Control of surface forces through hydrated boundary layers

Hydration layers surrounding charges or zwitterionic moieties have long been known to play important roles in areas including antifouling and colloidal stability, and particularly over the past 15 years or so, their role in boundary lubrication has been widely investigated. Hydration repulsion because of hydrated ions or polar groups present on surfaces may dominate their interactions at high electrolyte concentrations, so that Derjaguin–Landau–Verwey–Overbeek theory does not apply. Hydration shells, strongly held by the charges they surround, can sustain large pressures without being squeezed out, while by rapidly relaxing, and they behave like a fluid during shear; this may lead to their acting as lubrication vectors with outstanding friction–reduction properties. This review considers hydration layers around trapped ions, polymer brushes, and amphiphiles (surfactants and phosphatidylcholines), focusing on their lubrication properties. Finally, we suggest some prospects for further development of current hydrated vectors and designing new hydrated vectors for modifying surface interactions.     

Development of the theory of strong electrolytes considering the concentration dependence of hydration numbers

An expression for the Gibbs free energy is obtained that takes into account the contribution of interactions in the hydrate shells of ions and is compared with experimental data on the concentration dependence of hydration numbers. The activity coefficient derived from this expression is consistent with experiment up to the concentrations corresponding to the total solvation boundary (TSB). The relations describing the thermodynamics of solutions in the region of concentrations exceeding TSB are proposed. The analysis of the obtained expressions confirms their adequacy to experiments.     

Verified analysis of hydration of electrolytes

Rigorous thermodynamic analysis of hydration parameters has been fulfilled. Water solutions of potassium chloride were studied in a wide range of concentrations from 0 to 23 wt.% in the temperature range 283.15–308.15 K by ultrasonic and densimetry measurements using heat capacity data at constant pressure. The structural characteristics of hydrated complexes are analyzed: hydration number, volume of the stoichiometric mixture of K⁺ and Cl^? ions without hydration shells, compressibility and molar volume of water in hydration spheres, and their concentration and temperature dependences. The mean pressure in the hydration spheres of KCl ions is shown to be about 350 atm at 298.15 K.     

Interfacial chemistry of adhesives on hydrated aluminium and hydrated aluminium treated with an organosilane

The adsorption of a commercial adhesive and two of its major components—an amine curing agent [2,4‐toluene diisocyanate urone (TDI urone)] and an adhesive prepolymer resin [diglycidyl ether of bisphenol A (DGEBA)]—on a hydrated aluminium surface and the hydrated surface coated with γ‐glycidoxypropyltrimethoxysilane (GPS) has been investigated by x‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The study of TDI urone adsorption indicated that adsorption was of the chemisorption type, and a specific interaction involving this molecule and the GPS immobilized on the hydrated aluminium surface was identified. From XPS and ToF‐SIMS data it was found that the types of interaction of the curing agent with the bare substrate were of the donor–acceptor type. Study of the DGEBA adsorption showed different‐shaped isotherms for the bare and the GPS‐coated substrates. It was found that the typical Langmuir isotherm type was obtained for the GPS‐coated substrate whereas no adsorption plateau was observed for the bare substrate within the concentration range studied. This resulted from a change in the conformation of the DGEBA molecule on the substrate when the concentration of DGEBA solution was increased. The bonding of DGEBA with both types of substrates was assumed to be via acid–base interactions (i.e. donor–acceptor interactions). Adsorption of the commercial adhesive on the hydrated surfaces was of BET Type IV form, rather than the simple monolayer adsorption isotherm (Langmuir type). This indicates multilayer adsorption, presumably in the pores of the hydrated substrate, as a result of a process analogous to adsorption condensation. Copyright © 2004 John Wiley & Sons, Ltd.     

EXAFS studies of nickel nafion ionomers

Nafion membranes neutralized with Ni²⁺ have been examined by extended x-ray absorption fine-structure (EXAFS) and x-ray absorption near-edge-structure (XANES) spectroscopy. The results indicate that in both the dry and water-soaked membranes, the nickel is in an octahedral site with six oxygen atoms as nearest neighbors. The degree of disorder in the Ni? O distance is comparable to that in ionic crystals in both the dry and hydrated materials. A contribution from a second shell of neighbors is very weak in the dry samples but, surprisingly, this contribution is strongly accentuated in the hydrated membranes. The data indicate that this contribution is due to neighboring Ni²⁺ cations. Thus the water absorption seems to enhance the local ordering of the cation environment. The local structure does not depend strongly on the concentration of ionic groups in the materials.     

Role of hydration force in the self-assembly of collagens and amyloid steric zipper filaments

In protein self-assembly, types of surfaces determine the force between them. Yet the extent to which the surrounding water contributes to this force remains as a fundamental question. Here we study three self-assembling filament systems that respectively have hydrated (collagen), dry nonpolar, and dry polar (amyloid) interfaces. Using molecular dynamics simulations, we calculate and compare local hydration maps and hydration forces. We find that the primary hydration shells are formed all over the surface, regardless of the types of the underlying amino acids. The weakly oscillating hydration force arises from coalescence and depletion of hydration shells as two filaments approach, whereas local water diffusion, orientation, or hydrogen-bonding events have no direct effect. Hydration forces between hydrated, polar, and nonpolar interfaces differ in the amplitude and phase of the oscillation relative to the equilibrium surface separation. Therefore, water-mediated interactions between these protein surfaces, ranging in character from "hydrophobic" to "hydrophilic", have a common molecular origin based on the robustly formed hydration shells, which is likely applicable to a broad range of biomolecular assemblies whose interfacial geometry is similar in length scale to those of the present study.     

A pressure and temperature study on solubility and micelle formation of sodium perfluorodecanoate in aqueous solution

Both the critical solution temperature (CST, or the Krafft temperature) and the critical solution pressure (CSP, or the Tanaka pressure) were determined for sodium perfluorodecanoate (NaPFDe) in water, and the result shows that the Krafft temperature is raised with the increase in the Tanaka pressure. A thermodynamic analysis has been made on the data for the critical micellization concentration (cmc) and of the solubility at various temperatures and pressures. The estimated change in the partial molal volume, resulting from micelle formation from the singly dispersed state and from the hydrated solid state, was found to be conspicuously higher for NaPFDe compared to hydrocarbon surfactants. This has been ascribed to the more pronounced role of carbon chain-water interactions and water structure effects of the fluorocarbon surfactants.     

Computer simulation of dissociative equilibrium in aqueous NaCl electrolyte with account for polarization and ion recharging. Model of interactions

Comparative analysis of different models applied in theoretical studies of electrolytes points to the considerable role of polarization interactions. In order to study aqueous electrolytes on the molecular level, a detailed model is presented of intermolecular interactions that accounts in explicit form, apart from Coulombic, exchange, and dispersion interactions, also many-body interactions caused by polarization of solvent molecules in the field of ions and ion polarization in the field of solvent molecules, and also many-body covalent interactions, effects of excess charge transfer and effects of partial counterion recharging. Numeric values of parameters for an aqueous NaCl solution are obtained by correlation of the calculated values of free energies and entropy of the first reactions of vapor molecule addition to hydrate ion shells with the corresponding experimental values and also from the experimental data on the dissociation energy and IR vibration frequencies of the ion pair and quantum-chemical calculation of the energy of stable configurations of a hydrated ion pair. A special form of describing many-body interactions allows by more than an order of magnitudes reducing the extent of the required calculations and makes it possible to apply the developed model for computer simulation of aqueous electrolytes at the room temperatures.     

Hydration forces underlie the exclusion of salts and of neutral polar solutes from hydroxypropylcellulose

The distance dependence for the preferential exclusion of several salts and neutral solutes from hydroxypropyl cellulose (HPC) has been measured via the effect of these small molecules on the thermodynamic forces between HPC polymers in ordered arrays. The concentration of salts and neutral solutes decreases exponentially as the spacing between apposing nonpolar HPC surfaces decreases. For all solutes, the spatial decay lengths of this exclusion are remarkably similar to those observed between many macromolecules at close spacings where intermolecular forces have been ascribed to the energetics of water structuring. Exclusion magnitudes depend strongly on the nature and size of the particular salt or solute; for the three potassium salts studied, exclusion follows the anionic Hofmeister series. The change in the number of excess waters associated with HPC polymers is independent of solute concentration suggesting that the dominating interactions are between solutes and the hydrated polymer. These findings further confirm the importance of solvation interactions and reveal an unexpected unity of Hofmeister effects, preferential hydration, and hydration forces.     

Structural and dynamical properties of the Hg2+ aqua ion: a molecular dynamics study

Molecular dynamics simulations of the Hg2+ ion in aqueous solution have been carried out using an effective two-body potential derived from quantum mechanical calculations. A stable heptacoordinated structure of the Hg2+ first hydration shell has been observed and confirmed by extended X-ray absorption fine structure (EXAFS) experimental data. The structural properties of the Hg2+ hydration shells have been investigated using radial and angular distribution functions, while the dynamical behavior has been discussed in terms of reorientational correlation functions, mean residence times of water molecules in the first and second hydration shells, and self-diffusion coefficients. The effect of water-water interactions on the Hg2+ hydration properties has been evaluated using the SPC/E and TIP5P water models.     

Ion hydration co-sphere interactions in the double-layer and ionic solutions

Two-dimensional concentrations of adsorbed ions in double-layers at charged interfaces, especially when appreciable specific adsorption obtains, are equivalent to quite substantial (1–4 M) three-dimensional concentrations in regular electrolyte solutions. Under such conditions, ion-specific Gurney co-sphere overlap interactions give an important contribution to the non-ideal free energy of electrolytes in solution. It is proposed that similar interaction effects arise two-dimensionally in double-layers, giving rise to a contribution to the lateral interaction energy in monolayer arrays of ions. Three types of calculations are described by which these interaction effects can be evaluated. One is applied to some recent data on tetrapropylammonium ion adsorption at Hg, where hydrophobic interactions arise.Related problems concerned with solvent dipole orientation in the inner layer, when appreciable surface concentrations of hydrated ions are present, are referred to. The probable role of field-gradient/quadrupole interactions is noted.     

Formation and interaction of hydrated alkali metal ions at the graphite-water interface

Ion hydration at a solid surface ubiquitously exists in nature and plays important roles in many natural processes and technological applications. Aiming at obtaining a microscopic insight into the formation of such systems and interactions therein, we have investigated the hydration of alkali metal ions at a prototype surface-graphite (0001), using first-principles molecular dynamics simulations. At low water coverage, the alkali metal ions form two-dimensional hydration shells accommodating at most four (Li, Na) and three (K, Rb, Cs) waters in the first shell. These two-dimensional shells generally evolve into three-dimensional structures at higher water coverage, due to the competition between hydration and ion-surface interactions. Exceptionally K was found to reside at the graphite-water interface for water coverages up to bulk water limit, where it forms an "umbrellalike" surface hydration shell with an average water-ion-surface angle of 115 degrees . Interactions between the hydrated K and Na ions at the interface have also been studied. Water molecules seem to mediate an effective ion-ion interaction, which favors the aggregation of Na ions but prevents nucleation of K. These results agree with experimental observations in electron energy loss spectroscopy, desorption spectroscopy, and work function measurement. In addition, the sensitive dependence of charge transfer on dynamical structure evolution during the hydration process, implies the necessity to describe surface ion hydration from electronic structure calculations.     

The water molecule arrangement over the side chain of some aliphatic amino acids: A quantum chemical and bottom-up investigation

The geometry of surrounding water molecules on the side chain of glycine, alanine, α-aminoisobutyric acid, α-aminobutyric acid, valine, and related hydrocarbons has been analyzed combining bottom-up and quantum chemical methodologies. To minimize the cavity size and to prevent water-water hydrogen bonding loss, the water molecules adopt a shape, resembling the one found in crystal structure of gas clathrate hydrates, with water molecules tangentially oriented to the surface of hydrophobic side chain. The cage is directly hydrogen bonded to the backbone's polar groups, thus hydration shells around hydrophobic and hydrophilic groups are folded together in amphiphilic molecules. The hydrophobe enclathration implies a substantial freedom degree reduction which makes it entropically disfavored. This disadvantageous entropic contribution is partially compensated by the favorable van der Waals interactions with guest in stabilizing clathrate hydrate formation. The water shell around the side chain relates intimately with the side-chain rotational isomerism. Present data are correlated with the experimental determined populations of the three rotamers, yielding promising results for both α-aminobutyric acid and valine.     

Evidence of solvation of aqueous electrolytes in a range from diluted to concentrated solutions

Parameters of solvation of strong electrolytes in aqueous solutions have been investigated based on literature data on their densities, thermal capacities, and rates of ultrasound propagation. By using appropriate thermodynamic equations, such quantitative parameters of solvation as hydration number (h), molar adiabatic compressibility of the hydrated forms (β _h V _h ), volume (V _1h ), and compressibility (β_1h ) of water in the hydrated shells of ions have been determined in the temperature interval from 278.15 to 323.15 K. It has been demonstrated that the h and β _h V _h values are temperature-independent within the studied interval and that electrostrictive compression near ions has a stronger effect on their structure than a simple change in pressure.     

Interactions between a dsDNA Oligonucleotide and Imidazolium Chloride Ionic Liquids: Effect of Alkyl Chain Length,Part I

Ionic liquids (ILs) have become nearly ubiquitous solvents and their interactions with biomolecules has been a focus of study. Here, we used the fluorescence emission of DAPI, a groove binding fluorophore, coupled with molecular dynamics (MD) simulations to report on interactions between imidazolium chloride ([Im_n,1]⁺) ionic liquids and a synthetic DNA oligonucleotide composed entirely of T/A bases (7(TA)) to elucidate the effects ILs on a model DNA duplex. Spectral shifts on the order of 500–1000 cm⁻¹, spectral broadening (~1000 cm⁻¹), and excitation and emission intensity ratio changes combine to give evidence of an increased DAPI environment heterogeneity on added IL. Fluorescence lifetimes for DAPI/IL solutions yielded two time constants 0.15 ns (~80% to 60% contribution) and 2.36–2.71 ns for IL up to 250 mM. With DNA, three time constants were required that varied with added IL (0.33–0.15 ns (1–58% contribution), ~1.7–1.0 ns (~5% contribution), and 3.8–3.6 ns (94–39% contribution)). MD radial distribution functions revealed that π-π stacking interactions between the imidazolium ring were dominant at lower IL concentration and that electrostatic and hydrophobic interactions become more prominent as IL concentration increased. Alkyl chain alignment with DNA and IL-IL interactions also varied with IL. Collectively, our data showed that, at low IL concentration, IL was primarily bound to the DNA minor groove and with increased IL concentration the phosphate regions and major groove binding sites were also important contributors to the complete set of IL-DNA duplex interactions.     

Influence of Hydronium Ions in Zeolites on Sorption

In the presence of sufficient concentrations of water, stable, hydrated hydronium ions are formed in the pores and at the surface of solid acids such as zeolites. For a medium‐pore zeolite, such as zeolite MFI, hydrated hydronium ions consist of eight water molecules and have an effective volume of 0.24 nm³. In their presence, larger organic molecules can only adsorb in the portions of the pore that are not occupied by hydronium ions. As a consequence, the available pore volume decreases proportionally to the concentration of the hydronium ions. The higher charge density (the increasing ionic strength) that accompanies an increasing concentration of hydronium ions leads to an increase in the activity coefficients of the adsorbed substrates, thus, weakening the interactions between the organic part of the molecules and the zeolite and favoring the interactions with polar groups. The quantitative understanding of these interactions makes it possible to link a collective property such as hydrophilicity and hydrophobicity of zeolites to specific interactions on molecular level.     

Bulk versus interfacial aqueous solvation of dicarboxylate dianions

Solvation of dicarboxylate dianions of varying length of the aliphatic chain in water clusters and in extended aqueous slabs was investigated using photoelectron spectroscopy and molecular dynamics simulations. Photoelectron spectra of hydrated succinate, adipate, and tetradecandioic dianions with up to 20 water molecules were obtained. Even-odd effects were observed as a result of the alternate solvation mode of the two negative charges with increasing solvent numbers. The competition between hydrophilic interactions of the charged carboxylate groups and hydrophobic interactions of the aliphatic chain leads to conformation changes in large water clusters containing dicarboxylates bigger than adipate. It also leads to a transition from bulk aqueous solvation of small dicarboxylates to solvation at the water/vapor interface of the larger ones. Whereas oxalate and adipate solvate in the inner parts of the aqueous slab, suberate and longer dicarboxylate dianions have a strong propensity to the surface. This transition also has consequences for the folding of the flexible aliphatic chain and for the structure of aqueous solvation shells around the dianions.     

Tailored core-shell-shell nanostructures: sandwiching gold nanoparticles between silica cores and tunable silica shells

Size tunable and structure tailored core-shell-shell nanospheres containing silica cores, gold nanoparticle shells, and controlled thicknesses of smooth, corrugated, or porous silica shells over the gold nanoparticles have been synthesized. The synthesis involved the deposition of gold nanoparticles on silica cores, followed by sol-gel processing of tetraethoxysilane (TEOS) or sodium silicate to form dense or porous silica shells, respectively, over the gold nanoparticles. The structures and sizes of the resulting core-shell-shell nanospheres were found to heavily depend on the sizes of the core nanoparticles, the relative population of the gold nanoparticles on each core, and the concentration of TEOS. While a higher TEOS concentration resulted in thicker and more uniform silica shells around individual larger silica cores (approximately > or =250 nm in diameter), the same TEOS concentration resulted in aggregated and twin core-shell-shell nanostructures for smaller silica cores (approximately < or =110 nm in diameter). The thinner silica shells were synthesized by using a lower TEOS concentration. By using sodium silicate (Ung et al. J. Phys. Chem. B 1999, 103, 6770), the porous silica shells were synthesized. Controlled chemical etching of the core-shell-shell nanoparticles with an aqueous KCN solution resulted in corrugated silica shells around the gold nanoparticles or corrugated silica nanospheres with few or no gold nanoparticles. This has allowed synthesis of new types of core-shell-shell nanoparticles with tailored corrugated shells. The nanoporous silica shells provided accessible structures to the embedded metal nanoparticles as observed from the electrochemical response of the gold nanoparticles.     

Direct Quantification of Aspergillus niger Spore Adhesion in Liquid Using an Atomic Force Microscope

An atomic force microscope has been used to quantify directly the adhesion between single Aspergillus niger spores and freshly cleaved mica surfaces. The measurements used "spore probes" constructed by immobilizing a single spore at the apex of a tipless AFM cantilever. Adhesion was quantified from force-distance data for the retraction of the spore from the surface. Studies in NaCl solutions over a range of pH and electrolyte concentration showed that the decrease of long-range electrostatic repulsion with decreasing pH provided a contribution in increasing the overall adhesion, but the variation of such repulsion with ionic strength did not correlate with changes in the magnitude of adhesion. Specific interactions between appendages and protusions on the spore surface must play an important role in adhesion. The AFM spore probe technique provides a useful new method for evaluating the interactions of spores and surfaces. It has the potential to become a powerful asset for both fundamental studies and the assessment of new materials with low adhesion properties. Copyright 2000 Academic Press.