Research Progress of Natural Products and Their Derivatives in Marine Antifouling.

With the increasing awareness of environmental protection, it is necessary to develop natural product extracts as antifouling (AF) agents for alternatives to toxic biocides or metal-based AF paints to control biofouling. This paper briefly summarizes the latest developments in the natural product extracts and their derivatives or analogues from marine microorganisms to terrestrial plants as AF agents in the last five years. Moreover, this paper discusses the structures-activity relationship of these AF compounds and expands their AF mechanisms. Inspired by the molecular structure of natural products, some derivatives or analogues of natural product extracts and some novel strategies for improving the AF activity of protective coatings have been proposed as guidance for the development of a new generation of environmentally friendly AF agents.

Supramolecular assembly inspired molecular engineering to dynamically tune non-Newtonian fluid:from quasi-static flowability-free to shear thickening.

Shear thickening fluids (STFs) have been the research focus for decades because of the prospect as a damping ingredient. However, their inherent liquid character confines their practical applications. In this work, inspired by the assembly engineering, novel gelatinous shear thickening fluids (GSTFs) are fabricated by integrating low molecular weight gelators (LMWGs) into STFs and investigated by rheological experiments. The results show that the apparent performances of GSTFs are determined by the LMWGs content. LMWGs inside GSTFs can assemble into three-dimensional network that can constraint the flowability of liquid molecular and their content dominate the density and strength of assembly network. At a moderate content, GSTFs exhibit desired properties with restricted quasi-static flowability and almost undamaged dynamic shear thickening character. While a higher content will disappear shear thickening and a lower content cannot gelate STFs. Besides, three different LMWGs are employed to gelate STFs and all they can gelate STFs in spite of the distinct minimum gelation concentration, indicating the universality for GSTFs preparation and the superiority of a reasonable molecular structure of LMWGs. Further, the temperature sweep experiments suggest that GSTFs can endure higher temperature without flowing due to its higher gel-sol transition temperature. Basing on these advanced mechanical properties, we believe that the GSTFs with more expected characters have significance for the study of non-Newtonian fluids and will broaden the special application field of STFs.

One-step zwitterionization and quaternization of thick PDMAEMA layer grafted through subsurface-initiated ATRP for robust antibiofouling and antibacterial coating on PDMS.

In this work, we demonstrate the grafting of thick poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) layer on PDMS via subsurface-initiated atom transfer radical polymerization (SSI-ATRP). The self-migration of DMAEMA monomers into the subsurface of PDMS is proven to be the dominant factor for the success of SSI-ATRP. The as-prepared thick microscale graft layer on PDMS shows much better abrasion resistance than nanoscale graft layer obtained by conventional surface-initiated atom transfer radical polymerization (SI-ATRP) under identical condition. Taking advantage of the tertiary amines of PDMAEMA, the simultaneous zwitterionization and quaternization of the PDMAEMA thick layer is realized through a facile one-step process. The effect of zwitterionization and quaternization degree on the antibiofouling and antibacterial properties is investigated. The results show that a relatively high zwitterionization degree (75 mol%) and a low quaternization degree (25 mol%) exhibit a good well-balanced effect on both fouling repellence and bactericidal activity. This work may lead to the development of robust bifunctional antibiofouling and antibacterial surfaces via SSI-ATRP strategy.

Transparent Janus Hydrogel Wet Adhesive for Underwater Self-Cleaning.

The optical window is a key part of a sensor specially used for oceanographic detection, but it is often severely affected by marine biofouling and oil pollution, resulting in reduced transparency and lifespan. Hydrogel, as a hydrophilic polymer network, has excellent antifouling effects with good transparency, but it is difficult to adhere to substrates, which greatly limits its practical applications. To solve the above problem, a transparent Janus hydrogel wet adhesive was prepared through modifying poly(vinyl alcohol)/glycerol-tannic acid/Cu2+ (PVA/Gly-TA/Cu2+) hydrogel with the underwater adhesive poly(dopamine methacrylamide-co-methoxyethyl acrylate) (P(DMA-co-MEA)) via the coordination effect between Cu2+ and catechol. Even when coated with adhesive, the sample still retained good transmittance. The presence of Cu2+ endowed the hydrogel with better tensile strength and, at the same time, can improve the adhesion of the hydrogel to the substrate through the coordination effect with the adhesive. The tensile stress of Janus hydrogels can even reach 4.4 MPa, and the adhesion strength of the obtained Janus hydrogel can reach about 14 kPa in seawater. Furthermore, the Cu-rich Janus hydrogel presented a significant inhibitory effect on the growth of surface algae. The oil contact angle of the Janus hydrogel was as high as 148° underwater. After the hydrogel was reswollen, there were lower algae densities on the surfaces of the hydrogel and little change in transparency. Considering the above properties, this novel Janus hydrogel is anticipated to be a promising protective material to solve the marine pollution problem confronting optical equipment.

Natural Product Inspired Environmentally Friendly Strategy Based on Dopamine Chemistry toward Sustainable Marine Antifouling.

The combination of natural active antifouling composition and intelligent coatings has been regarded as a prospective approach to avoid marine biofouling. However, the relatively complex coating structure and the excessive rapid release of antifoulants maintain unresolved issues in their practical application. In this work, a novel environmentally friendly natural antifoulant (Stellera chamaejasme, SC) encapsulated in the polydopamine (PDA) microcapsule (SC@PDA) is prepared by emulsion interfacial polymerization and blended with the acrylate polymer to prepare a sustainable antifouling coating. Herein, the PDA shell acting as an "intelligent capsule" ensures the controlled release of the antifoulant SC, and the corresponding SC loading amount could be high up to 75.40%. As a model antifoulant, the impact of SC on the adsorption activity of the protein bovine serum albumin (BSA) is studied, as well as the settlement of presentative fouling communities (diatom Navicula sp. and red algae Porphyridium sp.) on the constructed coating. The experimental results demonstrate that the natural product SC integrated eco-friendly antifouling coating occupies the superior capacity of impeding the adsorption of both protein BSA and algae. Such antifoulant (SC) integrating with controlled release character is a great advance in terms of marine antifouling applications. It is, therefore, expected that this innovation will provide guiding significance for developing the next generation of antifouling techniques, especially in the field of marine antifouling.

Embedded polyzwitterionic brush-modified nanofibrous membrane through subsurface-initiated polymerization for highly efficient and durable oil/water separation.

HYPOTHESIS: Developing separation membranes functionalized by polymer brushes with high separation efficiency and good cycling stability is of great importance for oil/water separation, yet is still challenged. EXPERIMENTS: In this work, the covalently embedded polyzwitterionic brush-functionalized nanofibrous membrane was developed for efficient and durable oil/water separation. The nanofibrous membrane was prepared by the electrospinning method using initiator-embedded polyacrylonitrile (PAN) resin, followed by novel subsurface-initiated atom transfer radical polymerization (SSI-ATRP) to graft embedded poly(sulfobetaine methacrylate) brushes (PSBMA). The hydration ability, underwater oil adhesion, oil/water separation performance as well as self-cleaning properties of the as prepared membrane (PAN-sg-PSBMA) were systematically studied. FINDINGS: The PAN-sg-PSBMA membrane exhibited extraordinary hydration ability and underwater superoleophobicity with extremely low oil adhesion, which outperformed conventional polymer brush-modified membrane (PAN-g-PSBMA). The PAN-sg-PSBMA membrane was able to separate both oil/water mixture and surfactant-stabilized emulsions with ultrahigh permeation flux and separation efficiency. Moreover, compared with PAN-g-PSBMA, PAN-sg-PSBMA membrane exhibited unprecedented recycling stability in both permeation flux and separation efficiency, which is attributed to mechanical robustness of embedded polymer brushes and outstanding antifouling ability. The current findings revealed that embedded polymer brushes from SSI-ATRP could offer a promising design of functionalized nanofibrous membrane for highly efficient and durable oil/water separation.

Solvent-driven migration of highly polar monomers into hydrophobic PDMS produces a thick graft layer via subsurface initiated ATRP for efficient antibiofouling.

The sucessful grafting of highly polar polymer chains both on the surface and in the subsurface of PDMS via subsurface initiated ATRP for the improved antibiofouling performance is enabled by the diffusion of organic solvents (in a water-based binary solvent) which act as not only a "carrier" for hydrophilic monomers but also a "sweller" for the PDMS substrate.

In Situ Grafting Hydrophilic Polymeric Layer for Stable Drag Reduction.

Developing drag reduction techniques has attracted great attention because of their need in practical applications. However, many of the proposed strategies exhibit some inevitable limitations, especially for long period of adhibition. In this work, the dynamic but stable drag reduction effect of superhydrophilic hydrogel-coated iron sphere falling freely in a cylindrical water tank was investigated. The absolute instantaneous velocities and displacements of either the hydrogel-encapsulated or unmodified iron sphere falling freely in water were monitored via a high-speed video. It was revealed that, in the range of Reynolds number from 104 to 106, the optimized hydrogel-coated iron sphere with uniform stability could reduce the resistance by up to 40%, which was mainly due to the boundary slip of water and the delayed boundary separation that resulted from the coated hydrogel. Besides, the deliberate experiments and analysis further indicated that the superhydrophilic hydrogel layer accompanied by the emergence of the drag crisis has largely effected the distribution of flow field at the boundary around the sphere. More importantly, the drag reduction behavior based on the proposed method was thermodynamically stable and resistant to external stimulus, including fluidic oscillator and hydrodynamic pressure. The effective long-term drag reduction performance of the hydrophilic substrate can be expected, correspondingly, and also provides a novel preliminary protocol and avenues for the development of durable drag reduction technologies.

Contribution of Charges in Polyvinyl Alcohol Networks to Marine Antifouling.

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, field emission scanning electron microscopy, and tensile tests were used to characterize the physicochemical properties of the prepared SIPNs. To investigate the contribution of charges to marine antifouling, the adhesion behaviors of green algae Dunaliella tertiolecta and diatoms Navicula sp. in the laboratory and of the actual marine animals in field test were studied for biofouling assays. The results suggest that less algae accumulation densities are observed for 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 nontoxic antifouling coating is a long-standing and cosmopolitan industrial challenge, the SIPNs may provide a useful reference for marine antifouling and some other relevant fields.

Contribution of Surface Chemistry to the Shear Thickening of Silica Nanoparticle Suspensions.

Shear thickening is a general process crucial for many processed products ranging from food and personal care to pharmaceuticals. Theoretical calculations and mathematical simulations of hydrodynamic interactions and granular-like contacts have proved that contact forces between suspended particles dominate the rheological characteristic of colloidal suspensions. However, relevant experimental studies are very rare. This study was conducted to reveal the influence of nanoparticle (NP) interactions on the rheological behavior of shear-thickening fluids (STFs) by changing the colloidal surface chemistries. Silica NPs with various surface chemical compositions are fabricated and used to prepare dense suspensions. Rheological experiments are conducted to determine the influence of NP interactions on corresponding dense suspension systems. The results suggest that the surface chemistries of silica NPs determine the rheological behavior of dense suspensions, including shear-thickening behavior, onset stress, critical volume fraction, and jamming volume fraction. This study provides useful reference for designing effective STFs and regulating their characteristics.