Yonas Gizaw

Asymmetric Electrostatic and Hydrophobic–Hydrophilic Interaction Forces between Mica Surfaces and Silicone Polymer Thin Films

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.

Extraction of polysaccharides from a species of Chlorella

The objective of this project was to devise a method to recover the total, water-soluble cell-wall polysaccharides of Chlorella. It was found that substantial quantities of polysaccharides could be extracted after treatment of the cells with a mildly acidic solution of sodium chlorite (yield of recovered polysaccharide, 19-22%). Water-soluble (13-19% yield) and 2% NaOH-soluble (3-6% yield) fractions were obtained. A second treatment gave a total yield of water-soluble polysaccharides of 24-25%, while reducing the amount of material soluble in 2% NaOH to 0.3%. Each polysaccharide fraction was composed of 6 different neutral sugars (rhamnose, arabinose, xylose, mannose, galactose, and glucose). There was evidence of the presence of uronic acid in all fractions. An alkaline hydrogen peroxide treatment of the cells resulted in a 19% yield of polysaccharides that were not further examined.

New synthesis of 1,4-dideoxy-1,4-imino-d-galactitol from d-glucose propane-1,3-diyl dithioacetal

Abstract The treatment of 4-azido-4-deoxy-2,3:5,6-di- O -isopropylidene- d -galactose propane-1,3-diyl dithioacetal (derived from d -glucose) with mercuric chloride and mercuric oxide in aqueous acetone afforded 4-azido-4-deoxy-2,3:5,6-di- O -isopropylidene- d -galactose. Acid-catalyzed deprotection of the azido derivative, followed by catalytic hydrogenation and concomitant intramolecular reductive amination in the presence of 10% palladium on carbon, gave 1,4-dideoxy-1,4-imino- d -galactitol in good yield.

Effects of Surfactants and Polyelectrolytes on the Interaction between a Negatively Charged Surface and a Hydrophobic Polymer Surface

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.

Hydrophobic, Electrostatic, and Dynamic Polymer Forces at Silicone Surfaces Modified with Long-Chain Bolaform Surfactants

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.

Rates of cavity filling by liquids

Significance In engineering and natural phenomena, various fluids contact rough/textured surfaces, e.g., wicking, facial creams, corrosion-preventive paints, and rain on plant leaves. Liquids on rough surfaces, especially those with cavities, pits, or pores, may or may not transit from the unfilled or partially filled (wetted) state to the fully filled (fully wetted) state. Either one of these states may be desired for a given application (compare superhydrophobicity) or even survival (compare oil-soaked feathers). In this article, we present five variables that control the wetting behavior (cavity filling) of water on intrinsically hydrophilic surfaces with micrometer-sized cavities. Our experimental results and theoretical analysis provide criteria for maintaining either the partially filled state, or quickly transiting to the fully filled state, and insights into other related wetting phenomena. Understanding the fundamental wetting behavior of liquids on surfaces with pores or cavities provides insights into the wetting phenomena associated with rough or patterned surfaces, such as skin and fabrics, as well as the development of everyday products such as ointments and paints, and industrial applications such as enhanced oil recovery and pitting during chemical mechanical polishing. We have studied, both experimentally and theoretically, the dynamics of the transitions from the unfilled/partially filled (Cassie–Baxter) wetting state to the fully filled (Wenzel) wetting state on intrinsically hydrophilic surfaces (intrinsic water contact angle <90°, where the Wenzel state is always the thermodynamically favorable state, while a temporary metastable Cassie–Baxter state can also exist) to determine the variables that control the rates of such transitions. We prepared silicon wafers with cylindrical cavities of different geometries and immersed them in bulk water. With bright-field and confocal fluorescence microscopy, we observed the details of, and the rates associated with, water penetration into the cavities from the bulk. We find that unconnected, reentrant cavities (i.e., cavities that open up below the surface) have the slowest cavity-filling rates, while connected or non-reentrant cavities undergo very rapid transitions. Using these unconnected, reentrant cavities, we identified the variables that affect cavity-filling rates: (i) the intrinsic contact angle, (ii) the concentration of dissolved air in the bulk water phase (i.e., aeration), (iii) the liquid volatility that determines the rate of capillary condensation inside the cavities, and (iv) the presence of surfactants.