Surface water dynamic properties

It is important to propose molecular and theoretical models to describe the forces, energy, structure and dynamics of water near mineral surfaces. Our understanding of experimental results concerning hydration forces, the hydrophobic effect, swelling, reaction kinetics and adsorption mechanisms in aqueous colloidal systems is rapidly advancing as a result of recent Monte Carlo (MC) and molecular dynamics (MO) models for water properties near model surfaces. This paper reviews the basic MC and MD simulation techniques, compares and contrasts the merits and limitations of various models for water-water interactions and surface-water interactions, and proposes an interaction potential model which would be useful in simulating water near hydrophilic surfaces. In addition, results from selected MC and MD simulations of water near hydrophobic surfaces are discussed in relation to experimental results, to theories of the double layer, and to structural forces in interfacial systems. 

The study of liquids near solid surfaces using microscopic (atomistic-based) descriptions of liquid molecules is relatively new. Given a potential energy function for the interaction between liquid molecules and between the liquid molecules and the solid surface, the integral equation for the liquid density profile and the liquid molecules orientation can be solved approximately, or the molecular dynamics method can be used to calculate these and many other structural and dynamic properties. In applying these methods to water near a metal surface, care must be taken to include additional features that are unique to this system (see later discussion). 

It is very well known that the nature of the monolayer partially depends on the strength of interfacial interactions with substrate molecules and that of polymer in-tersegmental interactions. And it is normal to expect that the viscoelastic properties of polymer monolayer are also dependent on these factors. The static and dynamic properties of several different polymer monolayers at the air - water interface have been examined with the surface quasi-elastic Light Scattering technique combined with the static Wilhelmy plate method [101]. 

The robust observation of surface hydration dynamics on two time scales and a series of correlations with protein properties provides a molecular picture of water motions and their coupling with protein fluctuations in the layer, as shown in Fig. 46. The dynamic exchange of hydration layer water with outside bulk... 

Measurements of the dynamic properties of the surface water, particularly NMR measurements, have shown that the characteristic time of the water motion is slower than the bulk water value by a factor of less than 100. The motion is anisotropic. There is litde or no irrotadonally bound water. Study of a protein labeled covalently with a nitroxide spin probe (Polnaszek and Bryant, 1984a,b) has shown that the diffusion constant of the surface water is about 5-fold below the bulk water value. The NMR results are in agreement with measurements of dielectric relaxation of water in protein powders (Harvey and Hoekstra, 1972). 

The most expensive part of a simulation of a system with explicit solvent is the computation of the long-range interactions because this scales as Consequently, a model that represents the solvent properties implicitly will considerably reduce the number of degrees of freedom of the system and thus also the computational cost. A variety of implicit water models has been developed for molecular simulations [56-60]. Explicit solvent can be replaced by a dipole-lattice model representation [60] or a continuum Poisson-Boltzmann approach [61], or less accurately, by a generalised Bom (GB) method [62] or semi-empirical model based on solvent accessible surface area [59]. Thermodynamic properties can often be well represented by such models, but dynamic properties suffer from the implicit representation. The molecular nature of the first hydration shell is important for some systems, and consequently, mixed models have been proposed, in which the solute is immersed in an explicit solvent sphere or shell surrounded by an implicit solvent continuum. A boundary potential is added that takes into account the influence of the van der Waals and the electrostatic interactions [63-67]. 

Haas KC, Schneider WF, Crrrioni A, Andreoni W (1998) The chemistry of water on alumina surfaces reaction dynamics from first principles. Science 282 265-268 Hemingway BS, Robie RA, Apps JA (1991) Revised values for the thermodynamic properties of boehmite, AIO(OH) and related species and phases in the system Al-H-0. Am Mineral 76 445-457 Hemingway BS, Nitkiewicz A (1995) Variation of the enthalpy of solution of quartz in aqueous HF as a function of sample particle size. U S Geological Survey Open File Report 95-510... 

Water has an essential role in living systems and is ultimately involved in the structure and function of biological polymers such as proteins. However, in this contribution we sh tll focus primarily not on what the water does for the blopolymer but rather on the effects that the biopolymer has on the water that Interacts with it. Of Interest are alterations in the structural, energetic, and dynamic properties of the water molecules. Studies of the rotational mobility of water molecules at protein surfaces have been interpreted by dividing the solvent molecules into three groups U). The most rapidly reorienting group has a characteristic rotational reorientation time (t ) of not more than about... 

Dynamic properties of interfaces have attracted attention for many years because they help in understanding the behaviour of polymer, surfactant or mixed adsorption layers.6 In particular, interfacial rheology (dilational properties) is crucial for many technological processes (emulsions, flotation, foaming, etc).1 The present work deals with the adsorption of MeC at the air-water interface. Because of its amphiphilic character MeC is able to adsorb at the liquid interface thus lowering the surface tension. Our aim is to quantify how surface active this polymer is, and to determine the rheological properties of the layer. A qualitative and quantitative evaluation of the adsorption process and the dilata-tional surface properties have been realised by dynamic interface tension measurements using a drop tensiometer and an axisymmetric drop shape analysis. 

In contrast to the conventional BLM system just described, a novel yet extremely simple method for formation of a stable BLM was recently developed in our laboratory (19-23). The technique involves the formation of self-assembled lipid bilayers on solid supports. The supported BLM (s-BLM) has a greatly improved mechanical stability (lasting indefinitely) and has desirable dynamic properties. One of the methods of formation of a s-BLM consists of two distinct steps. In the first step, the tip of a PTFE-coated platinum wire is cut off. To provide the best cut of the platinum wire, we constructed a miniature guillotine (Figure 1) where the sharp knife moves vertically onto the wire placed on the flat base. The cut is performed while the wire is immersed in a drop of lipid solution so that the initial contact of the newly exposed wire surface is with the lipid solution. In the second step, this newly cut lipid-coated PTFE-covered platinum wire is transferred into an aqueous bathing solution. This two-step self-assembled lipid bilayer works because the freshly cut metal surface is hydrophilic and attracts the polar groups of the lipid molecules. Thus, a lipid monolayer is tenaciously formed on the nascent metallic surface. Immersion of the lipid-coated wire into an aqueous solution spontaneously thins the lipid layer to a BLM that is anchored on one side to the solid support and is exposed to water on the other side. Further details of this method are available in the literature (19-23, 41). 

The studies on the mode of interaction of prothrombin with phospholipid monolayers, using complementary methods of surface measurement are reviewed. They were investigated at air-water and Hg-water interfaces respectively by radioactivity and electrochemistry. A process more complex than a simple adsorption could be detected. Indeed, the variation of the differential capacity of a mercury electrode in direct contact with phospholipid monolayer, induced by the interaction with prothrombin could be interpreted as a model of its penetration into the layer this was confirmed by the study of the dynamic properties of the direct adsorption of this protein at the e-lectrode, followed in part by the reduction of S-S bridges at the electrode. It could be also concluded that prothrombin resists complete unfolding at these interfaces. 

As an example of a membrane model, phospholipid monolayers with negative charge of different density were used. It had already been found ( ) and discussed O) that the physical and biological behavior of phospholipid monolayers at air-water interfaces and of suspensions of liposomes are comparable if the monolayer is in a condensed state. Two complementary methods of surface measurements (using radioactivity and electrochemical measurements), were used to investigate the adsorption and the dynamic properties of the adsorbed prothrombin on the phospholipid monolayers. Two different interfaces, air-water and mercury-water, were examined. In this review, the behavior of prothrombin at these interfaces, in the presence of phospholipid monolayers, is presented as compared with its behavior in the absence of phospholipids. An excess of lipid of different compositions of phos-phatidylserine (PS) and phosphatidylcholine (PC) was spread over an aqueous phase so as to form a condensed monolayer, then the proteins were inject underneath the monolayer in the presence or in the absence of Ca. The adsorption occurs in situ and under static conditions. The excess of lipid ensured a fully compressed monolayer in equilibrium with the collapsed excess lipid layers. The contribution of this excess of lipid to protein adsorption was negligible and there was no effect at all on the electrode measurements. 

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