Real-time visualisation of ion exchange in molecularly confined spaces where electric double layers overlap.

Ion interactions with interfaces and transport in confined spaces, where electric double layers overlap, are essential in many areas, ranging from crevice corrosion to understanding and creating nano-fluidic devices at the sub 10 nm scale. Tracking the spatial and temporal evolution of ion exchange, as well as local surface potentials, in such extreme confinement situations is both experimentally and theoretically challenging. Here, we track in real-time the transport processes of ionic species (LiClO4) confined between a negatively charged mica surface and an electrochemically modulated gold surface using a high-speed in situ sensing Surface Forces Apparatus. With millisecond temporal and sub-micrometer spatial resolution we capture the force and distance equilibration of ions in the confinement of D ≈ 2-3 nm in an overlapping electric double layer (EDL) during ion exchange. Our data indicate that an equilibrated ion concentration front progresses with a velocity of 100-200 µm s-1 into a confined nano-slit. This is in the same order of magnitude and in agreement with continuum estimates from diffusive mass transport calculations. We also compare the ion structuring using high resolution imaging, molecular dynamics simulations, and calculations based on a continuum model for the EDL. With this data we can predict the amount of ion exchange, as well as the force between the two surfaces due to overlapping EDLs, and critically discuss experimental and theoretical limitations and possibilities.

Lubricants for osteoarthritis treatment: From natural to bioinspired and alternative strategies.

Osteoarthritis is the most common degenerative and highly prevalent joint disease, characterized by progressive loss and destruction of articular cartilage. The damaged cartilage surface has an increased friction, which causes patients to suffer from serious pain. Restoring the lubrication ability of the joint is central to the treatment of osteoarthritis, a key topic in medical research. A variety of lubricants have been designed to reduce friction in joints and promote cartilage tissue repair to alleviate the symptoms of osteoarthritis. Herein, we review the recent progress of lubricants from the three perspectives of natural, bioinspired, and alternative strategies for osteoarthritis treatment, as well as the structural characterization and lubrication properties of such lubricants. Specifically, natural lubricants include glycosaminoglycans, lubricin and lipids in joints, bioinspired lubricants include scaffolds mimicking hyaluronic acid or lubricin, and alternative lubricants include modified lubricants based on hyaluronic acid, lipids, nanoparticles, and peptides. We also discuss the current challenges and long-term perspectives for further research in this area.

Recombinant lubricin improves anti-adhesive, wear protection, and lubrication of collagen II surface.

Camptodactyly-arthropathy-coxa vara-pericarditis syndrome (CACP) is a joint disease caused by a lack of lubricin, resulting in failed lubrication and abnormal deposition at the cartilage surface. Injection of recombinant lubricin (R-LUB) is a promising approach to improve the symptoms of the disease. However, the antifouling and lubrication properties of R-LUB on cartilage surfaces have not yet been studied. Here, the adsorption and lubrication behavior of a type II collagen (COL II) mimicking the cartilage surface upon R-LUB injection was followed by surface plasmon resonance spectroscopy and surface forces apparatus. The results indicated R-LUB can bind well on a COL II surface and COL II/R-LUB complex layer exhibited ultralow nonspecific adsorption of BSA (3.25 ng/cm2) and LYS (0.26 ng/cm2) compared to those of the COL II layer (32.7 ng/cm2, 7.26 ng/cm2). Normal force measurements indicated there was always a repulsive force between COL II/R-LUB complex and different surfaces with -COO-, -NH3+, and -CH3 groups. Likewise, COL II had a high coefficient of friction (∼0.48) with surface damage at 2 µm/s and a wear pressure of 1.56 MPa, while that of COL II/R-LUB complex was down to ∼0.008-0.13 with surface damage at 13 µm/s and a wear pressure of 11.96 MPa, which was 7.7 times higher than for COL II. Hence, R-LUB may act as an anti-adhesive and lubrication layer adsorbed on COL II surfaces to prevent direct contact. Our findings provide fundamental insights into the adsorption and lubrication behavior for understanding biological lubrication, especially the potential supplementation of R-LUB for treating CACP disease.

Mussel adhesion: A fundamental perspective on factors governing strong underwater adhesion.

Protein-based underwater adhesives of marine organisms exhibit extraordinary binding strength in high salinity based on utilizing a variety of molecular interaction mechanisms. These include acid-base interactions, bidentate bindings or complex hydrogen bonding interactions, and electrochemical manipulation of interfacial bonding. In this Perspective, we briefly review recent progress in the field, and we discuss how interfacial electrochemistry can vary interfacial forces by concerted tuning of surface charging, hydration forces, and tuning of the interfacial ion concentration. We further discuss open questions, controversial findings, and new paths into understanding and utilizing redox-proteins and derived polymers for enhancing underwater adhesion in a complex salt environment.

Visualization of Ion|Surface Binding and In Situ Evaluation of Surface Interaction Free Energies via Competitive Adsorption Isotherms.

Function and properties at biologic as well as technological interfaces are controlled by a complex and concerted competition of specific and unspecific binding with ions and water in the electrolyte. It is not possible to date to directly estimate by experiment the interfacial binding energies of involved species in a consistent approach, thus limiting our understanding of how interactions in complex (physiologic) media are moderated. Here, we employ a model system utilizing polymers with end grafted amines interacting with a negatively charged mica surface. We measure interaction forces as a function of the molecule density and ion concentration in NaCl solutions. The measured adhesion decreases by about 90%, from 0.01 to 1 M electrolyte concentration. We further demonstrate by molecular resolution imaging how ions increasingly populate the binding surface at elevated concentrations, and are effectively competing with the functional group for a binding site. We demonstrate that a competing Langmuir isotherm model can describe this concentration-dependent competition. Further, based on this model we can quantitatively estimate ion binding energies, as well as binding energy relationships at a complex solid|liquid interface. Our approach enables the extraction of thermodynamic interaction energies and kinetic parameters of ionic species during monolayer level interactions at a solid|liquid interface, which to-date is impossible with other techniques.

Mechanistic understanding of catechols and integration into an electrochemically cross-linked mussel foot inspired adhesive hydrogel.

Catechol reaction mechanisms form the basis of marine mussel adhesion, allowing for bond formation and cross-linking in wet saline environments. To mimic mussel foot adhesion and develop new bioadhesive underwater glues, it is essential to understand and learn to control their redox activity as well as their chemical reactivity. Here, we study the electrochemical characteristics of functionalized catechols to further understand their reaction mechanisms and find a stable and controllable molecule that we subsequently integrate into a polymer to form a highly adhesive hydrogel. Contradictory to previous hypotheses, 3,4-dihydroxy-L-phenylalanine is shown to follow a Schiff-base reaction whereas dopamine shows an intramolecular ring formation. Dihydrocaffeic acid proved to be stable and was substituted onto a poly(allylamine) backbone and electrochemically cross-linked to form an adhesive hydrogel that was tested using a surface forces apparatus. The hydrogel's compression and dehydration dependent adhesive strength have proven to be higher than in mussel foot proteins (mfp-3 and mfp-5). Controlling catechol reaction mechanisms and integrating them into stable electrochemically depositable macroscopic structures is an important step in designing new biological coatings and underwater and biomedical adhesives.

Hydration Forces Dominate Surface Charge Dependent Lipid Bilayer Interactions under Physiological Conditions.

Lipid bilayer interactions are essential to a vast range of biological functions, such as intracellular transport mechanisms. Surface charging mediated by concentration dependent ion adsorption and desorption on lipid headgroups alters electric double layers as well as van der Waals and steric hydration forces of interacting bilayers. Here, we directly measure bilayer interactions during charge modulation in a symmetrically polarized electrochemical three-mirror interferometer surface forces apparatus. We quantify polarization and concentration dependent hydration and electric double layer forces due to cation adsorption/desorption. Our results demonstrate that exponential hydration layer interactions effectively describe surface potential dependent surface forces due to cation adsorption at high salt concentrations. Hence, electric double layers of lipid bilayers are exclusively dominated by inner Helmholtz charge regulation under physiological conditions. These results are important for rationalizing bilayer behavior under physiological conditions, where charge and concentration modulation may act as biological triggers for function and signaling.

Solid-supported lipid bilayers - A versatile tool for the structural and functional characterization of membrane proteins.

The cellular membrane is central to the development of single-and multicellular life, as it separates the delicate cellular interior from the hostile environment. It exerts tight control over entry and exit of substances, is responsible for signaling with other cells in multicellular organisms and prevents pathogens from entering the cell. In the case of bacteria and viruses, the cellular membrane also hosts the proteins enabling invasion of the host organism. In a very real sense therefore, the cellular membrane is central to all life. The study of the cell membrane and membrane proteins in particular has therefore attracted significant attention. Due to the enormous variety of tasks performed by the membrane, it is a highly complex and challenging structure to study. Ideally, membrane components would be studied in isolation from this environment, but unlike water soluble proteins, the amphiphilic environment provided by the cellular membrane is key to the structure and function of the cell membrane. Therefore, model membranes have been developed to provide an environment in which a membrane protein can be studied. This review presents a set of tools that enable the comprehensive characterization of membrane proteins: electrochemical tools, surface plasmon resonance, neutron scattering, the surface forces apparatus and atomic force microscopy are discussed, with a particular focus on experimental technique and data evaluation.

Adsorption and Diffusion Moderated by Polycationic Polymers during Electrodeposition of Zinc.

Electrodeposition of metals is relevant to much of materials research including catalysis, batteries, antifouling, and anticorrosion coatings. The sacrificial characteristics of zinc used as a protection for ferrous substrates is a central corrosion protection strategy used in automotive, aviation, and DIY industries. Zinc layers are often used for protection by application to a base metal in a hot dip galvanizing step; however, there is a significant interest in less energy and material intense electroplating strategies for zinc. At present, large-scale electroplating is mostly done from acidic zinc solutions, which contain potentially toxic and harmful additives. Alkaline electroplating of zinc offers a route to using environment-friendly green additives. Within the scope of this study an electrolyte containing soluble zinc hydroxide compound and a polyquarternium polymer as additive were studied during zinc deposition on gold model surfaces. Cyclic voltammetry experiments and in-situ electrochemical quartz crystal microbalance with dissipation (QCM-D) measurements were combined to provide a detailed understanding of fundamental steps that occur during polymer-mediated alkaline zinc electroplating. Data indicate that a zincate-loaded polymer can adsorb within the inner sphere of the electric double layer, which lowers the electrostatic penalty of the zincate approach to a negatively charged surface. X-ray photoelectron spectroscopy also supports the assertion that the zincate-loaded polymer is brought tightly to the surface. We also find an initial polymer depletion followed by an active deposition moderation via control of the zincate diffusion through the adsorbed polymer.

Gelation enabled charge separation following visible light excitation using self-assembled perylene bisimides.

Perylene bisimides (PBIs) can be functionalised to enable controlled aggregation into complex supramolecular structures and are promising materials for photovoltaic and solar fuel applications. Amino acid appended PBIs such as PBI-alanine (PBI-A) have been found to form photoconductive films containing worm-like structures that enable charge transport. However, despite being strong chromophores in the visible region, when PBI-A films are prepared by drying down solutions, activity only occurs under UV illumination. This limits potential applications. The requirement for UV illumination has previously been suggested to be due to the large ion-pair energy in the low dielectric environment of the dried samples. Hydrogel films, rehydrated xerogels and dry xerogels of PBI-A can also be prepared offering an ideal sample set to examine the influence of hydration on charge-separation. Using transient absorption (TA) spectroscopy, we demonstrate a correlation between water content and efficiency of generation of long-lived charge separated states within the PBI-A materials, highlighting their potential, particularly for light-driven water splitting.

Interaction Profiles and Stability of Rigid and Polymer-Tethered Lipid Bilayer Models at Highly Charged and Highly Adhesive Contacts.

Understanding interaction force versus distance profiles of supported lipid bilayers (SLBs) is relevant to a number of areas, which rely on these model systems, including, e.g., characterization of ligand/receptor interactions or bacterial adhesion. Here, the stability of 4 different SLB architectures was compared using the surface forces apparatus (SFA) and atomic force microscopy (AFM). Specifically, the outer envelope of the bilayer systems remained constant as 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). The inner layer was varied between DPPC and 1,2-dipalmitoyl-3-trimethylammonium-propane (DPTAP) both on mica, and self-assembled monolayers (SAMs) of hexadecanethiol and the polymer-tethered diphytanylglycerol-tetraethylene glycol-lipoid acid (DPhyTL) on smooth gold surfaces. In that same order these gave an increasing strength of interaction between the inner layer and the supporting substrate and hence improved stability under highly adhesive conditions. Detachment profiles from highly charged and highly adhesive contacts were characterized, and approach characteristics were fitted to DLVO models. We find increasing stability under highly adhesive loads, approaching the hydrophobic limit of the adhesive energy between the inner and outer layers for the SAM-based systems. For all four SLBs we further compare AFM surface topographies, which strongly depend on preparation conditions, and the DLVO fitting of the SFA approach curves finds a strong charge regulation behavior during interaction, dependent on the particular model system. In addition, we find undulation characteristics during approach and separation. The increased stability of the complex architectures on a gold support makes these model systems an ideal starting point for studying more complex strongly adhesive/interacting systems, including, for example, ligand/receptor interactions, biosensing interactions, or cell/surface interactions.

Optimizing multiple beam interferometry in the surface forces apparatus: Novel optics, reflection mode modeling, metal layer thicknesses, birefringence, and rotation of anisotropic layers.

Multiple beam interferometry (MBI) evolved as a powerful tool for the simultaneous evaluation of thin film thicknesses and refractive indices in Surface Forces Apparatus (SFA) measurements. However, analysis has relied on simplifications for providing fast or simplified analysis of recorded interference spectra. Here, we describe the implementation of new optics and a generalized fitting approach to 4 × 4 transfer matrix method simulations for the SFA. Layers are described by dispersive complex refractive indices, thicknesses, and Euler angles that can be fitted, providing modeling for birefringent or colored layers. Normalization of data by incident light intensities is essential for the implementation of a fitting approach. Therefore, a modular optical system is described that can be retrofit to any existing SFA setup. Real-time normalization of spectra by white light is realized, alignment procedures are considerably simplified, and direct switching between transmission and reflection modes is possible. A numerical approach is introduced for constructing transfer matrices for birefringent materials. Full fitting of data to the simulation is implemented for arbitrary multilayered stacks used in SFA. This enables self-consistent fitting of mirror thicknesses, birefringence, and relative rotation of anisotropic layers (e.g., mica), evaluation of reflection and transmission mode spectra, and simultaneous fitting of thicknesses and refractive indices of media confined between two surfaces. In addition, a fast full spectral fitting method is implemented for providing a possible real-time analysis with up to 30 fps. We measure and analyze refractive indices of confined cyclohexane, the thickness of lipid bilayers, the thickness of metal layers, the relative rotation of birefringent materials, contact widths, as well as simultaneous fitting of both reflection and transmission mode spectra of typical interferometers. Our analyses suggest a number of best practices for conducting SFA and open MBI in an SFA for increasingly complex systems, including metamaterials, multilayered anisotropic layers, and chiral layers.

Synthesis and electrokinetics of cationic spherical nanoparticles in salt-free non-polar media.

Cationic diblock copolymer nanoparticles have been prepared in n-dodecane via polymerization-induced self-assembly (PISA). A previously reported poly(stearyl methacrylate)-poly(benzyl methacrylate) (PSMA-PBzMA) PISA formulation (Chem. Sci. 2016, 7, 5078-5090) was modified by statistically copolymerizing an oil-soluble cationic methacrylic monomer, (2-(methacryloyloxy)ethyl)trimethylammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, with either SMA or BzMA, to produce either charged shell or charged core nanoparticles. The electrokinetics were studied as a function of many variables (function of volume function, particle size, solvent viscosity, and number of ions per chain). These data are consistent with electrophoresis controlled by counterion condensation, which is typically observed in salt-free media. However, there are several interesting and unexpected features of interest. In particular, charged shell nanoparticles have a lower electrophoretic mobility than the equivalent charged core nanoparticles, and the magnitude of the electrophoretic mobility increases as the fraction of cationic stabilizer chains in the shell layer is reduced. These results show that cationic PSMA-PBzMA spheres provide an interesting new example of electrophoretic nanoparticles in non-polar solvents. Moreover, they should provide an ideal model system to evaluate new electrokinetic theories.

Self-sorted Oligophenylvinylene and Perylene Bisimide Hydrogels.

We describe two component hydrogels with networks composed of self-sorted fibres. The component gelators are based on 1,4-distyrylbenzene (OPV3) and perylene bisimide (PBI) units. Self-sorted gels can be formed by a slow decrease in pH, which leads to sequential assembly. We demonstrate self-sorting by NMR, rheology and small angle X-ray scattering (SAXS). Photoconductive xerogels can be prepared by drying these gels. The wavelength response of the xerogel is different to that of the PBI alone.

Drying Affects the Fiber Network in Low Molecular Weight Hydrogels.

Low molecular weight gels are formed by the self-assembly of a suitable small molecule gelator into a three-dimensional network of fibrous structures. The gel properties are determined by the fiber structures, the number and type of cross-links and the distribution of the fibers and cross-links in space. Probing these structures and cross-links is difficult. Many reports rely on microscopy of dried gels (xerogels), where the solvent is removed prior to imaging. The assumption is made that this has little effect on the structures, but it is not clear that this assumption is always (or ever) valid. Here, we use small angle neutron scattering (SANS) to probe low molecular weight hydrogels formed by the self-assembly of dipeptides. We compare scattering data for wet and dried gels, as well as following the drying process. We show that the assumption that drying does not affect the network is not always correct.

On the syneresis of an OPV functionalised dipeptide hydrogel.

We describe a new dipeptide hydrogel based on an oligophenylene vinylene core. After gelation, the initial network evolves, expelling solvent and resulting in syneresis. We describe this process and the effects in the bulk properties of the material.

Linking micellar structures to hydrogelation for salt-triggered dipeptide gelators.

Some functionalised dipeptides can form hydrogels when salts are added to solutions at high pH. We have used surface tension, conductivity, rheology, optical, confocal and scanning electron microscopy, (1)H NMR and UV-Vis spectroscopy measurements to characterise fully the phase behaviour of solutions of one specific gelator, 2NapFF, at 25 °C at pH 10.5. We show that this specific naphthalene-dipeptide undergoes structural transformations as the concentration is increased, initially forming spherical micelles, then worm-like micelles, followed by association of these worm-like micelles. On addition of a calcium salt, gels are generally formed as long as worm-like micelles are initially present in solution, although there are structural re-organisations that occur at lower concentrations, allowing gelation at lower than expected concentration. Using IR and SANS, we show the differences between the structures present in the solution and hydrogel phases.

Measuring the structure of thin soft matter films under confinement: a surface-force type apparatus for neutron reflection, based on a flexible membrane approach.

A unique surface force type apparatus that allows the investigation of a confined thin film using neutron reflection is described. The central feature of the setup consists of a solid substrate (silicon) and a flexible polymer membrane (Melinex(®)). We show that inflation of the membrane against the solid surface provides close and even contact between the interfaces over a large surface area. Both heavy water and air can be completely squeezed out from between the flexible film and the solid substrate, leaving them in molecular contact. The strength of confinement is controlled by the pressure used to inflate the membrane. Dust provides a small problem for this approach as it can get trapped between membrane and substrate to prevent a small part of the membrane from making good contact with the substrate. This results in the measured neutron reflectivity containing a small component of an unwanted reflection, between 10% and 20% at low confining pressures (1 bar) and between 1% and 5% at high confining pressures (5 bar). However, we show that this extra signal does not prevent good and clear information on the structure of thin films being extracted from the neutron reflectivity. The effects of confinement are illustrated with data from a poly(vinyl pyrollidone) gel layer in water, a polyelectrolyte multilayer in water, and with data from a stack of supported lipid-bilayers swollen with D(2)O vapor. The data demonstrates the potential of this apparatus to provide information on the structure of thin films under confinement for a known confining pressure.

Surface modification of polyethylene with multi-end-functional polyethylene additives.

We have prepared and characterized a series of multifluorocarbon end-functional polyethylene additives, which when blended with polyethylene matrices increase surface hydrophobicity and lipophobicity. Water contact angles of >112° were observed on spin-cast blended film surfaces containing less than 1% fluorocarbon in the bulk, compared to ~98° in the absence of any additive. Crystallinity in these films gives rise to surface roughness that is an order of magnitude greater than is typical for amorphous spin-cast films but is too little to give rise to superhydrophobicity. X-ray photoelectron spectroscopy (XPS) confirms the enrichment of the multifluorocarbon additives at the air surface by up to 80 times the bulk concentration. Ion beam analysis was used to quantify the surface excess of the additives as a function of composition, functionality, and molecular weight of either blend component. In some cases, an excess of the additives was also found at the substrate interface, indicating phase separation into self-stratified layers. The combination of neutron reflectometry and ion beam analysis allowed the surface excess to be quantified above and below the melting point of the blended films. In these films, where the melting temperatures of the additive and matrix components are relatively similar (within 15 °C), the surface excess is almost independent of whether the blended film is semicrystalline or molten, suggesting that the additive undergoes cocrystallization with the matrix when the blended films are allowed to cool below the melting point.