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Coatings · 2023 ·Vol. 13 ·期 9 ·1643 · IF 3.4

The Synthesis and Synergistic Effect of Heterocyclic Groups Grafted on Acrylic Polymers by Ester Groups for Marine Antifouling

Dazhuang Wang,Ruotong Liu,Xiaohui Liu,Guangwen Hu,Zhineng Fu,Miao Dong,Liju Liu,Xinrui Lin,Ping Zhang,Junhua Chen,Jianxin Yang,Xinghua Xue

Using a synthetic antifoulant is an alternative technique to using a natural antifoulant for its economical and large-scale production characteristics. In this study, we synthesized allyl 3-oxzo[d]isothiazole-2(3H)-carboxylate (BIT-C) and a series of other heterocyclic compounds, including triazole, pyridine, and thiazole derivatives. These heterocyclic monomers were used to prepare a new series of acrylic polymers by grafting them onto the side chains. The weight change on the 42nd day was less than −0.091 mg/cm−2, indicating that antifoulants can be released into seawater consistently and enduringly. The antibacterial and anti-algae tests revealed that all the polymers had exceptional inhibition rates onE. coli,S. aureus,Chlorella, andChaetoceros curvisetus, with the highest inhibition rates of 99.81%, 99.22%, 92.70%, and 95.42%, respectively. Furthermore, the oyster and barnacle density and algae coverage rate were only about 200 per square meter and 10%, compared to 1800 per square meter and 100% of a blank plate after 90 days hanging in a real marine environment, showing a promising antifouling performance. This work verifies the possibility of a method for grafting different heterocycles on a single polymer to make a series of polymers that can be useful as an environmentally friendly antifouling coating.Keywords:antifouling coating;heterocyclic antifoulant;antibacterial;anti-algae;marine fouling

研究领域: 材料科学 · 海洋生物学
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ACS Applied Polymer Materials · 2022 · IF 4.855

Metal-Free, Low-Surface Energy, and Self-Healing Polyurethane Coating with an Excellent Antifouling Property

Rijia Jiang,Mengyue Liu,Xiangyu Zheng,Xing Zhou

The prevention and control of water biofouling has always been the focus of antifouling research. Coatings containing metal ions can effectively inhibit biofouling. However, the application of this type of coating has been limited as a result of its toxicity, irreparability, and poor antifouling ability under static conditions. Here, we have synthesized a self-repairing polymer antifouling coating with hydrophobic and multiple self-repairing systems through structural design with polytetrahydrofuran (PTMEG), isophorone diisocyanate (IPDI), perfluorooctyl ethyl acrylate (TEAc-8), triclosan (TCS), and 3,3-dithiodipropionic acid as a raw material. The prepared coating can realize a self-repairing function at room temperature in both air and water, thereby prolonging the antifouling life of the coating. A large number of hydrogen bonds in the molecular structure enable the coating to have good adhesion to the substrate. At the same time, the lower surface energy (<20 mN/m) and higher hydrophobic angle (>110°) of the coating determine the material’s good fouling release ability. In addition, the lake antifouling experiments show that the coating has good static antifouling ability. The coatings prepared will provide an alternative strategy for designing self-healing marine antifouling coatings in practical applications.

研究领域: 材料科学 · 海洋生物学
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RSC Advances · 2015 ·Vol. 5 ·期 84 ·68998-69005 · IF 3.84

Dual-mode antifouling ability of PVDF membrane with a surface-anchored amphiphilic polymer

Yongliang Chen,Xinzhen Zhao,Chunju He

Polydimethylsiloxane-graft-polyethylene glycol (PDMS-graft-PEG), an amphiphilic polymer with four hydrophilic arms, was prepared and used to improve the antifouling property of PVDF membranes by a dip-coating method. The interface properties of the modified PVDF membranes were investigated and it was found that the increased molecular weight of the PEG segment exhibited a negative effect on the anchoring ability of the PDMS-graft-PEG on the membrane surface. However, the antifouling properties of the modified membranes were significantly improved due to the dual-mode antifouling ability of fouling repulsion (PEG) and fouling release (PDMS). The adsorption mass of BSA on the modified membrane surface decreased to a low level, and an enhanced water flux recovery ratio after washing (FRR-W) of the modified membranes was obtained for two typical pollutants of bovine serum albumin and sodium alginate. It was demonstrated that surface anchoring is an effective way to improve the interface characteristics of membrane materials with functional polymers.

CAS / MDL: 4422-95-1 9005-38-3
研究领域: 材料科学 · 环境工程 · 生物技术
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ACS Sustainable Chemistry & Engineering · 2017 · IF 5.951

Environmentally Friendly Antifouling Coatings Based on Biodegradable Polymer and Natural Antifoulant

Chunfeng Ma,Weipeng Zhang,Guangzhao Zhang,Pei-Yuan Qian

Marine biofouling causes huge economic losses and serious problems to maritime industries. Consequently, there is a great demand for environmentally friendly antibiofouling technology. In the present study, we developed novel antifouling coatings by incorporating butenolide derived from marine bacteria into biodegradable poly(ε-caprolactone) based polyurethane. Measurements of mass loss indicated that the polymer was degraded in seawater and that the degradation rate increased in the presence of marine organisms or enzymes. Moreover, measured release rates indicated that butenolide could be released from the biodegradable polymer for at least 3 months and the release rate depended on both the concentration of butenolide and the temperature. Incorporating a naturally occurring resin (rosin) into the biodegradable polymer increased the self-renewal rate and improved the later release rate of butenolide. The field test indicated that the system had excellent antifouling properties.

CAS / MDL: 4098-71-9
研究领域: 材料科学 · 海洋生物学 · 环境科学
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PROGRESS IN ORGANIC COATINGS · 2021 · IF 5.161

Preparation and evaluation of natural rosin-based zinc resins for marine antifouling

Wenjun Zhou,Yanjian Wang,Chunhua Ni,Liangmin Yu

Currently, it is highly desirable to develop a novel antifouling resin with a controllable hydrolysis rate and stable and effective antifouling performance for marine antifouling coatings. In our study, we prepared natural rosin-based zinc (RZn-x) resins by a relatively facile and green synthetic method from Zn(OH) 2 and antimicrobial natural rosin, which is considered a toxicity-free raw material, thus ensuring the green and antimicrobial character of the material. In their optimal combination, the RZn-x coating surface exhibited ideal peeling behaviour upon immersion in seawater, which caused the WCA of the material surface to change from 55° before immersion to 135° after immersion for 60 days and enhanced the antifouling properties. Dynamic simulation experiments of these resins also demonstrated that the hydrolysis rate of this material immersed in dynamic seawater was related to the zinc content, and we could control the self-polishing ability of the resins by adjusting the content of Zn(OH) 2 participating in the reaction. Moreover, hydrolysis led to a hydrophobic surface, which could prevent fouling organisms from adhering. Laboratory bioassays against BSA adsorption (immersed for 4 h: 1.986 μg/cm 2 ), bacterial (over 95 % reduction) and marine algal adhesion (more than 60 % reduction) revealed outstanding anti-protein, bacteriostasis and anti-algal growth and adhesion properties compared to pure rosin and the control sample. The long-term antifouling capability in marine field tests indicated that the RZn-x resins maintained their antifouling activity for more than 6 months, especially RZn-50, which showed excellent antifouling performance.

CAS / MDL: 9048-46-8
研究领域: 材料科学 · 海洋生物学 · 环境科学
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Nanomaterials · 2019 ·Vol. 9 ·期 5 ·706 · IF 4.034

P4VP Modified Zwitterionic Polymer for the Preparation of Antifouling Functionalized Surfaces

Chaoqun Wu,Yudan Zhou,Haitao Wang,Jianhua Hu

Zwitterionic polymers are suitable for replacing poly(ethylene glycol) (PEG) polymers because of their better antifouling properties, but zwitterionic polymers have poor mechanical properties, strong water absorption, and their homopolymers should not be used directly. To solve these problems, a reversible-addition fragmentation chain transfer (RAFT) polymerization process was used to prepare copolymers comprised of zwitterionic side chains that were attached to an ITO glass substrate using spin-casting. The presence of 4-vinylpyridine (4VP) and zwitterion chains on these polymer-coated ITO surfaces was confirmed using 1H NMR, FTIR, and GPC analyses, with successful surface functionalization confirmed using water contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) studies. Changes in water contact angles and C/O ratios (XPS) analysis demonstrated that the functionalization of these polymers with β-propiolactone resulted in hydrophilic mixed 4VP/zwitterionic polymers. Protein adsorption and cell attachment assays were used to optimize the ratio of the zwitterionic component to maximize the antifouling properties of the polymer brush surface. This work demonstrated that the antifouling surface coatings could be readily prepared using a “P4VP-modified” method, that is, the functionality of P4VP to modify the prepared zwitterionic polymer. We believe these materials are likely to be useful for the preparation of biomaterials for biosensing and diagnostic applications.Keywords:copolymer;biofilms;spin-casting;antifouling

研究领域: 材料科学 · 生物医学工程
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Coatings · 2022 ·Vol. 12 ·期 6 ·855 · IF 3.236

Fluorinated-Triazole-Modified ZnO and Its Application in Marine Antifouling

Yu Yang,Guoqing Wang,Longlin Lei,Yangkai Xiong,Zhiqiang Fang,Lei Huang,Jinbo Liu,Daxiong Hu,Jianhe Liao

The accumulation of marine biological growth has irreversible negative effects on shipping and coastal fisheries. In this paper, a new antibacterial nanofiller—triazole fluoroaromatic hydrocarbon−modified nano−zinc oxide (ZnO−APTES−TRF)—was prepared by a Cu(I)−catalyzed azide–alkyne click chemical reaction. The modification of nano−ZnO with triazole ring fluoroaromatic hydrocarbons were testified by FT−IR, XPS, and EDS. The grafting rate of ZnO−APTES−TRF can reach 32.38%, which was verified by the TGA test. The ZnO−APTES−TRF was mixed with zinc acrylate resin to produce a low surface energy antifouling coating with a surface water contact angle of 106°. The bactericidal rate of ZnO−APTES−TRF againstEscherichia coli,Staphylococcus aureus, andPseudoalteromonassp. can reach more than 98% due to the synergistic effect of triazole and fluorine. The 120−day marine experiment shows that the low surface energy antifouling coating of ZnO−APTES−TRF/ZA is expected to be widely used in the field of marine antifouling.Keywords:antifouling;marine;ZnO;triazole;modification;hydrophobic

研究领域: 材料科学 · 海洋生物学
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ACS Nano · 2022 · IF 18.027

Ultrasmall Cu3(PO4)2 Nanoparticles Reinforced Hydrogel Membrane for Super-antifouling Oil/Water Emulsion Separation

Yuyue Mo,Feng Zhang,Hefeng Dong,Xingzhen Zhang,Shoujian Gao,Shenxiang Zhang,Jian Jin

Membrane fouling is a persistent and crippling challenge for oily wastewater treatment due to the high susceptibility of membranes to contamination. A feasible strategy is to design a robust and stable hydration layer on the membrane surface to prevent contaminates. A hydrogel illustrates a distinct category of materials with outstanding antifouling performance but is limited by its weak mechanical property. In this research, we report a reinforced hydrogel on a membrane by in situ growing ultrasmall hydrophilic Cu3(PO4)2 nanoparticles in a copper alginate (CuAlg) layer via metal-ion-coordination-mediated mineralization. The embeddedness of hydrophilic Cu3(PO4)2 nanoparticle with a size of 3–5 nm endows the CuAlg/Cu3(PO4)2 composite hydrogel with enhanced mechanical property as well as reinforced hydrate ability. The as-prepared CuAlg/Cu3(PO4)2 modified membrane exhibits a superior oil-repulsive property and achieves a nearly zero flux decline for separating surfactant stabilized oil-in-water emulsions with a high permeate flux up to ∼1330 L m–2 h–1 bar–1. Notably, it is capable of keeping similar permeate flux for both pure water and oil-in-water emulsions during filtration, which is superior to the currently reported membranes, indicating its super-antifouling properties.

研究领域: 环境工程 · 材料科学 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2023 · IF 9.5

Fouling- and chlorine- resistant bilayer heterostructured Janus charged nanofiltration membranes constructed via novel electrospray polymerization-based method

Zhongbao Ma,Chao Wang,Ran Li,Yi Zhao,Chenglin Zhang,Long-Fei Ren,Jiahui Shao

Janus charged nanofiltration (NF) membranes are appealing for efficient separation of both positively and negatively charged ions/molecules. Nevertheless, polyamide-based Janus charged membranes still face bottlenecks in engineering applications due to their poor fouling and chlorine resistance. To overcome this limitation, herein, bilayer heterostructured Janus charged NF membranes with a negatively charged non-polyamide outer selection layer and a positively charged polyamide inner selection layer were prepared via electrospray polymerization-based strategy for the first time. The evolutionary behavior of the mutually charge neutralization effect between two charged selection layers was explored. Results showed the membrane inner selection layer with denser cross-linked structures and lower positive charge densities exhibited a weak charge neutralization effect, leading to ∼90% rejection for both Na 2 SO 4 and MgCl 2 and >95% rejection for charged dyes. Impressively, the flux recovery rate of Janus NF membrane could reach 91.9% after three bovine serum albumin fouling cycles. More importantly, the non-polyamide outer selection layer could serve as an “armor” to safeguard polyamide inner selection layer, allowing Janus NF membranes to maintain a normalized salt rejection of 0.94 even under 12000 mg L −1 h chlorination conditions. Thus, this work provides an easy strategy for developing Janus NF membranes with high antifouling properties and chlorine resistance.

研究领域: 材料科学 · 化学工程 · 环境工程 · 膜技术
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CHEMOSPHERE · 2022 · IF 8.943

A novel janus membrane modified by MXene for enhanced anti-fouling and anti-wetting in direct contact membrane distillation

Xiaoju Yan,Chengyu Yang,Cong Ma,Hui Tao,Shirong Cheng,Lin Chen,Guodong Wang,Xinping Lin,Chengzhi Yao

Membrane fouling and wetting limit the applications of membrane distillation (MD) for wastewater treatment , especially when treating the wastewater with a high concentration of low surface tension substances such as oil and surfactants. In this paper, virgin polyvinylidene fluoride (PVDF) membrane was modified by polydimethylsiloxane (PDMS) to enhance anti-wetting ability. Then a thin polydopamine (PDA) layer was coated as a reaction platform for further modification. Polyethyleneimine (PEI) was cross-linked with PDA to form a uniform and stable layer, through hydrogen bonds and electrostatic interaction to immobilize hydrophilic MXene, which formed a Janus MXene-PVDF membrane. The MXene layer was the key for superoleophobicity and high liquid entry pressure (LEP) of membrane, capable of mitigating membrane fouling and wetting when dealing with low surface tension wastewater (LSTW). From the experiments results, pristine PVDF membrane showed severe fouling and wetting with flux decline and salt leakage during treatment of LSTW (surfactants containing water, oil-in-water emulsion and sodium dodecyl sulfate stabilized oil-in-water emulsion). However, under the same conditions, the Janus MXene-PVDF membrane exhibited remarkably stable flux (9.3 kg m −2 h −1 , 9.1 kg m −2 h −1 , 10.2 kg m −2 h −1 ) and salt rejection (almost 99.9%) after 15 h operation. Excellent fouling and wetting resistance of MXene-PVDF membrane was mainly attributed to its superhydrophilic and superoleophobic top surface (in-air water contact angle: 30.2°, under-water oil contact angle: 169.9°) and hydrophobic substrate (in-air water contact angle: 130.8°), together with high LEP value (91.1 Kpa). This study provides a viable route to fabricated a Janus membrane with outstanding fouling and wetting resistance for LSTW, oily wastewater and it has great potential for sewage treatment in the future.

研究领域: 环境科学 · 材料科学
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JOURNAL OF MEMBRANE SCIENCE · 2014 · IF 4.908

High efficient protocol for the modification of polyethersulfone membranes with anticoagulant and antifouling properties via in situ cross-linked copolymerization

Hui Qin,Chuangchao Sun,Chao He,Dongsheng Wang,Chong Cheng,Shengqiang Nie,Shudong Sun,Changsheng Zhao

In this paper, we provide a highly efficient, convenient and universal protocol for blood-compatible modification of polyethersulfone (PES) membranes via in situ cross-linked copolymerization of 2-hydroxyethl methacrylate (HEMA) and acrylic acid (AA) in PES solutions. Static water contact angle, protein adsorption, platelet adhesion, and clotting time of the modified PES membranes are systematically studied, and the results indicate that the modified membranes show improved hydrophilicity, good blood anticoagulant and antifouling properties after introducing HEMA and AA. Meanwhile, the modified membranes perform low contact activation and complement activation when they come in contact with blood. The effect of the HEMA/AA ratios on the blood compatibility is also investigated to identify the different roles played by HEMA and AA in the modification; the HEMA could more effectively enhance the membrane antifouling property, while the AA could more effectively improve the anticoagulant property. The results indicated that the blood-compatible PES membranes prepared via the in situ cross-linked copolymerization had potential to be used in the field of blood purification.

研究领域: 材料科学 · 生物医学工程
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2024 · IF 5.4

PEG-functionalized aliphatic polycarbonate brushes with self-polishing dynamic antifouling properties

Yijia Yu,Wenjuan Xia,Wenjin Wang,Zhaoqiang Wu,Hong Chen

Hydrophilic antifouling polymers provide excellent antifouling effects under usual short-term use conditions, but the long-term accumulation of contaminants causes them to lose their antifouling properties. To overcome this drawback, surface-initiated ring-opening graft polymerization (SI-ROP) was performed on the surface of the material by applying the cyclic carbide monomer 4′-(fluorosulfonyl)benzyl-5-methyl-2-oxo-1,3-dioxane-5-carboxylate (FMC), which contains a sulfonylfluoride group on the side chain, followed by a “sulfur(IV)-fluorine exchange” (SuFEx) post click modification reaction to link the hydrophilic polyethylene glycol (PEG) to the polyFMC (PFMC) brush, and a novel antifouling strategy for self-polishing dynamic antifouling surfaces was developed. The experimental results showed that the antifouling surface could effectively prevent the adsorption of proteins such as bovine serum albumin (BSA, ∼96.4%), fibrinogen (Fg, ∼87.8%) and lysozyme (Lyz ∼69.4%) as well as the adhesion of microorganisms such as the bacteria Staphylococcus aureus ( S. aureus ) (∼87.5%) and HeLa cells (∼67.2%). Moreover, the enzymatically self-polished surface still has excellent antifouling properties. Therefore, this modification method has potential applications in the field of biosensors and novel antifouling materials.

研究领域: 材料科学 · 表面化学 · 生物医学工程 · 高分子科学 · 生物材料
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