The interaction forces between bilayers of the cationic surfactant di(tallow ethyl ester)dimethyl ammonium chloride (DEEDMAC) were measured using a Surface Forces Apparatus (SFA) with and without an adsorbing polymer, polyacrylamide (PAM). In the absence of PAM, the forces measured between the bilayer surfaces were purely repulsive on approach and separation and is charge regulated. Addition of PAM induced structural changes to the bilayer interfaces, and resulted in the formation of bilayer-like patches of DEEDMAC decorated PAM (hydrated) on the mica surface. The interaction potential between these surfaces showed a modified DLVO interaction with an additional monotonic steric hydration repulsion on approach with an exponential force decay length of D steric ∼ 1 nm consistent with the measurements of hydration forces. On separating the surfaces, interdigitated polymers bridge between the two surfaces, resulting in a weak adhesion (adhesion energy, W0 ∼ 0.1 mJ m-2). Our results provide a picture of the complex molecular structure and interactions between uncharged adsorbing water soluble polymers and supported charged bilayers, and highlight the effects of adsorbing polymers on the structure of bilayers. Implications for the stability of vesicles in dispersions have been also discussed. © The Royal Society of Chemistry 2013.

Dimethyl sulfoxide (DMSO) is a common solvent and biological additive possessing well-known utility in cellular cryoprotection and lipid membrane permeabilization, but the governing mechanisms at membrane interfaces remain poorly understood. Many studies have focused on DMSO-lipid interactions and the subsequent effects on membrane-phase behavior, but explanations often rely on qualitative notions of DMSO-induced dehydration of lipid head groups. In this work, surface forces measurements between gel-phase dipalmitoylphosphatidylcholine membranes in DMSO-water mixtures quantify the hydration- and solvation-length scales with angstrom resolution as a function of DMSO concentration from 0 mol% to 20 mol%. DMSO causes a drastic decrease in the range of the steric hydration repulsion, leading to an increase in adhesion at a much-reduced intermembrane distance. Pulsed field gradient NMR of the phosphatidylcholine (PC) head group analogs, dimethyl phosphate and tetramethylammonium ions, shows that the ion hydrodynamic radius decreases with increasing DMSO concentration up to 10 mol% DMSO. The complementary measurements indicate that, at concentrations below 10 mol%, the primary effect of DMSO is to decrease the solvated volume of the PC head group and that, from 10 mol% to 20 mol%, DMSO acts to gradually collapse head groups down onto the surface and suppress their thermal motion. This work shows a connection between surface forces, head group conformation and dynamics, and surface water diffusion, with important implications for soft matter and colloidal systems.

We have measured and characterized how three classes of surface-active molecules self-assemble at, and modulate the interfacial forces between, a negatively charged mica surface and a hydrophobic end-grafted polydimethylsiloxane (PDMS) polymer surface in solution. We provide a broad overview of how chemical and structural properties of surfactant molecules result in different self-assembled structures at polymer and mineral surfaces, by studying three characteristic surfactants: (1) an anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), (2) a cationic aliphatic surfactant, myristyltrimethylammonium bromide (MTAB), and (3) a silicone polyelectrolyte with a long-chain PDMS midblock and multiple cationic end groups. Through surface forces apparatus measurements, we show that the separate addition of three surfactants can result in interaction energies ranging from fully attractive to fully repulsive. Specifically, SDS adsorbs at the PDMS surface as a monolayer and modifies the monotonic electrostatic repulsion to a mica surface. MTAB adsorbs at both the PDMS (as a monolayer) and the mica surface (as a monolayer or bilayer), resulting in concentration-dependent interactions, including a long-range electrostatic repulsion, a short-range steric hydration repulsion, and a short-range hydrophobic attraction. The cationic polyelectrolyte adsorbs as a monolayer on the PDMS and causes a long-range electrostatic attraction to mica, which can be modulated to a monotonic repulsion upon further addition of SDS. Therefore, through judicious selection of surfactants, we show how to modify the magnitude and sign of the interaction energy at different separation distances between hydrophobic and hydrophilic surfaces, which govern the static and kinetic stability of colloidal dispersions. Additionally, we demonstrate how the charge density of silicone polyelectrolytes modifies both their self-assembly at polymer interfaces and the robust adhesion of thin PDMS films to target surfaces.

We review recent developments in experimental techniques that simultaneously combine measurements of the interaction forces or energies between two extended surfaces immersed in electrolyte solutions-primarily aqueous-with simultaneous monitoring of their (electro)chemical reactions and controlling the electrochemical surface potential of at least one of the surfaces. Combination of these complementary techniques allows for simultaneous real time monitoring of angstrom level changes in surface thickness and roughness, surface-surface interaction energies, and charge and mass transferred via electrochemical reactions, dissolution, and adsorption, and/or charging of electric double layers. These techniques employ the surface forces apparatus (SFA) combined with various "electrochemical attachments" for in situ measurements of various physical and (electro)chemical properties (e.g., cyclic voltammetry), optical imaging, and electric potentials and currents generated naturally during an interaction, as well as when electric fields (potential differences) are applied between the surfaces and/or solution-in some cases allowing for the chemical reaction equation to be unambiguously determined. We discuss how the physical interactions between two different surfaces when brought close to each other (<10 nm) can affect their chemistry, and suggest further extensions of these techniques to biological systems and simultaneous in situ spectroscopic measurements for chemical analysis.

We have synthesized model hydrophobic silicone thin films on gold surfaces by a two-step covalent grafting procedure. An amino-functionalized gold surface reacts with monoepoxy-terminated polydimethylsiloxane (PDMS) via a click reaction, resulting in a covalently attached nanoscale thin film of PDMS, and the click chemistry synthesis route provides great selectivity, reproducibility, and stability in the resulting model hydrophobic silicone thin films. The asymmetric interaction forces between the PDMS thin films and mica surfaces were measured with the surface forces apparatus in aqueous sodium chloride solutions. At an acidic pH of 3, attractive interactions are measured, resulting in instabilities during both approach (jump-in) and separation (jump-out from adhesive contact). Quantitative analysis of the results indicates that the Derjaguin-Landau-Verwey-Overbeek theory alone, i.e., the combination of electrostatic repulsion and van der Waals attraction, cannot fully describe the measured forces and that the additional measured adhesion is likely due to hydrophobic interactions. The surface interactions are highly pH-dependent, and a basic pH of 10 results in fully repulsive interactions at all distances, due to repulsive electrostatic and steric-hydration interactions, indicating that the PDMS is negatively charged at high pH. We describe an interaction potential with a parameter, known as the Hydra parameter, that can account for the extra attraction (low pH) due to hydrophobicity as well as the extra repulsion (high pH) due to hydrophilic (steric-hydration) interactions. The interaction potential is general and provides a quantitative measure of interfacial hydrophobicity/hydrophilicity for any set of interacting surfaces in aqueous solution.

Surfactant self-assembly on surfaces is an effective way to tailor the complex forces at and between hydrophobic-water interfaces. Here, the range of structures and forces that are possible at surfactant-adsorbed hydrophobic surfaces are demonstrated: certain long-chain bolaform surfactants-containing a polydimethylsiloxane (PDMS) mid-block domain and two cationic α, ω-quarternary ammonium end-groups-readily adsorb onto thin PDMS films and form dynamically fluctuating nanostructures. Through measurements with the surface forces apparatus (SFA), it is found that these soft protruding nanostructures display polymer-like exploration behavior at the PDMS surface and give rise to a long-ranged, temperature- and rate-dependent attractive bridging force (not due to viscous forces) on approach to a hydrophilic bare mica surface. Coulombic interactions between the cationic surfactant end-groups and negatively-charged mica result in a rate-dependent polymer bridging force during separation as the hydrophobic surfactant mid-blocks are pulled out from the PDMS interface, yielding strong adhesion energies. Thus, (i) the versatile array of surfactant structures that may form at hydrophobic surfaces is highlighted, (ii) the need to consider the interaction dynamics of such self-assembled polymer layers is emphasized, and (iii) it is shown that long-chain surfactants can promote robust adhesion in aqueous solutions.