Quantitative Comparison of the Hydration Capacity of Surface-Bound Dextran and Polyethylene Glycol.

We have quantified and compared the hydration capacity (i.e., capability to incorporate water molecules) of the two surface-bound hydrophilic polymer chains, dextran (dex) and poly(ethylene glycol) (PEG), in the form of poly(l-lysine)-graft-dextran (PLL-g-dex) and poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG), respectively. The copolymers were attached to a negatively charged silica-titania surface through the electrostatic interaction between the PLL backbone and the surface in neutral aqueous media. While the molecular weights of PLL and PEG were fixed, that of dex and the grafting density of PEG or dex on the PLL were varied. The hydration capacity of the polymer chains was quantified through the combined experimental approach of optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation monitoring (QCM-D) to yield a value for areal solvation (Ψ), i.e., mass of associated solvent molecules within the polymer chains per unit substrate area. For the two series of copolymers with comparable stretched chain lengths of hydrophilic polymers, namely, PLL(20)-g-PEG(5) and PLL(20)-g-dex(10), the Ψ values gradually increased as the initial grafting density on the PLL backbone increased or as g decreased. However, the rate of increase in Ψ was higher for PEG than dextran chains, which was attributed to higher stiffness of the dextran chains. More importantly, the number of water molecules per hydrophilic group was clearly higher for PEG chains. Given that the -CH2CH2O- units that make up the PEG chains form a cage-like structure with 2-3 water molecules, these "strongly bound" water molecules can account for the slightly more favorable behavior of PEG compared to dextran in both aqueous lubrication and antifouling behavior of the copolymers.

Measuring Rolling Friction at the Nanoscale.

Colloidal probe microscopy, a technique whereby a microparticle is affixed at the end of an atomic force microscopy (AFM) cantilever, plays a pivotal role in enabling the measurement of friction at the nanoscale and is of high relevance for applications and fundamental studies alike. However, in conventional experiments, the probe particle is immobilized onto the cantilever, thereby restricting its relative motion against a countersurface to pure sliding. Nonetheless, under many conditions of interest, such as during the processing of particle-based materials, particles are free to roll and slide past each other, calling for the development of techniques capable of measuring rolling friction alongside sliding friction. Here, we present a new methodology to measure lateral forces during rolling contacts based on the adaptation of colloidal probe microscopy. Using two-photon polymerization direct laser writing, we microfabricate holders that can capture microparticles, but allow for their free rotation. Once attached to an AFM cantilever, upon lateral scanning, the holders enable both sliding and rolling contacts between the captured particles and the substrate, depending on the interactions, while simultaneously giving access to normal and lateral force signals. Crucially, by producing particles with optically heterogeneous surfaces, we can accurately detect the presence of rotation during scanning. After introducing the workflow for the fabrication and use of the probes, we provide details on their calibration, investigate the effect of the materials used to fabricate them, and report data on rolling friction as a function of the surface roughness of the probe particles. We firmly believe that our methodology opens up new avenues for the characterization of rolling contacts at the nanoscale, aimed, for instance, at engineering particle surface properties and characterizing functional coatings in terms of their rolling friction.

Polymeric Friction Modifiers: Influence of Anchoring Chemistry on Their Adsorption and Effectiveness.

Correlated adsorption and lubricity have been investigated using polymeric friction modifiers, specifically designed with an oleophilic brush-forming block and an anchoring block of comparable length. Through adsorption, rheology, and friction measurements, we have highlighted the existence of boundary layers, whose molecular organization and mechanical properties govern the frictional behavior. We have demonstrated that changing the anchoring chemistry controls the final ordering in the boundary layer. The stability of the surface anchoring governs the onset of repulsion between the polymer layers and the capacity of the layer to withstand shear. The higher degree of molecular order provided by the most firmly anchored polymer to the surface was thereby responsible for the significant friction reduction observed.

Dispersity within Brushes Plays a Major Role in Determining Their Interfacial Properties: The Case of Oligoxazoline-Based Graft Polymers.

Many synthetic polymers used to form polymer-brush films feature a main backbone with functional, oligomeric side chains. While the structure of such graft polymers mimics biomacromolecules to an extent, it lacks the monodispersity and structural purity present in nature. Here we demonstrate that side-chain heterogeneity within graft polymers significantly influences hydration and the occurrence of hydrophobic interactions in the subsequently formed brushes and consequently impacts fundamental interfacial properties. This is demonstrated for the case of poly(methacrylate)s (PMAs) presenting oligomeric side chains of different length (n) and dispersity. A precise tuning of brush structure was achieved by first synthesizing oligo(2-ethyl-2-oxazoline) methacrylates (OEOXMAs) by cationic ring-opening polymerization (CROP), subsequently purifying them into discrete macromonomers with distinct values of n by column chromatography, and finally obtaining poly[oligo(2-ethyl-2-oxazoline) methacrylate]s (POEOXMAs) by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Assembly of POEOXMA on Au surfaces yielded graft polymer brushes with different side-chain dispersities and lengths, whose properties were thoroughly investigated by a combination of variable angle spectroscopic ellipsometry (VASE), quartz crystal microbalance with dissipation (QCMD), and atomic force microscopy (AFM) methods. Side-chain dispersity, or dispersity within brushes, leads to assemblies that are more hydrated, less adhesive, and more lubricious and biopassive compared to analogous films obtained from graft polymers characterized by a homogeneous structure.

Applying an Oleophobic/Hydrophobic Fluorinated Polymer Monolayer Coating from Aqueous Solutions.

Despite major advancements in the fabrication of low-surface-energy surfaces, the environmental consequences of their fabrication can be a serious issue, particularly in an industrial context. This is especially the case for fluorine-based coatings, which often require fluorinated solvents for their processing and applications. These solvents are not only detrimental to the ozone layer but also represent a potential workplace hazard because they tend to bioaccumulate. We describe the design, synthesis, and characterization of a new fluorinated-polymer coating that can be simply applied to surfaces from an aqueous environment using a dip-coating technique. This was made possible by copolymerizing three different methacrylate monomers, each serving a specific function. Namely, fluorinated methacrylate providing oleo/hydrophobicity, photocleavable polyethylene glycol (PEG) methacrylate promoting water solubility of the copolymer, and thioether-based methacrylate serving as an anchoring unit to a number of different substrates. This copolymer is initially grafted to the surface as a monolayer from an aqueous solvent, after which the system is treated with ultraviolet (UV) light, cleaving away the protecting PEG moieties to yield an oleo/hydrophobic surface.

Oxygen inhibition of free-radical polymerization is the dominant mechanism behind the "mold effect" on hydrogels.

Hydrogel surfaces are of great importance in numerous applications ranging from cell-growth studies and hydrogel-patch adhesion to catheter coatings and contact lenses. A common method to control the structure and mechanical/tribological properties of hydrogel surfaces is by synthesizing them in various mold materials, whose influence has been widely ascribed to their hydrophobicity. In this work, we examine possible mechanisms for this "mold effect" on the surface of hydrogels during polymerization. Our results for polyacrylamide gels clearly rule out the effect of mold hydrophobicity as well as any thermal-gradient effects during synthesis. We show unequivocally that oxygen diffuses out of certain molding materials and into the reaction mixture, thereby inhibiting free-radical polymerization in the vicinity of the molding interface. Removal of oxygen from the system results in homogeneously cross-linked hydrogel surfaces, irrespective of the substrate material used. Moreover, by varying the amount of oxygen at the surface of the polymerizing solutions using a permeable membrane we are able to tailor the surface structures and mechanical properties of PAAm, PEGDA and HEMA hydrogels in a controlled manner.

Roughness-dependent tribology effects on discontinuous shear thickening.

Surface roughness affects many properties of colloids, from depletion and capillary interactions to their dispersibility and use as emulsion stabilizers. It also impacts particle-particle frictional contacts, which have recently emerged as being responsible for the discontinuous shear thickening (DST) of dense suspensions. Tribological properties of these contacts have been rarely experimentally accessed, especially for nonspherical particles. Here, we systematically tackle the effect of nanoscale surface roughness by producing a library of all-silica, raspberry-like colloids and linking their rheology to their tribology. Rougher surfaces lead to a significant anticipation of DST onset, in terms of both shear rate and solid loading. Strikingly, they also eliminate continuous thickening. DST is here due to the interlocking of asperities, which we have identified as "stick-slip" frictional contacts by measuring the sliding of the same particles via lateral force microscopy (LFM). Direct measurements of particle-particle friction therefore highlight the value of an engineering-tribology approach to tuning the thickening of suspensions.

Oxygen Tolerant and Cytocompatible Iron(0)-Mediated ATRP Enables the Controlled Growth of Polymer Brushes from Mammalian Cell Cultures.

The use of zerovalent iron (Fe0)-coated plates, which act both as a source of catalyst and as a reducing agent during surface-initiated atom transfer radical polymerization (SI-ATRP), enables the controlled growth of a wide range of polymer brushes under ambient conditions utilizing either organic or aqueous reaction media. Thanks to its cytocompatibility, Fe0 SI-ATRP can be applied within cell cultures, providing a tool that can broadly and dynamically modify the substrate's affinity toward cells, without influencing their viability. Upon systematically assessing the application of Fe-based catalytic systems in the controlled grafting of polymers, Fe0 SI-ATRP emerges as an extremely versatile technique that could be applied to tune the physicochemical properties of a cell's microenvironments on biomaterials or within tissue engineering constructs.

The hierarchical bulk molecular structure of poly(acrylamide) hydrogels: beyond the fishing net.

The polymeric structure of hydrogels is commonly presented in the literature as resembling a fishing net. However, this simple view cannot fully capture all the unique properties of these materials. Crucial for a detailed description of the bulk structure in free-radical polymerized vinylic hydrogels is a thorough understanding of the cross-linker distribution. This work focuses on the precise role of the tetra-functional cross-linker in the hydrogel system: acrylamide-N,N'-methylenebis(acrylamide). Clusters of crosslinker smaller than 4 nm and their agglomerates, as well as polymer domains with sizes from the 100 nm to the µm-range, have been identified by means of both X-ray and visible-light scattering. Placed in the context of the extensive literature on this system, these observations demonstrate the heterogeneous organisation of the polymer within the hydrogel network structure, and can be accounted for by the different polymerization behavior of the monomer and crosslinker. Together with polymer-network chain-length approximations based on swelling experiments and structural observations with scanning electron microscopy, these results indicate a hierarchical structure of the polymer network surrounding pockets of water.

Synthesis of Polymers Containing Potassium Acyltrifluoroborates (KATs) and Post-polymerization Ligation and Conjugation.

We report the synthesis of monomers for atom-transfer radical polymerization (ATRP) and a reversible addition-fragmentation chain transfer (RAFT) agent bearing trifluoroborate iminiums (TIMs), which are quantitatively converted into potassium acyltrifluoroborates (KATs) after polymerization. The resulting KAT-containing polymers are suitable for rapid amide-forming ligations for both post-polymerization modification and polymer conjugation. The polymer conjugation occurs rapidly, even under dilute (micromolar) aqueous conditions at ambient temperatures, thereby enabling the synthesis of a variety of linear and star-shaped block copolymers. In addition, we applied post-polymerization modification to the covalent linking of a photocaged cyclic antibiotic (gramicidin S) to the side chains of the KAT-containing copolymer. Cellular assays revealed that the polymer-antibiotic conjugate is biocompatible and provides efficient light-controlled release of the antibiotic on demand.

Load and Velocity Dependence of Friction Mediated by Dynamics of Interfacial Contacts.

Studying the frictional properties of interfaces with dynamic chemical bonds advances understanding of the mechanism underlying rate and state laws, and offers new pathways for the rational control of frictional response. In this work, we revisit the load dependence of interfacial chemical-bond-induced (ICBI) friction experimentally and find that the velocity dependence of friction can be reversed by changing the normal load. We propose a theoretical model, whose analytical solution allows us to interpret the experimental data on timescales and length scales that are relevant to experimental conditions. Our work provides a promising avenue for exploring the dynamics of ICBI friction.

Linking Friction and Surface Properties of Hydrogels Molded Against Materials of Different Surface Energies.

Biological tissues subjected to rubbing, such as the cornea and eyelid or articular cartilage, are covered in brushy, hydrated mucous structures in order to reduce the shear stress on the tissue. To mimic such biological tissues, we have prepared polyacrylamide (PAAm) hydrogels with various concentrations of un-cross-linked chains on their surfaces by synthesizing them in molds of different surface energies. The selected molding materials included hydrophilic glass, polyoxymethylene (POM), polystyrene (PS), polyethylene (PE), polypropylene (PP), and polytetrafluoroethylene (PTFE). After synthesis, demolding, and equilibration in water, the elastic modulus at the hydrogel surface decreased with increasing water contact angle of the mold. The softer, brushier surfaces did not completely collapse under compressive pressures up to 10 kPa, remaining better hydrated compared to their denser, cross-linked analogs. The hydrogels with brushier surfaces displayed an order of magnitude lower coefficient of friction than the cross-linked ones, which is attributed to the ability of their near-surface regions to retain larger amounts of liquid at the interface. The characteristic speed-dependent friction of the denser, cross-linked hydrogel surface is compared to the speed-independent friction of the brushy hydrogels and discussed from the perspectives of (elasto)hydrodynamic lubrication, permeability, and shear-induced hydrodynamic penetration depth.

Brushes, Graft Copolymers, or Bottlebrushes? The Effect of Polymer Architecture on the Nanotribological Properties of Grafted-from Assemblies.

Surface-grafted polyzwitterions (PZW) have gained a foothold in the design of synthetic materials that closely mimic the lubricious properties of articular joints in mammals. Besides their chemical composition, the architecture of PZW brushes strongly determines their morphological, nanomechanical, and nanotribological characteristics. This emerges while comparing the properties of linear poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) brushes with those displayed by graft copolymer and bottlebrush brushes, either featuring a low or a high content of PMPC side chains. Surface-initiated atom transfer radical polymerization (SI-ATRP) enabled the synthesis of different branched-brush architectures from multifunctional macroinitiators via multiple grafting steps, and allowed us to modulate their structure by tuning the polymerization conditions. At relatively low grafting densities (σ), long PMPC side segments extend at the interface of bottlebrush and graft copolymer brushes, providing both morphology and lubrication properties comparable to those shown by loosely grafted, linear PMPC brushes. When σ > 0.1 chains nm-2 the effect of the branched-brush architecture on the nanotribological properties of the films became evident. Linear PMPC brushes showed the lowest friction among the studied brush structures, with a coefficient of friction (µ) that reached 1 × 10-4, as measured by atomic force microscopy (AFM). Bottlebrush brushes showed comparatively higher friction, although the high content of hydrophilic PMPC side chains along their backbone substantially improved lubrication compared to that displayed by the more sparsely substituted graft copolymer brushes.

Chemical Design of Non-Ionic Polymer Brushes as Biointerfaces: Poly(2-oxazine)s Outperform Both Poly(2-oxazoline)s and PEG.

The era of poly(ethylene glycol) (PEG) brushes as a universal panacea for preventing non-specific protein adsorption and providing lubrication to surfaces is coming to an end. In the functionalization of medical devices and implants, in addition to preventing non-specific protein adsorption and cell adhesion, polymer-brush formulations are often required to generate highly lubricious films. Poly(2-alkyl-2-oxazoline) (PAOXA) brushes meet these requirements, and depending on their side-group composition, they can form films that match, and in some cases surpass, the bioinert and lubricious properties of PEG analogues. Poly(2-methyl-2-oxazine) (PMOZI) provides an additional enhancement of brush hydration and main-chain flexibility, leading to complete bioinertness and a further reduction in friction. These data redefine the combination of structural parameters necessary to design polymer-brush-based biointerfaces, identifying a novel, superior polymer formulation.

Fabrication and Microscopic and Spectroscopic Characterization of Planar, Bimetallic, Micro- and Nanopatterned Surfaces.

Micropatterns and nanopatterns of gold embedded in silver and titanium embedded in gold have been prepared by combining either photolithography or electron-beam lithography with a glue-free template-stripping procedure. The obtained patterned surfaces have been topographically characterized using atomic force microscopy and scanning electron microscopy, showing a very low root-mean-square roughness (<0.5 nm), high coplanarity between the two metals (maximum height difference ≈ 2 nm), and topographical continuity at the bimetallic interface. Spectroscopic characterization using X-ray photoelectron spectroscopy (XPS), time-of-flight secondary-ion mass spectrometry (ToF-SIMS), and Auger electron spectroscopy (AES) has shown a sharp chemical contrast between the two metals at the interface for titanium patterns embedded in gold, whereas diffusion of silver into gold was observed for gold patterns embedded in silver. Surface flatness combined with a high chemical contrast makes the obtained surfaces suitable for applications involving functionalization with molecules by orthogonal adsorption chemistries or for instrumental calibration. The latter possibility has been tested by determining the image sharpness and the analyzed area on circular patterns of different sizes for each of the spectroscopic techniques applied for characterization.This is the first study in which the analyzed area has been determined using XPS and AES on a flat surface, and the first example of a method for determining the analyzed area using ToF-SIMS.

Modeling soft, permeable matter with the proper generalized decomposition (PGD) approach, and verification by means of nanoindentation.

Understanding sliding and load-bearing mechanisms of biphasic soft matter is crucial for designing synthetic replacements of cartilage, contact-lens materials or coatings for medical instruments. Interstitial fluid pressurization is believed to be the intrinsic load-carrying phenomenon governing the frictional properties. In this study, we have characterized permeability and identified the fluid contribution to the support of load during Atomic Force Microscopy (AFM) nanoindentation of soft polymer brushes in aqueous environments, by means of the Proper Generalized Decomposition (PGD) approach. First, rate-dependent AFM nanoindentation was performed on a poly(acrylamide) (PAAm) brush in an aqueous environment, to probe the purely elastic as well as poro-viscoelastic properties. Second, a biphasic model decoupling the fluid and solid load contributions was proposed, using Darcy's equation for liquid flow in porous media. Using realistic time-dependent simulations requires many direct solutions of the 3D partial differential equation, making modeling very time-consuming. To efficiently alleviate the time-consumption of multi-dimensional modeling, we used PGD to solve a Darcy model defined in a 7D domain, considering all the unknowns and material properties as extra coordinates of the problem. The obtained 7D simulation results were compared to the experimental results by using a direct Newton algorithm, since all sensitivities with respect to the model parameters are readily available. Thus, a simulation-based solution for depth- and rate-dependent permeability can be obtained. From the PGD-based model permeability is calculated, and the velocity- and pressure-fields in the material can be obtained in real-time in 3D by adjusting the parameters to the experimental values. The result is a step forward in understanding the fluid flow, permeability and fluid contributions to the load support of biphasic soft matter.

Crosslinking Polymer Brushes with Ethylene Glycol-Containing Segments: Influence on Physicochemical and Antifouling Properties.

The introduction of different types and concentrations of crosslinks within poly(hydroxyethyl methacrylate) (PHEMA) brushes influences their interfacial, physicochemical properties, ultimately governing their adsorption of proteins. PHEMA brushes and brush-hydrogels were synthesized by surface-initiated, atom-transfer radical polymerization (SI-ATRP) from HEMA, with and without the addition of di(ethylene glycol) dimethacrylate (DEGDMA) or tetra(ethylene glycol) dimethacrylate (TEGDMA) as crosslinkers. Linear (pure PHEMA) brushes show high hydration and low modulus and additionally provide an efficient barrier against nonspecific protein adsorption. In contrast, brush-hydrogels are stiffer and less hydrated, and the presence of crosslinks affects the entropy-driven, conformational barrier that hinders the surface interaction of biomolecules with brushes. This leads to the physisorption of proteins at low concentrations of short crosslinks. At higher contents of DEGDMA or in the presence of longer TEGDMA-based crosslinks, brush-hydrogels recover their antifouling properties due to the increase in interfacial water association by the higher concentration of ethylene glycol (EG) units.

ATR-IR Investigation of Solvent Interactions with Surface-Bound Polymers.

Solvent interactions with bulk and surface-bound polymer brushes are crucial for functionalities such as controlled friction and thermoresponsive adhesion. To study such interactions, the temperature-induced solvent-quality changes and the effect of surface tethering on the mechanical and tribological properties of poly(dodecyl methacrylate) (P12MA) brushes have been investigated by means of attenuated total reflection infrared spectroscopy (ATR-IR), as well as atomic force microscopy (AFM) and lateral force microscopy (LFM). These results have been compared with temperature-dependent UV-visible spectrophotometry (UV-vis) data for the corresponding bulk polymer solutions. The ATR-IR results clearly show that increasing temperature enhances ethanol uptake in P12MA, which results in film swelling. This is accompanied by a marked increase in both adhesion and friction. We have also shown that a combination of solvents, such as toluene and ethanol, can lead to a temperature-dependent solvent partitioning within the polymer brush. To our knowledge this is the first time preferential solvent uptake in a grafted-from brush has been monitored via in situ ATR-IR. Moreover, we have observed remarkably different behavior for polymer chains in solution compared to the behavior of similar chains bound to a surface. The presented findings on the temperature-dependent solvent interactions of surface-grafted P12MA reveal previously unknown solvation phenomena and open up a range of possible applications in the area of stimuli-responsive materials.

Imparting Nonfouling Properties to Chemically Distinct Surfaces with a Single Adsorbing Polymer: A Multimodal Binding Approach.

Surface-active polymers that display nonfouling properties and carry binding groups that can adsorb onto different substrates are highly desirable. We present a postmodification protocol of an active-ester-containing polymer that allows the creation of such a versatile platform. Poly(pentafluorophenyl acrylate) has been postmodified with a fixed grafting ratio of a nonfouling function (mPEG) and various combinations of functional groups, such as amine, silane and catechol, which can provide strong affinity to two model substrates: SiO2 and TiO2 . Adsorption, stability and resistance to nonspecific protein adsorption of the polymer films were studied. A polymer was obtained that maintained its surface functionality under a variety of harsh conditions. EG surface-density calculations show that this strategy generates a denser packing when both negatively and positively charged groups are present within the backbone, and readily allows the fabrication of a broad combinatorial matrix.