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Contribution of Charges in Polyvinyl Alcohol Networks to Marine Antifouling Wufang Yang, Peng Lin, Daocang Cheng, Longzhou Zhang, Yang Wu, Yupeng Liu, Xiaowei Pei, and Feng Zhou ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 10 May 2017 Downloaded from http://pubs.acs.org on May 10, 2017

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ACS Applied Materials & Interfaces

Contribution of Charges in Polyvinyl Alcohol Networks to Marine Antifouling Wufang Yanga,c, Peng Lina,c, Daocang Chengb, Longzhou Zhangb,Yang Wua, Yupeng Liua, Xiaowei Peia, Feng Zhoua,* a． State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China b． China Nuclear Power Design Company. Ltd (Shenzhen), Shenzhen 518172, China c．University of Chinese Academy of Sciences, Beijing 100049, China E-mail: [email protected]

Abstract: Semi-interpenetrated polyvinyl alcohol polymer networks (SIPNs) were prepared by integrating various charged components into polyvinyl alcohol polymer. Contact angle measurement, attenuated total reflection fourier transform infrared spectroscopy (ART-FTIR), field emission scanning electron microscope (FE-SEM) and tensile tests were used to characterize the physicochemical properties of the prepared SIPNs. In order to investigate the contribution of charges to the marine antifouling, the adhesion behaviors of green alga D. tertiolecta and diatom Navicula sp. in lab and of the actual marine animals in field test were carried out for biofouling assays. Results suggest that less algae accumulation densities are observed on neutral, anionic and zwitterionic component integrated SIPNs. However, for the cationic SIPNs, despite the hydration shell induced by the ion-dipole interaction, the resistance to biofouling largely depends on the amount of cationic component because of the possible favorable electrostatic attraction between the cationic groups in SIPNs and the negatively charged algae. Considering that the preparation of novel non-toxic antifouling coating is a long-standing and cosmopolitan industrial challenge, the

ACS Paragon Plus Environment


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SIPNs may provide a useful reference for marine antifouling and some other relevant fields. Keywords: charge contribution, anti-adhesion, marine antifouling, polymer networks, diatom, green algae

Introduction: An important challenge in the field of the maritime operations, food industries, biotechnology and other devices is to stop the attachment of nonspecific biomolecule, cell, microorganism and macro-algae. Especially for marine industry, biofouling adversely affect the economic and ecological environment, such as the increased fluid frictional drag, fuel consumption and the potential hazard to the ocean biosphere.1-2 In order to cope with these ubiquitous questions, many research efforts have been devoted to revealing the factors that impact the settlement of marine organisms and developing the surfaces with foul-resistant property. Various antifouling surfaces are prepared by tailoring surface characteristic parameters, including elasticity modulus,3 wettability,4-6

surface

deformation,7

chemical

constitution,8-10

and

surface

texturization,11-13 For example, diatom adhesion can be significantly inhibited by a coating of polyethylene glycol adhered by polyphenolic chemistry.11 Besides, compared with flat surface, hierarchically wrinkled surface could prevent the adhesion of sea creatures for a prolonged exposure to seawater, especially for the adhesion of barnacle fouling, zoospores of the green Ulva and sporelings.7 Despite some special marine species could settle on the pristine surface directly, such as Balanus Amphitrite,14 it has been generally conceptualized that biofouling is a multiple stage process from simplicity to complexity. The immerged substratum is usually subject to the formation of conditioning film,15 which is not only one of the major causes but a precursor to subsequent adhesion of more microorganisms.16 An acceptable way of preventing the biofouling is, therefore, avoiding or postponing the formation of conditioning film.17-18 Considering that the formation of biofilm is a


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nonspecific and reversible process, highly hydrated surface is proposed as a feasible approach to develop promising materials for fouling resistance applications.19 For example, zwitterion materials (sulfobetaine methacrylate and carboxybetain methacrylate) exhibit the resistance to barnacle cyprids adhesion and the triggered fouling-release function.20 Besides, recent studies have also investigated the anionic21 (e.g. 2-acrylamide-2-methyl propane sulfonic acid), neutral22 (e.g. hydroxyl group) and cationic23 (e.g. 2-methacryloxy ethyltrimethyl ammonium chloride) surfaces for marine antifouling respectively. However, these single-component materials can only resist biofouling in a short time. For example, neutral poly (ethylene glycol) (PEG) polymer chains are relatively chemically vivacious and confronted with oxidation damage, which hinders its long-term applications.24-25 In the recent years, it has been recognized hydrophilic polymer exhibits less number of marine micro-organisms adherence.26 The potential of polymer networks and other highly hydrophilic materials as the marine antifouling candidates for long-term

applications

have

been

studied

as

well.27

Especially

the

semi-interpenetrating polymer networks (SIPNs), the polymers consist of one or more networks, but the linear or branched network penetrate each other on molecular scale at the same time,28 have emerged as innovative environment friendly materials in the area of anti-bioadhesion.29-31 Considering that most fouling alga are negatively charged,32 by using polymer brushes, the resistance of charged surfaces to biofouling has been studied,10 but relevant work based on charged multi-components bulk materials was rare reported. In addition, the effect of the charged polymer on the natural marine antifouling application isn’t yet fully understood. In order to investigate the effect of charged multi-components materials on the resistance to marine organisms, various charged polyvinyl alcohol SIPNs samples were prepared. 3-sulfopropyl

methacrylate

potassium

salt

(SPMA),

[2-(methacryloyloxy)

ethyl]trimethylammonium chloride (METAC), sulfobetaine methacrylate (SBMA), poly (ethylene glycol) methyl ether methacrylate (OEGMA) acted as anionic, cationic, zwitterionic, and neutral components respectively, and their corresponding chemical



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structures are shown in Scheme 1. For the preparation, a certain amount of acrylamide (AAm) is used for auxiliary formation of SIPNs, and the content of charged active component can be tailored by changing the molar ratio of charged monomer to AAm. The resistances to micro-organisms were studied by the settlement of marine organism green algae D. tertiolecta and diatoms Navicula sp. under quasi-static condition. Besides, a field test assay was conducted to prove the mechanical stability and broad spectrum antifouling property. Considering that the preparation of novel non-toxic antifouling coating is a cosmopolitan industrial challenge, SIPNs materials are beneficial to environmental protection and could deliver multiple green-economy benefits. The charged semi-interpenetrated polymer networks might provide a new approach to produce the high-performance and environmental friendly antifouling material.

Scheme 1. Chemical structures of active components with charged functional groups. Experimental Section Materials: Acrylamide (AAm, 95%), acrylic acid (AAc, 99%), potassium persulfate (KPS,

99%),

N,N’-methylenebis

acrylamide

(MBAA,

99%),

3-sulfopropyl

methacrylate potassium salt (SPMA, 98%), Sulfobetaine methacrylate (SBMA, 97%) [2-(Methacryloyloxy)ethyl]trimethylammonium chloride (METAC), Poly (ethylene glycol) methyl ether methacrylate (OEGMA, Mn=360 g/mol) were purchased from J&K Chemical Ltd. N,N,N’,N’- tetramethyldiamine (TEMED) was purchased from Sigma-Aldrich

Chemicals.

Polyvinyl

alcohol

(PVA,


Mn=1750±50g/mol),

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diiodomethane and dichloroethane were obtained from Sinopharm Chemical Reagent. Raw petroleum was obtained from the Northern China Oil Field. Both the green algal D. tertiolecta (D. t) and diatoms Navicula sp. (N. sp) were supported by Freshwater Algae Culture Collection at the Institute of Hydrobiology. All the reagents were used as received and deionized water was used in all the experiments. Sample preparation The charged SIPNs structures based on PVA matrix are prepared by a feasible radical copolymerization.33 A certain amount of AAm is used to tailor the content of charged active component conveniently and ensure the formation of second polymer chain. Meanwhile, the physicochemical properties of SIPNs including swollen behavior and mechanical properties can be tailored by changing the molar ratio of charged active monomer to AAm component at fixed crosslinker and initiator content. As schematically delineated in Figure 1, charge-neutral PVA (10 wt%) is used as the first polymer network and the second polymer network composed of AAm and charged/neutral polymerizable monomers are loaded into the swollen PVA networks via free-radical polymerization. Here, the fabrication of PVA-pAAm-SBMA-x sample (x refers to the molar ratio of SBMA to AAm) is taken as an example. AAm (2.13 g, 0.03 mol)，0.05% (molar ratio of AAm) chemical cross-linker MBAA, different molar ratios of SBMA to AAm (0.1, 0.07, 0.05, 0.03, and 0.01), 2 wt% initiator KPS were added into 20 g PVA. Before the solution was transferred into the mold consisted of a pair of glass substrates with 1.8 mm interval, 5.0 µL TEMED as accelerator was added and degassed for 10 min. The radical polymerization was expected to take place at room temperature for 4 h. Then the sample was lyophilized to ensure that the moisture was evaporated absolutely, after that the dehydrated sample was immersed in deionized water again for 48 h to realize swelling equilibrium. Finally, this dehydration and swelling process were conducted three times to form the SIPNs structure and remove un-reacted monomer as much as possible. All of the prepared SIPNs samples were stored in water medium before characterization.



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Figure 1. The schematic of SIPN composition and structure. Underwater contact angle characterization Using DSA-100 optical contact angle meter (Kruss Company, Ltd., Germany), the underwater contact angles of various oil droplets were determined by placing a 5 µL drop of oil on sample surface which was immerged into the deionized water prior to measuring. Three tests were conducted for one sample and the mean values were calculated. Swelling studies In order to insure the samples were fully hydrated, the SIPNs samples were immersed in deionized water or seawater medium more than 24 h. For the swelling study, the adsorbing water on the SIPN surface was removed quickly with filter paper, and the swollen weights (Ws) were measured using an analytical balance. Then, the weights of dehydrated sample (Wd) were obtained after the swollen samples were dried for 24 h at 120 °C in vacuum. The equilibrium water content (EWC) is calculated by equations as follow:

EWC = [

Ws − Wd ] ∗100% Ws

FE-SEM characterization The micro-scope morphologies of the charged SIPNs were obtained using JSM-6701F field emission scanning electron microscope (FE-SEM) at 5-10 kV. In


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order to ensure the proper macro-structure could be maintained, the fully hydrated samples were frozen via liquid nitrogen firstly. Then the samples were lyophilized for FE-SEM characterization. Although the true hydrated structure can’t be observed directly because of chains collapse during lyophilization, their corresponding macro-structure (frozen-dried morphology) can be maintained as much as possible.

Bio-fouling assessment The auto-fluorescence image analysis (Olympus, BX51) was applied to detect the amount of attached algae. For the microorganism settlement assays, the SIPNs samples were placed in petri dish, then 5 mL algae suspension containing 1.5×106 algae/ml was added. After 24 h culture, artificial seawater was used to wash the sample gently to remove the unsettled algae firstly. Ten fields of view, each 0.14 mm2, were recorded for each sample. Algae amounts adhered on the sample surface were calculated via Cell Profiler Software and the mean densities were regarded as the number of adhered algae (/mm2).

Mechanical characterization A material testing machine with a 500N load cell (EZ-Test, SHIMADZU) was used to conduct the tensile tests of SIPNs samples. The samples were cut into long strips shape with length 40 mm, width 5 mm and thickness 1.6~2.0 mm. The crosshead velocity was keep at 100 mm/min during the normal tensile tests. Three trials were conducted for the same sample. The measurements were conducted at the time when the sample was taken out from the water medium and the measure procedure was accomplished in one minute at room temperature. Thus there are reasons for thinking that these properties conducted under current experimental condition are similar with that in the presence of water/moisture. The nominal tensile stress (σ, determined by the rupture point) and elastic modulus (E, calculated from the slope over 5~15% of strain ratio) were obtained as derivate of the stress-strain curve.

Results and discussion



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Physicochemical properties characterization of SIPNs samples The chemical composition of the as-prepared SIPNs was evaluated by ATR-FTIR. The stretching vibration absorption of ester carbonyl (C=O) around 1711–1723 cm−1 is prominent in all polymers networks, which indicates that the charged components are integrated into the SIPNs samples successfully. The characteristic absorption peaks at 1298 cm−1are assigned to the C-O ester stretching in the spectra. Besides, depending on the structural characteristic of charged polymer, the C-H stretching vibrations appear in the range 2864-2975 cm−1 for all the samples. The adsorption peaks around 1046 and 1039 cm−1 (Figure 2(1) and (2)) are attributed to the strong symmetric stretching adsorption peaks of S=O, and the peaks at 1170 cm−1 and 1174 cm−1 are assigned to the asymmetric S=O absorptions. These characteristic adsorption peaks confirm the presence of sulfonate in the SPMA and SBMA integrated SIPNs samples.34 For the spectrum of PVA-pAAm-METAC SIPNs (Figure 2(3)), C-N stretching peaks are observed near 1157 and 1177 cm−1, which might be influenced by the C-H deformations in the quaternary ammonium salt groups.13 The successful integration of the OEGMA into the SIPNs is confirmed by the feature peak of C-O-C stretching vibration at 1168 cm−1 in the spectrum (Figure

2(4)) and the CH2 stretching mode of OEGMA around 2900 cm−1.

Figure 2. ATR-FTIR spectrums of the prepared charged SIPNs samples. (1) PVA-pAAm-SPMA; (2) PVA-pAAm-SBMA; (3) PVA-pAAm-METAC; and (4) PVA-pAAm-OEGMA.


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Although the true hydrated structure of SIPNs can’t be observed directly because of the collapse of polymer chain, freeze-drying procedure was used to retain its real structure as much as possible. As shown in the Figure 3, for the pure PVA-pAAm SIPNs sample, highly macro-porous sponge-like structure (Figure 3a1-a1'') and three-dimensional networks characteristic can be observed obviously. On the contrary, the pAAm-SBMA (Figure 3a2) and pAAm-SPMA samples (Figure 3a3) exhibit compact structure and no three-dimensional networks are observed. Besides, only sag and fold surface and micro-bulge but flat surfaces are exhibited respectively. After the combination of either AAm/SBMA or AAm/SPMA with PVA polymer, although there are highly variable in size and distribution of the pore structure, three-dimensional reticulate structure is observed (Figure 3a2' and 3a2'', Figure 3a3' and 3a3''), which is analogous to PVA-pAAm sample. The results indicate that PVA polymer chains act as skeleton and ensure the 3D spatial structure characteristics in SIPNs. Inspired from fish and nacre, underwater self-cleaning and underwater superoleophobic surfaces are expected to be biofouling resistant. Therefore, underwater oil wettabilities of as-prepared SIPNs were investigated. Because of the dipole-dipole interaction between hydroxyl groups and water molecules, a strong hydrophilicity is induced for the PVA based SIPNs samples. What’s more, the hydrophilicity of anionic integrated PVA-pAAm-SPMA serial samples is further enhanced by the solvation of sulfonate ions; Similar to other zwitterionic components, the SBMA can be hydrated by electrostatic interaction induced hydration, and so the SBMA integrated SIPNs are more hydrophilic than electrically neutral hydrophilic polymers.19 The cationic integrated PVA-pAAm-METAC serial samples exhibit higher hydration effect because of the ion-dipole interactions between ammonium ions and water molecules. As shown in the Figure 3, the hydration characteristics of SIPNs samples ensure its underwater superoleophobicity and all utilized oil droplets showed round ball idiosyncrasy. The corresponding contact angles of both pure PVA-pAAm and charged PVA-pAAm SIPNs samples are above 150°.



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Figure 3. (a) Surface FE-SEM images characterization. (1), (1'), and (1'') are PVA-pAAm reference substrate; (2) is pure pAAm-SBMA; (2') and (2'') are PVA-pAAm-SBMA-0.1 sample; (3) is pure pAAm-SPMA sample; (3') and (3'') are PVA-pAAm-SPMA-0.1 sample. (b) Underwater oil wettability characterization of the as-prepared polymer networks. From top to bottom, the inserted photographs are underwater oil droplets of diiodomethane, dichlorothane and raw petroleum. Any materials which could maintain multiple structures permanently and contain over 20 wt% water are known as hydrogel.35 As depicted in the Figure 4, to characterize the stability of SIPNs samples when hydrated, equilibrium water content (EWC) characterization is performed under deionized water and artificial seawater (ASW) respectively. Compared with the EWC of PVA-pAAm sample, anionic SPMA integrated SIPNs exhibit relative higher water uptake ability under the both deionized water and ASW. The EWC raises gradually with the increase of molar ratios of SPMA to AAm, even the PVA-pAAm-SPMA-0.1 sample is able to retain water content as high as 97% in deionized water (Figure 4a). However, the EWCs of zwitterionic SBMA integrated samples (Figure 4b) are equal with the PVA-pAAm sample and even don’t alter with the increase of SBMA molar ratio in both deionized water and ASW. In addition, compared with the SPMA component, SBMA integrated SIPNs samples are overall neutral, there are therefore no mobile counter ions trapped in the chain layers, as a consequence the higher water uptake for SPMA-based SIPNs were induced. These results suggest that the SIPNs samples could retain high EWCs which depends on the concentration of SPMA but is almost independent of the content of SBMA. As it has been reported the EWC is mainly determined by the


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amount of hydrated groups and the chain rigidity which restricts the swelling procession.36 The sulfonic group is capable of excellent solvation and quick salt responsiveness, thus SPMA integrated SIPNs samples exhibit relative higher water uptake ability. While compared with the sample soaked in deionized water, a decrease in EWCs in the ASW soaked sample was shown that resulted from partial dehydration by electrostatic screening of charges. The negligible effect of SBMA on EWCs in both deionized water and SAW condition implies that the zwitterionic component possesses excellent ion-resistant stability and unique anti-electrolyte behavior. As depicted in the Figure S1, like the SPMA integrated samples, the similar behaviors also can be observed for the cationic METAC serial SIPNs.

Figure 4. The equilibrium water content of anionic and zwitterionic components integrated SIPNs soaked in deionized water (red) and in artificial seawater (black). (a) PVA-pAAm-SPMA-x serial samples and (b) PVA-pAAm-SBMA-x serial samples.

Figure 5 and 6 show the characterization of mechanical properties of charged SIPNs. It is easy to find that the tensile strength of pure pAAm-SPMA sample and pAAm-SBMA sample are only about 20 kPa. However, after integration with PVA networks, both tensile strengths and elastic modules are improved greatly and subjected to the content of charged components. These experimental results indicate that during a deformation, the more ductile neutral networks extend extensively, and thereby sustaining a relative larger deformation. On the other hand, since the mutual strength between networks decides the mechanical properties of SIPNs samples to some extent. A more loose aggregation of polymeric networks decrease the resistance



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for external strain forms when charged components are integrated. Either tensile strengths or elastic modules decrease with increasing the molar content of SPMA and SBMA.

For

example,

the

stress

strength

and

elastic

modulus

of

the

PVA-pAAm-SPMA-0.01 sample are 350 kPa and 170 kPa, respectively. And the stress strength and elastic module decrease to 120 kPa and 90 kPa for the PVA-pAAm-SPMA-0.03 sample, respectively. Besides, the strains follow the decrease trend with the molar ratios of charged component to AAm. A similar mechanical behavior also can be observed for the cationic METAC serial SIPNs (Figure S2).

Figure 5. The effect of the SPMA and SBMA content on the mechanical properties of SIPNs samples. (a) The stress-strain curves for PVA-pAAm-SPMA-x serial samples. (b) The stress-strain curves for PVA-pAAm-SBMA-x samples.

Figure 6. Elastic modulus of the anionic and zwitterionic components integrated SIPNs

antifouling

samples.

(a)

PVA-pAAm-SPMA-x

PVA-pAAm-SBMA-x serial samples.


serial

samples.

(b)

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Antifouling characterization of PVA-pAAm-SPMA-x samples The antifouling performances of PVA-pAAm polymer networks were conducted firstly for the resistance to the green algae D. tertiolecta and the diatoms Navicula sp in lab. As shown in Figure 7, after culturing at quasi-static condition for 24 hours, there are large amount of algae adhered to the silicon wafer (Figure S3) and the fouling densities are 17282 /mm2 and 3093 /mm2 for green algae D. tertiolecta and diatoms Navicula sp. respectively, whereas few algae attached on the PVA-pAAm SIPNs sample, the fouling densities are 3922 /mm2 and 1057 /mm2 for green algae and diatoms, respectively, and their corresponding fouling densities decreased by 77% and 66%, respectively. This obvious reduction of fouling amount indicates that the PVA-pAAm has resistance to the adhesion of micro-organisms, which might be due to hydrophilic characteristic of PVA polymer chain. Besides, pAAm is regarded as another key contributing to their resistance to microorganism settlement as well.37

Figure 7. The attached algae density of (a) green algae D. tertiolecta and (b) diatoms Navicula sp. from an algae medium of 106 cells·mL-1after exposure to PVA-pAAm reference antifouling samples for 24 hours (n=10). To better understand the effect of extraneous charge on PVA antifouling behavior, four well-known charged monomers, including anionic SPMA, zwitterionic SBMA, neutral OEGMA, and cationic METAC, were integrated. As shown in the

Figure 7, although relative low attached densities are found on PVA-pAAm sample, for anionic SPMA integrated PVA-pAAm-SPMA-x (x refers to the molar ratio of SPMA to AAm) serial samples, the representative fluorescence microscopy images in



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the Figure S4 indicate that attach densities of either green algae or diatom are further decreased. What’s more, algae amount adhered on the PVA-pAAm-SPMA-x surfaces decrease with the increase of the content of SPMA. Algae densities attaching to PVA-pAAm-SPMA-x SIPNs are shown in Figure 8. Compared with the PVA-pAAm control surface, it can be concluded that the biological fouling quantities decrease by 48%, 53% and 80% for the green alga with increasing the molar ratios of SPMA to AAm from 0.01 to 0.1, and the attached algae densities decrease by 37%, 49% and 80% for diatom respectively. The improved antifouling behavior might be induced by the formation of hydration layer barrier by PVA and sulfonate enhanced hydration effect. As a result, the anionic SPMA integrated PVA-pAAm-SPMA SIPNs could greatly whittle the adhesive force between algae and substrate, and are highly resistant to algae adsorption than pure PVA-pAAm control ones.

Figure 8. The attached algae densities of (a) green algae D. tertiolecta and (b) diatoms Navicula sp. from an algae medium of 106 cells·mL-1 after exposure to anionic SPMA integrated PVA samples for 24 hours (n=10). The PVA-pAAm sample was used as control substrate.

Antifouling

characterization

of

PVA-pAAm-SBMA-x

and

PVA-pAAm-OEGMA-x samples Results for the adhesion of D. tertiolecta and Navicula sp. on zwitterion SBMA and neutral OEGMA integrated SIPNs samples are depicted in the Figure 9 and

Figure 10 respectively. Significant decrease in adhesion densities of both D. tertiolecta and Navicula sp. is observed on the two serial samples, especially for the


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adhesion of diatom Navicula sp. (Figure S5 and S6) For the adhesion of green algae D. tertiolecta on PVA-pAAm-SBMA-x samples, compared with the pure PVA-pAAm sample, the biological fouling quantities decrease by 46%, 54% and 57% with increasing the molar ratio of SBMA to AAm from 0.01 to 0.1, respectively (Figure 9a). Even the corresponding diatoms adhesion density decreases by more than 95% for PVA-pAAm-SBMA-0.1 sample (Figure 9b). On the other hand, similar antifouling behavior also can be observed for the PVA-pAAm-OEGMA-x serial SIPNs samples (Figure 10), compared with pure PVA-pAAm control surface, the neutral OEGMA based SIPNs samples could repress the attachment of green algae and diatom by at least 60%. Like the anionic SPMA based SIPNs, these results illustrate that the zwitterionic and neutral components modified SIPNs are qualified with ultralow microorganisms fouling. The improved biofouling resistance might be assigned to the formation of a more stable and high-efficient hydration layer barrier by the active groups of SBMA (including sulfonate and quaternary ammonium), and OEGMA and hydroxyl groups from PVA matrix.

Figure 9. The attached algae densities of (a) green algae D. tertiolecta and (b) diatoms Navicula sp. from an algae medium of 106 cells·mL-1 after exposure to zwitterionic SBMA integrated PVA samples for 24 hours (n=10). The PVA-pAAm sample was used as control substrate.



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Figure 10. The attached algae densities of (a) green algae D. tertiolecta and (b) diatoms Navicula sp. from an algae medium of 106 cells·mL-1 after exposure to neutral OEGMA integrated antifouling samples for 24 hours (n=10). The PVA-pAAm sample was used as control substrate.

Antifouling characterization of PVA-pAAm-METAC-x samples To our surprise, the accumulation behaviors of both green algae D. tertiolecta and diatoms Navicula sp. on cationic integrated PVA-pAAm-METAC-x system are largely different from that on the other three SIPNs samples above. As depicted in the

Figure S7, at the first stage, a decline of adhered algae densities for both D. tertiolecta and Navicula sp. is exhibited with increasing the MEATC content. While, once the molar ratio of METAC to pAAm exceeds a critical value, algae accumulation increases significantly, even higher than the pure PVA-pAAm control sample. Through experimental statistics results (Figure 11), one can find clearly when the molar ratio of METAC to AAm is 0.05, the lowest adhesion densities for both green algae and diatom are obtained. Compared with PVA-AAm control sample, the biological fouling quantities decrease by 80% and 70% for D. tertiolecta and Navicula sp., respectively. After that, microorganism accumulation tends to increase in a more acute way with further increase of the cationic METAC contents. The antifouling capacity of PVA-pAAm-METAC-x might indicate that the affinity between algae and sample decreases firstly and then increases with the raise of METAC content. For the first stage, the lower number of algae is attributed to the formation of solvation shell which might be induced by ion–dipole interactions


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among ammonium ions, water and PVA matrix. After that, because the presence of net positive charge is raised with the increase of the METAC contents, the role of hydration shell is masked gradually. As a consequence, the higher settlements are induced because of the favorable electrostatic attraction between the positively charged surface and the negatively charged algae. In this case, the algae appear to attach directly onto the METAC based SIPNs without the primary detecting process. Using the single-component METAC substrate, a similar adhesion behavior was reported on the attachment of marine organisms.13, 38

Figure 11. The attached algae densities of (a) green algae D. tertiolecta and (b) diatoms Navicula sp. from an algae medium of 106 cells·mL-1 after exposure to cationic METAC integrated antifouling samples for 24 hours (n=10). The PVA-pAAm sample was used as control substrate.

The effect of charge on the settlement of algae For the neutral OEGMA integrated SIPNs, the antifouling behavior is significantly different with the cationic METAC integrated SIPNs, but similar with the anionic SPMA and the zwitterionic SBMA based SIPNs. As it has been reported that the zwitterionic and anionic functional groups are capable of binding water molecules via ionic solvation and hydrogen bonding interactions,39-40 which results to remove the attached diatoms more easily from poly(sulfobetaine methacrylate)surface than glass substrate.41-42 For the anionic SPMA based SIPNs, the lower biofouling might be attributed to the higher hydration resulted from solvation of the sulfonate groups and the electrostatic repulsion between the negatively charged SPMA in



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SIPNs and the negatively charged algae. For the SBMA based SIPNs, the zwitterionic, i.e., overall neutral but containing negative sulfonate and positive quaternary ammonium groups, are very highly hydrated than PVA polymers. For the neutral OEGMA, polar groups, such as -O- groups, are expected to be hydrated, the dramatically reduced algae attachment is attributed to the enhanced hydration effect. Differently, quaternary ammonium compounds could kill microorganisms despite its hydration ability that called “contact active anti-algal” mechanism.13, 43-44 As it has been shown in Figure 11, because strong hydration shell is resulted from the ion-dipole interactions between water molecule and ammonium ion, an evidently improved antifouling performance is observed for the settlement of both green algae and diatoms when the molar ratio of METAC to AAm located in the range of 0.01~0.05. Under this situation, the enhanced hydration effect plays an important and decisive role in the decrease of microorganism settlement. However, a net positive charge is presented with further increasing the content of METAC. Thus the higher settlements

observed

in

the

systems,

i.e.,

PVA-AAm-METAC-0.07

and

PVA-AAm-METAC-0.1, are expected to be induced by electrostatic attraction of the cationic METAC based SIPNs to the negatively charged algae. Based on the special structure of SIPNs (the linear or branched network penetrate each other on molecular scale), there are reasons to believe the charge exists at both bulk and surface of the as-prepared samples. What’s more, a number of algae fouling experiments with charged SAMs or polymer brush also can be found in the published papers.38-39,44,49-51 It was found that the settlements of barnacle cyprids of B.improvisus and Balanus amphitrite were charge sensitive and the fouling organisms have a higher tendency to attach and settle on charged surface, especially for positively charged condition. These results confirm our experimental results obtained on charged SIPNs samples to some extent. As a result, it is easy to conclude that the antifouling behavior does heavily depend on the amount of cationic component for the METAC based polymer networks.

An ocean field assay of SIPNs samples


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In order to prove the practicability of the as-prepared SIPNs samples, the samples were held to the steel plates for an ocean field assay in the South China Sea.

Figure 12 shows the photographs of biofouling assessment of samples. For the first week immersion, all the samples, including the control plate (silicon wafer), show scarcely any sign of biofouling. After two weeks, the control plate begins to be fouled by Barnacle larva, which might mean the formation of “condition film”,45 and there is no obvious biofouling phenomenon appears for both SPMA and SBMA embedded SIPNs. For six weeks of immersion, the biofouling is still dominated by Barnacle larva and Callyspongin vaginalis larva. However, the performance of as-prepared SIPNs are different from the control one, either SPMA or SBMA integrated SIPNs still remain relatively clean and there is only very small amount of Callyspongin vaginalis larva attached on the samples, which means the SIPNs samples possess very good chemical and mechanical stability under the circumstances including water currents and salinity. These experimental results are accorded with the static antifouling experiment. As a conclusion, despite of the unexpected but negligible damages on the as-prepared SIPNs, such as some small cuts, the active components integrated SIPNs truly provide excellent resistance to microorganism accumulation. Lastly, since the hydrogels based materials are beneficial to environmental protection and could deliver multiple green-economy benefits. They exhibit the potential application in the field of marine biofouling. However, polymer networks (hydrogels) usually need to be anchored firmly to the substrate for practical application. Unfortunately, the weak and brittle bonding between hydrogels and substrate hampers their integration in substrate. In this paper, considering the poor adhesion between as-prepared polymer networks and substrate, the samples were held to the steel plate by specially designed fixture for ocean field assay. Despite there are some strategies which have been devoted to overcome the poor adhesive interface between polymer networks and substrate,46-48 an appropriate surface bonding technology for the as-prepared SIPNs sample also should be developed in the future.



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Figure 12. Images of marine antifouling surfaces after immerged in the South China Sea (N22°33', E114°32') for different periods.

Conclusion In summary, various charged components, including cationic, anionic, zwitterionic and neutral precursors, were integrated into semi-interpenetrating network (SIPNs). The effect of charged multi-component polymer networks on the marine antifouling was investigated. Compared with silicon wafer and PVA-pAAm reference sample, the improved antifouling activity of neutral OEGMA integrated SIPNs against green alga D. tertiolecta and diatom Navicula sp. is on a par with the anionic and zwitterionic integrated SIPNs. These relative less accumulation densities are attributed to various reasons as follows: for the anionic SPMA embedded SIPNs, the lower biofouling is attributed to the higher hydration resulted from solvation of the sulfonate groups and the electrostatic repulsion between negatively charged algae and anionic polymer substrate; for the SBMA based SIPNs, the improved antifouling behavior is induced because the zwitterionic are highly hydrated than PVA polymers; for the neutral OEGMA integrated SIPNs, the reduced algae attachment is attributed to the enhanced hydration effect by polar groups, such as -O- groups. While for the cationic METAC embedded SIPNs system, despite the hydration shell induced by the


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ion-dipole interactions, the resistance to microorganism heavily depends on the content of cationic METAC because of the favorable electrostatic attraction between negatively charged algae and cationic METAC based SIPNs. What’s more, the ocean field assay indicated that both anion and zwitterion integrated SIPNs exhibited better antifouling performance. Furthermore, the SIPNs are common, commercially cheap, and environmentally friendly materials with flexible but tunable mechanical property, these might permit the SIPNs to be a good candidate for marine antifouling and some other relevant fields. ASSOCIATED CONTENT Supporting Information The equilibrium water content of cationic METAC components integrated SIPNs; the effect of the METAC content on the mechanical properties of SIPNs samples; representative fluorescence microscopy images of attached green algae and diatoms after exposure to anionic, zwitterionic, neutral and cationic components integrated PVA samples for 24 hours. AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]. Tel: +86-931-46968466. Fax: +86-931-8277088.

Notes The authors declare no competing financial interest.

Acknowledgment This work was financially supported by NSFC (21434009, 51403220 and 51573198) and Ministry of Science and Technology (2016YFC1100401)

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