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This works reports a set of new functionalized polyethyleneimine (PEI) polymers, including a neutral PEGylated polymer PEI-g-PEGMA, a negatively charged polymer PEI-g-SA, and a zwitterionic polymer PEI-g-SBMA, and their use as antibiofouling coating agent for human teeth protection. Polymers were synthesized by Michael addition, XPS analysis revealed that each polymer could be efficiently coated onto hydroxyapatite, ceramic material used as a model tooth. Polymers carrying a negative net charge were more efficiently adsorbed, because of the establishment of electrostatic interactions with calcium ions. Protein adsorption tests revealed that two factors were important in the reduction of protein adsorption. Both the surface charge and the surface ability to bind and entrap water molecules had to be considered. PEI-g-SBMA, which zeta potential in PBS solution was negative, was efficient to inhibit the adsorption of BSA, a negative protein. On the other hand, it also resisted the adsorption of lysozyme, a positive protein, because zwitterionic molecules can easily entrap water and provide a very hydrophilic environment. Streptococcus mutans attachment tests performed unveiled that all modified polymers were efficient to resist this type of bacteria responsible for dental carries. Best results were also obtained with PEI-g-SBMA coating. This polymer was also shown to efficiently resist the adsorption of positively charged bacteria (Stenotrophomonas maltophilia). Tests performed on real human tooth showed that PEI-g-SBMA could inhibit up to 70% of bacteria adhesion, which constitutes a major result considering that surface of teeth is very rough, therefore physically promoting the attachment of proteins and bacteria.

In the present work, the focus is laid on the formation, and low-biofouling properties of polyvinylidene fluoride (PVDF) membranes modified using an amphiphilic copolymer additive: polystyrene-b-poly (ethylene glycol) methacrylate (PS-b-PEGMA). PVDF was blended with PS-b-PEGMA and membranes were prepared by liquid-induced phase separation. The additive played a significant role on membrane formation, slightly decreasing surface porosity, reducing the shrinkage during phase separation, and increasing both the size and porosity of macrovoids. Owing to its numerous hydrophilic moieties, the copolymer was believed to promote solvent and nonsolvent exchanges during phase inversion. In addition, it significantly enhanced surface hydrophilicity and matrix hydration capability. Indeed, water was easily trapped by the PEGylated chains spread onto the surface and within the matrix, and then stored in the larger macrovoids. It led to an important reduction of protein adsorption, including bovine serum albumin (65%) and lysozyme (89%). Bacterial attachment tests revealed that adhesion of Escherichia coli and Staphylococcus epidermidis was almost totally prevented (over 99% reduction of attachment), which demonstrates the excellent efficiency of PS-b-PEGMA copolymer to provide PVDF membranes with low-biofouling properties.

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Development of bioinert membranes to prevent blood clotting, tissue adhesion, and bacterial attachment is important for the wound healing process. In this work, two wound-contacting membranes of expanded poly(tetrafluoroethylene) (ePTFE) grafted with zwitterionic poly(sulfobetaine methacrylate) (PSBMA) and hydrophilic poly(ethylene glycol) methacrylate (PEGMA) via atmospheric plasma-induced surface copolymerization were studied. The surface grafting chemical structure, hydrophilicity, and hydration capability of the membranes were determined to illustrate the correlations between bioadhesive properties and wound recovery of PEGylated and zwitterionic ePTFE membranes. Bioadhesive properties of the membranes were evaluated by the plasma protein adsorption, platelet activation, blood cell hemolysis, tissue cell adhesion, and bacterial attachment. It was found that the zwitterionic PSBMA-grafted ePTFE membrane presented high hydration capability and exhibited the best nonbioadhesive character in contact with protein solution, human blood, tissue cells, and bacterial medium. This work shows that zwitterionic membrane dressing provides a moist environment, essential for "deep" skin wound healing observed from the animal rat model in vivo and permits a complete recovery after 14 days, with histology of repaired skin similar to that of normal skin tissue. This work suggests that the bioinert nature of grafted PSBMA polymers obtained by controlling grafting structures gives them great potential in the molecular design of antibioadhesive membranes for use in skin tissue regeneration.

Zwitterionic materials are the latest generation of materials for nonfouling interfaces and membranes. They outperform poly(ethylene glycol) derivatives because they form tighter bonds with water molecules and can trap more water molecules. This feature article summarizes our laboratory's fundamental developments related to the functionalization of interfaces and membranes using zwitterionic materials. Our molecular designs of zwitterionic polymers and copolymers, sulfobetaine-based, carboxybetaine-based, or phosphobetaine-based, are first reviewed. Then, the strategies used to functionalize surfaces/membranes by coating, grafting onto, grafting from, or in situ modification are examined and discussed, and the third part of this article shifts the focus to key applications of zwitterionic materials. Finally, some potential future directions for molecular designs, functionalization processes, and applications are presented.

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Herein, a pseudozwitterionic structure bearing moieties with mixed positive and negative charges is introduced to develop a potential biomaterial for wound dressing applications. New mixed-charge matrices were prepared by copolymerization of the negatively charged 3-sulfopropyl methacrylate (SA) and positively charged [2-(methacryloyloxy)ethyl] trimethylammonium (TMA) onto expanded polytetrafluoroethylene (ePTFE) membranes. The charge balance was effectively regulated through the control of the initial SA/TMA ratio. The focus was then laid on the assessment of a variety of essential properties of efficient wound dressings including, hydration property, resistance to fibrinogen adsorption, hemocompatibility, as well as resistance to fibroblast attachment and bacteria colonization. It was found that the pseudozwitterionic membranes, compared to those with charge bias in the poly(SA-co-TMA) structure, exhibited the best combination of major properties. Therefore, they were further tested for wound healing. Histological examination of mouse wound treated with the pseudozwitterionic membranes exhibited complete re-epithelialization and total formation of new connective tissues after 14 days, even leading to faster healing than using commercial dressing. Results presented in this work suggest that the mixed-charge copolymers with a perfect balance of positive and negative moieties represent the newest generation of biomaterials for wound dressings.