Bioinspired universal monolayer coatings by combining concepts from blood protein adsorption and mussel adhesion

Despite the increasing need for universal polymer coating strategies, only a few approaches have been successfully developed, and most of them are suffering from color, high thickness, or high roughness. In this paper, we present for the first time a universal monolayer coating that is only a few nanometers thick and independent of the composition, size, shape, and structure of the substrate. The coating is based on a bioinspired synthetic amphiphilic block copolymer that combines two concepts from blood protein adsorption and mussel adhesion. This polymer can be rapidly tethered on various substrates including both planar surfaces and nanosystems with high grafting density. The resulting monolayer coatings are, on the one hand, inert to the adsorption of multiple polymer layers and prevent biofouling. On the other hand, they are chemically active for secondary functionalization and provide a new platform for selective material surface modification

Biomimetic PDMS-hydroxyurethane terminated with catecholic moieties for chemical grafting on transition metal oxide-based surfaces

The aim of this work was to synthesize a non-isocyanate poly(dimethylsiloxane) hydroxyurethane with biomimetic terminal catechol moieties, as a candidate for inorganic and metallic surface modification. Such surface modifier is capable to strong lyattach onto metallic and inorganic substrates forming layers and, in addition, providing water-repellent surfaces. The non-isocyanate route is based on carbon dioxide cycloaddition into bis-epoxide, resulting in a precursor bis(cyclic carbonate)-polydimethylsiloxane(CCPDMS), thus fully replacing isocyanate in the manufacture process. A biomimetic approach was chosen with the molecular composition being inspired by terminal peptides present in adhesive proteins of mussels, like Mefp (Mytilus edulis foot protein), which bear catechol moieties and are strong adhesives even under natural and saline water. The catechol terminal groups were grafted by aminolysis reaction into a polydimethylsiloxane backbone. The product, PDMSUr-Dopamine, presented high affinity towards inhomogeneous alloy surfaces terminated by native oxide layers as demonstrated by quartz crystal microbalance (QCM-D), as well as stability against desorption by rinsing with ethanol. As revealed by QCM-D, X-ray photoelectron spectroscopy (XPS) and computational studies, the thickness and composition of the resulting nanolayers indicated an attachment of PDMSUr-Dopamine molecules to the substrate through both terminal catechol groups, with the adsorbate exposing the hydrophobicPDMS backbone. This hypothesis was investigated by classical molecular dynamic simulation (MD) of pure PDMSUr-Dopamine molecules on SiO2surfaces. The computationally obtained PDMSUr-Dopamine assembly is in agreement with the conclusions from the experiments regarding the conformation of PDMSUr-Dopamine towards the surface. The tendency of the terminal catechol groups to approach the surface is in agreement with proposed model for the attachment PDMSUr-Dopamine. Remarkably, the versatile PDMSUr-Dopamine modifier facilitates such functionalization for various substrates such as titanium alloy, steel and ceramic surfaces

Interfactant action of an amphiphilic polymer upon directing graphene oxide layer formation on sapphire substrates

Quality assured surface pre-treatment may greatly enhance adhesive interactions and, thus, the performance and durability of material joints. This holds true as well for substrates used in coating processes as for adherents introduced into bonding processes. Wet table polymeric wetting agents—shortly called polymeric interfactants—contribute to modifying surfaces and governing the properties of interphases. This is demonstrated for amphiphilic polymers directing the adsorption of graphene oxide(GO) nano-sheets from aqueous dispersion on alumina surfaces. In this contribution, contact angle measurements as well as X-ray photoelectron spectroscopy and scanning force microscopy investigations are applied for the characterization of thin films. GO is adsorbed either from a buffered dispersion on pristine aluminum oxide surfaces or on alumina modified with a few nanometers thin layer of a polymeric interfactant. Laterally extended nanoparticles and GO nano-sheets are preferentially found on interfactant layers whereas on pristine aluminum oxide smaller adsorbates dominate. The driving forces directing the GO attachment are discussed using a phenomenological model based on polymer/substrate interactions governing the sticking probabilities of GO nano-sheets with different sizes

Functionalization of hydrophobic surfaces with antimicrobial peptides immobilized on a bio-interfactant layer

The design of functionalized polymer surfaces using bioactive compounds has grown rapidly over the past decade within many industries including biomedical, textile, microelectronics, bioprocessing and food packaging sectors. Polymer surfaces such as polystyrene (PS) must be treated using surface activation processes prior to the attachment of bioactive compounds. In this study, a new peptide immobilization strategy onto hydrocarbonaceus polymer surfaces is presented. A bio-interfactant layer made up of a tailored combination of laccase from trametes versicolor enzyme and maltodextrin is applied to immobilize peptides. Using this strategy, immobilization of the bio-inspired peptide KLWWMIRRWG-bromophenylalanine-3,4- dihydroxyphenylalanine-G and KLWWMIRRWG-bromophenylalanine-G on polystyrene (PS) was achieved. The interacting laccase layers allows to immobilize antimicrobial peptides avoiding the chemical modification of the peptide with a spacer and providing some freedom that facilitates different orientations. These are not strongly dominated by the substrate as it is the case on hydrophobic surfaces; maintaining the antimicrobial activity. Films exhibited depletion efficiency with respect to the growth of Escherichia coli bacteria and did not show cytotoxicity for fibroblast L929. This environmentally friendly antimicrobial surface treatment is both simple and fast, and employs aqueous solutions. Furthermore, the method can be extended to three-dimensional scaffolds as well as rough and patterned substrates

Effect of interface-active proteins on the salt crystal size in waterborne hybrid materials

Aqueous processes yielding hybrid or composite materials are widespread in natural environments and their control is fundamental for a multiplicity of living organisms. Their design and in vitro engineering require knowledge about the spatiotemporal evolution of the interactions between the involved liquid and solid phases and, especially, the interphases governing the development of adhesion during solidification. The present study illustrates the effects of distinct proteins on the precipitation of sodium chloride encompassing the size, shape and distribution of halite crystals formed during the drying of droplets containing equally concentrated saline protein solutions. The precipitates obtained from aqueous sodium chloride formulations buffered with tris(hydroxymethyl)aminomethane (Tris) contained either bovine serum albumin (BSA), fibrinogen or collagen and were characterized with respect to their structure and composition using optical and electron microscopy as well as x-ray analysis. The acquired findings highlight that depending on the protein type present during droplet drying the halite deposits predominantly exhibit cubic or polycrystalline dendritic structures. Based on the phenomenological findings, it is suggested that the formation of the interphase between the growing salt phase and the highly viscous saline aqueous jelly phase containing protein governs not only the material transport in the liquid but also the material exchange between the solid and liquid phases.9

High-Antifouling Polymer Brush Coatings on Nonpolar Surfaces via Adsorption-Cross-Linking Strategy

A new “adsorption-cross-linking” technology is presented to generate a highly dense polymer brush coating on various nonpolar substrates, including the most inert and low-energy surfaces of poly­(dimethylsiloxane) and poly­(tetrafluoroethylene). This prospective surface modification strategy is based on a tailored bifunctional amphiphilic block copolymer with benzophenone units as the hydrophobic anchor/chemical cross-linker and terminal azide groups for in situ postmodification. The resulting polymer brushes exhibited long-term and ultralow protein adsorption and cell adhesion benefiting from the high density and high hydration ability of polyglycerol blocks. The presented antifouling brushes provided a highly stable and robust bioinert background for biospecific adsorption of desired proteins and bacteria after secondary modification with bioactive ligands, e.g., mannose for selective ConA and Escherichia coli binding

Multivalent Anchoring and Cross-Linking of Mussel-Inspired Antifouling Surface Coatings

In this work, we combine nature’s amazing bioadhesive catechol with the excellent bioinert synthetic macromolecule hyperbranched polyglycerol (hPG) to prepare antifouling surfaces. hPG can be functionalized by different amounts of catechol groups for multivalent anchoring and cross-linking because of its highly branched architecture. The catecholic hPGs can be immobilized on various surfaces including metal oxides, noble metals, ceramics, and polymers via simple incubation procedures. The effect of the catechol amount on the immobilization, surface morphology, stability, and antifouling performance of the coatings was studied. Both anchoring and cross-linking interactions provided by catechols can enhance the stability of the coatings. When the catechol groups on the hPG are underrepresented, the tethering of the coating is not effective; while an overrepresentation of catechol groups leads to protein adsorption and cell adhesion. Thus, only a well-balanced amount of catechols as optimized and described in this work can supply the coatings with both good stability and antifouling ability

Multivalent anchored and crosslinked hyperbranched polyglycerol monolayers as antifouling coating for titanium oxide surfaces

A set of new catecholic monolayer coatings was developed to improve the antifouling performance of TiO2 surfaces. To solve the problem of the weak charge-transfer interaction between a single catechol anchor and TiO2, multiple catechol groups were combined with hyperbranched polyglycerol (hPG) which is a distinct dendritic scaffold that exposes its multivalent anchor groups on the surface. Thus, multivalent catecholic hPGs can be easily prepared for surface modification. The immobilization of the compounds was monitored by quartz crystal microbalance with dissipation monitoring. Surface properties of the coatings were analyzed by water contact angle, X-ray photoelectron spectroscopy, and atomic force microscopy. The antifouling ability and stability were investigated by protein adsorption and cell adhesion. By increasing the number of catechol groups on the hPG scaffold, the stability and surface coverage could be significantly enhanced. Moreover, the inner-layer crosslinking of the coatings by grafting and initiating vinyl groups clearly improved their long-term stability. As a result, hPG with a catecholic functional degree of 10% (hPG-Cat10) and hPG with both catecholic and vinylic functional degree of 5% (hPG-Cat5-V5) were identified as the best catecholic hPGs to prepare bioinert and stable monolayer coatings on TiO2

Application of Poly-L-Lysine for Tailoring Graphene Oxide Mediated Contact Formation between Lithium Titanium Oxide LTO Surfaces for Batteries

When producing stable electrodes, polymeric binders are highly functional materials that are effective in dispersing lithium-based oxides such as Li4Ti5O12 (LTO) and carbon-based materials and establishing the conductivity of the multiphase composites. Nowadays, binders such as polyvinylidene fluoride (PVDF) are used, requiring dedicated recycling strategies due to their low biodegradability and use of toxic solvents to dissolve it. Better structuring of the carbon layers and a low amount of binder could reduce the number of inactive materials in the electrode. In this study, we use computational and experimental methods to explore the use of the poly amino acid poly-L-lysine (PLL) as a novel biodegradable binder that is placed directly between nanostructured LTO and reduced graphene oxide. Density functional theory (DFT) calculations allowed us to determine that the (111) surface is the most stable LTO surface exposed to lysine. We performed Kubo–Greenwood electrical conductivity (KGEC) calculations to determine the electrical conductivity values for the hybrid LTO–lysine–rGO system. We found that the presence of the lysine-based binder at the interface increased the conductivity of the interface by four-fold relative to LTO–rGO in a lysine monolayer configuration, while two-stack lysine molecules resulted in 0.3-fold (in the plane orientation) and 0.26-fold (out of plane orientation) increases. These outcomes suggest that monolayers of lysine would specifically favor the conductivity. Experimentally, the assembly of graphene oxide on poly-L-lysine-TiO2 with sputter-deposited titania as a smooth and hydrophilic model substrate was investigated using a layer-by-layer (LBL) approach to realize the required composite morphology. Characterization techniques such as X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), Kelvin probe force microscopy (KPFM), scanning electron microscopy (SEM) were used to characterize the formed layers. Our experimental results show that thin layers of rGO were assembled on the TiO2 using PLL. Furthermore, the PLL adsorbates decrease the work function difference between the rGO- and the non-rGO-coated surface and increased the specific discharge capacity of the LTO–rGO composite material. Further experimental studies are necessary to determine the influence of the PLL for aspects such as the solid electrolyte interface, dendrite formation, and crack formation