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Microgels have been widely used for stabilizing emulsions due to their softness and stimulus responsiveness. Although ultrastable emulsions have been prepared by microgel nanoparticles, the role of electrostatic interactions on emulsion stability is still a controversial topic and further investigation of the effect of microgel deformability is required. In the present study, neutral poly( N -vinylcaprolactam) (PVCL) and charged poly( N -vinylcaprolactam) -co- methacrylic acid (P(VCL -co- MAA)) microgels were synthesized and further used as emulsifiers to stabilizing emulsion. The P(VCL -co- MAA) microgel has a swelling ratio larger than that of the PVCL microgel in water. The nanomechanical properties of the microgels in water were characterized by atomic force microscopy with using the tip of different radii. The result reveals that the P(VCL -co- MAA) microgel is more deformable than the PVCL counterpart. Stability tests of the emulsions showed that below the volume phase transition temperature (VPTT) of the microgels, both microgel types can stabilize the emulsions under various conditions. Unexpectedly, most of the emulsions still remain stable above the VPTT. Further increasing the temperature to 60 °C, P(VCL -co- MAA) microgel emulsions remained stable at a pH value above the p K a of MAA while the emulsion was unstable below the p K a . However, phase separation occurs in PVCL microgel-stabilized emulsions at 60 °C. These results demonstrate that electrostatic repulsion and deformability of the microgels can enhance the emulsion stability, providing insights into the rational design and preparation of ultrastable Pickering emulsions.

Strongly attractive forces act between superhydrophobic surfaces across water due to the formation of a bridging gas capillary. Upon separation, the attraction can range up to tens of micrometers as the gas capillary grows, while gas molecules accumulate in the capillary. We argue that most of these molecules come from the pre-existing gaseous layer found at and within the superhydrophobic coating. In this study, we investigate how the capillary size and the resulting capillary forces are affected by the thickness of the gaseous layer. To this end, we prepared superhydrophobic coatings with different thicknesses by utilizing different numbers of coating cycles of a liquid flame spraying technique. Laser scanning confocal microscopy confirmed an increase in gas layer thickness with an increasing number of coating cycles. Force measurements between such coatings and a hydrophobic colloidal probe revealed attractive forces caused by bridging gas capillaries, and both the capillary size and the range of attraction increased with increasing thickness of the pre-existing gas layer. Hence, our data suggest that the amount of available gas at and in the superhydrophobic coating determines the force range and capillary growth.

Calcium carbonate, particularly in the form of calcite, is an abundant mineral widely used in both human-made products and biological systems. The calcite surface possesses a high surface energy, making it susceptible to the adsorption of organic contaminants. Moreover, the surface is also reactive towards a range of chemicals, including water. Consequently, studying and maintaining a clean and stable calcite surface is only possible under ultrahigh vacuum conditions and for limited amounts of time. When exposed to air or solution, the calcite surface undergoes rapid transformations, demanding a comprehensive understanding of the properties of calcite surfaces in different environments. Similarly, attention must also be directed towards the kinetics of changes, whether induced by fluctuating environments or at constant condition. All these aspects are encompassed in the expression "dynamic nature", and are of crucial importance in the context of the diverse applications of calcite. In many instances, the calcite surface is modified by adsorption of fatty acids to impart a desired nonpolar character. Although the binding between carboxylic acid groups and calcite surfaces is strong, the fatty acid layer used for surface modification undergoes significant alterations when exposed to water vapour and liquid water droplets. Therefore, it is also crucial to understand the dynamic nature of the adsorbed layer. This review article provides a comprehensive overview of the current understanding of both the dynamics of the calcite surface as well as when modified by fatty acid surface treatments.

Organic semiconductors are a family of pi-conjugated compounds used in many applications, such as displays, bioelectronics, and thermoelectrics. However, their susceptibility to processing-induced contamination is not well understood. Here, it is shown that many organic electronic devices reported so far may have been unintentionally contaminated, thus affecting their performance, water uptake, and thin film properties. Nuclear magnetic resonance spectroscopy is used to detect and quantify contaminants originating from the glovebox atmosphere and common laboratory consumables used during device fabrication. Importantly, this in-depth understanding of the sources of contamination allows the establishment of clean fabrication protocols, and the fabrication of organic field effect transistors (OFETs) with improved performance and stability. This study highlights the role of unintentional contaminants in organic electronic devices, and demonstrates that certain stringent processing conditions need to be met to avoid scientific misinterpretation, ensure device reproducibility, and facilitate performance stability. The experimental procedures and conditions used herein are typical of those used by many groups in the field of solution-processed organic semiconductors. Therefore, the insights gained into the effects of contamination are likely to be broadly applicable to studies, not just of OFETs, but also of other devices based on these materials., (© 2023 The Authors. Small Methods published by Wiley-VCH GmbH.)

A fundamental understanding of the interactions between mineral surfaces and amphiphilic surface modification agents is needed for better control over the production and uses of mineral fillers. Here, we controlled the carboxylic acid layer formation conditions on calcite surfaces with high precision via vapor deposition. The properties of the resulting carboxylic acid layers were analyzed using surface-sensitive techniques, such as atomic force microscopy (AFM), contact angle measurements, angle resolved X-ray photoelectron spectroscopy (XPS), and vibrational sum-frequency spectroscopy. A low wettability was achieved with long hydrocarbon chain carboxylic acids such as stearic acid. The stearic acid layer formed by vapor deposition is initially patchy, but with increasing vapor exposure time, the patches grow and condense into a homogeneous layer with a thickness close to that expected for a monolayer as evaluated by AFM and XPS. The build-up process of the layer occurs more rapidly at higher temperatures due to the higher vapor pressure. The stability of the deposited fatty acid layer in the presence of a water droplet increases with the chain length and packing density in the adsorbed layer. Vibrational sum frequency spectroscopy data demonstrate that the stearic acid monolayers on calcite have their alkyl chains in an all-trans conformation and are anisotropically distributed on the plane of the surface, forming epitaxial monolayers. Vibrational spectra also show that the stearic acid molecules interact with the calcite surface through the carboxylic acid headgroup in both its protonated and deprotonated forms. The results presented provide new molecular insights into the properties of adsorbed carboxylic acid layers on calcite.

The formation of a bridging gas capillary between superhydrophobic surfaces in water gives rise to strongly attractive interactions ranging up to several micrometers on separation. However, most liquids used in materials research are oil-based or contain surfactants. Superamphiphobic surfaces repel both water and low-surface-tension liquids. To control the interactions between a superamphiphobic surface and a particle, it needs to be resolved whether and how gas capillaries form in non-polar and low-surface-tension liquids. Such insight will aid advanced functional materials development. Here, we combine laser scanning confocal imaging and colloidal probe atomic force microscopy to elucidate the interaction between a superamphiphobic surface and a hydrophobic microparticle in three liquids with different surface tensions: water (73 mN m -1 ), ethylene glycol (48 mN m -1 ) and hexadecane (27 mN m -1 ). We show that bridging gas capillaries are formed in all three liquids. Force-distance curves between the superamphiphobic surface and the particle reveal strong attractive interactions, where the range and magnitude decrease with liquid surface tension. Comparison of free energy calculations based on the capillary menisci shapes and the force measurements suggest that under our dynamic measurements the gas pressure in the capillary is slightly below ambient., (© 2023. The Author(s).)

Conjugated polymer field-effect transistors are emerging as an enabling technology for flexible electronics due to their excellent mechanical properties combined with sufficiently high charge-carrier mobilities and compatibility with large-area, low-temperature processing. However, their electrical stability remains a concern. ON-state (accumulation mode) bias-stress instabilities in organic semiconductors have been widely studied, and multiple mitigation strategies have been suggested. In contrast, OFF-state (depletion mode) bias-stress instabilities remain poorly understood despite being crucial for many applications in which the transistors are held in their OFF-state for most of the time. Here, a simple method of using an antisolvent treatment is presented to achieve significant improvements in OFF-state bias-stress and environmental stability as well as general device performance for one of the best performing polymers, solution-processable indacenodithiophene-co-benzothiadiazole (IDT-BT). IDT-BT is weakly crystalline, and the notable improvements to an antisolvent-induced, increased degree of crystallinity, resulting in a lower probability of electron trapping and the removal of charge traps is attributed. The work highlights the importance of the microstructure in weakly crystalline polymer films and offers a simple processing strategy for achieving the reliability required for applications in flexible electronics., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Hyaluronan-collagen composites have been employed in numerous biomedical applications. Understanding the interactions between hyaluronan and collagen is particularly important in the context of joint cartilage function and the treatment of joint diseases. Many factors affect the affinity of collagen for hyaluronan. One of the important factors is the ratio of 3- or 4-hydroxy proline to proline residues. This article presents the results from molecular dynamics calculations of HA-collagen type II interactions with hyaluronan. The applied protocol employed docking and geometry optimization of complexes built using collagen structures with different numbers of hydroxyl groups attached to proline moieties. It was established that the hydroxyproline/proline ratio affects both structural and energetic features of the collagen-hyaluronan complex. Proline hydroxylation was found to significantly influence the number of all identified types of molecular forces, hydrophobic interactions, water bridges and hydrogen bonds, which can be formed between collagen and hyaluronan. Importantly, an increase in the hydroxyproline/proline ratio in the collagen chain increases the binding affinity for hyaluronan. This is illustrated by the linear correlation between the binding free energy and the hydroxylation degree. A comparison of the results obtained for 3 and 4 hydroxylation of proline indicates that the hydroxyl group attachment position plays a minor role in complex stabilization. However, a slightly stronger affinity was observed for 4 hydroxylation. In order to evaluate the effect of the aqueous environment on the collagen-hyaluronan complex stability, the enthalpic and entropic contributions to the free energy of solvation were analyzed.

An extremely efficient lubrication system is achieved in synovial joints by means of bio-lubricants and sophisticated nanostructured surfaces that work together. Molecular bottlebrush structures play crucial roles for this superior tribosystem. For example, lubricin is an important bio-lubricant, and aggrecan associated with hyaluronan is important for the mechanical response of cartilage. Inspired by nature, synthetic bottlebrush polymers have been developed and excellent aqueous boundary lubrication has been achieved. In this review, we summarize recent experimental investigations of the interfacial lubrication properties of surfaces coated with bottlebrush bio-lubricants and bioinspired bottlebrush polymers. We also discuss recent advances in understanding intermolecular synergy in aqueous lubrication including natural and synthetic polymers. Finally, opportunities and challenges in developing efficient aqueous boundary lubrication systems are outlined.

The field of organic electronics has profited from the discovery of new conjugated semiconducting polymers that have molecular backbones which exhibit resilience to conformational fluctuations, accompanied by charge carrier mobilities that routinely cross the 1 cm 2 /Vs benchmark. One such polymer is indacenodithiophene-co-benzothiadiazole. Previously understood to be lacking in microstructural order, we show here direct evidence of nanosized domains of high order in its thin films. We also demonstrate that its device-based high-performance electrical and thermoelectric properties are not intrinsic but undergo rapid stabilization following a burst of ambient air exposure. The polymer's nanomechanical properties equilibrate on longer timescales owing to an orthogonal mechanism; the gradual sweating-out of residual low molecular weight solvent molecules from its surface. We snapshot the quasistatic temporal evolution of the electrical, thermoelectric and nanomechanical properties of this prototypical organic semiconductor and investigate the subtleties which play on competing timescales. Our study documents the untold and often overlooked story of a polymer device's dynamic evolution toward stability., (© 2022. The Author(s).)

A profound understanding of the properties of unmodified and saturated fatty acid-modified calcite surfaces is essential for elucidating their resistance and stability in the presence of water droplets. Additional insights can be obtained by also studying the effects of carboxylic acid-saturated aqueous solutions. We elucidate surface wettability, structure, and nanomechanical properties beneath and at the edge of a deposited droplet after its evaporation. When calcite was coated by a highly packed monolayer of stearic acid, a hydrophilic region was found at the three-phase contact line. In atomic force microscopy mapping, this region is characterized by low adhesion and a topographical hillock. The surface that previously was covered by the droplet demonstrated a patchy structure of about 6 nm height, implying stearic acid reorganization into a patchy bilayer-like structure. Our data suggest that during droplet reverse dispensing and droplet evaporation, pinning of the three-phase contact line leads to the transport of dissolved fatty carboxylic acid and possibly calcium bicarbonate Ca(HCO 3 ) 2 molecules to the contact line boundary. Compared to the surface of intrinsically hydrophobic materials, such as polystyrene, the changes in contact angle and base diameter during droplet evaporation on stearic acid-modified calcite are strikingly different. This difference is due to stearic acid reorganization on the surface and transport to the water-air interface of the droplet. An effect of the evaporating droplet is also observed on unmodified calcite due to dissolution and recrystallization of the calcite surface in the presence of water. In the case where a water droplet saturated with octanoic acid is used instead of water, the stearic acid-coated calcite remains considerably more stable. Our findings are discussed in terms of the coffee-ring effect.

The lubrication mechanism in synovial fluid and joints is not yet fully understood. Nevertheless, intermolecular interactions between various neutral and ionic species including large macromolecular systems and simple inorganic ions are the key to understanding the excellent lubrication performance. An important tool for characterizing the intermolecular forces and their structural consequences is molecular dynamics. Albumin is one of the major components in synovial fluid. Its electrostatic properties, including the ability to form molecular complexes, are closely related to pH, solvation, and the presence of ions. In the context of synovial fluid, it is relevant to describe the possible interactions between albumin and hyaluronate, taking into account solution composition effects. In this study, the influence of Na + , Mg 2+ , and Ca 2+ ions on human serum albumin-hyaluronan interactions were examined using molecular dynamics tools. It was established that the presence of divalent cations, and especially Ca 2+ , contributes mostly to the increase of the affinity between hyaluronan and albumin, which is associated with charge compensation in negatively charged hyaluronan and albumin. Furthermore, the most probable binding sites were structurally and energetically characterized. The indicated moieties exhibit a locally positive charge which enables hyaluronate binding (direct and water mediated).

Poly-NIPAm microgel particles with two different cross-linking densities were prepared with the classical batch polymerization process. These particles were adsorbed onto modified silica surfaces, and their nanomechanical properties were measured by means of atomic force microscopy. It was found that these particles have a hard core-soft shell structure both below and above the volume transition temperature. The core-shell-like structure appears due to a higher reaction rate of the cross-linker compared to that of the monomer, leading to depletion of cross-linker in the shell region. The microgel beads with lower average cross-linking density were found to be less stiff below the volume transition temperature than the microgel with higher cross-linking density. Increasing the temperature further to just above the volume transition temperature led to lower stiffness of the more highly cross-linked microgel compared to its less cross-linked counterpart. This effect is explained with the more gradual deswelling with temperature for the more cross-linked microgel particles. This phenomenon was confirmed by dynamic light scattering measurements in the bulk phase, which showed that the larger cross-linking density microgel showed a more gradual collapse in aqueous solution as the temperature was increased.

Understanding the wear of mineral fillers is crucial for controlling industrial processes, and in the present work, we examine the wear resistance and nanomechanical properties of bare calcite and stearic acid-modified calcite surfaces under dry and humid conditions at the nanoscale. Measurements under different loads allow us to probe the situation in the absence and presence of abrasive wear. The sliding motion is in general characterized by irregular stick-slip events that at higher loads lead to abrasion of the brittle calcite surface. Bare calcite is hydrophilic, and under humid conditions, a thin water layer is present on the surface. This water layer does not affect the friction force. However, it slightly decreases the wear depth and strongly influences the distribution of wear particles. In contrast, stearic acid-modified surfaces are hydrophobic. Nevertheless, humidity affects the wear characteristics by decreasing the binding strength of stearic acid at higher humidity. A complete monolayer coverage of calcite by stearic acid results in a significant reduction in wear but only a moderate reduction in friction forces at low humidity and no reduction at 75% relative humidity (RH). Thus, our data suggest that the wear reduction does not result from a lowering of the friction force but rather from an increased ductility of the surface region as offered by the stearic acid layer. An incomplete monolayer of stearic acid on the calcite surface provides no reduction in wear regardless of the RH investigated. Clearly, the wear properties of modified calcite surfaces depend crucially on the packing density of the surface modifier and also on the air humidity.

We investigated the gelation of cellulose nanocrystals (CNCs) in polyelectrolyte and neutral polymer solutions. Cellulose nanocrystals (CNCs) with half-ester sulfate groups produced by acid hydrolysis of wood pulp were used in this study. The microstructure of CNCs/polymer suspensions was investigated in semidilute concentration regimes by selecting carboxymethyl cellulose (CMC700) as an anionic polymer and poly(ethylene oxide) (PEO600) as a neutral polymer solution. Together with quartz crystal microbalance with dissipation monitoring (QCM-D), rheology, scanning electron microscopy (SEM), and cryo-transmission electron microscopy (cryo-TEM), we characterized CNCs-polymer interactions, the suspension microstructure, and the macroscopic gel flow. Significant viscosity increases at low shear rates coupled with high shear-thinning behaviors were observed in CNC colloid-CMC700 polymer mixtures, but not those CNCs in PEO600 solutions. The apparent differences between CNCs-CMC700 and CNCs-PEO600 mixtures were due to their chain confirmations. On the basis of the evaluations from STEM, cryo-TEM, and polarized optical microscopy, we proposed that the excess CMC700 molecules in solutions result in the depletion of CNCs and the formation of anisotropic domains.

The temperature dependence of nanomechanical properties of adsorbed poly-NIPAm microgel particles prepared by a semibatch polymerization process was investigated in an aqueous environment via indentation-based atomic force microscopy (AFM) methods. Poly-NIPAm microgel particles prepared by the classical batch process were also characterized for comparison. The local mechanical properties were measured between 26 and 35 °C, i.e., in the temperature range of the volume transition. Two different AFM tips with different shapes and end radii were utilized. The nanomechanical properties measured by the two kinds of tips showed a similar temperature dependence of the nanomechanical properties, but the actual values were found to depend on the size of the tip. The results suggest that the semibatch synthesis process results in the formation of more homogeneous microgel particles than the classical batch method. The methodological approach reported in this work is generally applicable to soft surface characterization in situ.

The modular construction of defect-free nanofilms with a large area remains a challenge. Herein, we present a scalable strategy for the preparation of calix[4]pyrrole (C[4]P)-based nanofilms through acryl hydrazone reaction conducted in a tetrahydrazide calix[4]pyrrole (CPTH)-based self-assembled layer at the air/DMSO interface. With this strategy, robust, regenerable, and defect-free nanofilms with an exceptionally large area (∼750 cm 2 ) were constructed. The thickness and permeability of the film systems can be fine-tuned by varying the precursor concentration or by changing another building block. A typical nanofilm (C[4]P-TFB, ∼67 nm) depicted high water flux (39.9 L m -2 h -1 under 1 M Na 2 SO 4 ), narrow molecular weight cut-off value (∼200 Da), and promising antifouling properties in the forward osmosis (FO) process. In addition, the nanofilms are stable over a wide pH range and tolerable to different organic solvents. Interestingly, the introduction of C[4]P endowed the nanofilms with both outstanding mechanical properties and unique group-selective separation capability, laying the foundation for wastewater treatment and pharmaceutical concentration.

Hyaluronan is an essential physiological bio macromolecule with different functions. One prominent area is the synovial fluid which exhibits remarkable lubrication properties. However, the synovial fluid is a multi-component system where different macromolecules interact in a synergetic fashion. Within this study we focus on the interaction of hyaluronan and phospholipids, which are thought to play a key role for lubrication. We investigate how the interactions and the association structures formed by hyaluronan (HA) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) are influenced by the molecular weight of the bio polymer and the ionic composition of the solution. We combine techniques allowing us to investigate the phase behavior of lipids (differential scanning calorimetry, zeta potential and electrophoretic mobility) with structural investigation (dynamic light scattering, small angle scattering) and theoretical simulations (molecular dynamics). The interaction of hyaluronan and phospholipids depends on the molecular weight, where hyaluronan with lower molecular weight has the strongest interaction. Furthermore, the interaction is increased by the presence of calcium ions. Our simulations show that calcium ions are located close to the carboxylate groups of HA and, by this, reduce the number of formed hydrogen bonds between HA and DPPC. The observed change in the DPPC phase behavior can be attributed to a local charge inversion by calcium ions binding to the carboxylate groups as the binding distribution of hyaluronan and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine is not changed.

Surface disinfection of water facilities such as water wells requires measures that can remove pathogens from the walls to ensure a high drinking water quality, but many of these measures might increase corrosion of the contact surfaces (often highly pure steel) and affect the environment negatively due to disinfectant-contaminated waste sludge and wastewater. Today, most treatments worldwide are based on hypochlorites. We investigated the extent of corrosion during treatments of steel at relevant conditions of ozone, sodium, and calcium hypochlorite for drinking water preparation, utilizing weight loss, electrochemical, solution analytical, and surface analytical methods. The ozone treatment caused significantly less corrosion as compared with sodium or calcium hypochlorite with 150-250 mg/L active chlorine. Hypochlorite or other chlorine-containing compounds were trapped in corrosion products after the surface disinfection treatment with hypochlorite, and this risked influencing subsequent corrosion after the surface disinfection treatment. A life cycle impact assessment suggested ozone treatment to have the lowest negative effects on human health, ecosystems, and resources. Calcium hypochlorite showed the highest negative environmental impact due to its production phase. Our study suggests that ozone surface disinfection treatments are preferable as compared with hypochlorite treatments from corrosion, economic, and environmental perspectives.

Mussel adhesive polymers owe their ability to strongly bind to a large variety of surfaces under water to their high content of 3,4-dihydroxy-l-phenylalanine (DOPA) groups and high positive charge. In this work, we use a set of statistical copolymers that contain medium-length poly(ethylene oxide) side chains that are anchored to the surface in three different ways: by means of (i) electrostatic forces, (ii) catechol groups (as in DOPA), and (iii) the combination of electrostatic forces and catechol groups. A nanotribological scanning probe method was utilized to evaluate the wear resistance of the formed layers as a function of normal load. It was found that the combined measurement of surface topography and stiffness provided an accurate assessment of the wear resistance of such thin layers. In particular, surface stiffness maps allowed us to identify the initiation of wear before a clear topographical wear scar was developed. Our data demonstrate that the molecular and abrasive wear resistance on silica surfaces depends on the anchoring mode and follows the order catechol groups combined with electrostatic forces > catechol groups alone > electrostatic forces alone. The devised methodology should be generally applicable for evaluating wear resistance or "robustness" of thin adsorbed layers on a variety of surfaces.

The manner in which nature has solved lubrication issues has fascinated scientists for centuries, in particular when considering that lubrication is achieved in aqueous media. The most outstanding system in this respect is likely the synovial joint, where close to frictionless motion is realized under different loads and shear rates. This review article focuses on two components present in the synovial area, hyaluronan and phospholipids. We recapitulate what has been learned about their interactions at interfaces from recent experiments, with focus on results obtained using reflectivity techniques at large scale facilities. In parallel, modelling experiments have been carried out and from these efforts new detailed knowledge about how hyaluronan and phospholipids interact has been gained. In this review we combine findings from modelling and experiments to gain deeper insight. Finally, we summarize what has been learned of the lubrication performance of mixtures of phospholipids and hyaluronan., (Copyright © 2019. Published by Elsevier B.V.)

Hyaluronic acid and phospholipids are two components that are present in the synovial fluid, and both are implicated as important facilitators of joint lubrication. In this work we aim to clarify how hyaluronic acid interacts with a phospholipid bilayer through their molecular interactions at the bilayer surface. To this end we performed molecular dynamics simulations of one hyaluronic acid molecule at a phospholipid bilayer in aqueous solution. The simulations were carried out for two aqueous solutions of equal concentrations, containing either NaCl or CaCl 2 . We analyzed hydrogen bonds, hydrophobic contacts and cation mediated bridges to clarify how hyaluoronic acid binds to a phospholipid bilayer. The analysis shows that calcium ions promote longer lasting bonds between the species as they create calcium ion bridges between the carboxylate group of hyaluronic acid and the phosphate group of the phospholipid. This type of additional bonding does not significantly influence the total number of contact created, but rather stabilizes the contact. The presented results can facilitate understanding of the role of hyaluronic acid and phospholipid interactions in terms of lubrication of articular cartilage., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Superhydrophobic surfaces in the Cassie-Baxter wetting state retain an air layer at the surface which prevents liquid water from reaching into the porous surface structure. In this work we explore how addition of ethanol, which reduces the surface tension, influences the wetting properties of superhydrophobic and smooth hydrophobic surfaces. Wetting properties are measured by dynamic contact angles, and the air layer at the superhydrophobic surface is visualized by laser scanning confocal microscopy. Colloidal probe atomic force microscopy measurements between a hydrophobic microsphere and the macroscopic surfaces showed that the presence of ethanol strongly affects the interaction forces. When the macroscopic surface is superhydrophobic, attractive forces extending up to a few micrometers are observed on retraction in water and in 20 vol % ethanol, signifying the presence of a large and growing gas capillary. Submicrometer attractive forces are observed between the probe particle and a smooth hydrophobic surface, and in this case a smaller gas capillary is formed. Addition of ethanol results in markedly different effects between superhydrophobic and hydrophobic surfaces. In particular, we show that the receding contact angle on the superhydrophobic surface is of paramount importance for describing the interaction forces.

The mechanical properties of hydrogels are of importance in many applications, including scaffolds and drug delivery vehicles where the release of drugs is controlled by water transport. While the macroscopic mechanical properties of hydrogels have been reported frequently, there are less studies devoted to the equally important nanomechanical response to local load and shear. Scanning probe methods offer the possibility to gain insight on surface nanomechanical properties with high spatial resolution, and thereby provide fundamental insights on local material property variations. In this work, we investigate the local response to load and shear of poly(2-hydroxyethyl methacrylate) hydrogels with two different cross-linking densities submerged in aqueous solution. The response of the hydrogels to purely normal loads, as well as the combined action of load and shear, was found to be complex due to viscoelastic effects. Our results show that the surface stiffness of the hydrogel samples increased with increasing load, while the tip-hydrogel adhesion was strongly affected by the load only when the cross-linking density was low. The combined action of load and shear results in the formation of a temporary sub-micrometer hill in front of the laterally moving tip. As the tip pushes against such hills, a pronounced stick-slip effect is observed for the hydrogel with low cross-linking density. No plastic deformation or permanent wear scar was found under our experimental conditions.

The molecular mechanisms responsible for outstanding lubrication of natural systems, like articular joints, have been the focus of scientific research for several decades. One essential aspect is the lubrication under pressure, where it is important to understand how the lubricating entities adapt under dynamic working conditions in order to fulfill their function. We made a structural investigation of a model system consisting of two of the molecules present at the cartilage interface, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine and hyaluronan, at high hydrostatic pressure. Phospholipid layers are found at the cartilage surfaces and are able to considerably reduce friction. Their behavior under load and varied solution conditions is important as pressures of 180 bar are encountered during daily life activities. We focus on how divalent ions, like Ca2+, affect the interaction between DPPC and hyaluronan, as other investigations have indicated that calcium ions influence their interaction. It could be shown that already low amounts of Ca2+ strongly influence the interaction of hyaluronan with DPPC. Our results suggest that the calcium ions increase the amount of adsorbed hyaluronan indicating an increased electrostatic interaction. Most importantly, we observe a modification of the DPPC phase diagram as hyaluronan absorbs to the bilayer which results in an Lα-like structure at low temperatures and a decoupling of the leaflets forming an asymmetric bilayer structure.

Understanding the complex and dynamic nature of calcite surfaces under ambient conditions is important for optimizing industrial applications. It is essential to identify processes, their reversibility, and the relevant properties of CaCO 3 solid-liquid and solid-gas interfaces under different environmental conditions, such as at increased relative humidity (RH). This work elucidates changes in surface properties on freshly cleaved calcite (topography, wettability and surface forces) as a function of time (≤28 h) at controlled humidity (≤3-95 %RH) and temperature (25.5 °C), evaluated with atomic force microscopy (AFM) and contact angle techniques. In the presence of humidity, the wettability decreased, liquid water capillary forces dominated over van der Waals forces, and surface domains, such as hillocks, height about 7.0 Å, and trenches, depth about -3.5 Å, appeared and grew primarily in lateral dimensions. Hillocks demonstrated lower adhesion and higher deformation in AFM experiments. We propose that the growing surface domains were formed by ion dissolution and diffusion followed by formation of hydrated salt of CaCO 3 . Upon drying, the height of the hillocks decreased by about 50% suggesting their alteration into dehydrated or less hydrated CaCO 3 . However, the process was not entirely reversible and crystallization of new domains continued at a reduced rate., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

The formation of a bridging gas meniscus via cavitation or nanobubbles is considered the most likely origin of the submicrometer long-range attractive forces measured between hydrophobic surfaces in aqueous solution. However, the dynamics of the formation and evolution of the gas meniscus is still under debate, in particular, in the presence of a thin air layer on a superhydrophobic surface. On superhydrophobic surfaces the range can even exceed 10 μm. Here, we report microscopic images of the formation and growth of a gas meniscus during force measurements between a superhydrophobic surface and a hydrophobic microsphere immersed in water. This is achieved by combining laser scanning confocal microscopy and colloidal probe atomic force microscopy. The configuration allows determination of the volume and shape of the meniscus, together with direct calculation of the Young-Laplace capillary pressure. The long-range attractive interactions acting on separation are due to meniscus formation and volume growth as air is transported from the surface layer.

The adsorption of hydrophilic or amphiphilic multiblock copolymers provides a powerful means to produce well-defined "smart" surfaces, especially if one or several blocks are sensitive to external stimuli. We focus here on an A-B-A-B-A copolymer, where A is a cationic poly((3-acrylamido-propyl)-trimethylammonium chloride) (PAMPTMA) block containing 15 (end blocks) or 30 (middle block) repeat units and B is a neutral thermosensitive water-soluble poly(2-isopropyl-2-oxazoline) (PIPOZ) block with 50 repeat units. X-ray reflectivity and quartz crystal microbalance with dissipation monitoring were employed to study the adsorption of PAMPTMA 15 -PIPOZ 50 -PAMPTMA 30 -PIPOZ 50 -PAMPTMA 15 on silica surfaces. The latter technique was employed at different temperatures up to 50 °C. Surface forces and friction between the two silica surfaces across aqueous pentablock copolymer solutions at different temperatures were determined with the atomic force microscopy colloidal probe force and friction measurements. The cationic pentablock copolymer was found to have a high affinity to the negatively charged silica surface, leading to a thin (2 nm) and rigid adsorbed layer. A steric force was encountered at a separation of around 3 nm from hard wall contact. A capillary condensation of a polymer-rich phase was observed at the cloud point of the solution. The friction forces were evaluated using Amontons' rule modified with an adhesion term.

Exposure to cobalt (Co), chromium (Cr), and nickel (Ni) occurs often via skin contact and from different dental and orthopedic implants. The metal ions bind to proteins, which may induce structural changes and aggregation, with different medical consequences. We investigated human serum albumin (HSA) aggregation in the presence of Co II , Cr III , and/or Ni II ions and/or their nanoparticle precipitates by using scattering, spectroscopic, and imaging techniques, at simulated physiological conditions (phosphate buffered saline - PBS, pH 7.3) using metal salts that did not affect the pH, and at HSA:metal molar ratios of up to 1:8. Co ions formed some solid nanoparticles in PBS at the investigated conditions, as determined by nanoparticle tracking analysis, but the Cr III anions and Ni II ions remained fully soluble. It was found that all metal ions induced HSA aggregation, and this effect was significantly enhanced when a mixture of all three metal ions was present instead of any single type of ion. Thus, the metal ions induce aggregation synergistically. HSA aggregates formed linear structures on a mica surface in the presence of Cr III ions. A clear tendency of aggregation and linearly aligned aggregates was seen in the presence of all three metal ions. Spectroscopic investigations indicated that the majority of the HSA molecules maintained their alpha helical secondary structure and conformation. This study highlights the importance of synergistic effects of metal ions and/or their precipitates on protein aggregation, which are highly relevant for implant materials and common exposures to metals., (Copyright © 2018 The Author(s). Published by Elsevier B.V. All rights reserved.)

Propofol is an amphiphilic small molecule that strongly influences the function of cell membranes, yet data regarding interfacial properties of propofol remain scarce. Here we consider propofol adsorption at the air/water interface as elucidated by means of vibrational sum frequency spectroscopy (VSFS), neutron reflectometry (NR), and surface tensiometry. VSFS data show that propofol adsorbed at the air/water interface interacts with water strongly in terms of hydrogen bonding and weakly in the proximity of the hydrocarbon parts of the molecule. In the concentration range studied there is almost no change in the orientation adopted at the interface. Data from NR show that propofol forms a dense monolayer with a thickness of 8.4 Å and a limiting area per molecule of 40 Å2, close to the value extracted from surface tensiometry. The possibility that islands or multilayers of propofol form at the air/water interface is therefore excluded as long as the solubility limit is not exceeded. Additionally, measurements of the 1H NMR chemical shifts demonstrate that propofol does not form dimers or multimers in bulk water up to the solubility limit.

Correction for 'Physical crosslinking of hyaluronic acid in the presence of phospholipids in an aqueous nano-environment' by Piotr Bełdowski et al., Soft Matter, 2018, DOI: 10.1039/c8sm01388h.

Hyaluronic acid and phospholipids are two components in the synovial joint cavity that contribute to joint lubrication synergistically. Molecular dynamics simulations were performed and hydrogen bonds in hyaluronic acid were analyzed to identify specific sites that are responsible for its physical cross-linking. Two molecular masses of hyaluronic acid, 10 kDa and 160 kDa, were considered. We use molecular dynamics simulations and the small world network approach to investigate dynamic couplings using a distance map applied to oxygen atoms in a chain of hyaluronic acid in the presence of phospholipids and water. The distance characterizing the coupling can be defined in various ways to bring out the most evident differences between various scenarios of the polymer chain conformation We show herein a physical distance understood as H-bond length and classes of these distances which are defined in a coarse-grained picture of the molecule. Simulation results indicate that addition of phospholipids has little influence on hyaluronic acid crosslinking. However, longer chains and addition of lipids promote appreciably long lasting (resilient) networks that may be of importance in biological systems. Specific sites for hydrogen bonding of phospholipids to hyaluronic acid have also been identified.

Mucins are high molar mass glycoproteins that assume an extended conformation and can assemble into mucus hydrogels that protect our mucosal epithelium. In nature, the challenging task of generating a mucus layer, several hundreds of micrometers in thickness, from micrometer-sized cells is elegantly solved by the condensation of mucins inside vesicles and their on-demand release from the cells where they suddenly expand to form the extracellular mucus hydrogel. We aimed to recreate and control the process of compaction for mucins, the first step toward a better understanding of the process and creating biomimetic in vivo delivery strategies of macromolecules. We found that by adding glycerol to the aqueous solvent, we could induce drastic condensation of purified mucin molecules, reducing their size by an order of magnitude down to tens of nanometers in diameter. The condensation effect of glycerol was fully reversible and could be further enhanced and partially stabilized by cationic cross-linkers such as calcium and polylysine. The change of structure of mucins from extended molecules to nano-sized particles in the presence of glycerol translated into macroscopic rheological changes, as illustrated by a dampened shear-thinning effect with increasing glycerol concentration. This work provides new insight into mucin condensation, which could lead to new delivery strategies mimicking cell release of macromolecules condensed in vesicles such as mucins and heparin.

Vibrational sum frequency spectroscopy (VSFS) complemented by surface pressure isotherm and neutron reflectometry (NR) experiments were employed to investigate the interactions between propofol, a small amphiphilic molecule that currently is the most common general anaesthetic drug, and phospholipid monolayers. A series of biologically relevant saturated phospholipids of varying chain length from C 18 to C 14 were spread on either pure water or propofol (2,6-bis(1-methylethyl)phenol) solution in a Langmuir trough, and the change in the molecular structure of the film, induced by the interaction with propofol, was studied with respect to the surface pressure. The results from the surface pressure isotherm experiments revealed that propofol, as long as it remains at the interface, enhances the fluidity of the phospholipid monolayer. The VSF spectra demonstrate that for each phospholipid the amount of propofol in the monolayer region decreases with increasing surface pressure. Such squeeze out is in contrast to the enhanced interactions that can be exhibited by more complex amphiphilic molecules such as peptides. At surface pressures of 22-25 mN m -1 , which are relevant for biological cell membranes, most of the propofol has been expelled from the monolayer, especially in the case of the C 16 and C 18 phospholipids that adopt a liquid condensed phase packing of its alkyl tails. At lower surface pressures of 5 mN m -1 , the effect of propofol on the structure of the alkyl tails is enhanced when the phospholipids are present in a liquid expanded phase. Specifically, for the C 16 phospholipid, NR data reveal that propofol is located exclusively in the head group region, which is rationalized in the context of previous studies. The results imply a non-homogeneous distribution of propofol in the plane of real cell membranes, which is an inference that requires urgent testing and may help to explain why such low concentration of the drug are required to induce general anaesthesia., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Polymersomes are hollow spheres self-assembled from amphiphilic block copolymers of certain molecular architecture. Whilst they have been widely studied for biomedical applications, relatively few studies have reported their interfacial properties. In particular, lubrication by polymersomes has not been previously reported. Here, interfacial properties of polymersomes self-assembled from poly(butadiene)-poly(ethylene oxide) (PBD-PEO; molecular weight 10,400 g mol -1 ) have been studied at both hydrophilic and hydrophobic surfaces. Their morphology at silica and mica surfaces was imaged with quantitative nanomechanical property mapping atomic force microscopy (QNM AFM), and friction and surface forces they mediate under confinement between two surfaces were studied using colloidal probe AFM (CP-AFM). We find that the polymersomes remained intact but adopted flattened conformation once adsorbed to mica, with a relatively low coverage. However, on silica these polymersomes were unstable, rupturing to form donut shaped residues or patchy bilayers. On a silica surface hydrophobized with a 19 nm polystyrene (PS) film, the polymer vesicles formed a more stable layer with a higher surface coverage as compared to the hydrophilic surface, and the interfacial structure also evolved over time. Moreover, friction was greatly reduced on hydrophobized silica surfaces in the presence of polymersomes, suggesting their potential as effective aqueous lubricants., (Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.)

To slide surfaces against each other with application of a minimum force and minimum wear has been important since ancient times, and it remains equally important today. The use of oil-soluble lubricants is widely spread in technology, whereas living organisms have developed water-soluble lubricants to facilitate sliding motions. In this perspective article we focus on water-based lubrication in the boundary lubrication regime, and particularly lubrication synergies. This focus has, of course, found inspiration from the outstanding lubrication properties of synovial joints. It has ignited significant amount of research, mostly aimed at answering the question: Which molecule is the magic biolubricant? Different research groups have advocated different answers, and the debate has been intensive. In this article we argue that the question in itself is inappropriate. The relevant question is rather the following: How do molecules work in synergy to provide superior lubrication?

Surface science, which spans the fields of chemistry, physics, biology and materials science, requires information to be obtained on the local properties and property variations across a surface. This has resulted in the development of different scanning probe methods that allow the measurement of local chemical composition and local electrical and mechanical properties. These techniques have led to rapid advancement in fundamental science with applications in areas such as composite materials, corrosion protection and wear resistance. In this perspective article, we focussed on the branch of scanning probe methods that allows the determination of surface nanomechanical properties. We discussed some different AFM-based modes that were used for these measurements and provided illustrative examples of the type of information that could be obtained. We also discussed some of the difficulties encountered during such studies.

Hypothesis: Synovial surfaces are lubricated by biomolecular aggregates that act in synergy, and lubricin is one key biolubricant. Its molecular structure allows extensive hydration and this is conducive to its lubrication performance. However, in order to fullfil its lubrication function it needs to be anchored and oriented on the surface in a proper way. We suggest that cartilage oligomeric matrix protein (COMP) is one of the biomolecules that promotes anchoring of lubricin in a fashion that facilitates lubrication., Experiments: Weakly hydrophobic poly(methyl methacrylate) (PMMA) surfaces were coated by COMP and lubricin, individually and in combinations. Adsorption was investigated using a quartz crystal microbalance, and friction between the biopolymer-coated surfaces was determined by employing the atomic force microscope-colloidal probe technique., Findings: It was found that COMP facilitated firm directed attachment of lubricin in a manner that resulted in low friction forces, significantly lower than what was achieved when lubricin was directly adsorbed to PMMA. Evidently, COMP provides means for lubricin to attach strongly and in a favourable conformation for efficient lubrication of this surface. We suggest that our findings can be extrapolated to cartilage surfaces, where co-localization of COMP and lubricin has been demonstrated., (Copyright © 2017 The Author(s). Published by Elsevier Inc. All rights reserved.)

In polymer nanocomposites, particle-polymer interactions influence the properties of the matrix polymer next to the particle surface, providing different physicochemical properties than in the bulk matrix. This region is often referred to as the interphase, but detailed characterization of its properties remains a challenge. Here we employ two atomic force microscopy (AFM) force methods, differing by a factor of about 15 in probing rate, to directly measure the surface nanomechanical properties of the transition region between filler particle and matrix over a controlled temperature range. The nanocomposite consists of poly(ethyl methacrylate) (PEMA) and poly(isobutyl methacrylate) (PiBMA) with a high concentration of hydrophobized silica nanoparticles. Both AFM methods demonstrate that the interphase region around a 40-nm-sized particle located on the surface of the nanocomposite could extend to 55-70nm, and the interphase exhibits a gradient distribution in surface nanomechanical properties. However, the slower probing rate provides somewhat lower numerical values for the surface stiffness. The analysis of the local glass transition temperature (T g ) of the interphase and the polymer matrix provides evidence for reduced stiffness of the polymer matrix at high particle concentration, a feature that we attribute to selective adsorption. These findings provide new insight into understanding the microstructure and mechanical properties of nanocomposites, which is of importance for designing nanomaterials., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Interfacial properties of two brush-with-anchor mucins, C-P55 and C-PSLex, have been investigated at the aqueous solution/poly(methyl methacrylate) (PMMA) interface. Both are recombinant mucin-type fusion proteins, produced by fusing the glycosylated mucin part of P-selectin glycoprotein ligand-1 (PSLG-1) to the Fc part of a mouse immunoglobulin in two different cells. They are mainly expressed as dimers upon production. Analysis of the O-glycans shows that the C-PSLex mucin has the longer and more branched side chains, but C-P55 has slightly higher sialic acid content. The adsorption of the mucins to PMMA surfaces was studied by quartz crystal microbalance with dissipation. The sensed mass, including the adsorbed mucin and water trapped in the layer, was found to be similar for these two mucin layers. Atomic force microscopy with colloidal probe was employed to study surface and friction forces between mucin-coated PMMA surfaces. Purely repulsive forces of steric origin were observed between mucin layers on compression, whereas a small adhesion was detected between both mucin layers on decompression. This was attributed to chain entanglement. The friction force between C-PSLex-coated PMMA is lower than that between C-P55-coated PMMA at low loads, but vice versa at high loads. We discuss our results in terms of the differences in the glycosylation composition of these two mucins.

Phospholipids and hyaluronan have been implied to fulfil important roles in synovial joint lubrication. Since both components are present in synovial fluid, self-assembly structures formed by them should also be present. We demonstrate by small angle X-ray scattering that hyaluronan associates with the outer shell of dipalmitoylphophatidylcholine (DPPC) vesicles in bulk solution. Further, we follow adsorption to silica from mixed hyaluronan/DPPC vesicle solution by Quartz Crystal Microbalance with Dissipation measurements. Atomic Force Microscope imaging visualises the adsorbed layer structure consisting of non-homogeneous phospholipid bilayer with hyaluronan/DPPC aggregates on top. The presence of these aggregates generates a long-range repulsive surface force as two such surfaces are brought together. However, the aggregates are easily deformed, partly rearranged into multilayer structures and partly removed from between the surfaces under high loads. These layers offer very low friction coefficient (<0.01), high load bearing capacity (≈23MPa), and self-healing ability. Surface bound DPPC/hyaluronan aggregates provide a means for accumulation of lubricating DPPC molecules on sliding surfaces., (Copyright © 2016 The Author(s). Published by Elsevier Inc. All rights reserved.)

Equilibration in adsorbing polymer systems can be very slow, leading to different physical properties at a given condition depending on the pathway that was used to reach this state. Here we explore this phenomenon using a diblock copolymer consisting of a cationic anchor block and a thermoresponsive block of poly(2-isopropyl-2-oxazoline), PIPOZ. We find that at a given temperature different polymer chain densities at the silica surface are achieved depending on the previous temperature history. We explore how this affects surface and friction forces between such layers using the atomic force microscope colloidal probe technique. The surface forces are purely repulsive at temperatures <40°C. A local force minimum at short separation develops at 40°C and a strong attraction due to capillary condensation of a polymer-rich phase is observed close to the bulk phase separation temperature. The friction forces decrease in the cooling stage due to rehydration of the PIPOZ chain. A consequence of the adsorption hysteresis is that the friction forces measured at 25°C are significantly lower after exposure to a temperature of 40°C than prior to heating, which is due to higher polymer chain density on the surface after heating., (Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.)