Synthesis of a Stretchable Polyampholyte Hydrophilic Film with Compositional Gradient for Long‐Term Stable, Substrate‐Independent Fouling‐Resistant Coating

Abstract

The prevention of nonspecific biofouling is crucial for technological development in biomaterials and medical devices. Thus, zwitterionic materials have attracted significant attention due to their effective fouling‐resistance, long‐term durability against oxidation, and biocompatibility. However, fabricating a substrate‐independent zwitterionic surface with outstanding fouling‐resistance remains a challenge. In this study, a polyampholyte coating that satisfies the aforementioned requirements is obtained using a vapor‐phase method. The polyampholyte coating consists of a bilayer of poly(1,3,5,7‐tetramethyl‐1,3,5,7‐tetravinyl cyclotetrasiloxane) (pV4D4) and polyampholyte, poly(2‐carboxyethyl acrylate‐co‐2‐(dimethylamino)ethyl acrylate) (pCD), stacked with compositional gradient, which are obtained via sequential deposition using initiated chemical vapor deposition. The heavily crosslinked pV4D4 acts as an adhesion promoter layer that may be applied conformally to various substrate materials with high interfacial adhesion. The pCD surface exhibits a long‐lasting, superior fouling‐resistance to proteins (20.3 ± 1.8 ng cm−2 for undiluted human serum) and microorganisms. The pCD‐grad‐pV4D4 films, coupled with the stress‐dissipative gradient interface, are highly stretchable up to 50% without compromising the fouling‐resistance. The fouling‐resistance is maintained after 1 day of sonication, 10 days of water flushing, and 30 days of water shearing. Further, the pCD‐grad‐pV4D4 films are fully transparent and patternable, making them a prospective alternative for future non‐fouling biomedical applications.

Vapor-Deposited Polymer Films and Structure: Methods and Applications

“…38 The scheme for producing gradient copolymer materials is shown in Figure 3D.The compositional gradient of PV4D4 and the polyampholyte poly(2-carboxyethyl acrylate-co-2-(dimethylamino)ethyl acrylate) (PCD) was fabricated via iCVD by controlling the flow rate of monomers. 51 The flow rate of V4D4 was decreased over the processing time, while the flow rate of PCD was increased.…”

“…56 An iCVD-polymerized gradient membrane of PV4D4 and PCD provided good antifouling properties with the outer layer of pCD and strong substrate-independent adhesion of PV4D4. 50 Poly(dimethyl amino methyl styrene-co-1H,1H,2H,2H-perfluorodecyl acrylate) (P(DMAMS-co-PFDA)) was modified on the negatively charged and hydrophilic surface of polyester textile via iCVD to provide anti-fouling properties. 57 The schematic diagram of the coating process and antifouling is shown in Figure 4A.…”

Nano-CeO2-Loaded Polyzwitterionic Double-Network High-Strength Hydrogel for Highly Enhanced Synergistic Marine Antifouling

“…The bactericidal mechanism was the same as that of the simulated enzyme, and the bactericidal rate can be as high as 100% . On the other hand, the AAE can be obtained through modifying or coating to form the superhydrophilic surface, including polymer brushes, special topologically structured surfaces, and zwitterionic surfaces with a dense hydration membrane, to resist the adhesion of some defilement organisms. For instance, Yang et al grafted the polyzwitterionic poly­(sulfobetaine methacrylate) onto the surface of poly­(vinylmethylsiloxane) elastomer substrates, which can exhibit good fouling resistance and triggered the release of scaling .…”

Ultrathin organosiloxane membrane for precision organic solvent nanofiltration

“…1a ). Within the pV4D4, the organosiloxane bond, –Si–O–Si–, offers flexibility with low bond rotational energy of 0.2 kcal mol −1 , and the highly interconnected structure, derived from its multifunctionality, enhances mechanical robustness, chemical resilience, and structural longevity in the harsh solvent environment 25 , 26 . Additionally, flexible octagonal rings and a dense bridging microstructure can play a crucial role in discriminating small molecules at the nanoscale, enabling precise separation.…”