of the proposed protocol has been gauged by investigating the microsolvation and electronic absorption of the anionic green fluorescent protein chromophore in methanol and aqueous solution. Satisfactory results are obtained, reproducing the microsolvation layout of the chromophore and, as a consequence, the experimental trends shown by the optical absorption in different solvents.     

Stability of Ag<Superscript>+</Superscript> Complexes with Cryptand 222 in Ionic Liquids

Stability constants of silver(I) complexes with cryptand 222 were measured in a number of ionic liquids, applying potentiometric titration. The ionic liquids were based on 1-butyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-1-methyl-pyrrolidinium and 1-methyl-1-propyl-pyrrolidinium cations, as well as on tetrafluoroborate, triflate and bis(trifluoromethane sulfonyl) imide. The stability constants, expressed in log K scale, were within the broad range of 8.4–17.2. The formation of the Ag⁺222 cryptates was not detected in ionic liquids based on halide anions. Free enthalpy of silver(I) transfer from dimethylsulfoxide as a reference molecular solvent to ionic liquids was calculated applying the cryptate assumption. The results were discussed in terms of the competition between silver(I) complexation by ion forming ionic liquid and its complexation by cryptand 222.in final form: 6 December 2004This revised version was published online in July 2005 with a corrected issue number.