Boundary Lubrication Performance of Polyelectrolyte-Surfactant Complexes on Biomimetic Surfaces.

Aqueous mixtures of oppositely charged polyelectrolytes and surfactants are useful in many industrial applications, such as shampoos and hair conditioners. In this work, we investigate the friction between biomimetic hair surfaces in the presence of adsorbed complexes formed from cationic polyelectrolytes and anionic surfactants in an aqueous solution. We apply nonequilibrium molecular dynamics (NEMD) simulations using the coarse-grained MARTINI model. We first developed new MARTINI parameters for cationic guar gum (CGG), a functionalized, plant-derived polysaccharide. The complexation of CGG and the anionic surfactant sodium dodecyl sulfate (SDS) on virgin and chemically damaged biomimetic hair surfaces was studied using a sequential adsorption approach. We then carried out squeeze-out and sliding NEMD simulations to assess the boundary lubrication performance of the CGG-SDS complex compressed between two hair surfaces. At low pressure, we observe a synergistic friction behavior for the CGG-SDS complex, which gives lower shear stress than either pure CGG or SDS. Here, friction is dominated by viscous dissipation in an interfacial layer comprising SDS and water. At higher pressures, which are probably beyond those usually experienced during hair manipulation, SDS and water are squeezed out, and friction increases due to interdigitation. The outcomes of this work are expected to be beneficial to fine-tune and screen sustainable hair care formulations to provide low friction and therefore a smooth feel and reduced entanglement.

Effects of surfactant adsorption on the wettability and friction of biomimetic surfaces.

The properties of solid-liquid interfaces can be markedly altered by surfactant adsorption. Here, we use molecular dynamics (MD) simulations to study the adsorption of ionic surfactants at the interface between water and heterogeneous solid surfaces with randomly arranged hydrophilic and hydrophobic regions, which mimic the surface properties of human hair. We use the coarse-grained MARTINI model to describe both the hair surfaces and surfactant solutions. We consider negatively-charged virgin and bleached hair surface models with different grafting densities of neutral octadecyl and anionic sulfonate groups. The adsorption of cationic cetrimonium bromide (CTAB) and anionic sodium dodecyl sulfate (SDS) surfactants from water are studied above the critical micelle concentration. The simulated adsorption isotherms suggest that cationic surfactants adsorb to the surfaces via a two-stage process, initially forming monolayers and then bilayers at high concentrations, which is consistent with previous experiments. Anionic surfactants weakly adsorb via hydrophobic interactions, forming only monolayers on both virgin and medium bleached hair surfaces. We also conduct non-equilibrium molecular dynamics simulations, which show that applying cationic surfactant solutions to bleached hair successfully restores the low friction seen with virgin hair. Friction is controlled by the combined surface coverage of the grafted lipids and the adsorbed CTAB molecules. Treated surfaces containing monolayers and bilayers both show similar friction, since the latter are easily removed by compression and shear. Further wetting MD simulations show that bleached hair treated with CTAB increases the hydrophobicity to similar levels seen for virgin hair. Treated surfaces containing CTAB monolayers with the tailgroups pointing predominantly away from the surface are more hydrophobic than bilayers due to the electrostatic interactions between water molecules and the exposed cationic headgroups.

Tomographic Plane Visualization (ToPlaV): a Tool to Enhance Echocardiographic Training.

Visual learning is an important part of echocardiographic training. Our aim is to describe and evaluate a visual teaching tool, tomographic plane visualization (ToPlaV) as an adjunct to skills training in pediatric echocardiography image acquisition. This tool incorporates learning theory by applying psychomotor skills that closely emulate the skills used in echocardiography. ToPlaV was used as part of a transthoracic bootcamp for first year cardiology fellows. A qualitative survey was given to trainees to evaluate their perceptions of its usefulness. There was universal agreement among fellow trainees that ToPlaV is a useful training tool. ToPlaV is a simple, low cost, education tool which can complement a simulator and live models. We propose that ToPlaV should be incorporated into early training in echocardiography skills for pediatric cardiology fellows.

Multisystem Inflammatory Syndrome in Children (MIS-C): Reduced Exercise Duration and Capacity at Six Month Follow-Up.

Myocarditis is common in Multisystem Inflammatory Syndrome in Children (MIS-C), and the mechanism may differ from idiopathic/viral myocarditis as MIS-C involves a hyper-inflammatory state weeks after COVID-19. We sought to evaluate exercise stress testing (EST) in these patients as EST may help guide return-to-play recommendations. Retrospective cohort study evaluating ESTs (standard Bruce treadmill protocol) from MIS-C patients from 2020 to 2022, compared to myocarditis patients and age, sex, and weight matched controls from 2005 to 2019. ESTs included 22 MIS-C patients (mean age 11.9 years) with 14 cardiopulmonary and 8 cardiovascular tests, 33 myocarditis (15.5 years), and 44 controls (12.0 years). Percent-predicted peak VO2 was abnormal (< 80% predicted) in 11/14 (79%) MIS-C patients, 13/33 (39%) myocarditis, and 17/44 (39%) controls (p = 0.04). Exercise duration was shorter in MIS-C than myocarditis or control cohorts (p = 0.01). Isolated atrial or ventricular ectopy was seen in 8/22 (36%) MIS-C, 9/33 (27%) myocarditis, and 5/44 (11%) controls (p = 0.049). No arrhythmias/complex ectopy or evidence of ischemia were noted, though non-specific ST/T wave abnormalities occurred in 4/22 (18%) MIS-C, 5/33 (15%) myocarditis, and 3/44 (7%) controls. Exercise duration and percent-predicted peak VO2 were significantly reduced in MIS-C at mean 6-month follow-up compared to pre-COVID era idiopathic/viral myocarditis and control cohorts. This may be secondary to deconditioning during the pandemic and/or chronic cardiopulmonary or autonomic effects of COVID/MIS-C. Although there were no exercise-induced arrhythmias in our MIS-C patients, larger cohort studies are warranted. EST in MIS-C follow-up may help evaluate safety and timing of return to play and potentially mitigate further deconditioning.

Simulation Based Mastery Learning of Transesophageal Echocardiography.

Transesophageal echocardiography (TEE) education is part of pediatric cardiology fellow training. Simulation-based mastery learning (SBML) is an efficient and valuable education experience. The aim of this project was to equip trainees with the basic knowledge and skill required to perform a pediatric TEE. The secondary aim was to assess the utility of using SBML for pediatric TEE training. The target group is trainees from pediatric cardiology and cardiac anesthesia who participated in a TEE bootcamp. A baseline knowledge pretest was obtained. The knowledge session consisted of preparation via reading material, viewing recorded lectures and completing an iterative multiple-choice examination, which was repeated until a minimum passing score of 90% was achieved. The skills session involved a review of TEE probe manipulation and image acquisition, followed by rapid cycle deliberate practice using simulation to acquire TEE skills at 3 levels, advancing in complexity from level 1 to level 3. Eight individuals (7 pediatric cardiology fellows at varying training levels and one anesthesia attending) participated in the TEE bootcamp. All reached a minimum knowledge post test score of at least 90% before the skills session. All subjects reached mastery in TEE probe manipulation. All reached mastery in image acquisition for the skill level that they attempted (level 1-8/8, level 2-8/8, level 3-4/4, with 4 participants not attempting level 3). A TEE bootcamp using SBML is a powerful medical education strategy. SBML is a rigorous approach that can be used to achieve high and uniform TEE learning outcomes among trainees of different training levels and backgrounds.

Coarse-grained molecular models of the surface of hair.

We present a coarse-grained molecular model of the surface of human hair, which consists of a supported lipid monolayer, in the MARTINI framework. Using coarse-grained molecular dynamics (MD) simulations, we identify a lipid grafting distance that yields a monolayer thickness consistent with both atomistic MD simulations and experimental measurements of the hair surface. Coarse-grained models for fully-functionalised, partially damaged, and fully damaged hair surfaces are created by randomly replacing neutral thioesters with anionic sulfonate groups. This mimics the progressive removal of fatty acids from the hair surface by bleaching and leads to chemically heterogeneous surfaces. Using molecular dynamics (MD) simulations, we study the island structures formed by the lipid monolayers at different degrees of damage in vacuum and in the presence of polar (water) and non-polar (n-hexadecane) solvents. We also use MD simulations to compare the wetting behaviour of water and n-hexadecane droplets on the model surfaces through contact angle measurements, which are compared to experiments using virgin and bleached hair. The model surfaces capture the experimentally-observed transition of the hair surface from hydrophobic (and oleophilic) to hydrophilic (and oleophobic) as the level of bleaching damage increases. By selecting surfaces with specific damage ratios, we obtain contact angles from the MD simulations that are in good agreement with experiments for both solvents on virgin and bleached human hairs. To negate the possible effects of microscale curvature and roughness of real hairs on wetting, we also conduct additional experiments using biomimetic surfaces that are co-functionalised with fatty acids and sulfonate groups. In both the MD simulations and experiments, the cosine of the water contact angle increases linearly with the sulfonate group surface coverage with a similar slope. We expect that the proposed systems will be useful for future molecular dynamics simulations of the adsorption and tribological behaviour of hair, as well as other chemically heterogeneous surfaces.

Rheology Control Using Nonionic Cosurfactants and pH Titration in an Amino Acid-Derived Surfactant Composition.

Sulfate-based formulations can be easily thickened by adding salt or amphoteric cosurfactants. However, sulfate-free and amino acid-based surfactants cannot. We explored an alternative thickening mechanism by studying the thickening effect of adding nonionic cosurfactants to a mixture of an amino acid-based surfactant, sodium lauroyl sarcosinate (SLSar), and a zwitterionic cosurfactant, cocamidopropyl hydroxysultaine (CAHS) at a 6:9 weight ratio. To characterize the formulations, we combined traditional rheometry with a state-of-the-art mesoscopic analysis of micelle dynamics obtained via diffusing wave spectroscopy. In addition, the formulations were characterized by cross-polarized light microscopy and dynamic light scattering. The cosurfactants studied included fatty alcohols, alkanediols, a fatty acid, and fatty alcohol ethoxylates (CnE3 and CnE6). Adding the nonionic cosurfactants increased the zero-shear viscosity up to 350 times the viscosity of the no-additive system at neutral pH. When pH titration was incorporated as a second thickening mechanism, the viscosity maximum was lower than the no-additive mixture. Furthermore, the pH of the viscosity maximum was shifted to higher pH for all systems except for CnE6, which shifted the maximum to lower pH. The nonionic amphiphiles also broadened the viscosity maximum, particularly in the C10OH system. Consequently, the C10OH system had a more favorable profile for development as a practical thickening system for an amino acid-based cleanser. Analysis according to the Zou and Larson micelle dynamics model revealed that the broadening effect was associated with substantially longer breakage times for the C10OH system (4-208 ms) compared to the no-additive system (4-38 ms).

Effect of pH on the Structure and Dynamics of Wormlike Micelles in an Amino Acid-Derived Surfactant Composition.

We studied the impact of pH as a thickening mechanism on the structure and dynamics of wormlike micelles in a mixture of sodium lauroyl sarcosinate (SLSar) and cocamidopropyl hydroxysultaine (CAHS). The viscoelastic properties were obtained using mechanical rheometry and diffusing wave spectroscopy, which provided access to a wide range of frequencies. By using a mesoscopic simulation method [Zou; Larson. J. Rheol. 2014, 58 (3), 681-721], characteristic micelle lengths and times were extracted including contour length, persistence length, entanglement length, reptation time, breakage time, breakage rate, and breakage rate constant. The interplay of pH-dependent reptation times (10-1000 ms) and breakage times (4-38 ms) leads to a minimum in the ratio of reptation time to breakage time of about 0.02 at pH 4.8. This minimum was closely associated with the sharp increase and decrease of the observed viscosity maximum at pH 4.8 in this system. These values may be contrasted with much longer breakage times (20-300 ms) that have been measured in more easily thickened sulfate-based systems. The low breakage times of the SLSar/CAHS system were attributed to the high and pH-sensitive breakage rate constants (0.01-0.17 ms-1 µm-1).

Rates of cavity filling by liquids.

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.

Pediatric Cardiology Fellowship Training in Exercise Medicine: A General Needs Assessment.

The aim of this study was to improve understanding of exercise medicine training needs for pediatric cardiology fellows. A survey was sent via email to all (N = 63) pediatric cardiology training program directors in the United States to evaluate the perceived exercise training needs of pediatric cardiology fellows. The survey consisted of multiple-choice responses as well as a few open-ended responses. A 60% response rate was achieved. 74% of programs did not have a pre-existing exercise core program. This type of training was felt to be important or very important in 84%. A wide variability of time allotted for exercise training exists amongst programs from < 1 week to > 4 weeks, with 2 weeks being most common. There was no consensus on a target number of total exercise tests nor types of tests in which fellows should participate. Preferred methods in training consisted of lectures and online media. Less preferred methods of teaching methods included dedicated reading of a handbook, a dedicated rotation, or live webinars. There was general support to develop exercise training competencies as well as the associated online learning materials with a focus on competency rather than target numbers. There is a need for educational recommendations for exercise training in pediatric cardiology fellowships as well as a unified method of achieving competencies.

Computer simulations of colloidal gels: how hindered particle rotation affects structure and rheology.

The effects of particle roughness and short-ranged non-central forces on colloidal gels are studied using computer simulations in which particles experience a sinusoidal variation in energy as they rotate. The number of minima n and energy scale K are the key parameters; for large K and n, particle rotation is strongly hindered, but for small K and n particle rotation is nearly free. A series of systems are simulated and characterized using fractal dimensions, structure factors, coordination number distributions, bond-angle distributions and linear rheology. When particles rotate easily, clusters restructure to favor dense packings. This leads to longer gelation times and gels with strand-like morphology. The elastic moduli of such gels scale as G'∝ω0.5 at high shear frequencies ω. In contrast, hindered particle rotation inhibits restructuring and leads to rapid gelation and diffuse morphology. Such gels are stiffer, with G'∝ω0.35. The viscous moduli G'' in the low-barrier and high-barrier regimes scale according to exponents 0.53 and 0.5, respectively. The crossover frequency between elastic and viscous behaviors generally increases with the barrier to rotation. These findings agree qualitatively with some recent experiments on heterogeneously-surface particles and with studies of DLCA-type gels and gels of smooth spheres.

Automated Measurement of Spatially Resolved Hair-Hair Single Fiber Adhesion.

The adhesion force between individual human hair fibers in a crosshair geometry was measured by observing their natural bending and adhesive jumps out of contact, using optical video microscopy. The hair fibers' natural elastic responses, calibrated by measuring their natural resonant frequencies, were used to measure the forces. Using a custom-designed, automated apparatus to measure thousands of individual hair-hair contacts along millimeter length scales of hair, it was found that a broad, yet characteristic, spatially variant distribution in adhesion force is measured on the 1 to 1000 nN scale for both clean and conditioner-treated hair fibers. Comparison between the measured adhesion forces and adhesion forces modeled from the hairs' surface topography (measured using confocal laser profilometry) shows they have a good order-of-magnitude agreement and have similar breadth and shape. The agreement between the measurements and the model suggests, perhaps unsurprisingly, that hair-hair adhesion is governed, to a first approximation, by the unique surface structure of the hairs' cuticles and, therefore, the large distribution in local mean curvature at the various individual contact points along the hairs' lengths. We posit that haircare products could best control the surface properties (or at least the adhesive properties) between hairs by directly modifying the hair surface microstructure.

From well-entangled to partially-entangled wormlike micelles.

We combine mechanical rheometry, diffusing wave spectroscopy (DWS), and small angle neutron scattering (SANS) with a simulation model, the "pointer algorithm", to obtain characteristic lengths and time constants for wormlike micelle (WLM) solutions over a range of salt concentrations encompassing the transition from unentangled to entangled solutions. The solutions contain sodium lauryl ethylene glycol sulfate (SLE1S), cocamidopropyl betaine (CAPB), and NaCl. The pointer algorithm is extended to include relaxation of unentangled micelles, allowing micelle parameters to be extracted from the rheology of partially entangled solutions. DWS provides the data at high frequency needed to determine micelle persistence length accurately. From pointer algorithm fits to rheology, we observe a salt-induced rapid change in micellar length as the solution enters the well-entangled regime and a weaker growth with surfactant concentration consistent with mean-field theory. At a lower surfactant concentration, micelle length and persistence length from SANS are roughly consistent with values from rheology once the lower surfactant concentration used in SANS is accounted for. This is, to our knowledge, the first time that quantitative comparisons of structural features including micelle length are made between rheology and SANS. Finally, scaling laws for micelle diffusion and recombination times indicate that micelle kinetics are reaction controlled leading to mean-field recombination with surrounding micelles over the entire range of concentration of interest except at very low and very high surfactant concentrations where either short micelles or branched micelle clusters are dominant.

Nonmonotonic Scission and Branching Free Energies as Functions of Hydrotrope Concentration for Charged Micelles.

Using coarse-grained molecular dynamics simulations and an umbrella sampling method that uses local surfactant density as a reaction coordinate, we directly calculate, for the first time, both the scission and branching free energies of a model charged micelle [cationic cetyltrimethylammonium chloride (CTAC)] in the presence of inorganic and organic salts (hydrotropes). We find that while inorganic salt only weakly affects the micelle scission energy, organic hydrotropes produce a strong, nonmonotonic dependence of both scission energy and branching on salt concentration. The nonmonotonicity in scission energy is traced to a competition between electrostatic screening of the repulsions among the surfactant head groups and thinning of the micellar core, which result from attachment of the hydrotropes to the micelle surface. We are able to correlate the nonmonotonicity in the scission energy of CTAC micelles with the peak observed experimentally in viscosity versus hydrotrope concentration and the location of this peak in CTAC solutions.

Scission Free Energies for Wormlike Surfactant Micelles: Development of a Simulation Protocol, Application, and Validation for Personal Care Formulations.

We present a scheme to calculate wormlike micelle scission free energies from a potential of mean force (PMF) derived from a weighted histogram analysis method (WHAM) applied to coarse grained dissipative particle dynamics (DPD) simulations. In contrast to previous related work, we use a specially chosen external potential based on a reaction coordinate that reversibly drives surfactants out of the nascent scission location. For the application to a model body wash formulation, we predict how addition of NaCl and small molecules such as perfume raw materials (PRMs) affect scission energies. The results show qualitative agreement and correct trends compared to recently determined scission energies for the same system; however, a more rigorous parametrization of the underlying DPD potential is required for quantitative agreement.

Probing Additive Loading in the Lamellar Phase of a Nonionic Surfactant: Gibbs Ensemble Monte Carlo Simulations Using the SDK Force Field.

Understanding solute uptake into soft microstructured materials, such as bilayers and worm-like and spherical micelles, is of interest in the pharmaceutical, agricultural, and personal care industries. To obtain molecular-level insight on the effects of solutes loading into a lamellar phase, we utilize the Shinoda-Devane-Klein (SDK) coarse-grained force field in conjunction with configurational-bias Monte Carlo simulations in the osmotic Gibbs ensemble. The lamellar phase is comprised of a bilayer formed by triethylene glycol mono- n-decyl ether (C10E3) surfactants surrounded by water with a 50:50 surfactant/water weight ratio. We study both the unary adsorption isotherm and the effects on bilayer structure and stability caused by n-nonane, 1-hexanol, and ethyl butyrate at several different reduced reservoir pressures. The nonpolar n-nonane molecules load near the center of the bilayer. In contrast, the polar 1-hexanol and ethyl butyrate molecules both load with their polar bead close to the surfactant head groups. Near the center of the bilayer, none of the solute molecules exhibits a significant orientational preference. Solute molecules adsorbed near the polar groups of the surfactant chains show a preference for orientations perpendicular to the interface, and this alignment with the long axis of the surfactant molecules is most pronounced for 1-hexanol. Loading of n-nonane leads to an increase of the bilayer thickness, but does not affect the surface area per surfactant. Loading of polar additives leads to both lateral and transverse swelling. The reduced Henry's law constants of adsorption (expressed as a molar ratio of additive to surfactant per reduced pressure) are 0.23, 1.4, and 14 for n-nonane, 1-hexanol, and ethyl butyrate, respectively, and it appears that the SDK force field significantly overestimates the ethyl butyrate-surfactant interactions.

Contact Angle and Adhesion Dynamics and Hysteresis on Molecularly Smooth Chemically Homogeneous Surfaces.

Measuring truly equilibrium adhesion energies or contact angles to obtain the thermodynamic values is experimentally difficult because it requires loading/unloading or advancing/receding boundaries to be measured at rates that can be slower than 1 nm/s. We have measured advancing-receding contact angles and loading-unloading adhesion energies for various systems and geometries involving molecularly smooth and chemically homogeneous surfaces moving at different but steady velocities in both directions, ±V, focusing on the thermodynamic limit of ±V → 0. We have used the Bell Theory (1978) to derive expressions for the dynamic (velocity-dependent) adhesion energies and contact angles suitable for both (i) dynamic adhesion measurements using the classic Johnson-Kendall-Roberts (JKR, 1971) theory of "contact mechanics" and (ii) dynamic contact angle hysteresis measurements of both rolling droplets and syringe-controlled (sessile) droplets on various surfaces. We present our results for systems that exhibited both steady and varying velocities from V ≈ 10 mm/s to 1 nm/s, where in all cases but one, the advancing (V > 0) and receding (V < 0) adhesion energies and/or contact angles converged toward the same theoretical (thermodynamic) values as V → 0. Our equations for the dynamic contact angles are similar to the classic equations of Blake & Haynes (1969) and fitted the experimental adhesion data equally well over the range of velocities studied, although with somewhat different fitting parameters for the characteristic molecular length/dimension or area and characteristic bond formation/rupture lifetime or velocity. Our theoretical and experimental methods and results unify previous kinetic theories of adhesion and contact angle hysteresis and offer new experimental methods for testing kinetic models in the thermodynamic, quasi-static, limit. Our analyses are limited to kinetic effects only, and we conclude that hydrodynamic, i.e., viscous, and inertial effects do not play a role at the interfacial velocities of our experiments, i.e., V < (1-10) mm/s (for water and hexadecane, but for viscous polymers it may be different), consistent with previously reported studies.

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.

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.