Antifouling Polymer Brushes Research Articles

Improved antifouling properties of polymer membranes using a 'layer-by-layer' mediated method.

Polymeric reverse osmosis membranes were modified with antifouling polymer brushes through a 'layer by layer' (LBL) mediated method. Based on pure physical electrostatic interaction, the attachment of LBL films did not alter separation performance of the membranes. In addition, the incorporation of an LBL film also helped to amplify the number of potential reaction sites on the membrane surfaces for attachment of antifouling polymer brushes, which were then attached to the surface. Attachment of the brushes included two different approaches, grafting to and grafting from. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and water contact angle measurements showed successful growth of the LBL films and subsequently the polymer brushes. Using this method to modify reverse osmosis membranes, preliminary performance testing showed the antifouling properties of the as-modified membranes were much better than the virgin membrane with no significant loss in water flux and salt rejection.

Biomimetic non-fouling surfaces: extending the concepts.

In this study, we propose a substrate-independent biomimetic modification route for the creation of antifouling polymer brushes. This modification route consists of the formation/deposition of a biomimetic polydopamine anchor layer followed by a well-controlled surface-initiated atom transfer radical polymerization of antifouling polymer brushes initiated by 2-bromo-2-methylpropanoyl groups covalently attached to the hydroxyl and amine groups present in the anchor layer. In this way, we synthesized polymer brushes of methoxy- and hydroxy-capped oligoethylene glycol methacrylate, 2-hydroxyethyl methacrylate and carboxybetaine acrylamide. Spectroscopic ellipsometry (SE) indicated well-controlled polymerization kinetics of the brushes, thus the thickness of the ultra-thin films could be precisely tuned at a nanometer scale. The covalent structure and organization of the brushes grown from the polydopamine anchor layer were accessed by infrared reflection-adsorption spectroscopy (IRRAS) while the change in hydrophilicity caused by the presence of the brush was determined by dynamic water contact angle measurements. Surface plasmon resonance as well as ex situ IRRAS and SE measurements were applied to investigate the adsorption of model protein solutions and undiluted human blood plasma to the brushes. The biomimetic brushes completely suppressed the fouling from single protein solutions and reduced the fouling from plasma to less than 3% from the fouling measured on bare gold surfaces. The proposed modification procedure is non-destructive and does not require any chemical pre-activation or the presence of reactive groups on the substrate surface. Contrary to other antifouling modifications the coating can be performed on various classes of substrates and preserves its properties even in undiluted blood plasma. This work offers a promising technology for the facile fabrication of different surface-based biotechnological and biomedical devices able to perform tailor-made functions while resisting the fouling from the complex biological media where they operate.

Poly(vinylidene fluoride) Membranes with Hyperbranched Antifouling and Antibacterial Polymer Brushes

Graft copolymers of poly(vinylidene fluoride) (PVDF) with poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA) side chains (PVDF-g-PDMAEMA copolymers) were synthesized via activators generated by electron transfer for atom transfer radical polymerization (AGET-ATRP) of 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) directly from the secondary fluorine atoms on the PVDF backbone. Microporous membranes were fabricated from the PVDF-g-PDMAEMA amphiphilic copolymers by phase inversion in an aqueous medium. After quaternization by propargyl bromide, the resulting PVDF-g-PQDMAEMA membrane and pore surfaces bearing pendant propargyl moieties could be further functionalized via surface-initiated alkyne–azide click reaction of azido-terminated hyperbranched polyglycerols (HPG-N3) to form the PVDF-g-P[QDMAEMA-click-HPG] membranes. The PVDF-g-P[QDMAEMA-click-HPG] membranes exhibit good resistance to protein adsorption and fouling. Alternatively, alkyne–azide click reaction of azido-terminated polyethylenimine (...

Surface-grafted polysarcosine as a peptoid antifouling polymer brush.

Poly(N-substituted glycine) "peptoids" are a class of peptidomimetic molecules receiving significant interest as engineered biomolecules. Sarcosine (i.e., poly(N-methyl glycine)) has the simplest side chain chemical structure of this family. In this Article, we demonstrate that surface-grafted polysarcosine (PSAR) brushes exhibit excellent resistance to nonspecific protein adsorption and cell attachment. Polysarcosine was coupled to a mussel adhesive protein-inspired DOPA-Lys pentapeptide, which enabled solution grafting and control of the surface chain density of the PSAR brushes. Protein adsorption was found to decrease monotonically with increasing grafted chain densities, and protein adsorption could be completely inhibited above certain critical chain densities specific to different polysarcosine chain lengths. The dependence of protein adsorption on chain length and density was also investigated by a molecular theory. PSAR brushes at high chain length and density were shown to resist fibroblast cell attachment over a 7 week period, as well as resist the attachment of some clinically relevant bacterial strains. The excellent antifouling performance of PSAR may be related to the highly hydrophilic character of polysarcosine, which was evident from high-pressure liquid chromatography measurements of polysarcosine and water contact angle measurements of the PSAR brushes. Peptoids have been shown to resist proteolytic degradation, and polysarcosine could be produced in large quantities by N-carboxy anhydride polymerization. In summary, surface-grafted polysarcosine peptoid brushes hold great promise for antifouling applications.

Fabrication of cell outer membrane mimetic polymer brush on polysulfone surface via RAFT technique

Cell membrane mimetic antifouling polymer brush was grown on polysulfone (PSF) membrane by surface-induced reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC). The RAFT agent immobilized PSF substrate was prepared by successive chloromethylation, amination with ethylenediamine (EDA) and amidation of the amine group of grafted EDA with the carboxylic group of 4-cyanopentanoic acid dithiobenzoate (CPAD). The surface RAFT polymerization of MPC was initiated in aqueous solution by 4,4′-azobis-4-cyanopentanoic acid (ACPA). The formation of PMPC brush coating is evidenced by X-ray photoelectron spectroscopy and water contact angle measurements. The degree of polymerization of PMPC and the polymer grafting density were calculated from the high resolution XPS spectra. The platelet adhesion and protein adsorption results showed that the PMPC-grafted PSF surface has excellent antifouling ability to resist platelet adhesion completely and suppress protein adsorption significantly. This biomimetic and bio-friendly surface RAFT polymerization strategy could be promising for a variety of biomedical applications.

Universal surface-initiated polymerization of antifouling zwitterionic brushes using a mussel-mimetic peptide initiator.

We report a universal method for the surface-initated polymerization (SIP) of an antifouling polymer brush on various classes of surfaces, including noble metals, metal oxides, and inert polymers. Inspired by the versatility of mussel adhesive proteins, we synthesized a novel bifunctional tripeptide bromide (BrYKY) that combines atom-transfer radical polymerization (ATRP) initiating alkyl bromide with l-3,4-dihydroxyphenylalanine (DOPA) and lysine. The simple dip-coating of substrates with variable wetting properties and compositions, including Teflon, in a BrYKY solution at pH 8.5 led to the formation of a thin film of cross-linked BrYKY. Subsequently, we showed that the BrYKY layer initiated the ATRP of a zwitterionic monomer, sulfobetaine methacrylate (SBMA), on all substrates, resulting in high-density antifouling pSBMA brushes. Both BrYKY deposition and pSBMA grafting were unambiguously confirmed by ellipsometry, X-ray photoelectron spectroscopy, and goniometry. All substrates that were coated with BrYKY/pSBMA dramatically reduced bacterial adhesion for 24 h and also resisted mammalian cell adhesion for at least 4 months, demonstrating the long-term stability of the BrYKY anchoring and antifouling properties of pSBMA. The use of BrYKY as a primer and polymerization initiator has the potential to be widely employed in surface-grafted polymer brush modifications for biomedical and other applications.

An experimental-theoretical analysis of protein adsorption on peptidomimetic polymer brushes.

Surface-grafted water-soluble polymer brushes are being intensely investigated for preventing protein adsorption to improve biomedical device function, prevent marine fouling, and enable applications in biosensing and tissue engineering. In this contribution, we present an experimental-theoretical analysis of a peptidomimetic polymer brush system with regard to the critical brush density required for preventing protein adsorption at varying chain lengths. A mussel adhesive-inspired DOPA-Lys (DOPA = 3,4-dihydroxy-phenylalanine; Lys = lysine) pentapeptide surface grafting motif enabled aqueous deposition of our peptidomimetic polypeptoid brushes over a wide range of chain densities. Critical densities of 0.88 nm(-2) for a relatively short polypeptoid 10-mer to 0.42 nm(-2) for a 50-mer were identified from measurements of protein adsorption. The experiments were also compared with the protein adsorption isotherms predicted by a molecular theory. Excellent agreements in terms of both the polymer brush structure and the critical chain density were obtained. Furthermore, atomic force microscopy (AFM) imaging is shown to be useful in verifying the critical brush density for preventing protein adsorption. The present coanalysis of experimental and theoretical results demonstrates the significance of characterizing the critical brush density in evaluating the performance of an antifouling polymer brush system. The high fidelity of the agreement between the experiments and molecular theory also indicate that the theoretical approach presented can aid in the practical design of antifouling polymer brush systems.

Poly(HEMA) brushes emerging as a new platform for direct detection of food pathogen in milk samples

Surface plasmon resonance (SPR) biosensors capable of in real time detection of Cronobacter at concentrations down to 10 6 cells mL −1 in samples of consumer fresh-whole fat milk, powder whole-fat milk preparation, and powder infant formulation were developed for the first time. Antibodies against Cronobacter were covalently attached onto polymer brushes of poly(2-hydroxyethyl methacrylate) (poly(HEMA)) grafted from the SPR chip surface. The lowest detection limit, 10 4 cells mL −1, was achieved in phosphate buffered saline (pH 7.4) with sensors prepared by covalent immobilization of the same antibodies onto a self assembled monolayer (SAM) of hexa(ethylene glycol) undecanethiol (EG 6). However, when the EG 6 based sensors were challenged with milk samples the non-specific response due to the deposition of non-targeted compounds from the milk samples was much higher than the specific response to Cronobacter hampering the detection in milk. Similar interfering fouling was observed on antifouling polymer brushes of hydroxy-capped oligoethylene glycol methacrylate and even a 10 times higher fouling was observed on the widely used SAM of mixed hydroxy- and carboxy-terminated alkanethiols. Only poly(HEMA) brushes totally suppressed the fouling from milk samples. The robust well-controlled surface initiated atom transfer radical polymerization of HEMA allowed the preparation of highly dense brushes with a minimal thickness so that the capture of antigens by the antibodies immobilized on the brush layer could take place close to the gold SPR surface to provide a stronger optical response while the fouling was still suppressed. A minimum thickness of 19 nm of poly(HEMA) brush layer was necessary to suppress completely non-specific sensor response to fouling from milk.

Binary Reactive/Inert Non‐Fouling Polymeric Surfaces

AbstractBinary reactive/inert antifouling polymer brushes were grafted via a two step surface initiated polymerization from printed initiator monolayer and provided robust, effective polymeric surfaces for bioattachment with distinguishably reduced non‐specific adsorption. This synthetic strategy can be harnessed to build complex binary polymeric structures on substrate surfaces and the polymer brush surfaces reported in the present paper can be widely used for versatile biological study.magnified image