Structure and Dynamics of Octamethylcyclotetrasiloxane Confined between Mica Surfaces

Using a molecular model for octamethylcydotetrasiloxane (OMCTS), molecular dynamics simulations are carried out to probe the phase state of OMCTS confined between two mica surfaces in equilibrium With a reservoir. Molecular dynamics simulations are carried out for elevations ranging from 5 to 35 K above the melting point for the OMCTS model used in this study. The Helmholtz free energy is, computed for a specific confinement using the :two-phase thermodynamic (2PT) method. Analysis of the in-plane pair correlation functions did not reveal signatures of freezing even under an extreme confinement of two layers. OMCTS is found to orient with a wide distribution of orientations with respect to the mica surface, with a distinct preference for the surface parallel configuration in the contact layers. The self-intermediate scattering function is found to decay with increasing relaxation times as the surface separation is decreased, and the two-step relaxation in the scattering function, a signature of glassy dynamics, distinctly evolves as the temperature is lowered. However, even at 5 K above the melting point, we did not observe a freezing transition and the self-intermediate scattering functions relax within 200 ps for the seven-layered confined system. The self diffusivity and relaxation times obtained from the Kohlrausch-Williams-Watts stretched exponential fits to the late alpha-relaxation exhibit power law scalings with the packing fraction as predicted by mode coupling theory. A distinct discontinuity in the Helmholtz free energy, potential energy, and a sharp change in the local bond order parameter, Q(4), was observed at 230 K for a five-layered system upon cooling, indicative of a first-order transition. A freezing point depression of about 30 K was observed for this five-layered confined system, and at the lower temperatures, contact layers were found to be disordered with long-range order present only in the inner layers. These dynamical signatures indicate that confined OMCTS undergoes a slowdown akin to a fluid approaching a glass transition upon increasing confinement, and freezing under confinement would require substantial subcooling below the bulk melting point of OMCTS.

Forces between mica surfaces in ethylene glycol

Measurements are presented of the force as a function of separation between two molecularly smooth mica surfaces immersed in ethylene glycol, and in solutions of lithium chloride and sulfuric acid in ethylene glycol. At surface separations greater than 3 nm the measured force is in very good agreement with double-layer theory, but at smaller separations there is an oscillatory solvation force which is superimposed on the double-layer repulsion. In contrast to the case in water, the adsorption of hydrogen ions at the mica surface does not markedly affect the short-range forces.

Measurement of aqueous film thickness between charged mercury and mica surfaces : a direct experimental probe of the Poisson-Boltzmann distribution

A stable aqueous electrolyte film is formed between a mercury drop and a flat mica surface due to electrical double-layer repulsion when a negative potential is applied to the mercury. Film thickness has been measured as a function of applied potential while keeping the film pressure constant. By making measurements in this way, it is possible to map the data directly according to the Poisson-Boltzmann equation. An excellent fit to the data is obtained, providing direct evidence for this classical equation and its use as the basis of the Gouy-Chapman model of the diffuse double layer in electrolyte solutions.

Relaxation and jump dynamics of water at the mica interface

The orientational relaxation dynamics of water confined between mica surfaces is investigated using molecular dynamics simulations. The study illustrates the wide heterogeneity that exists in the dynamics of water adjacent to a strongly hydrophilic surface such as mica. Analysis of the survival probabilities in different layers is carried out by normalizing the corresponding relaxation times with bulk water layers of similar thickness. A 10-fold increase in the survival times is observed for water directly in contact with the mica surface and a non-monotonic variation in the survival times is observed moving away from the mica surface to the bulk-like interior. The orientational relaxation time is highest for water in the contact layer, decreasing monotonically away from the surface. In all cases the ratio of the relaxation times of the 1st and 2nd rank Legendre polynomials of the HH bond vector is found to lie between 1.5 and 1.9 indicating that the reorientational relaxation in the different water layers is governed by jump dynamics. The orientational dynamics of water in the contact layer is particularly novel and is found to undergo distinct two-dimensional hydrogen bond jump reorientational dynamics with an average waiting time of 4.97 ps. The waiting time distribution is found to possess a long tail extending beyond 15 ps. Unlike previously observed jump dynamics in bulk water and other surfaces, jump events in the mica contact layer occur between hydrogen bonds formed by the water molecule and acceptor oxygens on the mica surface. Despite slowing down of the water orientational relaxation near the surface, life-times of water in the hydration shell of the K ion are comparable to that observed in bulk salt solutions. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4717710]

New insights on growth mechanisms of protein clusters at surfaces: an AFM and simulation study

Despite its relevance to a wide range of technological and fundamental areas, a quantitative understanding of protein surface clustering dynamics is often lacking. In inorganic crystal growth, surface clustering of adatoms is well described by diffusion-aggregation models. In such models, the statistical properties of the aggregate arrays often reveal the molecular scale aggregation processes. We investigate the potential of these theories to reveal hitherto hidden facets of protein clustering by carrying out concomitant observations of lysozyme adsorption onto mica surfaces, using atomic force microscopy. and Monte Carlo simulations of cluster nucleation and growth. We find that lysozyme clusters diffuse across the substrate at a rate that varies inversely with size. This result suggests which molecular scale mechanisms are responsible for the mobility of the proteins on the substrate. In addition the surface diffusion coefficient of the monomer can also be extracted from the comparison between experiments and simulations. While concentrating on a model system of lysozyme-on-mica, this 'proof of concept' study successfully demonstrates the potential of our approach to understand and influence more biomedically applicable protein-substrate couples.

The drainage of thin liquid films between solid surfaces

We present measurements of the thickness as a function of time of liquid films as they are squeezed between molecularly smooth mica surfaces. Three Newtonian, nonpolar liquids have been studied: octamethylcyclotetrasiloxane, n-tetradecane, and n-hexadecane. The film thicknesses are determined with an accuracy of 0.2 nm as they drain from ∼1 μm to a few molecular layers. Results are in excellent agreement with the Reynolds theory of lubrication for film thicknesses above 50 nm. For thinner films the drainage is slower than the theoretical prediction, which can be accounted for by assuming that the liquid within about two molecular layers of each solid surface does not undergo shear. In very thin films the continuum Reynolds theory breaks down, as drainage occurs in a series of abrupt steps whose size matches the thickness of molecular layers in the liquid. The presence of trace amounts of water has a dramatic effect on the drainage of a nonpolar liquid between hydrophilic surfaces, causing film rupture which is not observed in the dry liquids.

Structuring in liquid alkanes between solid surfaces : force measurements and mean-field theory

Measurements have been made of the solvation forces between mica surfaces in the even-numbered n-alkanes from hexane to hexadecane. In all cases the force law is qualitatively very similar, characterized by a decaying oscillatory function of distance, as occurs for simple isotropic liquids. The spacing between successive minima in the force does not increase with carbon number, and is comparable to the width of a linear alkane molecule rather than its length or any average diameter. This suggests that the alkanes have some tendency towards a parallel orientation near the mica surfaces. The measurements give no indication of any strong repulsive component expected from mean-field theories of higher alkanes or polymers. The results of one such theory are presented, and the reasons for its failure to match the experimental data are discussed.

Measurement of surface forces between mica sheets immersed in aqueous quaternary ammonium ion solutions

Forces between mica surfaces immersed in Me4NBr, Pr4NBr, and Pe4NBr solutions over a wide concentration range are reported (Me = methyl, Pr = propyl, Pe = pentyl). In each case the cation adsorbs quite strongly onto the negatively charged mica surface and determines the double-layer potential. However, this strong adsorption does not cause complete neutralization of the negative lattice charge apparently because of packing constraints due to the large size of these ions. Adsorption of Me4N+ ions gives rise to a short-range (<2 nm) repulsive force similar to that previously observed between bilayers of CTAB and may be due to the residual hydration of these ions. The large rations also, unexpectedly, give rise to short-range repulsive forces but of a somewhat different nature. In this case, the repulsive forces can be explained by assuming that the large adsorbed ions shift the plane of charge a distance of one ion diameter from the mica surface. At all but very high concentrations these larger ions could be displaced from the mica surfaces on forcing them together. No evidence of any “hydrophobic attraction” was observed between surfaces containing these adsorbed ions. Previous studies on coagulation are discussed in the light of our results.

Molecular organization and viscosity of a thin film of molten polymer between two surfaces as probed by force measurements

Measurements are presented of the force between two molecularly smooth mica surfaces immersed in liquid poly(dimethylsiloxane) (Dow Corning 200 of nominal viscosity 50 cS) over a range of film thicknesses from 3 to 200 nm. There is a repulsion, attributed to conformational restrictions, when the polymer molecules are confined to a gap less than about 15 nm thick. In extremely thin films (<5 nm) the force is an oscillatory function of thickness with a repeat spacing corresponding to the width of the polymer molecule, which suggests that the polymer segments are arranged in layers near the solid surfaces. Dynamic force measurements show that the polymer has a viscosity equal to its bulk value even in very thin films, but a region next to each surface, only about one radius of gyration thick, does not flow. Saturation of the polymer with water destabilizes the film when it is very thin.

Experimental investigation of the dissolution of quartz by a muscovite mica surface : implications for pressure solution

Using the surface forces apparatus, which can measure small changes in thickness occurring even at essentially geological timescales, we have measured dissolution of quartz sheets when pressed against muscovite mica surfaces in aqueous electrolyte solution, but no dissolution is observed under dry conditions. It is postulated that the dissolved quartz may reprecipitate outside the contact junction as a fragile silica gel, which could be the main factor limiting the rate of further dissolution.

The electrochemical surface forces apparatus : the effect of surface roughness, electrostatic surface potentials, and anodic oxide growth on interaction forces, and friction between dissimilar surfaces in aqueous solutions

We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with Å resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force–distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with Å-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal–ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg–Healy–Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force–distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)3 phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction forces while tuning electrochemical surface potentials.

Influence of Hydrophilic Surface Specificity on the Structural Properties of Confined Water

The influence of chemical specificity of hydrophilic surfaces on the structure of confined water in the subnanometer regime is investigated using grand canonical Monte Carlo Simulations. The structural variations for water confined between hydroxylated silica surfaces are contrasted with water confined between mica surfaces. Although both surfaces are hydrophilic, our Study shows that hydration of potassium ions on the mica surface has a strong influence on the water Structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between Mica Surfaces, water between silica surfaces retains its hydrogen bond network displaying bulklike structural features down to surface separations as small as 0.45 nm. Hydrogen bonding of all invariant contact water layer with the surface silanol groups aids in maintaining a constant number of hydrogen bonds per water molecule for the silica surfaces. As a consequence water depletion and rearrangement upon decreasing confinement is a strong function of the hydrophilic surface specificity, particularly at smaller separations. An oscillatory solvation force response is only observed for water confined between Silica surfaces, and bulklike features are observed for both Surfaces above a surface separation of about 1.2 nm. We evaluate and contrast the water density, dipole moment distributions, pi pair correlation functions, and solvation forces as a function of the surface separation.

Effects of pH on the Interactions and Conformation of Bovine Serum Albumin: Comparison between Chemical Force Microscopy and Small-Angle Neutron Scattering

The conformation of bovine serum albumin (BSA), as well as its interactions with negatively charged mica surfaces in saline solutions of different pH values, have been studied by small-angle neutron scattering (SANS) and chemical force microscopy (CFM), respectively. A new approach to extract the contribution of elementary interactions from the statistically averaged force-extension curves through self-consistent fitting was proposed and used to understand the effects of pH on the interactions and conformation of BSA in saline solutions. When pH increases, the SANS results reveal that the sizes of BSA molecules increase slightly, while the statistical analysis of the CFM results shows that the averaged pull-off force for the elongation monotonously decreases. The decrease of pull-off force with the increase of pH results from the decrease in the strength of hydrogen bonding and the number of interaction pairs, as well as the slight increase of the strength of van der Waals interaction. When pH approaches the isoelectric point (pI) of BSA, results from both SANS and CFM suggest a loss of long-range interactions in BSA molecules. Our results also suggest that the force-extension curve is mainly contributed by the van der Waals interaction. The combination of SANS and CFM provides new insight to understand the interactions and conformation of BSA molecules

A one-dimensional network from the self-assembly of gold nanoparticles by a necklace-like polyelectrolyte template mediated by metallic ion coordination

A new approach to one-dimensional organization of gold nanoparticles (2-4 nm) is described, using poly(4-vinylpyridine) (P4VP) molecular chain as a template with the mediation of free Cu2+ ion coordination. The assembly was conducted on freshly prepared mica surfaces and in aqueous solution, respectively. The surface assembly was characterized by tapping mode atomic force microscopy (AFM), observing the physisorbed molecules in their chain-like conformation with an average height of 0.4 nm.

Self-assembled monolayer growth of phospholipids on hydrophobic surface toward mimetic biomembranes: Scanning probe microscopy study

Atomic force microscopy (AFM) and lateral force microscopy (LFM) were used simultaneously to analyze a model membrane bilayer structure consisting of a phospholipid outer monolayer deposited onto organosilane-derivatized mica surfaces, which were constructed by using painting and self-assembly methods. The phospholipid used as outer monolayer was dimyristoylphosphatidylcholine (DMPC). The hydrocarbon-covered substrate that formed the inner half bilayer was composed of a self-assembly monolayer (SAM) of octadecyltrichloroorganosilane (OTS) on mica. SAMs of DMPC were formed by exposing hydrophobic mica to a solution of DMPC in decane/isobutanol and subsequently immersing into pure water. AFM images of samples immersed in solution for varying exposure times showed that before forming a complete monolayer the molecules aggregated into dense islands (2.2-2.6 nm high) on the surface. The islands had a compact and rounded morphology. LFM, coupled with topographic data obtained with the atomic force mode, had made possible the distinction between DMPC and OTS. The rate constant of DMPC growth was calculated. This is the first systematic study of the SAM formation of DMPC by AFM and LFM imaging. It reveals more direct information about the film morphology than previous studies with conventional surface analytical techniques such as infrared spectroscopy, X-ray, or fluorescence microscopy.