Advanced strategies for marine antifouling based on nanomaterial-enhanced functional PDMS coatings

Marine biofouling seriously affects human marine exploitation and transportation activities,to which marine antifouling(AF)coatings are considered to be the most cost-effective solution.Since the mid-20th century,human beings have dedicated their efforts on developing AF coatings with long cycle and high performance,leading to a large number of non-target organisms?distortion,death and marine environmental pollution.Polydimethylsiloxane(PDMS),is considered as one of the representative environment-friendly AF materials thanks to its non-toxic,hydrophobic,low surface energy and AF properties.However,PDMS AF coatings are prone to mechanical damage,weak adhesion strength to substrate,and poor static AF effect,which seriously restrict their use in the ocean.The rapid development of various nanomaterials provides an opportunity to enhance and improve the mechanical properties and antifouling properties of PDMS coating by embedding nanomaterials.Based on our research background and the problems faced in our laboratory,this article presents an overview of the current progress in the fields of PDMS composite coatings enhanced by different nanomaterials,with the discussion focused on the advantages and main bottlenecks currently encountered in this field.Finally,we propose an outlook,hoping to provide fundamental guidance for the development of marine AF field.

A timing self-cleaning nanoherbicide:Design of triple-structure nanovectors for weed control and pesticide residues treatment

Pesticide residues treatment is a crucial issue for both agricultural production and environmental protection.In recent years,designing self-cleaning nanoformulations has emerged as a promising strategy for reducing pesticide residues in a convenient and cost-effective manner.However,traditional physical blending methods of photodegradation reagents with nanocarriers have limitations in terms of pesticide residue degradation efficiency and active ingredient efficacy.Here,a new type of timing self-cleaning nanoherbicide dicamba@mSiO_(2)/ATA/TiO_(2)with a triple structure was fabricated.Dicamba,a widely used herbicide that was attracting increasing concern over its high efficiency and broad spectrum,was selected as the model herbicide and loaded on the mSiO_(2)shell.In the stage of pesticide release,the TiO_(2)and dicamba were separated by the timing-barrier.Therefore,the efficacy of dicamba was not affected by the photocatalyst.During the release process,the ATA layer continuously absorbed the reactive oxygen species(ROS)produced by TiO_(2)and was gradually degraded.Finally,the barrier was destroyed,and the residual dicamba in the carrier was degraded by TiO_(2).Compared with the traditional physical blending method,this triple structure avoided the degradation of active ingredients by photocatalysts during the pesticide release period.The experimental results suggested that this nanoformulation improved the efficacy of the herbicide,and reduced the pesticide residues,providing a new approach for self-cleaning nanopesticides research.

Extraction of Protease Produced by Sea Mud Bacteria and Evaluation of Antifouling Performance

Enzyme-based antifouling coatings are potential alternative to traditional tributyltin-based coatings in the marine biofouling control depended on its environmental friendliness.Proteases are usually the key antifouling active components in enzyme based antifouling coatings.In this work,based on biological antagonism effect,a marine proteolytic bacterial strain of Bacillus velezensis was isolated from the sea mud,and denoted as SM-1.The scanning electron microscope(SEM)revealed that the bacteria are rod-shaped with length 1-1.3μm.The protease-producing conditions of SM-1 were investigated,and it was found that the culture solution displays higher proteolytic activity under the culture conditions of 35℃,10‰-20‰salinity,pH 6-9 and more than 7 d culture time.Moreover,the 25 kDa protein was confirmed to be the main active component in the crude protease,which was revealed via the experiment of SDS-PAGE.The antifouling assay indicated that the protease SM-1 has remarkable effect on the decomposition of barnacle cement and diatom secretion,and also can effectively inhibit the attachment of barnacle cyprids,diatom and mussel byssus.Therefore,this protease potentially can be used as environmental-friendly antifoulant of enzyme-based marine antifouling coatings,and this work also provides a new approach to obtain antifouling protease via isolating proteolytic bacteria from the sea mud surrounding representative fouling organisms.

Construction of Self-Assembly Based Tunable Absorber:Lightweight,Hydrophobic and Self-Cleaning Properties

Although multifunctional aerogels are expected to be used in applications such as portable electronic devices,it is still a great challenge to confer multifunctionality to aerogels while maintaining their inherent microstructure.Herein,a simple method is proposed to prepare multifunctional NiCo/C aerogels with excellent electromagnetic wave absorption properties,superhydrophobicity,and self-cleaning by water-induced NiCo-MOF self-assembly.Specifically,the impedance matching of the three-dimensional(3D)structure and the interfacial polarization provided by CoNi/C as well as the defect-induced dipole polarization are the primary contributors to the broadband absorption.As a result,the prepared NiCo/C aerogels have a broadband width of 6.22 GHz at 1.9 mm.Due to the presence of hydrophobic functional groups,CoNi/C aerogels improve the stability in humid environments and obtain hydrophobicity with large contact angles>140°.This multifunctional aerogel has promising applications in electromagnetic wave absorption,resistance to water or humid environments.

Study on Marine Corrosion and Antifouling Behavior of Copper Alloys Exposed to Sea Areas in China

The relationship of corrosion resistance and antifouling behavior of 19 Cu alloys exposed to seawater of Qingdao ,Xiamen,Yulin sea areas in China for 1,2,4,8 year intervals was studied .The experiments were carried on by analyzing the composition of corrosion films formed on the surface of alloy specimens during the immersion time and by using OM,SEM,EDXA and AES experiment methods.The results verify the view point that it is the cuprous oxide film which played an important role in antifouling property of Cu alloys in seawater and throw a light on the view point in details further.The influence of different sea areas on the antifouling property of Cu alloys is also discussed.

Synthesis and Bacteriostatic Activity and Antifouling Capability of Benzamide Derivatives Containing Capsaicin

Five benzamide deriatives containing capsaicin were synthesized which have similar structures to capsaicin. Their yield was high. The monomers synthesized were characterized by IR, 1H NMR and MS spectroscopy. Cha-racterization data are in agreement with the proposed structures of the products. These five compounds exhibit bacterial inhibition and N-[4-hydroxy-2-methyl-5-（methylthio）benzyl]benzamide（HMMBBA）, for instance, shows that the minimal inhibitory concentrations（MIC） of HMMBBA are 0.125 and 0.25 mg/mL on Staphyloccocus aureus and Escherichia coli, respectively. A static test site was set up in the eighth harbor to investigate the antifouling effectiveness of the five new antifoulants. Five-month exposure experiments were performed on sets of panels coated with each of antifouling coatings, and the results were compared to that of the test panel without antifouling coating. Test boards with antifouling coating were covered with just a macroscopic fouling organism such as Balanus. The results of the present paper demonstrate that new antifoulants represent an alternative to the biocidal antifouling paint.

Antifouling evaluation of extracts from Red Sea soft corals against primary biofilm and biofouling

Objectives: To evaluate antifouling property of extracts from Red Sea soft corals against primary biofilm and biofouling.Methods: Seven species of soft corals Sarcophyton glaucum(a), Sinularia compressa,Sinularia cruciata(a), Heteroxenia fuscescens(a), Sarcophyton glaucum(b), Heteroxenia fuscescens(b) and Sinularia cruciata(b) were chosen to test their extracts as antibacterial and antifouling agents in Eastern Harbour of Alexandria, Mediterranean Sea.Bioactive compounds of soft corals were extracted by using methanol and concentrated under vacuum. The residues of extracts were mixed in formulation of inert paint which consisted of rosin, chlorinated rubber and ferrous oxide against micro and macro fouling organisms. The formulated paints were then applied on PVC panels twice by brush,hanged in a steel frame and immersed in Eastern Harbour of Alexandria Mediterranean Sea followed by visual inspection and photographic recordings.Results: After 185 days of immersion in seawater, the antifouling results agreed with the antibacterial results where extracts of Sinularia compressa and Heteroxenia fuscescens(b) gave the best activity against marine fouling tubeworms and barnacles. The inhibition activity was correlated with the major functional groups(hydroxyl, amino, carbonyl,aliphatic(fatty acids), C]C of alkene or aromatic rings and CeC l of aryl halides) of the extracts.Conclusions: The strong antifouling activity makes them promising candidates for new antifouling additives. After the screening and application of natural organic compounds from soft corals, marine organisms show activity against micro and macro fouling organisms.

Comparative Study of Structure and Property Changes in Corrosive Media for Self-cleaning Superhydrophobic Magnesium Alloys

Magnesium alloys with superhydrophobicity are constructed by controlling rough surface structure and grafting long hydrophobic alkyl chains. Changes of morphology, phase structure, chemical composition as well as wettability, corrosion resistance of superhydrophobic magnesium alloy upon immersing in corrosive media are investigated comparatively. Meanwhile, the contaminating particles on as-prepared superhydrophobic surfaces can be taken away easily by rolling water droplets. Therefore, the results show that as-prepared superhydrophobic magnesium alloys exhibit enhanced corrosion resistance and self-healing performance. Finally, anti-corrosion and self-cleaning mechanisms are deduced. It can be concluded that it is an effective strategy of preparing superhydrophobic surfaces for improving the corrosion resistance and selfcleaning performance of magnesium alloys.

Antifouling Activity of Bacterial Symbionts of Seagrasses against Marine Biofilm-Forming Bacteria

Marine biofouling has been regarded as a serious problem in the marine environment. The application of TBT and other heavy metal-based antifoulants has created another environmental problem. The present study explored the possible role of baterial symbionts of seagrasses Thalassia hemprichii, and Enhalus acoroides, which were successfully screened for antifouling activity against marine biofilm-forming bacteria isolated from the surrounding colonies of seagrasses. Bacterial symbionts were isolated and tested against biofilm-forming bacteria resulted in 4 bacterial symbionts capable of inhibiting the growth biofilm-forming isolates. Molecular identification based on 16S rRNA gene sequences revealed that the active bacterial symbionts belonged to the members of the genera Bacillus and Virgibacillus. Further tests of the crude extracts of the active bacterial symbionts supported the potential of these symbionts as the alternative source of environmentally friendly marine antifoulants.

Influence of microstructure and surface condition on antifouling property of 90Cu-10Ni alloy in seawater

Through the experiment of natural seawater exposure corrosion, the antifouling properties of the plate specimens of 90Cu 10Ni alloy were studied, which were processed by different deformations, annealing treatments and surface treatments. The results indicate that after exposure corrosion for half a year, the antifouling properties of the specimens are quite different. The specimens processed by suitable deformations, annealing treatment at 650?℃ and pretreatment of surface film possess both good corrosion resistance and antifouling properties. However, the specimens processed by different deformations and annealing treatment at 450?℃ possess lower corrosion resistance, although they are also treated by the pretreatment of surface film; their antifouling properties change with different deformations. The relationships among the corrosion morphology and microstructure with the antifouling property of 90Cu 10Ni alloy are observed under the scanning electron microscopy (SEM).

Synthesis and characterization of caprolactone based polyurethane with degradable and antifouling performance

In this work,a degradable polyurethane composed of caprolactone(CL)and L-Lactide(LLA)as soft segments,and 4,40-methylenebis(cyclohexyl isocyanate)(H12 MDI)and polytetramethylene ether glycol(PTMEG)as hard segments,was prepared.Hydrolytic degradation experiment revealed that the degradable polyurethane(PU)could be degraded in artificial seawater.It also showed that caprolactone-copolyurethane(CL-PU)copolymer with higher crystallinity degraded much slower in artificial seawater.However,the introduction of LLA resulted in an increase in the hydrophilicity and reduction in the crystallinity of degradable PU,as demonstrated by the contact angle analysis.The result of the scanning electron microscope showed that the surface of degradable PU renewed under static condition.Moreover,degradable PU was able to be used as a carrier,and it controlled the release rate of 4,5-dichloro-2-octyl-isothiazolone(DCOIT).The anti-diatom(Navicula incerta)test demonstrated that the(caprolactone-co-L-lactide)-co-polyurethane 4(CL/LAx-PU4)with DCOIT contents prevented the adhesion of diatom Navicula incerta(88.37%reduction)due to their self-polishing and the release of antifoulants.Therefore,the degradable PU consisted of CL,LLA,and DCOIT could be a durable resin with good antifouling activity for the application in the marine anti-biofouling field.

Preparation of antifouling ultrafiltration membranes from copolymers of polysulfone and zwitterionic poly(arylene ether sulfone)s

The past few decades have witnessed rapid gains in our demands of antifouling membranes such as water purification membranes and hemodialysis membranes.A variety of methodologies have been proposed for improving the antifouling performance and the hemocompatibility of the membranes.In this study,a series of copolymers(PSF-PESSB)containing polysulfone(PSF)and poly(arylene ether sulfone)bearing pendant zwitterionic sulfobetaine groups(PESSB)were prepared via one-pot polycondensation.Subsequently,the ultrafiltration(UF)membranes were prepared from different zwitterion-containing copolymers.The prepared membranes showed high thermal stability and mechanical properties.Besides,it also displayed attractive antifouling performance and blood compatibility.Compared with the original PSF membrane,the amount of protein absorption on the modified membrane was reduced;the flux recovery ratio and the resistance to blood cells were significantly improved.The results of this work suggest that PSF-PESSB membranes are expected to be applied in blood purification.The introduction of zwitterion-containing polymers to membranes paves ways for developing advanced hemodialysis technologies for crucial process.

Numerical Study on the Hydrodynamic Performance of Antifouling Paints

This study presents a simple numerical method that can be used to evaluate the hydrodynamic performances of antifouling paints.Steady Reynolds-averaged Navier-Stokes equations were solved through a finite volume technique,whereas roughness was modeled with experimentally determined roughness functions.First,the methodology was validated with previous experimental studies with a flat plate.Second,flow around the Kriso Container Ship was examined.Lastly,full-scale results were predicted using Granville’s similarity law.Results indicated that roughness has a similar effect on the viscous pressure resistance and frictional resistance around a Reynolds number of 10^7.Moreover,the increase in frictional resistance due to roughness was calculated to be approximately 3%-5%at the ship scale depending on the paint.

Self-cleaning glass coated with Fe^(3+)-TiO_2 thin film

The self-cleaning glass coated with Fe3+-TiO2 photocatalytic thin film was prepared by sol-gel process from the system Ti（OC4H9）4-NH（C2H4OH）2-C2H5OH-H2O containing FeCl3. The microstructure and properties of the film were studied using differential thermal analysis-thermogravimetry（DTA-TG）, X-ray diffration（XRD） and scanning electron microscope（SEM）. The transmittance of the self-cleaning glass was measured by using UV-Vis spectrometer. The effects of content of Fe3+ and the thickness of Fe3+-TiO2 thin film on the photocatalytic activity were examined. The results show that the photocatalytic thin films are mainly composed of Fe3O4 and TiO2 particles within 10100 nm. The appropriate amount of Fe3+ is effective for improving the photocatalytic activities of TiO2. The best photocatalytic activity is obtained when the molar ratio of Fe3+ to TiO2 is 0.005 and the glass is coated with 9 layers.

Marine antifouling behavior of the surfaces modified by dopamine and antibacterial peptide

Marine biofouling causes serious harms to surfaces of marine devices in transportation,aquaculture,and offshore construction.Traditional antifouling methods pollute the environment.A novel and green antifouling strategy was developed to prevent effectively the adhe sion of bacteria and microalgae.An antifouling surface was fabricated via coating Turgencin BMox2(TB)onto dopamine-modified 304stainless steel(304 SS).The surface physical and chemical properties before and after modification were characterized by Fourier transform infrared spectrometer(FTIR),X-ray photoelectron spectrometer(XPS),contact angle measurement(CA),3D optical profilometer,ellipsometer,and atomic force microscope(AFM).Antimicrobial peptide was coated onto the surface of 304 SS successfully,and the surface morphology and wettability of the modified sample were modified.Moreover,cytocompatibility of the peptide was evaluated by co-culture of peptide and cells,indicating promising cell biocompatibility at the modified sample surface.At last,antifouling performance and electrochemical corrosion were tested.Results show that the adhesion rates of Vibrio natriegens and Phaeodactylum tricornutum on the antifouling surface were reduced by 99.85% and 67.93%,respectively from those of untreated samples.Therefore,the modified samples retained superior corrosion resistance.The study provide a simply and green way against biofouling on ship hulls and marine equipment.

Antifouling Potential of Bacteria Isolated from a Marine Biofilm

Marine microorganisms are a new source of natural antifouling compounds. In this study, two bacterial strains, Kytococcus sedentarius QDG-B506 and Bacillus cereus QDG-B509, were isolated from a marine biofilm and identified. The bacteria fermentation broth could exert inhibitory effects on the growth of Skeletonema costatum and barnacle larvae. A procedure was employed to extract and identify the antifouling compounds. Firstly, a toxicity test was conducted by graduated pH and liquid-liquid extraction to determine the optimal extraction conditions. The best extraction conditions were found to be pH 2 and 100% petroleum ether. The EC50 value of the crude extract of K. sedentarius against the test microalgae was 236.7 ± 14.08 μg mL-1, and that of B. cereus was 290.6 ± 27.11 μg mL-1. Secondly, HLB SPE columns were used to purify the two crude extracts. After purification, the antifouling activities of the two extracts significantly increased: the EC50 of the K. sedentarius extract against the test microalgae was 86.4 ± 3.71 μg mL-1, and that of B. cereus was 92.6 ± 1.47 μg mL-1. These results suggest that the metabolites produced by the two bacterial strains are with high antifouling activities and they should be fatty acid compounds. Lastly, GC-MS was used for the structural elucidation of the compounds. The results show that the antifouling compounds produced by the two bacterial strains are myristic, palmitic and octadecanoic acids.

Characterization and antifouling activity analysis of extracellular polymeric substances produced by an epibiotic bacterial strain Kocuria flava associated with the green macroalga Ulva lactuca

Extracellular polymeric substances(EPS)are present externally to the microorganisms and play an important role in attachment and biofilm formation.These polymers possess antibacterial and antifouling activities.In this study,the antifouling activity of EPS produced by an epibiotic bacterium associated with macroalga Ulva lactuca was assessed against fouling bacteria and barnacle larvae.Results indicate that the EPS isolated from the epibiotic bacterium inhibits the biofilm formation of the bacteria without much antibacterial activity.Also,the EPS reduced the settlement of barnacle larvae on the hard substrate under laboratory conditions.The epibiotic bacterium was identified as Kocuria flava based on 16 S rRNA gene sequencing.The EPS was further analysed using Fourier transform infrared(FT-IR),nuclear magnetic resonance(NMR)and X-ray diffraction(XRD)to understand the biochemical composition.NMR analysis revealed the presence of polysaccharides,proteins,acetyl amine and succinyl groups.Scanning electron microscope analysis indicated that the EPS consisted of aggregated and irregular sphere-shaped particles.

A strong adhesive block polymer coating for antifouling of large molecular weight protein

Some proteins secreted by microorganisms have large molecular weights. We report here an approach to prepare coating by multilayer polymers for antifouling of proteins, especially the proteins with a large molecular weight.Stainless steel was used as the model substrate. The substrate was first coated with a hybrid polymer film, which was formed by simultaneous hydrolytic polycondensation of 3-aminopropyltriethoxysilane and polymerization of dopamine(HPAPD). After grafting the macroinitiator 2-bromoisobutyryl bromide, the block polymer brushes PMMA-b-PHEMA were grafted. Three proteins were used to test protein adsorption and antifouling behavior of the coating, including recombinant green fluorescent(54 k Da), recombinant R-transaminase(2 × 90 k Da), and recombinant catalase(4 × 98 k Da). It is demonstrated that the block polymer brushes not only can prevent the adsorption of small molecular weight proteins, but also can significantly reduce the adsorption of the large molecular weight proteins.

Development of Coatings Marine Antifouling Based on Perfluorinated Surfactants Synthesis and Physicochemical Study

The fight against dirt settling on the hulls of ships and more generally on all underwater structures is more than 2000 years. The need for effective antifouling paints, which prevents the establishment and growth of marine organisms on submerged structures, is universally recognized. In this work, we synthesize two perfluorinated surfactants from simple monomers. After describing the reactions, we discuss the different analyzes of the proton nuclear magnetic resonance (1H NMR), the fluorine nuclear magnetic resonance (NMR I9F), gel permeation chromatography (GPC) and the light scattering (LS) at a fixed angle 90. The glass transition temperature of the two surfactants diethylallylphosphonate and allylamine are obtained by Differential Scanning Calorimetry (DSC). Antifouling paint properties were followed by exposure of the plates to the marine environment by visual observation.

Superhydrophobic Micro/Nanostructured Copper Mesh with Self-Cleaning Property for E ective Oil/Water Separation

In this work, a simple method was carried out to successfully fabricate superoleophilic and superhydrophobic N-dodecyltrimethoxysilane@tungsten trioxide coated copper mesh. The as-fabricated copper mesh displayed prominent superoleophilicity and superhydrophobicity with a huge water contact angle about 154.39° and oil contact angle near 0° Moreover, the coated copper mesh showed high separation efficiency approximately 99.3%, and huge water flux about 9962.3 L·h^-1·m-2, which could be used to separate various organic solvents/ water mixtures. Furthermore, the coated copper mesh showed favorable stability that the separation efficiency remained above 90% after 10 separation cycles. Benefiting from the excellent photocatalytic degradation ability of tungsten trioxide, the coated copper mesh possessed the self-cleaning capacity. Therefore, the mesh contaminated with lubricating oil could regain superhydrophobic property, and this property of self-cleaning permitted that the fabricated copper mesh could be repeatedly used for oil and water separation.