One-pot method for preparation of capsaicin-containing double-network hydrogels for marine antifouling.

Marine biofouling which interferes with normal marine operation and also causes huge economic loss has become a worldwide problem. With the development of society, there is an urgent need to develop non-toxic and efficient anti-fouling strategies. Capsaicin is an environmentally friendly antifouling agent, but controlling the stable release of capsaicin from the coating is still a challenge to be solved. To achieve long-lasting antifouling property, in this work, we incorporate a derivative of capsaicin N-(4-hydroxy-3-methoxybenzyl)acrylamide (HMBA) to prepare double network (DN) hydrogels and make HMBA a part of the polymer network. Polyvinyl alcohol (PVA) has good hydrophilicity, and as a soft and ductile network, acrylamide (AM) and HMBA can polymerize to generate a rigid and brittle network. By adjusting the content of HMBA in the DN hydrogels, we can obtain a PVA-PAHX hydrogel with high mechanical strength, low swelling rate, and excellent antifouling effect, which provides a feasible way for the practical application of a hydrogel coating in long-term marine antifouling.

Fabrication of dual anti-corrosive polyaniline microcapsules via Pickering emulsion for active corrosion protection of steel.

A novel kind of inhibitor-loaded polyaniline (PANI) microcapsule was prepared by Pickering emulsion photopolymerization using polyaniline particles as the Pickering emulsifier. In our strategy, water-dispersible polyaniline nanoparticles were firstly synthesized using a micelle template method and used to stabilize oil-in-water emulsions, in which the oil phase contained photo-crosslinkable and pH sensitive monomers and a photo-initiator. Under UV light, the pH-responsive monomers underwent photo-polymerization and crosslinking and converted to microcapsule shells. During this process, polyaniline nanoparticles were trapped in the microcapsule shells, leading to the formation of PANI microcapsules. The structure and morphology of the synthesized PANI microcapsules were analyzed using FTIR spectroscopy, SEM, and EDX mapping. The inhibitor (mercaptobenzothiazole, MBT) was subsequently incorporated into the PANI microcapsule as a functional core and demonstrated pH-sensitive releasing behavior. With the anti-corrosive PANI as the microcapsule wall and the inhibitor MBT as the core, the as-prepared MBT loaded PANI (MBT@PANI) microcapsule could afford dual corrosion protection, allowing smart protection of metals when exposed to corrosive conditions. The MBT@PANI microcapsules were embedded in UV-cured coating for protecting steel. The corrosion protection performance of the coating with MBT@PANI microcapsules was evaluated using the electrochemical impedance spectroscopy technique and salt spray test, which demonstrated the synergistic inhibition effect of the PANI wall and the loaded MBT in improving anti-corrosion performance of the coating.

Study on the Core-Shell Reversion of PSBMA- b-PLMA Nanoparticles for the Fabrication of Antifouling Coatings.

In this paper, two series of poly(sulfobetaine methacrylate)- b-poly(lauryl methacrylate) (PSBMA- b-PLMA) diblock copolymers were prepared to investigate the core-shell reversion of amphiphilic copolymers. Experimental results proved that the PSBMA- b-PLMA copolymers can be self-assembled as core-shell nanoparticles in chloroform. Moreover, 1H NMR spectra and contact angle measurements revealed that there is a transitional PSBMA/PLMA block ratio of 0.6, above which the nanoparticles are capable of switching their core and shell in aqueous solution. Consequently, nanoparticles with PSBMA/PLMA block ratios above 0.6 showed superior antifouling and antibacterial abilities to those with block ratios below 0.4. Moreover, it was also found that the block chain length plays an important role in core-shell reversion as evidenced by 1H NMR spectra, water contact angle, and antifouling tests. As a result, coatings fabricated with the PLMA100 series of nanoparticles showed better antifouling abilities than those of the PLMA150 series at the same block ratio probably because of the thinner shell of PLMA100 copolymers. PSBMA100- b-PLMA100 was proved to be the best candidate for the fabrication of antifouling coatings as it exhibited the highest efficacy in antibacterial adhesion and antiprotein adsorption. This study provided a facile method to fabricate antifouling coatings by developing amphiphilic diblock copolymers with tuned hydrophobic/hydrophilic block ratio, block chain length, etc.

Creation of antifouling microarrays by photopolymerization of zwitterionic compounds for protein assay and cell patterning.

Nonspecific binding or adsorption of biomolecules presents as a major obstacle to higher sensitivity, specificity and reproducibility in microarray technology. We report herein a method to fabricate antifouling microarray via photopolymerization of biomimetic betaine compounds. In brief, carboxybetaine methacrylate was polymerized as arrays for protein sensing, while sulfobetaine methacrylate was polymerized as background. With the abundant carboxyl groups on array surfaces and zwitterionic polymers on the entire surfaces, this microarray allows biomolecular immobilization and recognition with low nonspecific interactions due to its antifouling property. Therefore, low concentration of target molecules can be captured and detected by this microarray. It was proved that a concentration of 10ngmL-1 bovine serum albumin in the sample matrix of bovine serum can be detected by the microarray derivatized with anti-bovine serum albumin. Moreover, with proper hydrophilic-hydrophobic designs, this approach can be applied to fabricate surface-tension droplet arrays, which allows surface-directed cell adhesion and growth. These light controllable approaches constitute a clear improvement in the design of antifouling interfaces, which may lead to greater flexibility in the development of interfacial architectures and wider application in blood contact microdevices.