海洋污损生物粘附机制及防污涂层表面工程

任何浸入海水的结构物均会受到海洋污损生物的附着。 在物体表面涂覆防污涂料是最广泛的防污方式,无毒污损脱附型防污涂料已成为当前的研究热点。 分析了污损生物的粘附过程及界面粘结作用,探讨了表面能、涂层模量、表面化学成分、微观形貌、颜色等因素对涂层防污效果的影响,并指出涂料工程化中必须解决的问题。     

海洋防污高分子材料的综合设计和研究

综述了海洋防污高分子材料与技术的发展现状.简介了海洋生物污损的形成过程,概述了杀生防污涂料、污损可脱附性涂层、阻止附着型防污技术以及其它现存的防污方法,并在此基础上提出了一种新的海洋防污高分子材料的综合设计方案,最后展示了有关海洋防污材料研究的最新成果.     

绿色海洋防污涂料技术及其研究进展

海洋生物污损给人类海洋生产和运输活动带来了严重的影响,涂覆防污涂料是解决这一问题根本办法。近年来大量使用的有机锡和氧化亚铜涂料,对海洋生物的生存环境造成了危害。因此,研究高效、低毒、绿色的海洋防污涂料成为目前发展的主要方向。本文综述了当前绿色环保型防污涂料的发展状况及研究进展,重点介绍了含氟、含硅低表面能防污涂料、天然产物防污涂料和新型无锡自抛光防污涂料的发展状况,并分析了今后绿色海洋防污涂料的发展趋势。     

包埋苯甲酸钠微球的制备及在海洋防污涂料中的抑菌研究

用溶剂挥发法制备了可以包埋海洋防污剂苯甲酸钠的聚苯乙烯聚合物微球,并实现了防污剂在海洋防污涂料中的的缓慢释放.讨论了影响微球性能的一些因素,聚合物微球的粒径分别随着温度的降低,分散剂浓度的升高以及搅拌速度的提高而减小.采用标准曲线法,对防污剂释放速度进行了分析,并与未用微球包埋的苯甲酸钠释放速度进行对比,缓释效果明显....     

气相色谱-质谱法同时检测海洋涂料中4种生物杀虫剂

建立了同时测定海洋防污涂料中4种生物杀虫剂(百菌清、苯氟磺胺、Sea-Nine 211和Irgarol1051)的气相色谱-质谱方法。该方法以乙酸乙酯为提取试剂,室温下超声提取4种生物杀虫剂,提取液经有机滤膜过滤后,在选择离子模式下用气相色谱-质谱联用仪进行检测。优化实验条件下,4种生物杀虫剂在测试的浓度范围内线性关系良好,相关系数(r2)均大于0.99,检出限(S/N≥3)为0.3~1.3 mg/kg,定量下限(S/N≥10)为1.0~4.3 mg/kg。方法的加标回收率为82.6%~109.9%,相对标准偏差小于5%。采用该方法对6种海洋防污涂料进行测定,2个样品分别检出百菌清和苯氟磺胺、Sea-Nine 211。该方法简便快速、定性定量准确、灵敏度高,能够满足海洋涂料中4种生物杀虫剂的检测要求。     

环境友好海洋防污体系的研究进展

海洋污损是海洋资源开发与利用中遇到的一个国际性难题,发展环境友好海洋防污体系是该领域最重要的方向。本文综述了近年来环境友好海洋防污体系的研究进展,并探讨了未来的发展方向。     

防污涂料进入“无锡”时代

含有机锡的防污涂料由于受海洋环境保护的压力和国际海事组织(IMO)的禁用,将逐渐淡出涂料大家庭;防污涂料将向无锡、无公害方向发展.     

具类辣素结构丙烯酰胺的合成及其抑菌和防污性能

以N-羟甲基丙烯酰胺和苯酚类化合物为原料,合成了N-(2-羟基-3-丙烯酰胺甲基-4,6-二甲基苄基)丙烯酰胺(HMABA)、N-(2-羟基-3-丙烯酰胺甲基-4,5-二甲基苄基)丙烯酰胺(AMHBA)、N-(3,5-二甲基-4-羟基苄基)丙烯酰胺(MHBA)、N-(3,6-二甲基-4-丙烯酰胺甲基-2-羟基苄基)丙烯酰胺(MAHBA)和N-(2甲氧基-4-甲基-5-丙烯酰胺甲基苄基)丙烯酰胺(MMABA)5个类辣素结构的丙烯酰胺衍生物。 通过红外光谱（IR）、核磁波谱（1H NMR）、质谱（HR-MS）和元素分析对化合物的结构进行了表征。 抑菌试验表明,HMABA对金黄色葡萄球菌和大肠杆菌的抑制效果最好,最低抑菌浓度均可达0.125 g/L。 将此5个化合物作为防污剂制备海洋防污涂料,120 d的实海结果表明,基本无污损海生物附着。     

灌注液体型光滑多孔表面制备及应用

仿猪笼草效应的灌注润滑液的光滑多孔表面(SLIPS)是将润滑液如全氟聚醚、硅油、离子液体等灌注到微/纳粗糙结构基材中制备的。SLIPS材料表面可达到分子尺度的光滑,能显著减小液滴滑动角和滞后角,具有全方位疏液、自修复、透明度高、温度和压力稳定性好等诸多优点,能够高效抑制各种基材包括油脂、血液、冰以及生物膜的黏附,在自清洁涂料、海洋防污、生物医用领域具有广阔的应用前景。近年来SLIPS材料因其具有的特殊表面润湿性能而备受研究者的关注,本文详细介绍了SLIPS材料的构建机理和制备方法,包括浸润法和溶胀法等。综述了SLIPS材料在防污、促进滴状冷凝、防霜防覆冰、油水分离等方面的最新进展,并对SLIPS目前存在的问题与发展方向进行了分析和展望。     

吲哚衍生物的合成及其海洋防污性能

以吲哚和酰氯(苯甲酰氯及苯磺酰氯)为原料，合成了7个N-酰基取代吲哚类化合物(a~g)，其结构经¹H NMR和元素分析确证。研究了化合物对球等鞭金藻、亚心形扁藻和舟形藻以及藤壶幼虫的生长抑制活性。结果表明：当吲哚结构连接电负性较高的基团时，化合物对藻类和藤壶幼虫的生长抑制性较好，其中以连接苯磺酰基化合物的抑制效果最佳。目标化合物对藤壶幼虫12 h和24 h的半致死浓度(LC₅₀)明显低于底物吲哚，其中以苯磺酰基取代的化合物最低。采用目标化合物制备的海洋防污涂料，浅海挂板90 d后，对海洋污损生物的附着表现出明显的抑制作用。     

Engineered nanoforce gradients for inhibition of settlement (attachment) of swimming algal spores

Current antifouling strategies are focused on the development of environmentally friendly coatings that protect submerged surfaces from the accumulation of colonizing organisms (i.e., biofouling). One ecofriendly approach is the manipulation of the surface topography on nontoxic materials to deter settlement of the dispersal stages of fouling organisms. The identification of effective antifouling topographies typically occurs through trial-and-error rather than predictive models. We present a model and design methodology for the identification of nontoxic, antifouling surface topographies for use in the marine environment by the creation of engineered nanoforce gradients. The design and fabrication of these gradients incorporate discrete micrometer-sized features that are associated with the species-specific surface design technique of engineered topography and the concepts of mechanotransduction. The effectiveness of designed nanoforce gradients for antifouling applications was tested by evaluating the settlement behavior of zoospores of the alga Ulva linza. The surfaces with nanoforce gradients ranging from 125 to 374 nN all significantly reduced spore settlement relative to a smooth substrate, with the highest reduction, 53%, measured on the 374 nN gradient surface. These results confirm that the designed nanoforce gradients may be an effective tool and predictive model for the design of unique nontoxic, nonfouling surfaces for marine applications as well as biomedical surfaces in the physiological environment.     

原位探测防污高分子材料与液体界面的分子结构

Marine organisms such as plants, algae or small animals can adhere to surfaces of materials that are submerged in ocean. The accumulation of these organisms on surfaces is a marine biofouling process that has considerable adverse effects. Marine biofouling on ship hulls can cause severe fuel consumption increase. Investigations on antifouling polymers are therefore becoming important research topics for marine vessel operations. Antifouling polymers can be applied as coating layers on the ship hull, protecting it against the settlement and growth of sea organisms. Polyethylene glycol (PEG) is a hydrophilic polymer that can effectively resist the accumulation of marine organisms. PEG-based antifouling coatings have therefore been extensively researched and developed. However, the inferior stability of PEG makes it subject to degradation, rendering it ineffective for long-term services. Zwitterionic polymers have also emerged as promising antifouling materials in recent years. These polymers consist of both positively charged and negatively charged functional groups. Various zwitterionic polymers have been demonstrated to exhibit exceptional antifouling properties. Previously, surface characterizations of zwitterionic polymers have revealed that strong surface hydration is critical for their antifouling properties. In addition to these hydrophilic polymers, amphiphilic materials have also been developed as potential antifouling coatings. Both hydrophobic and hydrophilic functional groups are incorporated into the backbones or sidechains of these polymers. It has been demonstrated that the antifouling performance can be enhanced by precisely controlling the sequence of the hydrophobic-hydrophilic functionalities. Since biofouling generally occurs at the outer surface of the coatings, the antifouling properties of these coatings are closely related to their surface characteristics in water. Therefore, understanding of the surface molecular structures of antifouling materials is imperative for their future developments. In this review, we will summarize our recent advancements of antifouling material surface analysis using sum frequency generation (SFG) vibrational spectroscopy. SFG is a surface-sensitive technique which can provide molecular information of water and polymer structures at interfaces in situ in real time. The antifouling polymers we will review include zwitterionic polymer brushes, mixed charged polymers, and amphiphilic polypeptoids. Interfacial hydration studies of these polymers by SFG will be presented. The salt effect on antifouling polymer surface hydration will also be discussed. In addition, the interactions between antifouling materials and protein molecules as well as algae will be reviewed. The above research clearly established strong correlations between strong surface hydration and good antifouling properties. It also demonstrated that SFG is a powerful technique to provide molecular level understanding of polymer antifouling mechanisms.     

Efficient and robust coatings using poly(2-methyl-2-oxazoline) and its copolymers for marine and bacterial fouling prevention

Molecular design, fabrication, and properties of thin-film coatings based on poly(2-methyl-2-oxazoline) (PMOX) and its copolymers were investigated to tackle problem of marine and bacterial fouling prevention. The ultraviolet crosslinkable macromonomer poly(2-methyl-2-oxazoline) dimethylacrylate was synthesized by cationic ring-opening polymerization in a microwave reactor initiated by 1,4-dibromobutane. In order to study the charge effect of the PMOX coatings on the adhesion of fouling organisms, PMOX surfaces with negative, neutral, and positive ζ-potential values were prepared by copolymerization with the positively charged monomer [2-(methacryloyloxy)-ethyl]trimethylammonium chloride. The coatings were stable in sea water for at least 1 month without significant reduction in the film thickness. The marine antifouling activity was evaluated against barnacle cyprids Amphibalanus amphitrite and algae Amphora coffeaeformis. Results showed that PMOX coatings provide effective reduction of the settlement regardless of the molar mass and surface charge of the polymer. Bacterial adhesion test showed that PMOX coatings effectively reduce Staphylococcus aureus and Escherichia coli adhesion. Owing to its good stability and antifouling activity PMOX has a great potential as antifouling coating for marine antifouling applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 275–283     

Structures and antifouling properties of low surface energy non-toxic antifouling coatings modified by nano-SiO_2 powder

Antifouling coatings are used to improve the speed and energy efficiency of ships by preventing or- ganisms, such as barnacles and weed, building up on the underwater hull and helping the ships movement through the water. Typically, marine coatings are tributyltin self-polishing copolymer paints containing toxic molecules called biocides. They have been the most successful in combating bio- fouling on ships, but their widespread use has caused severe pollution in the marine ecosystem. The low surface energy marine coating is an entirely non-toxic alternative, which reduces the adhesion strength of marine organisms, facilitating their hydrodynamic removal at high speeds. In this paper, the novel low surface energy non-toxic marine antifouling coatings were prepared with modified acrylic resin, nano-SiO2, and other pigments. The effects of nano-SiO2 on the surface structure and elastic modulus of coating films have been studied, and the seawater test has been carried out in the Dalian Bay. The results showed that micro-nano layered structures on the coating films and the lowest surface energy and elastic modulus could be obtained when an appropriate mass ratio of resin, nano-SiO2, and other pigments in coatings approached. The seawater exposure test has shown that the lower the sur- face energy and elastic modulus of coatings are, the less the marine biofouling adheres on the coating films.     

Novel marine antifouling coatings inspired by corals

Biofouling is a major problem facing the marine industry. Since toxic antifouling coatings were banned globally due to their negative impacts on the marine environment, the development of environmental-friendly and efficient antifouling coatings has been identified as a pressing need. As an alternative, the antifouling coatings inspired by corals have attracted a great deal of attention over these years. within the marine environment, corals have evolved an excellent antifouling capability. There are five major antifouling strategies applied by corals, including natural antifoulants, foul release effect, sloughing effect, soft tentacles, and fluorescence effect. In this paper, a brief review is conducted to introduce the antifouling coatings inspired by the five strategies. Moreover, a discussion is conducted about the existing problems with the five strategies and the direction of their further development is indicated.     

Automated image-based method for laboratory screening of coating libraries for adhesion of algae and bacterial biofilms

Assessment and down-selection of non-biocidal coatings that prevent the adhesion of fouling organisms in the marine environment requires a hierarchy of laboratory methods to reduce the number of experimental coatings for field testing. Automated image-based methods are described that facilitate rapid, quantitative biological screening of coatings generated through combinatorial polymer chemistry. Algorithms are described that measure the coverage of bacterial and algal biofilms on coatings prepared in 24-well plates and on array panels, respectively. The data are used to calculate adhesion strength of organisms on experimental coatings. The results complement a number of physical and mechanical methods developed to screen large numbers of samples.     

Biomimetic Bottlebrush Polymer Coatings for Fabrication of Ultralow Fouling Surfaces

Demand for long‐lasting antifouling surfaces has steered the development of accessible, novel, biocompatible and environmentally friendly materials. Inspired by lubricin (LUB), a component of mammalian synovial fluid with excellent antifouling properties, three block polymers offering stability, efficacy, and ease of use were designed. The bottlebrush‐structured polymers adsorbed strongly on silica surfaces in less than 10 minutes by a simple drop casting or online exposure method and were extremely stable in high‐salinity solutions and across a wide pH range. Antifouling properties against proteins and bacteria were evaluated with different techniques and ultralow fouling properties demonstrated. With serum albumin and lysozyme adsorption <0.2 ng cm^?2, the polymers were 50 and 25 times more effective than LUB and known ultralow fouling coatings. The antifouling properties were also tested under MPa compression pressures by direct force measurements using surface forces apparatus. The findings suggest that these polymers are among the most robust and efficient antifouling agents currently known.     

Zwitterionic Polysulfobetaine Coating and Antiplatelet Liposomes Reduce Fouling in Artificial Lung Circuits

The artificial lung has provided life-saving support for pulmonary disease patients and recently afforded patients with severe cases of COVID-19 better prognostic outcomes. While it addresses a critical medical need, reducing the risk of clotting inside the device remains challenging. Herein, a two-step surface coating process of the lung circuit using Zwitterionic polysulfobetaine methacrylate is evaluated for its nonspecific protein antifouling activity. It is hypothesized that similarly applied coatings on materials integrated (IT) or nonintegrated (NIT) into the circuit will yield similar antifouling activity. The effects of human plasma preconditioned with nitric oxide-loaded liposome on platelet (plt) fouling are also evaluated. Fibrinogen antifouling activities in coated fibers are similar in the IT and NIT groups. It however decreases in coated polycarbonate (PC) in the IT group. Also, plt antifouling activity in coated fibers is similar in the IT and NIT groups and is lower in coated PC and Tygon in the IT group compared to the NIT group. Coating process optimization in the IT lung circuit may help address difference in the coating appearance of outer and inner fiber bundle fibers, and the NO-liposome significantly reduces (86%) plt fouling on fibers indicating its potential use for blood anticoagulation.     

Biofouling studies on nanoparticle-based metal oxide coatings on glass coupons exposed to marine environment

Titania, niobia and silica coatings, derived from their respective nanoparticle dispersions or sols and fabricated on soda lime glass substrates were subjected to field testing in marine environment for antimacrofouling applications for marine optical instruments. Settlement and enumeration of macrofouling organisms like barnacles, hydroides and oysters on these nanoparticle-based metal oxide coatings subjected to different heat treatments up to 400 °C were periodically monitored for a period of 15 days. The differences observed in the antifouling behaviour between the coated and uncoated substrates are discussed based on the solar ultraviolet light induced photocatalytic activities as well as hydrophilicities of the coatings in case of titania and niobia coatings and the inherent hydrophilicity in the case of silica coating. The effect of heat treatment on the photocatalytic activity of the coatings is also discussed.