Grafting-to Approach Research Articles

Biocompatible Polymer-Grafted TiO2 Nanoparticle Sonosensitizers Prepared Using Phosphonic Acid-Functionalized RAFT Agent.

Sonodynamic therapy is widely used in clinical studies including cancer therapy. The development of sonosensitizers is important for enhancing the generation of reactive oxygen species (ROS) under sonication. Herein, we have developed poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC)-modified TiO2 nanoparticles as new biocompatible sonosensitizers with high colloidal stability under physiological conditions. To fabricate biocompatible sonosensitizers, a grafting-to approach was adopted with phosphonic-acid-functionalized PMPC, which was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) using a newly designed water-soluble RAFT agent possessing a phosphonic acid group. The phosphonic acid group can conjugate with the OH groups on the TiO2 nanoparticles. We have clarified that the phosphonic acid end group is more crucial for creating colloidally stable PMPC-modified TiO2 nanoparticles under physiological conditions than carboxylic-acid-functionalized PMPC-modified ones. Furthermore, the enhanced generation of singlet oxygen (1O2), an ROS, in the presence of PMPC-modified TiO2 nanoparticles was confirmed using a 1O2-reactive fluorescent probe. We believe that the PMPC-modified TiO2 nanoparticles prepared herein have potential utility as novel biocompatible sonosensitizers for cancer therapy.

Modular and Substrate-Independent Grafting-To Procedure for Functional Polymer Coatings.

The ability to tailor polymer brush coatings to the last nanometer has arguably placed them among the most powerful surface modification techniques currently available. Generally, the synthesis procedures for polymer brushes are designed for a specific surface type and monomer functionality and cannot be easily employed otherwise. Herein, we describe a modular and straightforward two-step grafting-to approach that allows introduction of polymer brushes of a desired functionality onto a large range of chemically different substrates. To illustrate the modularity of the procedure, gold, silicon oxide (SiO2), and polyester-coated glass substrates were modified with five different block copolymers. In short, the substrates were first modified with a universally applicable poly(dopamine) primer layer. Subsequently, a grafting-to reaction was performed on the poly(dopamine) films using five distinct block copolymers, all of which contained a short poly(glycidyl methacrylate) segment and longer segment of varying chemical functionality. Ellipsometry, X-ray photoelectron spectroscopy, and static water contact angle measurements confirmed successful grafting of all five block copolymers to the poly(dopamine)-modified gold, SiO2, and polyester-coated glass substrates. In addition, our method was used to provide direct access to binary brush coatings, by simultaneous grafting of two different polymer materials. The ability to synthesize binary brush coatings further adds to the versatility of our approach and paves the way toward production of novel multifunctional and responsive polymer coatings.

Surfaces Coated with Polymer Brushes Work as Carriers for Histidine Ammonia Lyase.

The immobilization of enzymes on solid supports is an important challenge in biotechnology and biomedicine. In contrast to other methods, enzyme deposition in polymer brushes offers the benefit of high protein loading that preserves enzymatic activity in part due to the hydrated 3D environment that is available within the brush structure. The authors equipped planar and colloidal silica surfaces with poly(2-(diethylamino)ethyl methacrylate)-based brushes to immobilize Thermoplasma acidophilum histidine ammonia lyase, and analyzed the amount and activity of the immobilized enzyme. The poly(2-(diethylamino)ethyl methacrylate) brushes are attached to the solid silica supports either via a "grafting-to" or a "grafting-from" method. It is found that the grafting-from method results in higher amounts of deposited polymer and, consequently, higher amounts of Thermoplasma acidophilum histidine ammonia lyase. All polymer brush-modified surfaces show preserved catalytic activity of the deposited Thermoplasma acidophilum histidine ammonia lyase. However, immobilizing the enzyme in polymer brushes using the grafting-from method resulted in twice the enzymatic activity from the grafting-to approach, illustrating a successful enzyme deposition on a solid support.

Polymer Brushes on Silica Nanostructures Prepared by Aminopropylsilatrane Click Chemistry: Superior Antifouling and Biofunctionality.

In nanobiotechnology, the importance of controlling interactions between biological molecules and surfaces is paramount. In recent years, many devices based on nanostructured silicon materials have been presented, such as nanopores and nanochannels. However, there is still a clear lack of simple, reliable, and efficient protocols for preventing and controlling biomolecule adsorption in such structures. In this work, we show a simple method for passivation or selective biofunctionalization of silica, without the need for polymerization reactions or vapor-phase deposition. The surface is simply exposed stepwise to three different chemicals over the course of ∼1 h. First, the use of aminopropylsilatrane is used to create a monolayer of amines, yielding more uniform layers than conventional silanization protocols. Second, a cross-linker layer and click chemistry are used to make the surface reactive toward thiols. In the third step, thick and dense poly(ethylene glycol) brushes are prepared by a grafting-to approach. The modified surfaces are shown to be superior to existing options for silica modification, exhibiting ultralow fouling (a few ng/cm2) after exposure to crude serum. In addition, by including a fraction of biotinylated polymer end groups, the surface can be functionalized further. We show that avidin can be detected label-free from a serum solution with a selectivity (compared to nonspecific binding) of more than 98% without the need for a reference channel. Furthermore, we show that our method can passivate the interior of 150 nm × 100 nm nanochannels in silica, showing complete elimination of adsorption of a sticky fluorescent protein. Additionally, our method is shown to be compatible with modifications of solid-state nanopores in 20 nm thin silicon nitride membranes and reduces the noise in the ion current. We consider these findings highly important for the broad field of nanobiotechnology, and we believe that our method will be very useful for a great variety of surface-based sensors and analytical devices.

Investigation of an oleophobic-hydrophilic polymer brush with switchable wettability for easy-to-clean coatings

The combination of different wetting states, such as hydrophilic and oleophobic, in an adaptive polymer layer provides new opportunities in the field of easy-to-clean and anti-fog coatings. In this work, the synthesis of new end-functionalized well-defined block copolymers consisting of a hydrophilic poly(acrylic acid) (PAA) block and an oleophobic poly(1,1,1,3,3,3-hexafluoroisopropyl methacrylate) (PHFIPMA) block of different block length was investigated. This was achieved by parallel synthesis of the single blocks separately using atom transfer radical polymerization (ATRP), and subsequent block coupling by copper(I)-catalyzed click chemistry. A hydroxy end-group functionalization allowed these polymers to be assembled into dense polymer brushes via a grafting-to approach. The architecture of theses brushes and the orientation of the chains within the films were studied using angle-resolved X-ray photoelectron spectroscopy (ARXPS). To study the influence of the lengths and ratio of the two blocks on the switching of the wettability, contact angle measurements were performed demonstrating the correlation between structure and functionality. It was found that an increasing length of the hydrophilic block, while keeping the length of the oleophobic block constant, leads to an increase of the switching amplitude. Molecular Dynamic Simulations, which gave deeper insights into changes of the brush architecture during switching, enabled in combination with chemical analysis at the nanometer scale (ARXPS) conclusions about the influence of molecular rearrangements inside the brush on macroscopic changes at the outer surface of the brush due to external stimuli. Finally, oil spray-off experiments demonstrated the potential of these new adaptive polymer brushes as easy-to-clean coatings.

Cooperativity in the Aldol Condensation Using Bifunctional Mesoporous Silica-Poly(styrene) MCM-41 Organic/Inorganic Hybrid Catalysts.

This work explores the efficacy of silica/organic hybrid catalysts, where the organic component is built from linear aminopolymers appended to the silica support within the support mesopores. Specifically, the role of molecular weight and polymer chain composition in amine-bearing atom transfer radical polymerization-synthesized poly(styrene-co-2-(4-vinylbenzyl)isoindoline-1,3-dione) copolymers is probed in the aldol condensation of 4-nitrobenzaldehyde and acetone. Controlled polymerization produces protected amine-containing poly(styrene) chains of controlled molecular weight and dispersity, and a grafting-to thiol-ene coupling approach followed by a phthalimide deprotection step are used to covalently tether and activate the polymer hybrid catalysts prior to the catalytic reactions. Site-normalized batch kinetics are used to assess the role of polymer molecular weight and chain composition in the cooperative catalysis. Lower-molecular-weight copolymers are demonstrated to be more active than catalysts built from only molecular organic components or from higher-molecular-weight chains. Molecular dynamics simulations are used to probe the role of polymer flexibility and morphology, whereby it is determined that higher-molecular-weight hybrid structures result in congested pores that inhibit active site cooperativity and the diffusivity of reagents, thus resulting in lower rates during the reaction.

Biocompatible polymer-modified gold nanocomposites of different shapes as radiation sensitizers.

Radiation therapy is a powerful approach for cancer treatment due to its low invasiveness. The development of radiation sensitizers is of great importance as they assist in providing radiation therapy at a low dose. In this study, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC)-modified gold nanocomposites of different shapes were created using the grafting-to approach to serve as a novel radiation sensitizer with high cellular uptake. The effect of the shape of the nanocomposite on cellular uptake by the breast cancer cell line MCF-7 was also investigated. The PMPC-modified gold nanostars showed the highest cellular uptake compared to the other gold nanocomposites (spheres and rods), whereas cell cytotoxicity was negligible among all candidates. Furthermore, the therapeutic effect of radiation of PMPC-modified nanostars was the highest among all the gold nanocomposites. These results clearly indicate that the shape of the gold nanocomposite is an important parameter for cellular uptake and radiation sensitizing effects in breast cancer cells.

Epoxy modified with polymer-grafted GO: Role of bimodal functionalization in formation of ordered structures

The modification of epoxy with polymer-grafted graphene oxide (GO) is a radical alternative to mere combination of GO with a polymeric modifier. Here, this aspect is revealed for the case of bimodal grafting of GO with hydrophobic polybutadiene and hydrophilic polyoxypropylene or polyethylene glycol utilizing grafting-to approach to link different chains in the plane and edge area of GO. The results indicate fair ability of bimodally grafted GO to form ordered lamellar structures in epoxy. However, these structures show larger distance between less aligned GO plates in contrast to tightly aligned GO arrangement in case of single grafting. This is enabled by repulsive interactions between dissimilar chains. Such a structure with higher mobility of grafted chains has favorable effect on mechanical performance of epoxy. The effect of chain type and geometry of grafting is highlighted as well. Important finding is promotion of lamellar structure formation also by grafted low-m. w. compounds.

Hyperbranched Polyethylenimine-Tethered Multiple Emulsion-Templated Hierarchically Macroporous Poly(acrylic acid)-Al2O3 Nanocomposite Beads for Water Purification.

Emulsion template-guided strategy has been used to produce porous architectures with exquisite structure, tailored morphology, and exclusive features for ubiquitous applications. Notwithstanding, the practical water remediation is often marred by their transport-limited behavior and fragility. To circumvent these conundrums, we prepared hierarchically porous poly(acrylic acid)-alumina nanocomposite beads by solidifying the droplets of emulsions jointly stabilized by the organic surfactants and alumina nanoparticles. By virtue of their positive charge, the alumina nanoparticles got entrapped within the poly(acrylic acid) scaffolds that excluded the risk of secondary contamination typically observed with conventional nanocomposites. Being amenable to surface modification, the carboxyl moieties of the beaded polymer were further exploited to covalently tether branched polyethylenimine throughout the exterior and interior surface of the porous matrix via a grafting-to approach. The macropores expedite an active fluid flow and easier adsorbate transport throughout the functionalized nanocomposites whose overall higher density of positive charge over a certain pH range electrostatically attracts and effectively adsorbs the negatively charged Cr(VI) complexes and anionic congo red ions/molecules from water. This proof-of-concept synthetic approach and postsynthetic modification offer an improved mechanical robustness to these macrosized multifunctional nanocomposite beads for their easier processing, thereby paving the way for the point-of-use water purification technology development.

Multiresponsive Transitions of PDMAEMA Brushes for Tunable Surface Patterning.

Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) is an attractive polymer for switchable surface coatings based on its multiresponsiveness toward environmental triggers (temperature, pH-value, ionic strength). In this in situ study, we present the complex and tunable thermoresponsiveness of PDMAEMA Guiselin brushes (9 nm, dry thickness), which were prepared via an efficient grafting-to approach. Combining in situ atomic force microscopy (AFM) visualizing the surface topography (x-y plane) and spectroscopic ellipsometry monitoring the swelling behavior of the polymer film (layer thickness, z-direction) offers for the first time a three-dimensional insight into thermoresponsive transitions on the nanoscale. While PDMAEMA films exhibit LCST behavior in the presence of monovalent counterions, it can easily be switched toward an UCST thermoresponsiveness via the addition of small quantities of multivalent ions. In both cases, the transition temperature as well as the sharpness and reversibility of the transition can be tuned via a second external trigger, the ionic strength. Whereas homogeneous surfaces were observed both below and above the LCST in monovalent salt solutions, the UCST transition was characterized by the in situ formation of a nanostructured surface of pinned PDMAEMA micelles with entrapped multivalent counterions. Moreover, it was demonstrated for the first time that the characteristic dimensions of the nanopattern (the diameter and height of the pinned micelles) could be tuned in situ by the pH- and induced UCST thermoresponsiveness of PDMAEMA. This approach therefore provides a novel bottom-up strategy to create and control polymeric nanostructures in an aqueous environment.

Effect of Buffer Anions on Pearl-Necklace Morphology of Tertiary Amine-Containing Binary Heterografted Linear Molecular Bottlebrushes in Acidic Aqueous Buffers.

Molecular bottlebrushes can exhibit a multitude of distinct conformations under different conditions, and precise control of their morphology can facilitate better use of such materials in potential applications. Herein, we report a study on the effect of buffer anions on the pearl-necklace morphology of linear binary heterografted molecular brushes consisting of pH-responsive poly(2-N,N-diethylamino)ethyl methacrylate) (PDEAEMA) with a pKa of 7.40 and thermoresponsive poly(ethoxydi(ethylene glycol) acrylate) (PDEGEA) with a lower critical solution temperature of 9 °C as side chains in various acidic aqueous buffers at 0 °C. The molecular brushes, denotated as BMB, were prepared by a grafting-to approach using copper(I)-catalyzed azide-alkyne cycloaddition reaction. Dynamic light scattering studies showed that the apparent hydrodynamic size of BMB in aqueous buffers with a pH of 6.50 at 1 °C decreased with increasing valency of buffer anions, from acetate anions with a charge of 1-, to phosphate anions carrying charges of 2- and 1- and citrate anions bearing charges of 3- and 2- at pH = 6.50. Atomic force microscopy revealed that BMB exhibited a pearl-necklace morphology from all three aqueous buffers with a pH of 6.50 when spin-cast at 0 °C. Analysis of AFM images showed that the average length of BMB and the number of beads per brush molecule decreased with increasing valency of buffer anions while the size and height of the beads increased. The pearl-necklace morphology of BMB was believed to be the result of microphase separation of the neutral PDEGEA and the charged PDEAEMA side chains along the brush backbone. Multivalent kosmotropic buffer anions formed bridging linkages between protonated tertiary amine moieties and thus "crosslinked" the charged PDEAEMA side chains, resulting in the shrinkage of BMB and enhanced microphase separation of two side chain polymers.

PLL-Poly(HPMA) Bottlebrush-Based Antifouling Coatings: Three Grafting Routes.

In this work, we compare three routes to prepare antifouling coatings that consist of poly(l-lysine)–poly(N-(2-hydroxypropyl)methacrylamide) bottlebrushes. The poly(l-lysine) (PLL) backbone is self-assembled onto the surface by charged-based interactions between the lysine groups and the negatively charged silicon oxide surface, whereas the poly(N-(2-hydroxypropyl)methacrylamide) [poly(HPMA)] side chains, grown by reversible addition–fragmentation chain-transfer (RAFT) polymerization, provide antifouling properties to the surface. First, the PLL–poly(HPMA) coatings are synthesized in a bottom-up fashion through a grafting-from approach. In this route, the PLL is self-assembled onto a surface, after which a polymerization agent is immobilized, and finally HPMA is polymerized from the surface. In the second explored route, the PLL is modified in solution by a RAFT agent to create a macroinitiator. After self-assembly of this macroinitiator onto the surface, poly(HPMA) is polymerized from the surface by RAFT. In the third and last route, the whole PLL–poly(HPMA) bottlebrush is initially synthesized in solution. To this end, HPMA is polymerized from the macroinitiator in solution and the PLL–poly(HPMA) bottlebrush is then self-assembled onto the surface in just one step (grafting-to approach). Additionally, in this third route, we also design and synthesize a bottlebrush polymer with a PLL backbone and poly(HPMA) side chains, with the latter containing 5% carboxybetaine (CB) monomers that eventually allow for additional (bio)functionalization in solution or after surface immobilization. These three routes are evaluated in terms of ease of synthesis, scalability, ease of characterization, and a preliminary investigation of their antifouling performance. All three coating procedures result in coatings that show antifouling properties in single-protein antifouling tests. This method thus presents a new, simple, versatile, and highly scalable approach for the manufacturing of PLL-based bottlebrush coatings that can be synthesized partly or completely on the surface or in solution, depending on the desired production process and/or application.

Photo-induced copper-mediated (meth)acrylate polymerization towards graphene oxide and reduced graphene oxide modification

The preparation of well-dispersed graphene/polymer nanocomposites is challenging due to the poor miscibility of graphene sheets in a polymer matrix. To enhance the interaction between both phases, graphene sheets can be decorated with polymer chains. Herein, different strategies to graft poly(methyl methacrylate) (PMMA) and poly(di(ethylene glycol) ethyl ether acrylate) (PDEGA) chains at various positions on graphene oxide and reduced graphene oxide (GO/rGO) sheets are compared. Chain attachment was achieved by “grafting-to” and “grafting-from” methods. Grafting-to was performed by classical copper (I)-catalyzed alkyne azide cycloaddition. Using a grafting-from approach, PMMA and PDEGA brushes were grown from GO and rGO sheets via surface-initiated photo-induced copper-mediated polymerization (SI-photoCMP). SI-photoCMP is a robust and efficient method that allows polymerizations to be carried out under mild conditions and with reduced catalyst concentration. Moreover, the successful implementation of SI-photoCMP in a continuous-flow set-up enables easy upscaling of the system and is, therefore, a more efficient and environmentally friendly process for GO/rGO surface modification. By using the grafting-to approach, the grafting density of PMMA (Mn = 2,600 g/mol) was one chain per 990 carbons of graphene. In contrast, longer PMMA chains (Mn = 40,300 g/mol) and higher grafting density were obtained via the grafting-from method (one PMMA chain per 140 carbons of graphene).

Mechanistic Investigation of the Counterion-Induced UCST Behavior of Poly(N,N-dimethylaminoethyl methacrylate) Polymer Brushes

Because of its multiresponsive behavior upon variation of pH value, temperature, and ionic strength, poly­(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) is an attractive candidate for adaptive surface coatings, especially in the field of biomedical sensors. In the presented article, PDMAEMA Guiselin brushes (5–12 nm, dry thickness) were prepared by the grafting-to approach, and the thermoresponsive UCST-type (upper critical solution temperature) behavior of the generated films, induced by [Fe­(CN)6]3–, was demonstrated for the first time. To clarify the specific mechanism of the temperature responsiveness, the molecular interactions between polymer chains and complex ions were studied by in situ infrared spectroscopy and in situ ellipsometry, showing wavenumber shifts of the ν­(CN) band due to ion pairing as well as changes of the ν­(OH) band intensity due to swelling. Conclusively, experimental data suggest that the electrostatic interaction between the two components plays a significant role in the thermoresponsive behavior of PDMAEMA films. Using this knowledge, the UCST of the PDMAEMA Guiselin brushes could be adjusted between 34.0 ± 1.2 °C at pH 8 and 40.7 ± 2.0 °C at pH 5.

Fabrication of high-capacity cation-exchangers for protein adsorption: Comparison of grafting-from and grafting-to approaches

In this work, we have synthesized two polymer-grafted cation exchangers: one via the grafting-from approach, in which sulfopropyl methacrylate (SPM) is grafted through atom transfer radical polymerization onto Sepharose FF (the thus resulting exchanger is referred as Sep-g-SPM), and another via the grafting-to approach, in which the polymer of SPM is directly coupled onto Sepharose FF (the thus resulting exchanger is called as Sep-pSPM). Protein adsorption on these two cation exchangers have been also investigated. At the same ligand density, Sep-g-SPM has a larger accessible pore radius and a smaller depth of polymer layer than SeppSPM, due to the controllable introduction of polymer chains with the regular distribution of the ligand. Therefore, high-capacity adsorption of lysozyme and γ-globulin could be achieved simultaneously in Sep-g-SPM with an ionic capacity (IC) of 308 mmol$L–1. However, Sep-pSPM has an irregular chain distribution and different architecture of polymer layer, which lead to more serious repulsive interaction to proteins, and thus Sep-pSPM has a lower adsorption capacity for γ-globulin than Sep-g-SPM with the similar IC. Moreover, the results from protein uptake experiments indicate that the facilitated transport of adsorbed γ-globulin occurs only in Sep-pSPM and depends on the architecture of polymer layers. Our research provides a clear clue for the development of high-performance protein chromatography.

Bio-inert interfaces via biomimetic anchoring of a zwitterionic copolymer on versatile substrates

Bio-inert biomaterial design is vital for fields like biosensors, medical implants, and drug delivery systems. Bio-inert materials are generally hydrophilic and electrical neutral. One limitation faced in the design of bio-inert materials is that most of the modifiers used are specific to their substrate. In this work, we synthesized a novel zwitterionic copolymer containing a catechol group, a non-substrate dependent biomimetic anchoring segment, that can form a stable coating on various materials. No previous study was conducted using a grafting-to approach and determined the critical amount of catechol groups needed to effectively modify a material. The synthesized copolymers of sulfobetaine acrylamide (SBAA) and dopamine methacrylamide (DMA) in this work contains varying numbers of catechol groups, in which the critical number of catechol groups that had effectively modified substrates to have the bio-inert property was determined. The bio-inert property and capability to do coating on versatile substrates were evaluated in contact with human blood by coating different material groups such as ceramic, metallic, and polymeric groups. The novel structure and the simple grafting-to approach provides bio-inert property on various materials, giving them non-specific adsorption and attachment of biomolecules such as plasma proteins, erythrocytes, thrombocytes, bacteria, and tissue cells (85–95% reduction).

Investigation on the Linker Length of Synthetic Zwitterionic Polypeptides for Improved Nonfouling Surfaces.

Zwitterionic polymers are outstanding nonfouling materials widely used for surface modification. However, works that systematically evaluate the structure-activity relationship of the side chain linker effect with related antifouling abilities are sparse. Here, we generate a series of well-defined zwitterionic polypeptides bearing oligoethylene glycol (EG) linkers in the side chain (P(CB-EG xGlu), x = 1-3) and anchor them on gold surfaces via the grafting-to approach to compare their antifouling performances. The surface properties are characterized by X-ray photoelectron spectroscopy (XPS), circular dichroism spectroscopy (CD), variable angle spectroscopic ellipsometry (VASE), static water contact angle (SCA), and atomic force microscopy (AFM). By use of quartz crystal microbalance with dissipation (QCM-D), confocal microscopy, and scanning electron microscope, our results convincingly demonstrate the excellent antifouling performance of all zwitterionic polypeptides. Importantly, the surface coated with P(CB-EG3Glu), the one with the longest EG linker, exhibits the best resistance to single protein (below the detection limit of QCM) and blood serum (∼96-98% reduction) adsorption, which largely outperforms those of the PEG positive control and the two P(CB-EG xGlu) analogues with shorter EG x linkers. The same P(CB-EG3Glu) surface also gives the highest degree of prevention of cell/platelet/bacterial attachment (∼99% reduction) among all samples tested. Together, our study highlights the linker effect to the nonfouling performance of zwitterionic polypeptides, and the results strongly support P(CB-EG3Glu) as a robust nonfouling material for numerous applications.

Salt-Induced Control of the Grafting Density in Poly(ethylene glycol) Brush Layers by a Grafting-to Approach.

In this work, a method to obtain control of the grafting density during the formation of polymer brush layers by the grafting-to method of thiolated poly(ethylene glycol) onto gold is presented. The grafting density of the polymer chains was adjusted by adding Na2SO4 in concentrations between 0.2 and 0.9 M to the aqueous polymer solution during the grafting process. The obtained grafting densities ranged from 0.26 to 1.60 chains nm-2, as determined by surface plasmon resonance. The kinetics of the grafting process were studied in situ by a quartz crystal microbalance with dissipation, and a mushroom to brush conformational transition was observed when the polymer was grafted in the presence of Na2SO4. The transition from mushroom to brush was only observed for long periods of grafting, highlighting the importance of time to obtain high grafting densities. Finally, the prepared brush layer with the highest grafting density showed high resistance to the adsorption of bovine serum albumin, while layers with a lower grafting density showed only limited resistance.

A versatile platform to achieve mechanically robust mussel-inspired antifouling coatings via grafting-to approach.

Although significant progress has been made in mussel-inspired antifouling coatings, most of them suffer from low mechanical stability. Herein, we present a facile and efficient method to fabricate mechanically robust mussel-inspired antifouling coatings. A polyvinyl alcohol (PVA)-based mussel-inspired coating material, which exhibits the highest adhesion capability (always at 5B level in a tape adhesion test based on the ASTM D3359 method) and excellent anti-abrasive properties (little mass loss after 1000 abrasion cycles), is used as a universal platform for further modification to introduce antifouling properties. Intriguingly, the hydroxyl groups in this PVA-based coating material are used as the anchor for the installation of either hydrophilic or hydrophobic segments (or both) via a grafting-to approach. Single modifiers, methoxypolyethylene glycol (MPEG), sodium 2-hydroxyethanesulfonate (SHS) and 1H,1H,2H,2H-perfluorooctan-1-ol (PFO), and complex modifiers, MPEG/PFO, are tethered onto the coating through an effective urethane bond formation reaction to endow the surfaces with antifouling efficacy. The functionalized surfaces are shown to be effective in preventing bovine serum albumin (BSA) adsorption and in reducing bacterial (Gram-positive bacteria S. aureus and Gram-negative bacteria E. coli) adhesion. More importantly, such modification does not influence the strong adhesion and excellent anti-abrasion properties of the coating. To the best of our knowledge, this is the first example of merging excellent mechanical properties and antifouling capability for mussel-inspired coatings, which might find niches in a broad range of applications in the industrial and biomedical fields.

Smart functional polymer coatings for paper with anti-fouling properties.

Cellulose, as the main component of paper, is becoming more and more important for several high tech applications because of its beneficial properties, such as abundance, low cost, renewability, mechanical robustness and biocompatibility. To make cellulose accessable for new applications it is necessary to introduce new properties, which can be done by surface modification e.g. grafting of polymers onto surfaces. In this work, two comb copolymers, poly[(2-methyl-2-oxazoline methacrylate)-co-glycidyl methacrylate] and poly[(2-methacryloyloxyethyl phosphorylcholine)-co-glycidyl methacrylate], were synthesized by free radical polymerization of glycidyl methacrylate and oligo(2-methyl-2-oxazoline) as well as 2-methacryloyloxyethyl phosphorylcholine. After extensive characterization the polymers were covalently attached to thin cellulose model layers and filter paper using a one-step grafting-to approach. For the comprehensive analysis of these layers, thin cellulose films were fabricated on silicon wafers by spin coating of trimethylsilyl cellulose followed by acid hydrolysis which resulted in homogeneous layers as substrates for the grafting process of the functional polymers. The layers were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), atomic force microscopy (AFM) and energy-dispersive X-ray spectroscopy (EDX). To demonstrate the high potential of such polymer-modified cellulose materials, protein repellance of the cellulose films, containing peptidomimetic 2-methyl-2-oxazoline and zwitterionic phosphorylcholine groups after successful functionalization, is shown. Cell adhesion experiments using Bacillus subtilis, Escherichia coli and Saccharomyces cerevisiae indicate the considerable anti-fouling capacity against both Gram-positive and Gram-negatve bacteria as well as the yeast fungus.