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© 2015 Macmillan Publishers Limited. Despite the recent progress in and demand for wet adhesives, practical underwater adhesion remains limited or non-existent for diverse applications. Translation of mussel-inspired wet adhesion typically entails catechol functionalization of polymers and/or polyelectrolytes, and solution processing of many complex components and steps that require optimization and stabilization. Here we reduced the complexity of a wet adhesive primer to synthetic low-molecular-weight catecholic zwitterionic surfactants that show very strong adhesion (∼50 mJm-2) and retain the ability to coacervate. This catecholic zwitterion adheres to diverse surfaces and self-assembles into a molecularly smooth, thin (

Mussel adhesion to mineral surfaces is widely attributed to 3,4-dihydroxyphenylalanine (Dopa) functionalities in the mussel foot proteins (mfps). Several mfps, however, show a broad range (30%-100%) of tyrosine (Tyr) to Dopa conversion suggesting that Dopa is not the only desirable outcome for adhesion. Here, a partial recombinant construct of mussel foot protein-1 (rmfp-1) and short decapeptide dimers with and without Dopa are used and both their cohesive and adhesive properties on mica are assessed using a surface forces apparatus. Our results demonstrate that at low pH, both the unmodified and Dopa-containing rmfp-1s show similar energies for adhesion to mica and self-self-interaction. Cohesion between two Dopa-containing rmfp-1 surfaces can be doubled by Fe3+ chelation, but remains unchanged with unmodified rmfp-1. At the same low pH, the Dopa-modified short decapeptide dimer did not show any change in cohesive interactions even with Fe3+. The results suggest that the most probable intermolecular interactions are those arising from electrostatic (i.e., cation-π) and hydrophobic interactions. It is also shown that Dopa in a peptide sequence does not by itself mediate Fe3+ bridging interactions between peptide films: peptide length is a crucial enabling factor.

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. 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.

Crevice corrosion (CC) of metals remains a serious concern for structural materials. Yet a real-time in situ visualization of corrosion, and its inhibition within a confined geometry, remains challenging. Here, we present how multiple-beam interferometry in a Surface Forces Apparatus can be utilized to directly visualize corrosion processes in real-time and with Angstrom resolution within welldefined confinement geometries. We use atomically smooth muscovite mica surfaces to form round-shaped ∼1000 μm2 crevices on aluminum. After exposure to NaCl solutions we can detect and track active sites of aluminum corrosion within this confined geometry. CC of aluminum randomly initiates in the confined crevice mouth, where the distance between apposing surfaces is between 20-300 nm. We can directly track oxide dissolution/formation, and corrosion-rates as well as their retardation due to sodium vanadate inhibitors present in solution. Formation of a compacted oxide layer effectively inhibits CC in 5 mM NaCl solutions with 2.5 mM of added NaVO3, while inhibition rapidly breaks down at chloride concentrations above 50 mM. Breakdown of the inhibition-layers is initiated by rapid dissolution of the protective oxide within the confined zone. Our technique may be adapted for monitoring CC, corrosion inside of crack-tips, and evaluation of inhibitor efficiencies in a variety of metals.

The lubricating and structural properties of different mammalian synovial fluids in thin films undergoing shear between two mica surfaces are studied in detail using a surface force apparatus (SFA). A 10-13 nm thick film of synovial components (proteins, lipids, and polymers) adsorbs on the mica surfaces in less than an hour of incubation time, and induces a strong repulsion between the surfaces that prevents them from coming into contact. Upon shearing, the structure of the confined synovial fluid changes dramatically when sheared above a "critical" shear rate of about 2 s-1 (corresponding to approximately 40 nm s-1). Above this critical shear rate and up to at least 70 μm s-1, the proteins and biopolymers in the fluid gradually aggregate to form a homogenous gel layer on each mica surface. As shearing continues, the gel layer gradually breaks up into discrete/individual gel particles that can roll in the contact keeping the sheared surfaces far apart even under high compressive loads (pressure P ≈ 20 MPa). These particles eventually become elongated and finally behave as roller bearings. This mechanism is consistently observed for three mammalian synovial fluids and two types of surfaces suggesting that it actually occurs in articular joints and prostetic implants in vivo. The implications of these findings for joints and prosthetic implants structure and lubrication are discussed; in particular the formation and function of the lamina splendens. Shear-induced aggregation of synovial fluid components is observed under boundary lubrication conditions. The aggregation process starts with the formation of a gel-like layer on the surfaces, which ultimately leads to the formation of rod-like aggregates. These aggregates provide enhanced wear protection and lubrication to the surfaces using rolling friction instead of pure sliding friction. This mechanism suggests new design criteria for future bioinspired lubricants. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The surface properties and self-adhesion mechanism of self-healing poly(butyl acrylate) (PBA) copolymers containing comonomers with 2-ureido-4[1H]-pyrimidinone quadruple hydrogen bonding groups (UPy) are investigated using a surface forces apparatus (SFA) coupled with a top-view optical microscope. The surface energies of PBA-UPy4.0 and PBA-UPy7.2 (with mole percentages of UPy 4.0% and 7.2%, respectively) are estimated to be 45-56 mJ m-2 under dry condition by contact angle measurements using a three probe liquid method and also by contact and adhesion mechanics tests, as compared to the reported literature value of 31-34 mJ m-2 for PBA, an increase that is attributed to the strong UPy-UPy H-bonding interactions. The adhesion strengths of PBA-UPy polymers depend on the UPy content, contact time, temperature and humidity level. Fractured PBA-UPy films can fully recover their self-adhesion strength to 40, 81, and 100% in 10 s, 3 h, and 50 h, respectively, under almost zero external load. The fracture patterns (i.e., viscous fingers and highly "self-organized" parallel stripe patterns) have implications for fabricating patterned surfaces in materials science and nanotechnology. These results provide new insights into the fundamental understanding of adhesive mechanisms of multiple hydrogen-bonding polymers and development of novel self-healing and stimuli-responsive materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymers arewidely utilized as protective coatings to prevent metal surfaces from wear, corrosion, or bio-fouling.Yet, stability and adhesive properties of polymer to metal bondings are not fully understood at themolecular level. Here,wemeasured the interaction forces between a gold electrode surface and amine-functionalized polymers (PEG) using a novel electrochemical surface forces apparatus. We examined the potential dependence of specific amine.gold interactions and measured that the binding strength of amine.gold bonds can range from 0.5 to 40 kBT per binding site, depending on the applied electrochemical potential. Notably, this interaction exhibits a pronounced minimum around the potential of zero charge, where the polymer.gold adhesion is dominated by non-specific interactions between the polymer backbone and electrode surface, consistent with the adhesion of PEG polymers with gold surfaces in the absence of amine functionalization. Further, repulsive hydration interactions were observed to be stronger for amine-terminated PEG compared to non-functionalized PEG, due to increased hydration and presence of counterions in the case of amine-terminated PEG. Our results provide molecular-scale insight into design and optimization of polymer coatings for numerous applications requiring strong, specific binding interactions between polymers and metals (or their native oxides), for example passivating layers in biomedical implants and electronic devices. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The gecko adhesive system has attracted significant attention since the discovery that van der Waals interactions, which are always present between surfaces, are predominantly responsible for their adhesion. The unique anisotropic frictional-adhesive capabilities of the gecko adhesive system originate from complex hierarchical structures and just as importantly, the anisotropic articulation of the structures. Here, by cleverly engineering asymmetric polymeric microstructures, a reusable switchable gecko-like adhesive can be fabricated yielding steady high adhesion (F⊥ ≈ 1.25 N/cm2) and friction (Fâ̂¥ ≈ 2.8 N/cm2) forces when actuated for "gripping", yet release easily with minimal adhesion (F⊥ ≈ 0.34 N/cm2) and friction (Fâ̂¥≈ 0.38 N/cm2) forces during detachment or "releasing", over multiple attachment/detachment cycles, with a relatively small normal preload of 0.16 N/cm2 to initiate the adhesion. These adhesives can also be used to reversibly suspend weights from vertical (e.g., walls), and horizontal (e.g., ceilings) surfaces by simultaneously and judiciously activating anisotropic friction and adhesion forces. This design opens the way for new gecko-like adhesive surfaces and articulation mechanisms that do not rely on intensive nanofabrication in order to recover the anisotropic tribological property of gecko adhesive pads, albeit with lower adhesive forces compared to geckos. A switchable gecko-inspired adhesive that shows anisotropic adhesion and friction properties is presented. With proper actuation, the polymer-based dry adhesive provides strong adhesion and friction forces for attachment (or gripping), or weak forces for detachment (or releasing). The reusability of the dry adhesive is also demonstrated over multiple attachment/detachment cycles. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Many studies on the deformation of soft films by liquids confirmed the increase in the radius of the deformation and the decrease in the apparent contact angle. However, due to the thinness, the dynamics of the deformation could not be observed until the thermodynamic equilibrium. Thus, the dynamics on thick soft materials was studied until equilibrium to contrast the effect of different interfacial energy between different soft materials and water. Therefore, we prepared two different polymeric fluids with similar rheology by cross-linking monomers, yet with different contact angles with water. Sometime after water droplets were placed on these thick polymers, 3D profiles of the deformation were recorded. Though the effect of the surface tension was not verified, the same trend in the dynamics was observed as with thin films, except for the decrease in the radius after the initial increase. The three-phase boundaries (TPBs) were found not at the apex of the ridges formed during the transition to equilibrium. By calculating the surface tensions and angles of each interface at the equilibrium, we found that the temporary imbalance among surface tensions induced the slip of the TPBs toward the center of water droplets, thus dislocating the TPBs and decreasing the radius., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Advances in the research of intermolecular and surface interactions result from the development of new and improved measurement techniques and combinations of existing techniques. Here, we present a new miniature version of the surface forces apparatus-the μSFA-that has been designed for ease of use and multimodal capabilities with the retention of the capabilities of other SFA models including accurate measurements of the surface separation distance and physical characterization of dynamic and static physical forces (i.e., normal, shear, and friction) and interactions (e.g., van der Waals, electrostatic, hydrophobic, steric, and biospecific). The small physical size of the μSFA, compared to previous SFA models, makes it portable and suitable for integration into commercially available optical and fluorescence light microscopes, as demonstrated here. The large optical path entry and exit ports make it ideal for concurrent force measurements and spectroscopy studies. Examples of the use of the μSFA in combination with surface plasmon resonance (SPR) and Raman spectroscopy measurements are presented. Because of the short working distance constraints associated with Raman spectroscopy, an interferometric technique was developed and applied to calculate the intersurface separation distance based on Newton's rings. The introduction of the μSFA will mark a transition in SFA usage from primarily physical characterization to concurrent physical characterization with in situ chemical and biological characterization to study interfacial phenomena, including (but not limited to) molecular adsorption, fluid flow dynamics, the determination of surface species and morphology, and (bio)molecular binding kinetics.

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.

Using a surface forces apparatus (SFA), we quantitatively study the influence of surface damage on the contact mechanics of self-mated glassy polystyrene (PS) films. We use the SFA to measure the contact radius, surface profile, and normal force between the films, including the adhesion force. The molecular weight (MW) of the polymer influences the repeatability of the adhesion measurements and the effective surface energy calculated using the Johnson-Kendall-Roberts (JKR) theory. For low-MW PS (MW = 2.33 kDa), the effective surface energy increases over repeated adhesion cycles as the films become progressively damaged. For high-MW PS (MW = 280 kDa), the effective surface energy is constant over repeated adhesion cycles, but hysteresis is still present, manifested in a smaller contact radius during compression of the surfaces than during separation. Our results demonstrate that while the JKR theory is appropriate for describing the contact mechanics of glassy polymer thin films on layered elastic substrates, the contact mechanics of low-MW polymer films can be complicated by surface damage to the films.

Dissolution of mineral surfaces at asymmetric solid-liquid-solid interfaces in aqueous solutions occurs in technologically relevant processes, such as chemical/mechanical polishing (CMP) for semiconductor fabrication, formation and corrosion of structural materials, and crystallization of materials relevant to heterogeneous catalysis or drug delivery. In some such processes, materials at confined interfaces exhibit dissolution rates that are orders of magnitude larger than dissolution rates of isolated surfaces. Here, the dissolution of silica and alumina in close proximity to a charged gold surface or mica in alkaline solutions of pH 10-11 is shown to depend on the difference in electrostatic potentials of the surfaces, as determined from measurements conducted using a custom-built electrochemical pressure cell and a surface forces apparatus (SFA). The enhanced dissolution is proposed to result from overlap of the electrostatic double layers between the dissimilar charged surfaces at small intersurface separation distances (<1 Debye length). A semiquantitative model shows that overlap of the electric double layers can change the magnitude and direction of the electric field at the surface with the less negative potential, which results in an increase in the rate of dissolution of that surface. When the surface electrochemical properties were changed, the dissolution rates of silica and alumina were increased by up to 2 orders of magnitude over the dissolution rates of isolated compositionally similar surfaces under otherwise identical conditions. The results provide new insights on dissolution processes that occur at solid-liquid-solid interfaces and yield design criteria for controlling dissolution through electrochemical modification, with relevance to diverse technologies.

Marine mussels secrete proteins rich in residues containing catechols and cationic amines that displace hydration layers and adhere to charged surfaces under water via a cooperative binding effect known as catechol-cation synergy. Mussel-inspired adhesives containing paired catechol and cationic functionalities are a promising class of materials for biomedical applications, but few studies address the molecular adhesion mechanism(s) of these materials. To determine whether intramolecular adjacency of these functionalities is necessary for robust adhesion, a suite of siderophore analog surface primers was synthesized with systematic variations in intramolecular spacing between catechol and cationic functionalities. Adhesion measurements conducted with a surface forces apparatus (SFA) allow adhesive failure to be distinguished from cohesive failure and show that the failure mode depends critically on the siderophore analog adsorption density. The adhesion of these molecules to muscovite mica in an aqueous electrolyte solution demonstrates that direct intramolecular adjacency of catechol and cationic functionalities is not necessary for synergistic binding. However, we show that increasing the catechol-cation spacing by incorporating nonbinding domains results in decreased adhesion, which we attribute to a decrease in the density of catechol functionalities. A mechanism for catechol-cation synergy is proposed based on electrostatically driven adsorption and subsequent binding of catechol functionalities. This work should guide the design of new adhesives for binding to charged surfaces in saline environments.

Polymer-based lubricant additives for friction reduction, wear protection, or viscosity improvement have been widely studied. However, single additives achieving all three functions are rare. To address this need, we have explored the combination of polymer topology with organic-inorganic hybrid chemistry to simultaneously vary the temperature- and shear-dependent properties of polymer additives in solution and at solid surfaces. A topological library of lubricant additives, based on statistical copolymers of stearyl methacrylate and methyl methacrylate, ranging from linear to branched star architectures, was prepared using ruthenium-catalyzed controlled radical polymerization. Control over the polymerization yielded additives with low dispersity and comparable molecular weights, allowing evaluation of the influence of polymer architecture on friction reduction, wear protection, and bulk viscosity improvement in a commercial base oil (Yubase 4). Structure-performance relationships for these functions were assessed by a combination of a high-speed surface force apparatus (HS-SFA) experiments, wear track profilometry, quartz crystal microbalance analysis, and solution viscometry. The custom-built HS-SFA provides a unique experimental environment to measure the boundary lubrication performance under extreme shear rates (≈10 7 s -1 ) for prolonged times (24 h), mimicking the extreme conditions of automotive applications. These experiments revealed that the performance of the additives as boundary lubricants and wear protectants scales with the degree of branching. The branched architectures prohibit ordering of the additives in thin films under high-load conditions, leading to a thicker absorbed polymer brush boundary layer and therefore enhanced film fluidity and lubricity. Additionally, star polymers with increasing arm number lead to bulk viscosity modification, reflected by a significant increase in the viscosity index compared to the commercial base oil. Although outperformed by linear polymers for bulk viscosity improvement, the (hybrid) star polymers successfully combine the three distinct lubricant additive functions: friction reduction, wear protection, and bulk viscosity improvement-in a single polymeric structure. It should also be noted that, judging from HS-SFA experiments, hybrid stars carrying a silicate-based core outperform their fully organic analogues as boundary lubricants. The enhanced performance is most likely driven by attractive forces between the silicate cores and the employed metallic surfaces. Combining three function in one minimizes formulation complexity and thus opens a route to fundamentally understand and formulate key design parameters for the development of novel multifunction lubricant additives.

Over the past few decades, field- and laboratory-scale studies have shown enhancements in oil recovery when reservoirs, which contain high-salinity formation water (FW), are waterflooded with modified-salinity salt water (widely referred to as the low-salinity, dilution, or SmartWater effect for improved oil recovery). In this study, we investigated the time dependence of the physicochemical processes that occur during diluted seawater (i.e., SmartWater) waterflooding processes of specific relevance to carbonate oil reservoirs. We measured the changes to oil/water/rock wettability, surface roughness, and surface chemical composition during SmartWater flooding using 10-fold-diluted seawater under mimicked oil reservoir conditions with calcite and carbonate reservoir rocks. Distinct effects due to SmartWater flooding were observed and found to occur on two different timescales: (1) a rapid (<15 min) increase in the colloidal electrostatic double-layer repulsion between the rock and oil across the SmartWater, leading to a decreased oil/water/rock adhesion energy and thus increased water wetness and (2) slower (>12 h to complete) physicochemical changes of the calcite and carbonate reservoir rock surfaces, including surface roughening via the dissolution of rock and the reprecipitation of dissolved carbonate species after exchanging key ions (Ca 2+ , Mg 2+ , CO 3 2- , and SO 4 2- in carbonates) with those in the flooding SmartWater. Our experiments using crude oil from a carbonate reservoir reveal that these reservoir rock surfaces are covered with organic-ionic preadsorbed films (ad-layers), which the SmartWater removes (detaches) as flakes. Removal of the organic-ionic ad-layers by SmartWater flooding enhances oil release from the surfaces, which was found to be critical to increasing the water wetness and significantly improving oil removal from carbonates. Additionally, the increase in water wetness is further enhanced by roughening of the rock surfaces, which decreases the effective contact (interaction) area between the oil and rock interfaces. Furthermore, we found that the rate of these slower physicochemical changes to the carbonate rock surfaces increases with increasing temperature (at least up to an experimental temperature of 75 °C). Our results suggest that the effectiveness of improved oil recovery from SmartWater flooding depends strongly on the formation of the organic-ionic ad-layers. In oil reservoirs where the ad-layer is fully developed and robust, injecting SmartWater would lead to significant removal of the ad-layer and improved oil recovery.

The hydrophobic (HB) interaction plays a critical role in many colloidal and interfacial phenomena, biophysical and industrial processes. Surface hydrophobicity, characterized by the water contact angle, is generally considered the most dominant parameter determining the HB interaction. Herein, we quantified the HB interactions between air bubbles and a series of hydrophobic surfaces with different nanoscale structures and surface chemistry in aqueous media using a bubble probe atomic force microscopy (AFM). Surprisingly, it is discovered that surfaces of similar hydrophobicity can show different ranges of HB interactions, while surfaces of different hydrophobicity can have similar ranges of HB interaction. The increased heterogeneity of the surface nanoscale structure and chemistry can effectively decrease the decay length of HB interaction from 1.60 nm to 0.35 nm. Our work provides insights into the physical mechanism of HB interaction., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., Competing Interests: The authors declare no conflict of interest.

An in-depth knowledge of the interaction of water with amorphous silica is critical to fundamental studies of interfacial hydration water, as well as to industrial processes such as catalysis, nanofabrication, and chromatography. Silica has a tunable surface comprising hydrophilic silanol groups and moderately hydrophobic siloxane groups that can be interchanged through thermal and chemical treatments. Despite extensive studies of silica surfaces, the influence of surface hydrophilicity and chemical topology on the molecular properties of interfacial water is not well understood. In this work, we controllably altered the surface silanol density, and measured surface water diffusivity using Overhauser dynamic nuclear polarization (ODNP) and complementary silica-silica interaction forces across water using a surface forces apparatus (SFA). The results show that increased silanol density generally leads to slower water diffusivity and stronger silica-silica repulsion at short aqueous separations (less than ∼4 nm). Both techniques show sharp changes in hydration properties at intermediate silanol densities (2.0-2.9 nm -2 ). Molecular dynamics simulations of model silica-water interfaces corroborate the increase in water diffusivity with silanol density, and furthermore show that even on a smooth and crystalline surface at a fixed silanol density, adjusting the spatial distribution of silanols results in a range of surface water diffusivities spanning ∼10%. We speculate that a critical silanol cluster size or connectivity parameter could explain the sharp transition in our results, and can modulate wettability, colloidal interactions, and surface reactions, and thus is a phenomenon worth further investigation on silica and chemically heterogeneous surfaces., Competing Interests: The authors declare no conflict of interest.

We report here that a dense liquid formed by spontaneous condensation, also known as simple coacervation, of a single mussel foot protein-3S-mimicking peptide exhibits properties critical for underwater adhesion. A structurally homogeneous coacervate is deposited on underwater surfaces as micrometer-thick layers, and, after compression, displays orders of magnitude higher underwater adhesion at 2 N m -1 than that reported from thin films of the most adhesive mussel-foot-derived peptides or their synthetic mimics. The increase in adhesion efficiency does not require nor rely on post-deposition curing or chemical processing, but rather represents an intrinsic physical property of the single-component coacervate. Its wet adhesive and rheological properties correlate with significant dehydration, tight peptide packing and restriction in peptide mobility. We suggest that such dense coacervate liquids represent an essential adaptation for the initial priming stages of mussel adhesive deposition, and provide a hitherto untapped design principle for synthetic underwater adhesives.

Biological tissues can accurately differentiate external mechanical stresses and actively select suitable strategies (e.g., reversible strain-stiffening, self-healing) to sustain or restore their integrity and related functionalities as required. Synthetic materials that can imitate the characteristics of biological tissues have a wide range of engineering and bioengineering applications. However, no success has been demonstrated to realize such strain-stiffening behavior in synthetic networks, particularly using flexible polymers, which has remained a great challenge. Here, we present one such synthetic hydrogel material prepared from two flexible polymers (polyethylene glycol and branched polyethylenimine) that exhibits both strain-stiffening and self-healing capabilities. The developed synthetic hydrogel network not only mimics the main features of biological mechanically responsive systems but also autonomously self-heals after becoming damaged, thereby recovering its full capacity to perform its normal physiological functions.

Materials often exhibit a trade-off between stiffness and extensibility; for example, strengthening elastomers by increasing their cross-link density leads to embrittlement and decreased toughness. Inspired by cuticles of marine mussel byssi, we circumvent this inherent trade-off by incorporating sacrificial, reversible iron-catechol cross-links into a dry, loosely cross-linked epoxy network. The iron-containing network exhibits two to three orders of magnitude increases in stiffness, tensile strength, and tensile toughness compared to its iron-free precursor while gaining recoverable hysteretic energy dissipation and maintaining its original extensibility. Compared to previous realizations of this chemistry in hydrogels, the dry nature of the network enables larger property enhancement owing to the cooperative effects of both the increased cross-link density given by the reversible iron-catecholate complexes and the chain-restricting ionomeric nanodomains that they form., (Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Marine mussels use catechol-rich interfacial mussel foot proteins (mfps) as primers that attach to mineral surfaces via hydrogen, metal coordination, electrostatic, ionic, or hydrophobic bonds, creating a secondary surface that promotes bonding to the bulk mfps. Inspired by this biological adhesive primer, it is shown that a ≈1 nm thick catecholic single-molecule priming layer increases the adhesion strength of crosslinked polymethacrylate resin on mineral surfaces by up to an order of magnitude when compared with conventional primers such as noncatecholic silane- and phosphate-based grafts. Molecular dynamics simulations confirm that catechol groups anchor to a variety of mineral surfaces and shed light on the binding mode of each molecule. Here, a ≈50% toughness enhancement is achieved in a stiff load-bearing polymer network, demonstrating the utility of mussel-inspired bonding for processing a wide range of polymeric interfaces, including structural, load-bearing materials., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.

Reactivity in confinement is central to a wide range of applications and systems, yet it is notoriously difficult to probe reactions in confined spaces in real time. Using a modified electrochemical surface forces apparatus (EC-SFA) on confined metallic surfaces, we observe in situ nano- to microscale dissolution and pit formation (qualitatively similar to previous observation on nonmetallic surfaces, e.g., silica) in well-defined geometries in environments relevant to corrosion processes. We follow "crevice corrosion" processes in real time in different pH-neutral NaCl solutions and applied surface potentials of nickel (vs. Ag|AgCl electrode in solution) for the mica-nickel confined interface of total area ∼0.03 mm 2 The initial corrosion proceeds as self-catalyzed pitting, visualized by the sudden appearance of circular pits with uniform diameters of 6-7 μm and depth ∼2-3 nm. At concentrations above 10 mM NaCl, pitting is initiated at the outer rim of the confined zone, while below 10 mM NaCl, pitting is initiated inside the confined zone. We compare statistical analysis of growth kinetics and shape evolution of individual nanoscale deep pits with estimates from macroscopic experiments to study initial pit growth and propagation. Our data and experimental techniques reveal a mechanism that suggests initial corrosion results in formation of an aggressive interfacial electrolyte that rapidly accelerates pitting, similar to crack initiation and propagation within the confined area. These results support a general mechanism for nanoscale material degradation and dissolution (e.g., crevice corrosion) of polycrystalline nonnoble metals, alloys, and inorganic materials within confined interfaces., Competing Interests: The authors declare no conflict of interest.

Cation-π interactions drive the self-assembly and cohesion of many biological molecules, including the adhesion proteins of several marine organisms. Although the origin of cation-π bonds in isolated pairs has been extensively studied, the energetics of cation-π-driven self-assembly in molecular films remains uncharted. Here we use nanoscale force measurements in combination with solid-state NMR spectroscopy to show that the cohesive properties of simple aromatic- and lysine-rich peptides rival those of the strong reversible intermolecular cohesion exhibited by adhesion proteins of marine mussel. In particular, we show that peptides incorporating the amino acid phenylalanine, a functional group that is conspicuously sparing in the sequences of mussel proteins, exhibit reversible adhesion interactions significantly exceeding that of analogous mussel-mimetic peptides. More broadly, we demonstrate that interfacial confinement fundamentally alters the energetics of cation-π-mediated assembly: an insight that should prove relevant for diverse areas, which range from rationalizing biological assembly to engineering peptide-based biomaterials.

Geckos have developed foot pads that allow them to maintain their unique climbing ability despite vast differences of surfaces and environments, from dry desert to humid rainforest. Likewise, successful gecko-inspired mimics should exhibit adhesive and frictional performance across a similarly diverse range of climates. In this work, we focus on the effect of relative humidity (RH) on the "frictional-adhesion" behavior of gecko-inspired adhesive pads. A surface forces apparatus was used to quantitatively measure adhesion and friction forces of a microfibrillar cross-linked polydimethylsiloxane surface against a smooth hemispherical glass disk at varying relative humidity, from 0 to 100% (including fully submerged under water). Geometrically anisotropic tilted half-cylinder microfibers yield a "grip state" (high adhesion and friction forces after shearing along the tilt of the fibers, F ad + and F ∥ + ) and a "release state" (low adhesion and friction after shearing against the tilt of the fibers, F ad - and F ∥ - ). By appropriate control of the loading path, this allows for transition between strong attachment and easy detachment. Changing the preload and shear direction gives rise to differences in the effective contact area at each fiber and the microscale and nanoscale structure of the contact while changing the relative humidity results in differences in the relative contributions of van der Waals and capillary forces. In combination, both effects lead to interesting trends in the adhesion and friction forces. At up to 75% RH, the grip state adhesion force remains constant and the ratio of grip to release adhesion force does not drop below 4.0. In addition, the friction forces F ∥ + and F ∥ - and the release state adhesion force F ad - exhibit a maximum at intermediate relative humidity between 40% and 75%.

Ionic liquids are pure salts that are liquid under ambient conditions. As liquids composed solely of ions, the scientific consensus has been that ionic liquids have exceedingly high ionic strengths and thus very short Debye screening lengths. However, several recent experiments from laboratories around the world have reported data for the approach of two surfaces separated by ionic liquids which revealed remarkable long range forces that appear to be electrostatic in origin. Evidence has accumulated demonstrating long range surface forces for several different combinations of ionic liquids and electrically charged surfaces, as well as for concentrated mixtures of inorganic salts in solvent. The original interpretation of these forces, that ionic liquids could be envisioned as "dilute electrolytes," was controversial, and the origin of long range forces in ionic liquids remains the subject of discussion. Here we seek to collate and examine the evidence for long range surface forces in ionic liquids, identify key outstanding questions, and explore possible mechanisms underlying the origin of these long range forces. Long range surface forces in ionic liquids and other highly concentrated electrolytes hold diverse implications from designing ionic liquids for energy storage applications to rationalizing electrostatic correlations in biological self-assembly.

Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relative to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity.

Water hampers the formation of strong and durable bonds between adhesive polymers and solid surfaces, in turn hindering the development of adhesives for biomedical and marine applications. Inspired by mussel adhesion, a mussel foot protein homologue (mfp3S-pep) is designed, whose primary sequence is designed to mimic the pI, polyampholyte, and hydrophobic characteristics of the native protein. Noticeably, native protein and synthetic peptide exhibit similar abilities to self-coacervate at given pH and ionic strength. 3,4-dihydroxy-l-phenylalanine (Dopa) proves necessary for irreversible peptide adsorption to both TiO 2 (anatase) and hydroxyapatite (HAP) surfaces, as confirmed by quartz crystal microbalance measurements, with the coacervate showing superior adsorption. The adsorption of Dopa-containing peptides is investigated by attenuated total reflection infrared spectroscopy, revealing initially bidentate coordinative bonds on TiO 2 , followed by H-bonded and eventually long-ranged electrostatic and Van der Waals interactions. On HAP, mfp3s-pep-3Dopa adsorption occurs predominantly via H-bond and outer-sphere complexes of the catechol groups. Importantly, only the Dopa-bearing compounds are able to remove interfacial water from the target surfaces, with the coacervate achieving the highest water displacement arising from its superior wetting properties. These findings provide an impetus for developing coacervated Dopa-functionalized peptides/polymers adhesive formulations for a variety of applications on wet polar surfaces.

Translating sticky biological molecules-such as mussel foot proteins (MFPs)-into synthetic, cost-effective underwater adhesives with adjustable nano- and macroscale characteristics requires an intimate understanding of the glue's molecular interactions. To help facilitate the next generation of aqueous adhesives, we performed a combination of surface forces apparatus (SFA) measurements and replica-exchange molecular dynamics (REMD) simulations on a synthetic, easy to prepare, Dopa-containing peptide (MFP-3s peptide), which adheres to organic surfaces just as effectively as its wild-type protein analog. Experiments and simulations both show significant differences in peptide adsorption on CH3-terminated (hydrophobic) and OH-terminated (hydrophilic) self-assembled monolayers (SAMs), where adsorption is strongest on hydrophobic SAMs because of orientationally specific interactions with Dopa. Additional umbrella-sampling simulations yield free-energy profiles that quantitatively agree with SFA measurements and are used to extract the adhesive properties of individual amino acids within the context of MFP-3s peptide adhesion, revealing a delicate balance between van der Waals, hydrophobic, and electrostatic forces.

Polyelectrolyte complexation is critical to the formation and properties of many biological and polymeric materials, and is typically initiated by aqueous mixing followed by fluid-fluid phase separation, such as coacervation. Yet little to nothing is known about how coacervates evolve into intricate solid microarchitectures. Inspired by the chemical features of the cement proteins of the sandcastle worm, here we report a versatile and strong wet-contact microporous adhesive resulting from polyelectrolyte complexation triggered by solvent exchange. After premixing a catechol-functionalized weak polyanion with a polycation in dimethyl sulphoxide (DMSO), the solution was applied underwater to various substrates whereupon electrostatic complexation, phase inversion, and rapid setting were simultaneously actuated by water-DMSO solvent exchange. Spatial and temporal coordination of complexation, inversion and setting fostered rapid (∼25 s) and robust underwater contact adhesion (Wad ≥ 2 J m(-2)) of complexed catecholic polyelectrolytes to all tested surfaces including plastics, glasses, metals and biological materials.

Wetting of rough surfaces involves time-dependent effects, such as surface deformations, nonuniform filling of surface pores within or outside the contact area, and surface chemistries, but the detailed impact of these phenomena on wetting is not entirely clear. Understanding these effects is crucial for designing coatings for a wide range of applications, such as membrane-based oil-water separation and desalination, waterproof linings/windows for automobiles, aircrafts, and naval vessels, and antibiofouling. Herein, we report on time-dependent contact angles of water droplets on a rough polydimethylsiloxane (PDMS) surface that cannot be completely described by the conventional Cassie-Baxter or Wenzel models or the recently proposed Cassie-impregnated model. Shells of sand dollars (Dendraster excentricus) were used as lithography-free, robust templates to produce rough PDMS surfaces with hierarchical, periodic features ranging from 1 × 10(-7) to 1 × 10(-4) m. Under saturated vapor conditions, we found that in the short term (<1 min), the contact angle of a sessile water droplet on the templated PDMS, θ(SDT) = 140 ± 3°, was accurately described by the Cassie-Baxter model (predicted θ(SDT) = 137°); however, after 90 min, θ(SDT) fell to 110°. Fluorescent confocal microscopy confirmed that the initial reduction in θ(SDT) to 110° (the Wenzel limit) was primarily a Cassie-Baxter to Wenzel transition during which pores within the contact area filled gradually, and more rapidly for ethanol-water mixtures. After 90 min, the contact line of the water droplet became pinned, perhaps caused by viscoelastic deformation of the PDMS around the contact line, and a significant volume of water began to flow from the droplet to pores outside the contact region, causing θ(SDT) to decrease to 65° over 48 h on the rough surface. The system we present here to explore the concept of contact angle time dependence (dynamics) and modeling of natural surfaces provides insights into the design and development of long- and short-lived coatings.

Dopa (l-3,4-dihydroxyphenylalanine) is a key chemical signature of mussel adhesive proteins, but its susceptibility to oxidation has limited mechanistic investigations as well as practical translation to wet adhesion technology. To investigate peptidyl-Dopa oxidation, the highly diverse chemical environment of Dopa in mussel adhesive proteins was simplified to a peptidyl-Dopa analogue, N-acetyl-Dopa ethyl ester. On the basis of cyclic voltammetry and UV-vis spectroscopy, the Dopa oxidation product at neutral to alkaline pH was shown to be α,β-dehydro-Dopa (ΔD), a vinylcatecholic tautomer of Dopa-quinone. ΔD exhibited an adsorption capacity on TiO2 20-fold higher than that of the Dopa homologue in the quartz crystal microbalance. Cyclic voltammetry confirmed the spontaneity of ΔD formation in mussel foot protein 3F at neutral pH that is coupled to a change in protein secondary structure from random coil to β-sheet. A more complete characterization of ΔD reactivity adds a significant new perspective to mussel adhesive chemistry and the design of synthetic bioinspired adhesives.