ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
Hydrogel surfaces are of great interest in applications ranging from cell scaffolds and transdermal drug-delivery patches to catheter coatings and contact lenses. In this work, we propose a method to control the surface structure of hydrogels, thereby tailoring their frictional properties. The method is based on oxygen inhibition of the free-radical polymerization reaction during synthesis and enables (i) control of friction over more than an order in magnitude and (ii) spatial control of friction as either a continuous gradient or a distinct pattern. The presented method has successfully been applied to acrylamide-, diacrylate- and methacrylate-based gels, illustrating the universality of the presented method, and its potential use in the above-mentioned applications.
ABSTRACT
A tripod molecule incorporating a C60 photocatalyst into a rigid scaffold with disulfide legs was designed and synthesized for the stable and robust attachment of C60 onto an Au-coated atomic force microscope (AFM) tip. The "tripod-C60" was immobilized onto the tip by forming S-Au bonds in the desired orientation and a dispersed manner, rendering it suitable for the oxidation and scission of single molecules on a countersurface, thereby functioning as "molecular shears". A DNA origami with a well-defined structure was chosen as the substrate for the tip-induced oxidation. The gold-coated, C60-functionalized AFM tip was used for both AFM imaging and oxidation of DNA origami upon visible-light irradiation. The localized and temporally controlled oxidative damage of DNA origami was successfully performed at the single-molecule level via singlet-oxygen (1O2) generation from the immobilized C60 on the AFM tip. This oxidative damage to DNA origami can be carried out under ambient conditions in a fluid cell at room temperature, rendering it well-suited for the manipulation of a variety of species on surfaces via a spatially and temporally controlled oxidation reaction triggered by 1O2 locally generated from the immobilized C60 on the AFM tip.
Subject(s)
DNA , Nanotechnology , Microscopy, Atomic Force , Oxygen , Reactive Oxygen SpeciesABSTRACT
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.
ABSTRACT
The efficient and bioorthogonal chemical ligation reaction between potassium acyltrifluoroborates (KATs) and hydroxylamines (HAs) was used for the surface functionalization of a self-assembled monolayer (SAM) with biomolecules. An alkane thioether molecule with one terminal KAT group (S-KAT) was synthesized and adsorbed onto a gold surface, placing a KAT group on the top of the monolayer (KAT-SAM). As an initial test case, an aqueous solution of a hydroxylamine (HA) derivative of poly(ethylene glycol) (PEG) (HA-PEG) was added to this KAT-SAM at room temperature to perform the surface KAT ligation. Quartz crystal microbalance with dissipation (QCM-D) monitoring confirmed the rapid attachment of the PEG moiety onto the SAM. By surface characterization methods such as contact angle and ellipsometry, the attachment of PEG layer was confirmed, and covalent amide-bond formation was established by X-ray photoelectron spectroscopy (XPS). In a proof-of-concept study, the applicability of this surface KAT ligation for the attachment of biomolecules to surfaces was tested using a model protein, green fluorescent protein (GFP). A GFP was chemically modified with an HA linker to synthesize HA-GFP and added to the KAT-SAM under aqueous dilute conditions. A rapid attachment of the GFP on the surface was observed in real time by QCM-D. Despite the fact that such biomolecules have a variety of unprotected functional groups within their structures, the surface KAT ligation proceeded rapidly in a chemoselective manner. Our results demonstrate the versatility of the KAT ligation for the covalent attachment of a variety of water-soluble molecules onto SAM surfaces under dilute and biocompatible conditions to form stable, natural amide bonds.
Subject(s)
Borates/chemistry , Green Fluorescent Proteins/chemistry , Immobilized Proteins/chemistry , Membranes, Artificial , Hydroxylamines/chemistry , Polyethylene Glycols/chemistry , Proof of Concept StudyABSTRACT
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.
Subject(s)
Hydrogels , Oxygen , Hydrophobic and Hydrophilic Interactions , PolymerizationABSTRACT
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.
ABSTRACT
Dense suspensions of colloidal or granular particles can display pronounced non-Newtonian behaviour, such as discontinuous shear thickening and shear jamming. The essential contribution of particle surface roughness and adhesive forces confirms that stress-activated frictional contacts can play a key role in these phenomena. Here, by employing a system of microparticles coated by responsive polymers, we report experimental evidence that the relative contributions of friction, adhesion, and surface roughness can be tuned in situ as a function of temperature. Modifying temperature during shear therefore allows contact conditions to be regulated, and discontinuous shear thickening to be switched on and off on demand. The macroscopic rheological response follows the dictates of independent single-particle characterization of adhesive and tribological properties, obtained by colloidal-probe atomic force microscopy. Our findings identify additional routes for the design of smart non-Newtonian fluids and open a way to more directly connect experiments to computational models of sheared suspensions.
ABSTRACT
Polymer composition and topology of surface-grafted polyacids determine the amplitude of their pH-induced swelling transition. The intrinsic steric constraints characterizing cyclic poly(2-carboxypropyl-2-oxazoline) (c-PCPOXA) and poly(2-carboxyethyl-2-oxazoline) (c-PCEOXA) forming brushes on Au surfaces induce an enhancement in repulsive interactions between charged polymer segments upon deprotonation, leading to an amplified expansion and a significant increment in swelling with respect to their linear analogues of similar molar mass. On the other hand, it is the composition of polyacid grafts that governs their hydration in both undissociated and ionized forms, determining the degree of swelling during their pH-induced transition.
Subject(s)
Polymers , Hydrogen-Ion Concentration , Molecular Weight , PolyelectrolytesABSTRACT
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.
ABSTRACT
Light-induced oxidative damage of DNA by 1O2 generated from photoexcited C60 was observed at the single-molecule level by atomic force microscopy (AFM) imaging. Two types of DNA origami with uniform morphologies were immobilized on a mica surface and used as DNA substrates. Upon visible light irradiation (528 nm) in the presence of a C60 aqueous solution, the morphology changes of DNA origami substrates were observed by time-lapse AFM imaging at the single-molecule level by tracking a discrete DNA molecule. The origami showed nicked and flattened morphologies with relaxed features caused by the covalent cleavage of the DNA strands. The involvement of 1O2 in the on-surface DNA damage was clearly confirmed by AFM experiments in the presence of a 1O2 quencher and ESR measurements with a spin-trapping agent for 1O2. This study is the first example of single-molecule observation of oxidative damage of DNA by AFM with corresponding morphology changes in a photocontrolled and time-dependent manner by 1O2 generated catalytically from photoexcited C60.
Subject(s)
DNA Damage , DNA/chemistry , Fullerenes/chemistry , Microscopy, Atomic Force , Photochemical Processes , Singlet Oxygen/chemistry , Adsorption , Aluminum Silicates/chemistry , Light , Molecular Structure , Surface PropertiesABSTRACT
The physicochemical properties of cyclic polymer adsorbates are significantly influenced by the steric and conformational constraints introduced during their cyclization. These translate into a marked difference in interfacial properties between cyclic polymers and their linear counterparts when they are grafted onto surfaces yielding nanoassemblies or polymer brushes. This difference is particularly clear in the case of cyclic polymer brushes that are designed to chemically interact with the surrounding environment, for instance, by associating with biological components present in the medium, or, alternatively, through a response to a chemical stimulus by a significant change in their properties. The intrinsic architecture characterizing cyclic poly(2-oxazoline)-based polyacid brushes leads to a broad variation in swelling and nanomechanical properties in response to pH change, in comparison with their linear analogues of identical composition and molecular weight. In addition, cyclic glycopolymer brushes derived from polyacids reveal an enhanced exposure of galactose units at the surface, due to their expanded topology, and thus display an increased lectin-binding ability with respect to their linear counterparts. This combination of amplified responsiveness and augmented protein-binding capacity renders cyclic brushes invaluable building blocks for the design of "smart" materials and functional biointerfaces.
Subject(s)
Polymers , Molecular Conformation , Molecular Weight , Protein Binding , Surface PropertiesABSTRACT
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 (gramicidinâ 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.
ABSTRACT
Surface-initiated controlled radical polymerization mediated by a Cu0 plate (SI-Cu0 CRP) emerges as a versatile and efficient method for the functionalization of the exposed surfaces of hydrogels with a wide variety of polymer brushes. When a Cu0 plate is placed in contact with initiator-bearing hydrogel surfaces in the presence of ligand and monomer and under ambient conditions, it rapidly consumes dissolved oxygen from the reaction mixture, further acting as a source of catalyst and leading to the rapid growth of hydrogel-bound polymer chains. Three types of functional surfaces have been prepared as examples of the wide range of potential materials that can be synthesized in this way, including a hydrogel with a protective, hydrophobic surface, a lubricious hydrogel, as well as a hydrogel with thermally switchable frictional properties.
ABSTRACT
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.
Subject(s)
Iron/chemistry , Oxygen/chemistry , Polymerization , Polymers/chemistry , Animals , Biocompatible Materials , Cells, Cultured , MammalsABSTRACT
Polymer-topology effects can alter technologically relevant properties when cyclic macromolecules are applied within diverse materials formulations. These include coatings, polymer networks, or nanostructures for delivering therapeutics. While substituting linear building blocks with cyclic analogues in commonly studied materials is itself of fundamental interest, an even more fascinating observation has been that the introduction of physical or chemical boundaries (e.g., a grafting surface or cross-links) can amplify the topology-related effects observed when employing cyclic polymer-based precursors for assembling multidimensional objects. Hence, the application of cyclic polymers has enabled the fabrication of coatings with enhanced biorepellency and superior lubricity, broadened the tuning potential for mechanical properties of polymer networks, increased the thermodynamic stability, and altered the capability of loading and releasing drugs within polymeric micelles.
ABSTRACT
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.