Antifouling coatings: recent developments in the design of surfaces that prevent fouling by proteins, bacteria, and marine organisms

The major strategies for designing surfaces that prevent fouling due to proteins, bacteria, and marine organisms are reviewed. Biofouling is of great concern in numerous applications ranging from biosensors to biomedical implants and devices, and from food packaging to industrial and marine equipment. The two major approaches to combat surface fouling are based on either preventing biofoulants from attaching or degrading them. One of the key strategies for imparting adhesion resistance involves the functionalization of surfaces with poly(ethylene glycol) (PEG) or oligo(ethylene glycol). Several alternatives to PEG-based coatings have also been designed over the past decade. While protein-resistant coatings may also resist bacterial attachment and subsequent biofilm formation, in order to overcome the fouling-mediated risk of bacterial infection it is highly desirable to design coatings that are bactericidal. Traditional techniques involve the design of coatings that release biocidal agents, including antibiotics, quaternary ammonium salts (QAS), and silver, into the surrounding aqueous environment. However, the emergence of antibiotic- and silver-resistant pathogenic strains has necessitated the development of alternative strategies. Therefore, other techniques based on the use of polycations, enzymes, nanomaterials, and photoactive agents are being investigated. With regard to marine antifouling coatings, restrictions on the use of biocide-releasing coatings have made the generation of nontoxic antifouling surfaces more important. While considerable progress has been made in the design of antifouling coatings, ongoing research in this area should result in the development of even better antifouling materials in the future.     

仿生防污材料的研究进展

船舶表面的生物污损会带来极大的危害,如何防除生物污损已成为一个世界难题。尽管氧化亚铜等有毒防污剂可以有效防止海生物的附着污损,但这类防污剂对非目标生物也具有负面作用,可能带来严重的生态问题。随着国际社会对有毒防污剂和海洋环境的日益关注,发展环境友好型防污材料已势在必行。人们经常观察到自然界许多生物并没有被其它生物种类寄生聚居,这是因为在自然界中生物自身存在着各不相同但极为有效的防污机制,包括化学性质、物理性质、机械清理、生活习性,以及各种防污机制的组合等,这为研制环境友好型仿生防污材料提供了依据。综述海洋环境中仿生防污材料的研究进展,重点介绍了基于生物防污剂、表面微结构、水凝胶、抗蛋白吸附等特性进行防污的仿生材料研究,并阐述了我国在该领域已经取得的重要技术突破和主要技术成果,展望了仿生防污技术的发展趋势。     

海洋船舶有机硅低表面能防污涂料的研究进展

海洋防污涂料是海洋工程与装备的重要防护材料,对于海洋资源开发利用发挥着极其重要的作用。在现用的海洋防污涂料中,低表面能防污涂料不会对海洋环境产生破坏,是将来的主要发展方向。本文简要介绍了低表面能防污涂料的机理及影响因素,重点论述了有机硅改性不同有机树脂的防污涂料、纳米材料改性有机硅防污涂料和有机硅仿生复合防污体系的技术发展现状,并展望了未来低表面能船舶防污涂料的发展方向。     

Determination of methylmercury and butyltin compounds in marine biota and sediments using microwave-assisted acid extraction,solid-phase microextraction,and gas chromatography with microwave-induced plasma atomic emission spectrometric detection

A method is described for the determination of methylmercury and butyltin compounds in marine sediment and tissue using microwave-assisted acid extraction or digestion and solid-phase microextraction (SPME) followed by analysis using gas chromatography with microwave-induced plasma atomic emission spectrometric detection (GC-MIP-AES). Using the SPME-GC-MIP-AES method, enrichment factors for methylmercury and butyltin compounds of 50-100 were achieved, as compared to the typical hexane extraction, and measurements in marine tissue and sediment matrixes were possible at 1-2 microg/kg (methylmercury) and 10-100 ng/kg (butyltins). The SPME-GC-MIP-AES method was validated using several marine sediment and tissue matrix certified reference materials (CRMs) with certified values for methylmercury and butyltin compounds. The SPME-GC-MIP-AES method was used to measure methylmercury in four marine tissue CRMs ranging from oyster tissue at 13.0 +/- 1.0 microg/kg to fish tissue at 397 +/- 13 microg/kg (as Hg dry mass). Results from the SPME-GC-MIP-AES method were used in conjunction with results from other techniques to assign certified values for methylmercury in oyster, mussel, and fish tissue CRMs. Mono-, di-, and tributyltin were measured in three sediment CRMs at concentration levels of (0.08 +/- 0.03)-(0.35 +/- 0.05) mg/kg (as Sn dry mass).     

舰船防污涂料的使用需求及研究进展

海洋生物附着导致的生物污损是舰船航行过程中面临的一大难题,涂装防污涂料被认为是防止海洋生物污损舰船最经济有效的方法。根据舰船的服役特点,介绍了舰船防污涂料对于长效性、动静普适性和海域广谱性的使用需求,提出研发环保型长效防污涂料是当前防污损研究领域的一大挑战。简单综述了自抛光型防污涂料、污损释放型防污涂料、仿生型防污涂料、表面自愈型防污涂料以及其他防污新技术的发展,指出自抛光型防污涂料仍是当前稳定批量应用的主流产品,其他新型防污技术的防污期效仍需经过实际应用验证。随着环保要求的日趋严格,防污损机理研究的不断深入以及防污性能评价方法的不断完善,新型环保防污涂料的研制将逐渐加快并得到广泛推广应用。     

海洋防污剂的研究进展

概述了海洋防污剂的研究现状,简要介绍了主要商业防污剂的特点,重点介绍了新型环保防污剂的研究进展,包括天然产物基防污剂、酶基防污剂、纳米防污剂以及硅酸盐防污剂。最后,对海洋防污剂的研究和发展方向进行了展望。      

Wear-resistant/antifouling integrated coating protection technology of polyethylene cable

Polymer cables are being applied increasingly in fields such as deep-sea mooring and cage culture. How to improve their wear resistance and prevent microbial adhesion is an urgent problem to be solved. In this work, the surface of the cable was treated by the polyvinylpyrrolidone cross-linking method and the anchoring effect of one-dimensional linear nanomaterials, which improved the adhesion of the water-based coating. Meanwhile, the protective effect of the coating was improved through the addition of antifouling agents and wear-resistant agents. The microstructure and intermolecular forces of the coating were characterized by scanning electron microscopy and infrared spectroscopy. The net hanging test results show that the surface-treated cable exhibits better abrasion resistance and antifouling effects, and the shedding phenomenon is significantly improved.     

Microtopography of the eye surface of the crab Carcinus maenas: an atomic force microscope study suggesting a possible antifouling potential

Marine biofouling causes problems for technologies based on the sea, including ships, power plants and marine sensors. Several antifouling techniques have been applied to marine sensors, but most of these methodologies are environmentally unfriendly or ineffective. Bioinspiration, seeking guidance from natural solutions, is a promising approach to antifouling. Here, the eye of the green crab Carcinus maenas was regarded as a marine sensor model and its surface characterized by means of atomic force microscopy. Engineered surface micro- and nanotopography is a new mechanism found to limit biofouling, promising an effective solution with much reduced environmental impact. Besides giving a new insight into the morphology of C. maenas eye and its characterization, our study indicates that the eye surface probably has antifouling/fouling-release potential. Furthermore, the topographical features of the surface may influence the wettability properties of the structure and its interaction with organic molecules. Results indicate that the eye surface micro- and nanotopography may lead to bioinspired solutions to antifouling protection.     

海洋防污涂料发展现状与研究趋势

本文概述了海洋防污涂料的发展情况,并重点介绍了新型环保防污涂料的发展现状及其作用机制,同时分析了其面临的问题,并提出了如何解决新型防污涂料的应用,以及海洋防污涂料未来发展的趋势。     

环保型防污涂料研究进展

简要介绍了防污涂料中的有毒防污剂和VOC对人体和环境的危害,以及一些国家的应对策略。从防污剂的无毒化、低表面自由能树脂、导电防污涂料、低VOC防污涂料等方面综述了环保型防污涂料研究和开发取得的进展。并提出了需要对导电防污涂料和低VOC防污涂料进一步加强研究的建议。     

舰船高性能防腐蚀防污涂料研究进展

简要论述了海洋防腐蚀防污涂料的发展历史和研究现状,重点论述了舰船高性能防腐蚀防污涂料的最新研究进展。有机锡自抛光防污涂料被禁止使用之后,基于丙烯酸锌、丙烯酸铜和丙烯酸硅烷酯的自抛光防污涂料得到了广泛应用。基于含防污功能基团树脂的防污涂料、基于降解树脂的防污涂料以及基于表面结构特性的防污涂料技术成为当前防污涂料研究的热点。文中详细报道了降解树脂的结构对降解性能及力学性能影响规律,以及表面结构特性对污损释放型防污涂料防污性能的影响规律。随着环境保护法规的日趋严格,防腐蚀涂料向无溶剂(或高固体)、长效方向发展。报道了提高涂层的湿态附着力和致密性的方法,采用该方法可以大幅提高涂层的力学性能和耐蚀性能,满足了远洋和深海装备发展需求。     

DCOIT防污剂在防污材料中的应用研究进展

鉴于4,5-二氯-2-正辛基-4-异噻唑啉-3-酮(DCOIT)具有广谱高效、环保低毒等优点,DCOIT逐渐成为替代有机锡(TBT)的一种新型防污剂,在防污材料中越来越得到广泛的关注和应用。本文总结了DCOIT环境归宿及其生态毒性的判断方法,介绍了DCOIT在防污材料的应用情况及防污效果,并对近年来DCOIT防污剂的控释技术进行了综述,最后对该防污剂的应用和发展趋势进行了展望。     

Species-specific isotope dilution analysis and isotope pattern deconvolution for butyltin compounds metabolism investigations

A methodology for the study of the absorption and metabolism of butyltin compounds in laboratory animals using isotopically enriched species was developed. The method is based on the oral administration of 119Sn-labeled monobutyltin (MBT), 118Sn-labeled dibutyltin (DBT), and 117Sn-labeled tributyltin (TBT) to the animals and the measurement of both the concentration and isotopic composition of these compounds in the different tissues by GC-ICPMS. The degradation of butyltin compounds during their metabolism was computed using least-squares isotope pattern deconvolution, and their concentration was measured by reverse isotope dilution analysis using natural-abundance MBT, DBT, and TBT standards. Male Wistar rats were used as models to evaluate the proposed methodology. Preliminary toxicological results obtained with one rat indicate that TBT is highly absorbed (64.4%), and it is found in all organs with relatively high levels in stomach and intestines. The apparent absorption of DBT was 27.3% and was mainly found in liver, kidney, and intestines. However, a large proportion of the found DBT is formed from the degradation of TBT (approximately 40% of the found DBT in liver is degraded TBT). The apparent absorption of MBT was found to be 12.5%, and the originally administered MBT was mainly recovered in the feces. However, MBT was clearly detected in liver, kidney, stomach, intestines, and urine as degradation products of DBT and TBT. Although a significant variability from rat to rat is expected to be obtained, the analytical variability provided by this methodology is small enough to yield meaningful biological results. The results obtained demonstrate that the developed methodology is able to follow qualitatively, quantitatively, and simultaneously the specific metabolic pathways of different species of a given element.     

Distillery spent wash: treatment technologies and potential applications

Distillery spent wash is the unwanted residual liquid waste generated during alcohol production and pollution caused by it is one of the most critical environmental issue. Despite standards imposed on effluent quality, untreated or partially treated effluent very often finds access to watercourses. The distillery wastewater with its characteristic unpleasant odor poses a serious threat to the water quality in several regions around the globe. The ever-increasing generation of distillery spent wash on the one hand and stringent legislative regulations of its disposal on the other has stimulated the need for developing new technologies to process this effluent efficiently and economically. A number of clean up technologies have been put into practice and novel bioremediation approaches for treatment of distillery spent wash are being worked out. Potential microbial (anaerobic and aerobic) as well as physicochemical processes as feasible remediation technologies to combat environmental pollution are being explored. An emerging field in distillery waste management is exploiting its nutritive potential for production of various high value compounds. This review presents an overview of the pollution problems caused by distillery spent wash, the technologies employed globally for its treatment and its alternative use in various biotechnological sectors.     

凝固浴组成对PVDF-g-PACMO共聚物膜结构与抗污染性能的影响

采用亲水、无毒、生物相容性好、对蛋白质吸附有排斥作用的丙烯酰吗啉(ACMO)对聚偏氟乙烯(PVDF)本体进行亲水改性,研究了凝固浴中不同乙醇含量(乙醇:去离子水的质量比分别为0∶100,15∶85,30∶70,45∶55)对PVDFg-PACMO共聚物膜抗污染性能的影响。结果表明,随着凝固浴中乙醇含量的增加,膜断面孔结构向海绵状转变,膜平均孔径和孔隙率增大,纯水通量增加,牛血清蛋白(BSA)截留率降低,膜表面亲水性增加,抗污染性能提高。当凝固浴中乙醇质量分数为45%时,膜表面BSA的吸附量由115.4μg/cm2降至20.6μg/cm2,通量恢复率高达97.6%,总污染指数低至0.148。因此,通过改变凝固浴中乙醇的含量,能使PVDF-g-PACMO膜表面亲水性明显提高,制得了具有良好抗蛋白质污染能力的改性PVDF膜。     

Direct determination of the "organic extent" of tin species in environmental samples by X-ray absorption near-edge structure spectroscopy

A direct method for the speciation of Sn compounds in solid environmental samples by X-ray absorption near-edge structure spectroscopy (XANES) has been developed. It was found that the method can provide the "organic extent", the average number of organic ligands bound to Sn, for environmental samples. For Sn XANES at the L(III), L(I), and K edges, systematic variations were found in the spectra for butyl-, phenyl-, and methyl-substituted Sn compounds depending on the organic extent. A quantitative relationship between the organic extent and the characteristics in the XANES spectra was determined based on the peak position, peak area ratio, and peak width. The detection limit was better than 10 microg/g Sn when using the K edge, which is sensitive enough for some environmental samples, e.g., sediments, biological samples, and antifouling paints, and the sensitivity will be better if a more intense X-ray source such as an undulator or Wiggler beamline is used. The present XANES method is totally nondestructive, having the advantage that no complicated pretreatment procedures are needed, whereas such procedures are essential in conventional chromatographic analyses, which may cause experimental error by alteration of Sn species and poor recovery during analyses. Although the XANES method only provides the average number of organic ligands, the direct speciation using XANES will be helpful for estimating roughly the ratio of organic and inorganic Sn species, which can be used to study organotin transformations in sediment cores and inspection of organotin compounds in antifouling paints. In particular, micro-XANES analysis based on the present method is a promising tool in obtaining the distribution of organotin species in biological samples and specific phases in sediments.     

Durable self-polishing antifouling Cu-Ti coating by a micron-scale Cu/Ti laminated microstructure design

Marine biofouling is a major issue deteriorating the service performance and lifespan of marine infrastruc-tures.The development of a durable,long-term,and environment-friendly antifouling coating is therefore of significant importance but still a critical challenge in maritime engineering.Herein,we developed a Cu-Ti composite antifouling coating with micron-sized alternating laminated-structure of Cu/Ti by plasma spraying of mechanically mixed Cu/Ti powders.The coating was designed to enable controlled release of Cu ions through galvanic dissolution of Cu laminates from the Cu/Ti micro-galvanic cell in aqueous solution.Results showed that remarkable antifouling efficiency against bacterial survival and adhesion up to ～100 ％ was achieved for the Cu-Ti coating.Cu/Ti micro-galvanic cell was in-situ formed within Cu-Ti coating and responsible for its Cu ions release.The successive dissolution of Cu laminates resulted in the formation of micro-channels under Ti laminates near surface,which contributed to controlled slow Cu ions release and self-polishing effect.Thus,environment-friendly antifouling capability and ～200 ％longer antifouling lifetime than that of the conventional organic antifouling coatings can be achieved for the Cu-Ti coating.On the other hand,as compared to the conventional organic antifouling coatings,the Cu-Ti composite coating presented much higher mechanical durability due to its strong adhesion strength,excellent mechanical properties,and two orders lower wear rate.The present laminated Cu-Ti coating exhibits combination of outstanding antifouling performance and high mechanical durability,which makes this coating very potentially candidates in marine antifouling application.     

低表面能防污涂料的最新研究进展

低表面能防污涂料(有机硅系列和氟化物系列)因具有独特的性能而在许多领域得到广泛应用.介绍了低表面能防污涂料防污的作用机理、特点,综述了低表面能防污涂料的应用和最新进展,并阐述了低表面能防污涂料有待解决的问题和今后的发展方向.     

Nanofunctionalized Superhydrophobic Antifouling Coatings for Environmental Sensor Applications—Advancing Deployment with Answers from Nature

In this work, a novel preparation for superhydrophobic nanofunctionalized silver and gold, copper‐coated substrates as potential antifouling coatings for environmental monitoring devices are fabricated. The superhydrophobic coating is topographically similar to the design of the Lotus leaf (Nelumbo necifera) and was synthesized by creating an electroless galvanic reaction between copper and the metal salt. In doing so, a nano‐ and micro‐topographical structure was created on the surface of a copper substrate which can be rendered superhydrophobic through the addition of a self‐assembled monolayer (SAM) of CF₃(CF₂)7CH₂CH₂SH. The work investigates whether the hydrophobicity of such materials affects micro‐organism attachment and subsequent biofouling. The materials are deployed in a marine environment in Dublin, Ireland for a 6 week study to determine the overall antifouling capacity. The materials are analyzed for biomass, slime (glycocalyx) production and more specifically protein and carbohydrate adsorption all of which are attributed to the inherent makeup of biofilm and exopolymeric substances (EPS) which are secreted by micro‐organisms during the biofouling process. This work highlights the dominance of combinational antifouling approaches rather than single tactics for such a complex problem and one that plagues multiple research areas. This novel approach in developing a new antifouling material for sensors, and indeed, any aquatic platform has shown excellent results throughout.     

Permeation characteristics of and extractables from gamma-irradiated and non-irradiated plastic laminates for a unit dosage injection device

Potential migrants were isolated by Soxhlet extraction from plastic laminates used to make a single-use injection system. The concentrated extracts were then subjected to GCIMS analyses and about 22 compounds were identified. The majority of these appeared to be oligorners derived from polyethylene. Other compounds included monomers, oligomers. cross-linking agents, processing aids such as fatty acids, plasticizers and anti-slip agents. Three major new compounds were identified in the Soxhlet extract of gamma-irradiated test laminates, all of which were considered to be reaction products of nonanedioic acid with alkoxy radicals. The effect of irradiation on the profile of potential migrants and the permeabilities of the laminates were also evaluated. The amount of extractives was determined using food simulating solvents such as n-heptane, 8% alcohol and water. Minimal changes were observed in the extractives from gamma-irradiated laminates compared with non-irradiated laminates. The oxygen permeability was significantly reduced after gamma irradiation, while the average water vapour transmission rate was not significantly changed after irradiation.