Ultralow Fouling Research Articles

One-Step Phase Separation and Mineralization Fabrication of Membranes for Oily Wastewater Treatment.

Oily wastewater threatens the environment and the human health. Membrane technology offers a simple and efficient alternative to separating oil and water. However, complex membrane modifications are usually employed to optimize the separation performance. In this research, we develop an extremely simple one-step method to in situ calcium carbonate (CaCO3) nanoparticles onto a porous polyketone (PK) membrane via a nonsolvent induced phase separation (NIPS)-mineralization strategy. We utilized the unique chemical property of PK, which allows it to dissolve in a resorcinol aqueous solution. PK was mixed with tannic acid (TA) and calcium chloride (CaCl2) in a resorcinol aqueous solution to fabricate a casting solution. The activated membrane was cast and immersed into a sodium carbonate (Na2CO3) aqueous solution for taking the one-step NIPS-mineralization process. This proposed NIPS-mineralization mechanism comes to two conclusions: (i) the resulting membrane with comprehensive oleophobic properties and enhanced permeation flux for applications of oil/water separation with ultralow fouling and (ii) simplified the procedure to optimize the membrane performance using regular NIPS steps. The current work explores a one-step NIPS-mineralization technique that offers a novel approach to preparing membranes with highly efficient oil/water separation performance.

Ionically annealed zwitterionic microgels for bioprinting of cartilaginous constructs

Foreign body response (FBR) is a pervasive problem for biomaterials used in tissue engineering. Zwitterionic hydrogels have emerged as an effective solution to this problem, due to their ultra-low fouling properties, which enable them to effectively inhibit FBR in vivo. However, no versatile zwitterionic bioink that allows for high resolution extrusion bioprinting of tissue implants has thus far been reported. In this work, we introduce a simple, novel method for producing zwitterionic microgel bioink, using alginate methacrylate (AlgMA) as crosslinker and mechanical fragmentation as a microgel fabrication method. Photocrosslinked hydrogels made of zwitterionic carboxybetaine acrylamide (CBAA) and sulfobetaine methacrylate (SBMA) are mechanically fragmented through meshes with aperture diameters of 50 and 90 µm to produce microgel bioink. The bioinks made with both microgel sizes showed excellent rheological properties and were used for high-resolution printing of objects with overhanging features without requiring a support structure or support bath. The AlgMA crosslinker has a dual role, allowing for both primary photocrosslinking of the bulk hydrogel as well as secondary ionic crosslinking of produced microgels, to quickly stabilize the printed construct in a calcium bath and to produce a microporous scaffold. Scaffolds showed ∼20% porosity, and they supported viability and chondrogenesis of encapsulated human primary chondrocytes. Finally, a meniscus model was bioprinted, to demonstrate the bioink’s versatility at printing large, cell-laden constructs which are stable for further in vitro culture to promote cartilaginous tissue production. This easy and scalable strategy of producing zwitterionic microgel bioink for high resolution extrusion bioprinting allows for direct cell encapsulation in a microporous scaffold and has potential for in vivo biocompatibility due to the zwitterionic nature of the bioink.

Comparison of Superhydrophilic, Liquid-Like, Liquid-Infused, and Superhydrophobic Surfaces in Preventing Catheter-Associated Urinary Tract Infection and Encrustation.

Over the past decade, superhydrophilic zwitterionic surfaces, slippery liquid-infused porous surfaces, covalently attached liquid-like surfaces, and superhydrophobic surfaces have emerged as the most promising strategies to prevent biofouling on biomedical devices. Despite working through different mechanisms, they have demonstrated superior efficacy in preventing the adhesion of biomolecules (e.g., proteins and bacteria) compared with conventional material surfaces. However, their potential in combating catheter-associated urinary tract infection (CAUTI) remains uncertain. In this research, we present the fabrication of these four coatings for urinary catheters and conduct a comparative assessment of their antifouling properties through a stepwise approach. Notably, the superhydrophilic zwitterionic coating demonstrated the highest antifouling activity, reducing 72.3% of fibrinogen deposition and over 75% of bacterial adhesion (Escherichia coli and Staphylococcus aureus) when compared with an uncoated polyvinyl chloride (PVC) surface. The zwitterionic coating also exhibited robust repellence against blood and improved surface lubricity, decreasing the dynamic coefficient of friction from 0.63 to 0.35 as compared with the PVC surface. Despite the fact that the superhydrophilic zwitterionic and hydrophobic liquid-like surfaces showed great promise in retarding crystalline biofilm formation in the presence of Proteus mirabilis, it is worth noting that their long-term antifouling efficacy may be compromised by the proliferation and migration of colonized bacteria as they are unable to kill them or inhibit their swarming. These findings underscore both the potential and limitations of these ultralow fouling materials as urinary catheter coatings for preventing CAUTI.

A Zwitterionic Hydrogel with Anti-Oxidative and Anti-Inflammatory Properties for the Prevention of Peritoneal Adhesion by Inhibiting Mesothelial-Mesenchymal Transition.

Postoperative peritoneal adhesion is a serious clinical complication. Various hydrogel barriers have been developed to prevent peritoneal adhesion. However, it remains a challenge to design a hydrogel with desirable physicochemical properties and bioactivities. In this study, a zwitterionic polysaccharide-based multifunctional hydrogel is developed using epigallocatechin-3-gallate (EGCG) to prevent postoperative abdominal adhesion. This hydrogel is simple to use and has desirable properties, such as excellent injectability, self-healing, and non-swelling properties. The hydrogel also has ultralow fouling capabilities, such as superior bactericidal performance, cell and protein adhesion, and low immunogenicity resistance. Moreover, the hydrogel exhibits good antioxidant activity, which is attributed to the integration of EGCG. Furthermore, the detailed mechanism from in vivo and in vitro experimental studies illustrates that hydrogel compositions can synergistically prevent adhesion formation through multiple pathways, including anti-inflammatory and antioxidant capabilities and inhibition effects on the mesothelial-mesenchymal transition (MMT) process induced by transforming growth factor (TGF-β). In summary, this zwitterionic multifunctional hydrogel has great potential to prevent postoperative adhesion formation in the clinical setting.

Gold nanoparticles-decorated peptide hydrogel for antifouling electrochemical dopamine determination.

A reliable and brief ultralow fouling electrochemical sensing system capable of monitoring targets in complex biological media was constructed and validated based on gold nanoparticles-peptide hydrogel-modified screen-printed electrode. The self-assembled zwitterionic peptide hydrogel was prepared by a newly designed peptide sequence of Phe-Phe-Cys-Cys-(Glu-Lys)3 with the N-terminal modified with a fluorene methoxycarbonyl group. The thiol groups on cysteine of the designed peptide are able to self-assemble with AuNPs to form a three-dimensional nanonetwork structure, which showed satisfactory antifouling capability in complex biological media (human serum). The developed gold nanoparticles-peptide hydrogel-based electrochemical sensing platform displayed notably sensing properties for dopamine determination, with a wide linear range (from 0.2 nM to 1.9 μM), a low limit of detection (0.12 nM), and an excellent selectivity. This highly sensitive and ultralow fouling electrochemical sensor was fabricated via simple preparation with concise components that avoid the accumulation of layers with single functional material and complex activation processes. This ultralow fouling and highly sensitive strategy based on the gold nanoparticles-peptide hydrogel with a three-dimensional nanonetwork offers a solution to the current situation of various low-fouling sensing systems facing impaired sensitivity and provides a potential path for the practical application of electrochemical sensors.

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.

Using a Novel Pervaporative Sequential-Co-immobilized Two-Sectional Bioreactor with an Ultralow Fouling–Biofouling Superhydrophobic Silicallite-1/PDMS Membrane to Enhance Bioethanol Production

This study is on the efficient fermentation of high glucose (G) and xylose (X) levels (G/X ratio of 1.5:1), simulating the hydrolysate of lignocellulosic wastes, via an innovative integrated two-stage fermentation–pervaporation process. Immobilized Zymomonas mobilis (Z) and Pichia stipitis (P) were exploited in a sequential-co-immobilized culture (Z in the first stage and Z and P in second stage) to simultaneously increase bioethanol productivity and lessen the inhibitions. The threshold inhibition was evaluated in 100 mL shake flasks by raising the initial total sugar concentration from 50 to 200 g/L where complete inhibition was observed at 200 g/L. Subsequently, fermentation (G: 120 g/L, X: 80 g/L) was examined in a sequential-co-immobilized two-sectional bioreactor (ITB-2L) during 200 h. ITB resulted in 100% glucose and 16% xylose conversion, showing ethanol productivity of 0.26 g/L·h and yield of 0.4 ge/gs. To investigate the effect of reducing inhibitions, a tubular superhydrophobic silicalite-1/PDMS pervaporative (TSP) autoclavable membrane with antiswelling properties was fabricated. The pervaporative sequential-co-immobilized two-sectional bioreactor (PITB) using TSP enhanced xylose conversion (57%), ethanol productivity (0.39 g/L·h), and yield (0.47 ge/gs). The membrane surface was probed after 161 h of usage, and the limited presence of only negative ions on its surface proved its superior ultralow fouling–biofouling formation. PITB proved itself as a robust integrated process for the second-generation bioethanol production.

Biomimetic redox-responsive smart coatings with resistance-release functions for reverse osmosis membranes.

Membrane fouling induces catastrophic loss of separation performance and seriously restricts the applications of reverse osmosis (RO) membranes. Inspired by the mussel structure, polydopamine (PDA) and cystamine molecules (CA) with excellent anti-fouling properties were used to prepare accessible, biocompatible, and redox-responsive coatings for RO membranes. The PDA/CA-coated RO membranes exhibit a superior water flux of 65 L m-2 h-1 with a favourable NaCl rejection exceeding 99%. The water permeability through the PDA/CA-coated membrane is much higher than that of most membranes with similar rejection rates. Due to the formed protective hydration layers by PDA/CA coatings, anti-fouling properties against proteins, polysaccharides and surfactants were evaluated separately, and ultralow fouling properties were demonstrated. Moreover, the disulfide linkages in CA molecules can cleave in a reducing environment, yielding the degradation of PDA/CA coatings, thereby removing the foulants deposited on the coatings. The degradation endows the coated membranes with satisfying longtime anti-fouling properties, where the flux recovery reaches up to 90%. The construction of redox-responsive smart coatings not only provided a promising route to alleviate membrane fouling but can also be upscaled for use in numerous practical applications like sensors, medical devices, and drug delivery.

Immobilization of hydrolytic/fermentative bacteria to achieve ultra-low fouling in anaerobic membrane bioreactor

Membrane fouling remains the key challenge that limits the application of anaerobic membrane bioreactors (AnMBRs). Free-living bacteria, particularly hydrolytic/fermentative bacteria (HFB) in sludge supernatant, have recently been identified as the predominant foulants in AnMBRs. Here, a pretreatment tank filled with porous polyurethane sponges as carriers for biomass attachment and/or entrapment was developed for influent organic hydrolysis/fermentation, named HFB-immobilization tank. Then, two parallel AnMBRs (i.e., with and without an HFB-immobilization tank) treating synthetic domestic wastewater were operated to determine the roles of HFB capture in fouling mitigation as well as reactor performance. Higher methane yields were observed in the experimental than in the control AnMBR. Interestingly, the HFB-immobilization helped to achieve a non-fouling state of the experimental AnMBR for more than 100 days, while the average fouling cycle of the control AnMBR was 20 days. Dead-end filtration tests corroborated better filterability of sludge supernatant in the experimental than the control AnMBR. The 16S rRNA gene sequencing revealed substantially lower abundances of HFB (e.g., Aminicenantales, SJA-15) but higher abundances of methanogens (e.g., Methanosaeta, Methanolinea, Methanospirillum) in the mixed liquor of the experimental than the control AnMBR, indicating efficient niche separation by the HFB immobilization. Particularly, the sequencing data, together with fluorescent staining, showed that the amounts and abundances of HFB in sludge supernatant were largely lower in the experimental than the control AnMBR. This study provides a promising alternative for fouling control in AnMBRs.

Hydration and antibiofouling of TMAO-derived zwitterionic polymers surfaces studied with atomistic molecular dynamics simulations

Zwitterionic polymers have emerged as a class of highly effective ultralow fouling materials for critical marine coating and biomedical applications. The recently developed trimethylamine N-oxide (TMAO)-derived zwitterionic polymers have demonstrated excellent antibiofouling capability in various chemical environments; however, it remains unclear how they interact with proteins at the microscopic level. To further investigate the antifouling mechanisms, we performed atomistic molecular dynamics (MD) simulations in combination with free-energy computations to provide an in-depth molecular understanding of the interactions of TMAO polymer brush (pTMAO) surfaces with proteins of opposite charges (positively charged lysozyme and negatively charged barnacle cement protein) in aqueous environments (pure water and saline solution). Our simulations revealed ordered structures of a condensed hydration water layer on the pTMAO surfaces in pure and saline water. The quantitative free energy analyses showed that the pTMAO surface has small protein desorption energy, but with a strong hydration energy barrier near the polymer surfaces to resist protein adsorption compared to other biofouling surfaces. The addition of salts only has a slight effect on the pTMAO surface’s exclusion of proteins due to the small interference of the structure of interfacial water. This study provides detailed knowledge of the strong surface hydration of zwitterionic polymers and its relation to salt impact, protein adsorption, and antibiofouling behavior of these important materials.

Click reaction-assisted construction of antifouling immunosensors for electrochemical detection of cancer biomarkers in human serum

Herein, an electrochemical immunosensor capable of detecting targets in human serum with ultralow fouling and high sensitivity was successfully constructed through a click reaction. One designed biotinylated peptide was associated with the other peptide functionalized with biotin and azide groups at its two terminals, to form a branched antifouling peptide through the streptavidin-biotin affinity interaction, and it was attached to the electrode to construct an antifouling interface. Then, the exposed azide group on the branched peptide was used to link the antibody modified with 5′-dibenzocyclooctyne (DBCO), and the immunosensor was thus constructed with the aid of the click reaction between the azide group and the DBCO. The developed antifouling immunosensor demonstrated a wide linear response range for carcinoembryonic antigen (CEA) and a low limit of detection of 40 fg mL−1, which is much superior to the sensing performance of the immunosensor prepared through the normal EDC/NHS method. The immunosensor was capable of assaying CEA in undiluted serum samples with satisfying accuracy when compared with a clinically approved method. This work offered an effective strategy to develop various biosensors through the conjugation of antifouling peptides with different antibodies.

Antifouling Peptides Combined with Recognizing DNA Probes for Ultralow Fouling Electrochemical Detection of Cancer Biomarkers in Human Bodily Fluids

Antifouling Peptides Combined with Recognizing DNA Probes for Ultralow Fouling Electrochemical Detection of Cancer Biomarkers in Human Bodily Fluids

An ultrasensitive biosensor for prostate specific antigen detection in complex serum based on functional signal amplifier and designed peptides with both antifouling and recognizing capabilities

The development of biosensors capable of averting biofouling and detecting biomarkers in complex biological media remains a challenge. Herein, an ultralow fouling and highly sensitive biosensor based on specifically designed antifouling peptides and a signal amplification strategy was designed for prostate specific antigen (PSA) detection in human serum. A low fouling layer of poly(ethylene glycol) (PEG) doped the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) was electrodeposited on the electrode surface, followed by the immobilization of streptavidin and further attachment of biotin-labelled peptides. The peptide was designed to include PSA specific recognition domain (HSSKLQK) and antifouling domain (PPPPEKEKEKE), and the terminal of the peptide was functionalized with –SH group. DNA functionalized gold nanorods (DNA/AuNRs) were then attached to the electrode, and methylene blue (MB) molecules were adsorbed to the DNA to form the signal amplifier. In the presence of PSA, the peptide was specifically cleaved and resulted in the loss of AuNRs together with DNA and MB, and thus significant decrease of the current signal. The biosensor exhibited a low limit of detection (LOD) of 0.035 pg mL-1 (S/N = 3), with a wide linear range from 0.10 pg mL-1 to 10.0 ng mL-1, and it was able to detect PSA in real human serum owing to the presence of the antifouling peptides, indicating great potential of the constructed biosensor for practical application.

Bioinspired ultra-low fouling coatings on medical devices to prevent device-associated infections and thrombosis

Addressing thrombosis and biofouling of indwelling medical devices within healthcare institutions is an ongoing problem. In this work, two types of ultra-low fouling surfaces (i.e., superhydrophobic and lubricant-infused slippery surfaces) were fabricated to enhance the biocompatibility of commercial medical grade silicone rubber (SR) tubes that are widely used in clinical care. The superhydrophobic (SH) coatings on the tubing substrates were successfully created by dip-coating in superhydrophobic paints consisting of polydimethylsiloxane (PDMS), perfluorosilane-coated hydrophobic zinc oxide (ZnO) and copper (Cu) nanoparticles (NPs) in tetrahydrofuran (THF). The SH surfaces were converted to lubricant-infused slippery (LIS) surfaces through the infusion of silicone oil. The anti-biofouling properties of the coatings were investigated by adsorption of platelets, whole blood coagulation, and biofilm formation in vitro. The results revealed that the LIS tubes possess superior resistance to clot formation and platelet adhesion than uncoated and SH tubes. In addition, bacterial adhesion was investigated over 7 days in a drip-flow bioreactor, where the SH-ZnO-Cu tube and its slippery counterpart significantly reduced bacterial adhesion and biofilm formation of Escherichia coli relative to control tubes (>5 log10 and >3 log10 reduction, respectively). The coatings also demonstrated good compatibility with fibroblast cells. Therefore, the proposed coatings may find potential applications in high-efficiency on-demand prevention of biofilm and thrombosis formation on medical devices to improve their biocompatibility and reduce the risk of complications from medical devices.

Designing a MOF-based slippery lubricant-infused porous surface with dual functional anti-fouling strategy

Material that resists biofouling adhesion is needed in a complex marine environment, but few of them can combine ultra-low fouling and environmental friendliness. Slippery lubricant-infused porous surface (SLIPS) is such a material, but it lacks the contact-killing ability, which limits its stability and anti-fouling efficiency. Here, we report a metal organic framework (MOF-based) Slippery ionic liquid-infused surface with excellent antifouling performance via synergistic release and contact-killing defense strategy. The dense needle-like MIL-110 array, grown in situ on the aluminum surface, is conducive to the stable storage of quaternary ammonium salt (QAS) ionic liquid. Compared to the control group with mature biofilm formed on the surface, SLIPS showed non-fouling performance in a 10-day test and another 21-day test under more challenging conditions. The adsorption amount of lipopolysaccharide (LPS) on SLIPS was 50% lower than that on the aluminum sheet and the aluminum sheet with MIL-110 grown on the surface as the control groups within three hours. The relationship between bacterial adhesion and LPS adsorption indicated that the anti-adhesion performance of SLIPS was mediated by the weak adhesion and easy release property of its surface to extracellular fouling molecules. This study provides the possibility to systematically reveal the antifouling mechanism of SLIPS on bacterial adhesion.

Ionic strength dependent forces between end-grafted Poly(sulfobetaine) films and mica

The molecular surface properties of zwitterionic polymer coatings are central to their ultra-low fouling properties and effectiveness as steric stabilizers in concentrated salt solutions. Here, Surface Force Apparatus measurements quantified the molecular forces between end-grafted poly(sulfobetaine) methacrylate thin films and mica, as a function of the chain grafting density and ionic strength. These results demonstrate that, at the ionic strengths considered, end-grafted poly(sulfobetaine) films can be described by models for polymers in good solvent. Parameters determined from data fits to the Milner-Witten-Cates or Dolan and Edwards models for dense or dilute chains, respectively, varied with ionic strength, in ways that reflect poly(sulfobetaine) swelling and the increased excluded volume strength of chain segments. These force measurements provide new insight into how polymer coverage and salt cooperate to regulate repulsive poly(sulfobetaine) steric barriers. These findings have implications for the design of grafted poly(sulfobetaine) as colloidal stabilizers or nonfouling surface coatings.

Amphiphilic Zwitterionic Acrylate/Methacrylate Copolymers for Marine Fouling-Release Coatings.

Methacrylate and acrylate monomers are popular building blocks for antifouling (AF) and fouling-release (FR) coatings to counteract marine biofouling. They are used in various combinations and often combined into amphiphilic materials. This study investigated the FR properties of amphiphilic ethylene glycol dicyclopentenyl ether acrylate (DCPEA) and the corresponding methacrylate (DCPEMA) blended with 5 wt % zwitterionic carboxybetaine acrylate (CBA) and the corresponding methacrylate (CBMA). A series of (co)polymers with different acrylate/methacrylate compositions were synthesized and tested against the attachment of the diatom Navicula perminuta and in short-term dynamic field exposure experiments. The more hydrophobic methacrylate DCPEMA homopolymer outperformed its acrylate counterpart DCPEA. Incorporated zwitterionic functionality of both CBMA and CBA imparted ultralow fouling capability in the amphiphilic polymers toward diatom attachment, whereas in the real ocean environment, only the employment of CBMA reduced marine biofouling. Moreover, it was observed that CBA-containing coatings showed different surface morphologies and roughnesses compared to the CBMA analogues. Particularly, a high impact was found when acrylic CBA was mixed with methacrylic DCPEMA. While the wettability of the coatings was comparable, investigated methacrylates in general exhibited superior fouling resistance compared to the acrylates.

Electrochemical sensing interfaces based on hierarchically architectured zwitterionic peptides for ultralow fouling detection of alpha fetoprotein in serum

Herein, an electrochemical sensing platform based on zwitterionic peptide with a hierarchical structure was constructed for ultralow fouling and highly sensitive protein quantification. Through the combination of CPPPPEKEKEKEK and CPPPPEKEKEK peptides, hierarchical antifouling peptide brushes were formed and exhibited excellent antifouling property, which can be further modified with alpha fetoprotein (AFP) aptamer to achieve highly sensitive detection of AFP. The hierarchical peptide brush-based sensor system achieved an AFP quantification range from 1.0 fg mL−1 to 1.0 ng mL−1, with a very low limit of detection as low as 0.59 fg mL−1. In addition, due to the superior antifouling property of the newly designed hierarchical peptide brushes, the electrochemical biosensor supported the quantification of AFP in solutions with a high concentration of nonspecific proteins without sacrifice in sensitivity. It is worth noting that the constructed antifouling biosensor ensured quantitative recruitment of AFP in clinical serum samples with acceptable accuracy when compared with the commonly used method in the hospital. The strategy of constructing sensing interfaces based on designed hierarchical peptide brushes provided an effective way to develop biosensors with both excellent antifouling capability and high sensitivity.

Amphiphilic Dicyclopentenyl/Carboxybetaine-Containing Copolymers for Marine Fouling-Release Applications.

Zwitterionic materials received great attention in recent studies due to their high antifouling potential, though their application in practical coatings is still challenging. Amphiphilic polymers have been proven to be an effective method to combat fouling in the marine environment. This study reports the incorporation of small amounts of zwitterionic carboxybetaine methacrylate (CBMA) into hydrophobic ethylene glycol dicyclopentenyl ether acrylate (DCPEA). A new set of copolymers with varying amphiphilicities was synthesized and coated on chemically modified glass substrates. The antifouling capabilities were assessed against the diatom Navicula perminuta and multiple species in the field. Unsurprisingly, high diatom densities were observed on the hydrophobic control coatings. The integration of small zwitterionic contents of only ∼5 wt % was already sufficient to rapidly form a hydrophilic interface that led to a strong reduction of fouling. Ultralow fouling was also observed for the pure zwitterionic coatings in laboratory experiments, but it failed when tested in the real ocean environment. We noticed that the ability to absorb large amounts of water and the diffuse nature of the interphase correlate with the adsorption of silt, which can mask the hydrophilic chemistries and facilitate the settlement of organisms. The amphiphilic coatings showed low fouling in dynamic short-term field exposures, which could be explained by the reduced tendency of the coatings for sediment adsorption.

Universal Strategy for Efficient Fabrication of Blood Compatible Surfaces via Polydopamine-Assisted Surface-Initiated Activators Regenerated by Electron Transfer Atom-Transfer Radical Polymerization of Zwitterions.

Implant and blood-contacting biomaterials are challenged by biofouling and thrombus formation at their interface. Zwitterionic polymer brush coating can achieve excellent hemocompatibility, but the preparation often involves tedious, expensive, and complicated procedures that are designed for specific substrates. Here, we report a facile and universal strategy of creating zwitterionic polymer brushes on variety of materials by polydopamine (PDA)-assisted and surface-initiated activators regenerated by electron transfer atom-transfer radical polymerization (PDA-SI-ARGET-ATRP). A PDA adhesive layer is first dipcoated on a substrate, followed by covalent immobilization of 3-trimethoxysilyl propyl 2-bromo-2-methylpropionate (SiBr, ATRP initiator) on the PDA via condensation. Meanwhile, the trimethoxysilyl group of SiBr also cross-links the PDA oligomers forming stabilized PDA/SiBr complex coating. Finally, SI-ARGET-ATRP is performed in a zwitterionic monomer solution catalyzed by the parts per million level of CuBr2 without deoxygenization. The conveniently fabricated zwitterionic polymer brush coatings are demonstrated to have stable, ultralow fouling, and extremely blood compatible and functionalizable characteristics. This facile, versatile, and universal surface modification strategy is expected to be widely applicable in various advanced biomaterials and devices.