Proton Ordering of Ice and Gas‐Hydrate Frameworks. Nanostructural Approach

This paper reviews the state of research into lowtemperature proton ordering of ice and the results of theoretical predictions of energetically preferred proton configurations of regular water systems based on the topological model of strong and weak Hbonds. All systems under study have noncrystalline proton ordering. It is concluded that in the context of proton ordering problems, ice is the object of nanostructural analysis.     

Proton Ordering in Cubic Ice. I. Combinatorial Optimization of the Structure

The model of strong and weak H-bonds suggested previously for hexagonal ice is used to study the structure of the ground energy state of the proton subsystem of cubic ice. Combinatorial optimization of the structure showed that the configurations containing only strong bonds may be of two types. The first type includes one-dimensionally disordered structures consisting of crystal-ordered layers; the second is characterized by stepwise ordering of twin type.     

Nanostructural Approach to Proton Ordering in Gas Hydrate Cages

A nanostructural approach to analysis of proton ordering in gas hydrate cages has been worked out within the framework of the topological model of strong and weak H-bonds. The approach involves rejection of the periodic boundary conditions, decomposition of the H-bond net into spherical layers, and two-dimensional drawing of the structure of spherical (spheroidal) fragments in the form of conjugate Schlegel diagrams. To analyze proton ordering in the spherical fragments composed of gas hydrate voids, we used the simulated annealing procedure and the correlation extension method proposed earlier.     

Frustrated Gas Hydrate Frameworks in the Model of Strong and Weak Hydrogen Bonds

The topological model of strong and weak H-bonds suggested previously was used for structure investigation of the ground energy state of the proton subsystem of gas hydrate frameworks. It is shown that gas hydrate frameworks are frustrated systems, that is, configurations consisting of exclusively strong H-bonds may not exist in view of combinatorial and topological constraints. Rough estimates were obtained for the maximal and minimal fractions of strong H-bonds (65 and 6%, respectively).     

Intermediate temperature proton conductors for PEM fuel cells based on phosphonic acid as protogenic group: a progress report

The melting behaviour and transport properties of straight chain alkanes mono- and difunctionalized with phosphonic acid groups have been investigated as a function of their length. The increase of melting temperature and decrease of proton conductivity with increasing chain length is suggested to be the consequence of an increasing ordering of the alkane segments which constrains the free aggregation of the phosphonic acid groups. However, the proton mobility is reduced to a greater extent than the proton diffusion coefficient indicating an increasing cooperativity of proton transport with increasing length of the alkane segment. The results clearly indicate that the "spacer concept", which had been proven successful in the optimization of the proton conductivity of heterocycle based systems, fails in the case of phosphonic acid functionalized polymers. Instead, a very high concentration of phosphonic acid functional groups forming "bulky" hydrogen bonded aggregates is suggested to be essential for obtaining very high proton conductivity. Aggregation is also suggested to reduce condensation reactions generally observed in phosphonic acid containing systems. On the basis of this understanding, the proton conductivities of poly(vinyl phosphonic acid) and poly(meta-phenylene phosphonic acid) are discussed. Though both polymers exhibit a substantial concentration of phosphonic acid groups, aggregation seems to be constrained to such an extent that intrinsic proton conductivity is limited to values below sigma = 10(-3) S cm(-1) at T = 150 degrees C. The results suggest that different immobilization concepts have to be developed in order to minimize the conductivity reduction compared to the very high intrinsic proton conductivity of neat phosphonic acid under quasi dry conditions. In the presence of high water activities, however, (as usually present in PEM fuel cells) the very high ion exchange capacities (IEC) possible for phosphonic acid functionalized ionomers (IEC >10 meq g(-1)) may allow for high proton conductivities in the intermediate temperature range (T approximately 120 -160 degrees C).     

XH-NH3(X=F,Cl,Br)质子传递的溶剂效应:簇模型,连续介质模型和离散-连续组合模型的比较

分别采用分子簇模型、连续介质模型和离散-连续组合模型研究了XH-NH3(X=F,Cl,Br)分子内质子传递的溶剂效应．结果表明,对于弱酸性化合物FH-NH3,其溶剂效应主要为短程作用,3个H2O分子即可使其发生质子传递,而简单的连续介质模型得到的仍为分子化合物形式,需进一步包含溶剂效应短程作用．对于强酸性化合物ClH-NH3和BrH-NH3,较弱的溶剂效应即可促使其发生质子传递,分子簇模型和连续介质模型均可合理描述,且与离散-连续组合模型的结果相近．离散-连续组合模型既在从头算水平考虑了溶质分子和第一溶剂化层中溶剂分子间的短程作用,又包含了溶剂效应的长程静电作用,能更准确地描述溶剂化作用,且对弱酸性化合物和强酸性化合物体系均适用．     

NMR relaxation investigation of water “ordering” in aqueous lysozyme solutions

Lysozyme in aqueous dilute solution has been chosen as a model system to investigate the state and the mobility of water molecules near macromolecular surfaces. The dependence of the water proton NMR T₁ on temperature and on denaturing processes is interpreted in terms of long-range interactions giving rise to“ordering” of water, as seen on the NMR time scale.     

Copper and zinc removal from aqueous solution by mixed mineral systems I. Reactivity and removal kinetics

This study investigates the reactivity and removal kinetics of Cu and Zn onto mixed mineral systems from aqueous solution related to acid mine drainage impacted areas. The sorbents used were kaolinite, Al-montmorillonite, goethite, and their mixtures. The effects of surface charge, proton coefficient, and sorption kinetics were studied at room temperature (23+/-2 degrees C). Using an empirical model, mineral mixing reduced the exchange of protons for sorbing ions and the acidity of the reactive sites, thus impeding Cu and Zn removal by proton exchange. Based on the amount of Cu and Zn sorbed on the mixed mineral suspensions at ionic strength 0.01 to 0.1 M and pH 4, it is suggested that Cu and Zn removal from aqueous solution was by both inner and outer sphere complexation. Mineral mixing reduced the transfer rate of Cu relative to the single mineral suspensions in both slow and fast reaction phases. The behavior of the mixed suspensions in Cu and Zn sorption suggest that different reactive sites were involved at the onset of sorption, becoming similar to those of the single mineral components over time.     

Electrical conductivity of aqueous acids in binary and ternary water-electrolyte systems

We analyze electrical conductivity data for aqueous solutions of strong and weak acids over a wide range of concentrations at various temperatures. Electrical conductivity isotherms in these solutions are characterized by peaks, whose parameters correlate with the molecular structure of solutions. On the basis of the concentration dependence of the activation energy of electrical conductivity, the acid solutions are divided into two groups. One includes HIO₃, H₂SO₄, and H₃PO₄; the other includes HCl, HBr, HI, HClO₄, HNO₃, and carboxylic acids. We show that anomalous proton migration is operative only in low-concentration solutions until their concentration reaches the peak on conductivity isotherms. The effect of extrinsic ions on proton mobility and on conductivity in acid-salt-water systems is considered.     

Proton hydration in aqueous solution: Fourier transform infrared studies of HDO spectra

This paper attempts to elucidate the number and nature of the hydration spheres around the proton in an aqueous solution. This phenomenon was studied in aqueous solutions of selected acids by means of Fourier transform infrared spectroscopy of semiheavy water (HDO), isotopically diluted in H(2)O. The quantitative version of difference spectrum procedure was applied for the first time to investigate such systems. It allowed removal of bulk water contribution and separation of the spectra of solute-affected HDO. The obtained spectral data were confronted with ab initio calculated structures of small gas-phase and polarizable continuum model (PCM) solvated aqueous clusters, H+(H2O)n, n=2-8, in order to help in establishing the structural and energetic states of the consecutive hydration spheres of the hydrated proton. This was achieved by comparison of the calculated optimal geometries with the interatomic distances derived from HDO band positions. The structure of proton hydration shells outside the first hydration sphere essentially follows the model structure of other hydrated cations, previously revealed by affected HDO spectra. The first hydration sphere complex in diluted aqueous solutions was identified as an asymmetric variant of the regular Zundel cation [The Hydrogen Bond: Recent Developments in Theory and Experiments, edited by P. Schuster, G. Zundel, and C. Sandorfy (North-Holland, Amsterdam, 1976), Vol. II, p. 683], intermediate between the ideal Zundel and Eigen structures [E. Wicke et al., Z. Phys. Chem. Neue Folge 1, 340 (1954)]. Evidence was found for the existence of strong and short hydrogen bonds, with oxygen-oxygen distance derived from the experimental affected spectra equal 2.435 A on average and in the PCM calculations about 2.41-2.44 A. It was also evidenced for the first time that the proton possesses four well-defined hydration spheres, which were characterized in terms of hydrogen bonds' lengths and arrangements. Additionally, an outer hydration layer, shared with the anion, as well as loosely bound water molecules interacting with free electron pairs of the central complex were detected in the affected spectra.     

LCAO-MO-SCF-Calculations on the stability and Sterochernistry of hydrogen bonds

CNDO and INDO calculations were performed on numerous structures with hydrogen bonds of different strength. An almost linear relationship is found between the strength of weak hydrogen bonds and the amount of charge transfered.π-electrons and lone pairs are nearly equivalent in hydrogen bonding. The stereochemistry of hydrogen bonds is determined largely by additional interactions betweenσ-bonds of the two molecules. Since proton affinities are calculated too large by the CNDO method, an error is introduced in the potential curves for proton transfer in weak hydrogen bonds. In systems with strong hydrogen bonds both structures with the proton on the right and left have almost the same energy and hence the potential curves for proton transfer are free of the errors mentioned above.     

DNA‐Mediated Assembly of Boron Nitride Nanotubes

The dispersion of nanomaterials in solutions is of primary importance for the improvement of their processability, but it also provides a way to investigate phase behavior and to assemble nanostructures in solvents. Several methods based on different interactions have been developed to disperse carbon nanotubes, whereas little development has been made for their boron nitride nanotube (BNNT) counterparts. A direct way to obtain long‐range ordering may be through spontaneous nematic ordering in solutions at sufficiently high concentrations of the nanomaterial fraction. Lyotropic nematics have been observed in various organic and inorganic systems. In this work, the strong interactions between DNA and BNNTs were exploited to fabricate high‐concentration BNNTs aqueous solutions by a simple method, and then, for the first time, nematic ordered ensembles of BNNTs were obtained by filtration. It is proposed that a localized liquid‐crystal phase appears during filtration, as the ordering trend for the BNNTs was found to depend on the concentration of the aqueous solutions of the BNNTs. Moreover, BNNTs were successfully localized on a predefined area by using a thiol‐modified DNA–BNNT hybrid.     

Direct participation of counter anion in acid hydrolysis of glycoside

The mechanism of acid hydrolysis of glycoside has been investigated since the end of the 19th century accompanied by lots of literatures published on the mechanism, although little attention has surprisingly been paid to the action of counter anion of acid. In this paper, it was investigated whether or not counter anion of acid directly participates in acid hydrolysis of glycosides, methyl α- and β-d-glucopyranosides (MGP) in water, aqueous 74%, and 82% 1,4-dioxane systems. Because proton activity of a reaction system is the important rate-determining parameter in the universally acknowledged mechanism, it was carefully estimated in this study. The results suggested that bromide anion directly participates in the acid hydrolysis reaction of MGP in a water solvent system and the participation of bromide anion is further pronounced in aqueous 74% and 82% 1,4-dioxane solvent systems. It was also suggested that chloride anion directly participates in these dioxane solvent systems.     

An S N2-Model for Proton Transfer in Hydrogen-Bonded Systems

A new mechanism of proton transfer in donor–acceptor complexes with long hydrogen bonds is suggested. The transition is regarded as totally adiabatic. Two closest water molecules that move synchronously by hindered translation to and from the reaction complex are crucial. The water molecules induce a shift of the proton from the donor to the acceptor with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. Expressions for the activation barrier and kinetic hydrogen isotope effect are derived. The general scheme is illustrated with the use of model molecular potentials, and with reference to the excess proton conductivity in aqueous solution.     

Proton Ordering in Cubic Ice. II. Structure of Optimal Configurations

The configurations of the ground energy state of cubic ice obtained previously using the model of strong and weak H-bonds are analyzed. It is established that the stepwise ordered structure is a defectless axial twin. A peculiarity of the twin lies in the fact that strict crystal ordering in its regions is due to the presence of the boundary and its structure. The difference between the structures of the hexagonal layers of ices Ih and Ic is revealed. It is shown that the one-dimensionally disordered layered state in the base planes has antiferroelectric ordering.     

膜/液界面浓度极化现象的介电解析

对由强、弱荷电膜和溶液构成的膜／液非均匀体系，在10－107Hz频率范围进行了介电测量，在直流偏压下，该体系显示了二个显著的介电弛豫．利用具有电导率分布相，即浓度极化相的介电理论对强行电的离子交换膜的结果进行了介电解析，从实验上测得的介电参数求出了反映膜／液界面浓度极化层构造的参数，讨论了该体系产生介电弛像的原因、说明了介电理论的合理性，并提出了膜／液界面体系产生介电弛豫现象的可能机理．     

溶液中Zn2+与腺嘌呤异构体间相互作用的理论研究

用B3LYP/6-311++G**方法和PCM及Onsager模型研究了Zn2+与腺嘌呤异构体在溶液中的11种较为稳定配合物. 结果显示, 这些配合物在溶液中的稳定性顺序与气相中明显不同, 其结合位点表现出如下的规律性, 在亚氨基类配合物中, Zn2+与腺嘌呤的N7、N6位结合比与N1、N6位结合形成的配合物更稳定; 氨基类配合物中, Zn2+以"双齿"形式与腺嘌呤异构体上的氮结合时的优先顺序为(N3和N9)>(N7和N6)>(N1和N6). 研究表明, 不论气相还是溶液相, 孤立的腺嘌呤分子内的质子转移较困难, 结合Zn2+后也不能明显降低关键步骤的活化能; 结合Cu2+却能明显地降低气相中关键步骤的活化能, 但溶剂效应却不利于Cu2+引发腺嘌呤分子内的质子转移.     

Effect of proton concentration on membrane potential across a weak amphoteric polymer membrane

An amphoteric membrane consists of both positively and negatively fixed charge groups chemically bound to the polymer chains. If the external solution is changed from alkali to acid, it is possible to obtain an experimental result in which the membrane potential changes from positive to negative through the isoelectric point. It was characterized by examining the relationship between membrane potential and proton concentration (pH) obtained from both experimental and theoretical considerations. The Nernst-Planck flux equation and the Donnan equilibrium theory were also solved for a four-component system combined with the dissociation constant, in order to discuss the pH dependence of membrane potential in a weak amphoteric membrane by comparing the experimental results with the calculated results. It was proven that the calculated results substantially deviated from the theoretical results despite a similar tendency. Such a deviation was caused by the fact that the original theory disregarded the activity coefficient and the ionic mobility, which were dependent on the fixed charge concentration in a membrane. The original theoretical model was modified by adding the effect of a fixed charge group to the activity coefficient and ionic mobility. The calculated results using the modified model explained well the experimental results if the parameter called charge effectiveness, phi, was introduced into the equations. Introduction of phi into the prediction of membrane potential was already done by Kobatake et al. in a system of a strong polyelectrolyte monopolar membrane/salt aqueous solution. In this study, it was proved that phi can also be introduced into a weak amphoteric polymer membrane/salt aqueous solution system. Finally it was also concluded that the Donnan equilibrium and the Nernst-Planck flux equation were still applicable for examining the transport phenomena for the system of a weak amphoteric charged membrane and electrolyte solutions at various pH.     

Structure formation peculiarities of complex sulfides with a short period and symmetry mirror planes

The geometry of cation and anion matrices is analyzed in the crystal structures of complex sulfides with the symmetry mirror planes perpendicular to the short translation of ~4 Å. In support of the developed crystalline state concept, the structures exhibit the spatial atomic ordering by the systems of crystallographic planes. This includes the absolute ordering by the symmetry mirror planes that tend to form hexagonal sublattices with trigon 36 nets.     

Elucidation of the Structure of Organic Solutions in Solvent Extraction by Combining Molecular Dynamics and X‐ray Scattering

Knowledge of the supramolecular structure of the organic phase containing amphiphilic ligand molecules is mandatory for full comprehension of ionic separation during solvent extraction. Existing structural models are based on simple geometric aggregates, but no consensus exists on the interaction potentials. Herein, we show that molecular dynamics crossed with scattering techniques offers key insight into the complex fluid involving weak interactions without any long‐range ordering. Two systems containing mono‐ or diamide extractants in heptane and contacted with an aqueous phase were selected as examples to demonstrate the advantages of coupling the two approaches for furthering fundamental studies on solvent extraction.