We present the results of investigations of high-speed drainage of a thin film confined between a microscopic colloidal probe and a substrate performed with a new atomic force microscope-related setup. Theoretical calculations are used to formulate the governing equation (force balance) for instantaneous deflection of a cantilever spring, which is due to both concentrated forces acting on a colloidal probe and viscous drag force on a cantilever itself. The suggested way to subtract the latter contribution allows design of a lubrication experiment. Two pairs of interacting solids, characterized by different wettability and smoothness, immersed into water-electrolyte solutions have been studied. Results for hydrophilic silica surfaces are in excellent agreement with the Reynolds theory of hydrodynamic lubrication. Faster drainage of a thin film confined between hydrophobic rough polystyrene surfaces is consistent with the theory of film drainage between slippery surfaces. The slip lengths are found to be of the order of the size of asperities, and do not depend on the separation and shear rate. The results are important for colloidal dynamics and nanofluidics.

We report results of investigations of a high-speed drainage of thin aqueous films squeezed between randomly nanorough surfaces. A significant decrease in the hydrodynamic resistance force as compared with that predicted by Taylor's equation is observed. However, this reduction in force does not represent the slippage. The measured force is exactly the same as that between equivalent smooth surfaces obeying no-slip boundary conditions, but located at the intermediate position between peaks and valleys of asperities. The shift in hydrodynamic thickness is shown to be independent of the separation and/or shear rate. Our results disagree with previous literature data reporting very large and shear-dependent boundary slip for similar systems.

The current accepted model for high-molecular-weight gastric mucins of the MUC family is that they adopt a polydisperse coil conformation in bulk solutions. We develop this model using well-characterized highly purified porcine gastric mucin Orthana that is genetically close to the human MUC6 type. It has short side chains and low levels of sialic acid residues and includes minute amounts of cysteine residues that, if abundant, can be responsible for the self-polymerization of mucin. We have established that the mucin structure in bulk solutions corresponds to a daisy-chain random coil. Dynamic light scattering experiments probe the internal dynamics of globular subunits (individual daisies) at the approximately 9 nm length scale, whereas viscosity and light scattering measurements indicate that the size of the whole mucin chains is much larger, approximately 50 nm. The bulk viscosity (eta) scales with mucin concentration (c) in a manner similar to that found for short-side-chain synthetic comb polyelectrolytes and is characterized by a transition between semidilute (eta approximately c1/2) and entangled (eta approximately c3/2) regimes.

The lubricating behavior of the weakly charged short-side-chain glycoprotein mucin "Orthana" (Mw=0.55 MDa) has been investigated between hydrophobic and hydrophilic PDMS substrates using soft-contact tribometry. It was found that mucin facilitates lubrication between hydrophobic PDMS surfaces, leading to a 10-fold reduction in boundary friction coefficient for rough surfaces. The presence of mucin also results in a shift of the mixed lubrication regime to lower entrainment speeds. The observed boundary lubrication behavior of mucin was found to depend on the bulk concentration, and we linked this to the structure and dynamics of the adsorbed mucin films, which are assessed using optical waveguide light spectroscopy. We observe a composite structure of the adsorbed mucin layer, with its internal structure governed by entanglement. The film thickness of this adsorbed layer increases with concentration, while the boundary friction coefficient for rough surfaces was found to be inversely proportional to the thickness of the adsorbed film. This link between lubrication and structure of the film is consistent with a viscous boundary lubrication mechanism, i.e., a thicker adsorbed film, at a given sliding speed, results in a lower local shear rate and, hence, in a lower local shear stress. The estimated local viscosities of the adsorbed layer, derived from the friction measurements and the polymer layer density, are in agreement with each other.

Mucus is characterized by multiple levels of assembly at different length scales which result in a unique set of rheological (flow) and mechanical properties. These physical properties determine its biological function as a highly selective barrier for transport of water and nutrients, while blocking penetration of pathogens and foreign particles. Altered integrity of the mucus layer in the small intestine has been associated with a number of gastrointestinal tract pathologies such as Crohn’s disease and cystic fibrosis. In this work, we uncover an intricate hierarchy of intestinal mucin (Muc2) assembly and show how complex rheological properties emerge from synergistic interactions between mucin glycoproteins, non-mucin proteins, and Ca2+. Using a novel method of mucus purification, we demonstrate the mechanism of assembly of Muc2 oligomers into viscoelastic microscale domains formed via hydrogen bonding and Ca2+-mediated links, which require the joint presence of Ca2+ ions and non-mucin proteins. These microscale domains aggregate to form a heterogeneous yield stress gel-like fluid, the macroscopic rheological properties of which are virtually identical to that of native intestinal mucus. Through proteomic analysis, we short-list potential protein candidates implicated in mucin assembly, thus paving the way for identifying the molecules responsible for the physiologically critical biophysical properties of mucus.

Mucilages are hydrocolloid solutions produced by plants for a variety of functions, including the creation of a water-holding barrier around seeds. Here we report our discovery of the formation of three distinct mucilage layers around Plantago ovata seeds upon their hydration. Each layer is dominated by different arabinoxylans (AXs). These AXs are unusual because they are highly branched and contain β-1,3-linked xylose in their side chains. We show that these AXs have similar monosaccharide and linkage composition, but vary in their polymer conformation. They also exhibit distinct rheological properties in aqueous solution, despite analytical techniques including NMR showing little difference between them. Using enzymatic hydrolysis and chaotropic solvents, we reveal that hydrogen bonding and side chain distribution are key factors underpinning the distinct rheological properties of these complex AXs.

We study the interaction between hydrophobized silica surfaces of defined contact angle in water using an AFM-related force measuring device. In all cases the attraction between surfaces leads to a jump into contact from separations larger than expected if only van der Waals forces were acting. The jump distance was found to vary dramatically for different pairs of interacting surfaces. For a given pair of interacting surfaces the jump-in distance is smallest for the first approach, then increases and reaches a steady-state value after measuring 3−10 force curves. This confirms that hydrophobic attraction is closely related to the formation of long-life submicrocavities in the gap between surfaces. These submicrocavities are formed due to the first contacts (separations) of surfaces. Their “stability” is probably a consequence of confinement between hydrophobic solids.

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