Zwitterionic Sulfobetaine-Grafted Poly(vinylidene fluoride) Membrane with Highly Effective Blood Compatibility via Atmospheric Plasma-Induced Surface Copolymerization

Abstract

Development of nonfouling membranes to prevent nonspecific protein adsorption and platelet adhesion is critical for many biomedical applications. It is always a challenge to control the surface graft copolymerization of a highly polar monomer from the highly hydrophobic surface of a fluoropolymer membrane. In this work, the blood compatibility of poly(vinylidene fluoride) (PVDF) membranes with surface-grafted electrically neutral zwitterionic poly(sulfobetaine methacrylate) (PSBMA), from atmospheric plasma-induced surface copolymerization, was studied. The effect of surface composition and graft morphology, electrical neutrality, hydrophilicity and hydration capability on blood compatibility of the membranes were determined. Blood compatibility of the zwitterionic PVDF membranes was systematically evaluated by plasma protein adsorption, platelet adhesion, plasma-clotting time, and blood cell hemolysis. It was found that the nonfouling nature and hydration capability of grafted PSBMA polymers can be effectively controlled by regulating the grafting coverage and charge balance of the PSBMA layer on the PVDF membrane surface. Even a slight charge bias in the grafted zwitterionic PSBMA layer can induce electrostatic interactions between proteins and the membrane surfaces, leading to surface protein adsorption, platelet activation, plasma clotting and blood cell hemolysis. Thus, the optimized PSBMA surface graft layer in overall charge neutrality has a high hydration capability and the best antifouling, anticoagulant, and antihemolytic activities when comes into contact with human blood.

Zwitterionic polymers grafted poly(ether sulfone) hollow fiber membranes and their antifouling behaviors for osmotic power generation

“…However, long term usage will cause a reduction in their antifouling properties due to the oxidative degradation of PEG chains. Zwitterionic-based materials have been considered as the most suitable alternative for the preparation of ultralow fouling surfaces [27][28][29][30][31][32][33]. Water molecules can be bound stronger than PEG chains via electrostatically induced hydration.…”

An intuitive thermal-induced surface zwitterionization for versatile, well-controlled haemocompatible organic and inorganic materials

“…Modifications to biomaterial surfaces, such as plasma-induced surface grafting [3,4], surface-initiated atom transfer radical polymerization [5,6], etc., as means to improve haemocompatibility have been proposed in recent years. While these modifications are effective in improving blood compatibility of materials, the processes involved remain both intricate and expensive; as a result, a robust, cost-effective protocol for enhancing blood compatibility via surface modification is necessary for practical and commercial purposes.…”

Poly(ethylene oxide)-based block copolymers with very high molecular weights for biomimetic calcium phosphate mineralization

“…Interestingly, positively charged, [75][76][77] properties that should also be interesting for dental applications. Additionally, these polymers are able to interact with solids.…”