Epoxylated Zwitterionic Triblock Copolymers Grafted onto Metallic Surfaces for General Biofouling Mitigation.

Titanium and stainless steel materials are widely used in numerous devices or in custom parts for their excellent mechanical properties. However, their lack of biocompatibility seriously limits their usage in the biomedical field. This study focuses on the grafting of triblock copolymers on titanium and stainless steel metal susbtrates for improving their general biofouling resistance. The series of copolymers that we designed is composed of two blocks of zwitterionic sulfobetaine (SBMA) monomers and one block of glycidyl methacrylate (GMA). The number of repeat units forming each block, n, was finely tuned and controlled to 25, 50, 75, or 100, permitting regulation of the grafting thickness, the morphology, and the dependent properties such as the surface hydrophilicity and biofouling resistance. It was shown that the copolymer possessing n = 50 repeat units in each block, corresponding to a molecular weight of about 15.2 kDa, led to the best nonfouling properties, assessed using plasma proteins, blood cells, fibroblasts cells, and various bacteria. This was explained by an optimized grafting degree and chain organization of the copolymer. Lower value (n = 25) and higher values (n = 75, 100) led to low surface coverage and the formation of aggregates, respectively. The best copolymer was grafted onto scalpels (steel) and dental roots (titanium), and antifouling properties demonstrated using Escherichia coli and HT1080 cells. Results of this work show that this unique triblock copolymer holds promise as a potential material for surface modification of biomedical metallic devices, provided a fine-tuning of the blocks organization and length.

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

In this study, a facile and effective strategy is presented for the preparation of a series of zwitterionic poly(sulfobetaine methacrylate) (pSBMA)-grafted organic and inorganic biomaterials with well-controlled haemocompatibility via intuitive thermal-induced graft polymerization. The research focused on the effects of zwitterionic surface packing density on human blood compatibility by varying the SBMA monomer concentration on the silanized silicon wafer substrates. A 0.2 M SBMA monomer solution was found to not only produce Si wafer surfaces with ideal zwitterionic surface packing density and uniform, evenly distributed pSBMA grafting coverage but also yield optimal hydrophilicity and haemocompatibility. SBMA monomer concentrations lower and greater than 0.2 M yielded a zwitterionic surface with low grafting coverage. This study also demonstrated that the same, intuitive thermal-induced graft polymerization strategy could be applied to a variety of organic polymeric, inorganic ceramic and metal oxide biomaterials to improve haemocompatibility. Among the tested organic and inorganic materials, however, it was found that inorganic biomaterials demonstrated greater resistance to protein and platelet adhesions. It was hypothesized that the ozone treatment, which generated an abundance of hydroxide groups on inorganic substrate interfaces, might have given the inorganic biomaterials a more stable silanized layer yielding a preferable reaction state and resulted in sturdier and more durable pSBMA grafting.

Zwitterionic-based stainless steel with well-defined polysulfobetaine brushes for general bioadhesive control.

Stainless steels are widely used as orthopaedic and dental implant; however, bioadhesion in the case of thrombosis, inflammation, and infection is one of their major limitations. One way to tackle this problem is to graft the stainless steel surface with a zwitterionic polymer known for being anti-bioadhesive. Controlled atom transfer radical polymerization (ATRP) of zwitterionic poly(sulfobetaine methacrylate) (polySBMA) grafted from biomedical grade stainless steel surface was employed in this study. The interactions of polySBMA-grafted surfaces with biomacromolecules were demonstrated in vitro by the adhesion tests of plasma protein, blood cells, human MG63 osteoblast- and HT1080 fibroblast-like cells in biological complex media to evaluate their bioadhesive properties. Anti-microbial effects were also assessed for two most ordinary seen clinical bacteria, i.e., Escherichia coli and Staphylococcus epidermidis. Results showed that polySBMA-grafted surface exhibited evident bioadhesion resistance and conferring antibacterial efficacy. This work is also dedicated to deduce the effectiveness of polySBMA brushes' conformational structure on the prevention of bioadhesion. To this aim, the anti-bioadhesive effect of polySBMA brushes prepared by dopamine- and silane-surfaced immobilization method was evaluated. Results show that polySBMA grafted from immobilized polydopamine interfacial layers achieved better bioadhesion resistance, which could be causally related to their greater grafting coverage, flexible brush conformational structures, and greater hydration capabilities.

Hemocompatibility of pseudozwitterionic polymer brushes with a systematic well-defined charge-bias control.

In this study, a pseudozwitterionic surface bearing positively and negatively mixed charged moieties was developed as a potential hemocompatible material for biomedical applications. In this work, hemocompatility of pseudozwitterionic surface prepared from copolymerization of negatively charged 3-sulfopropyl methacrylate (SA) and positively charged [2-(methacryloyloxy)ethyl] trimethylammonium (TMA) was delineated. Mixed charge distribution in the prepared poly(TMA-co-SA)-grafted surface can be controlled by regulating TMA and SA monomer ratios via surface-initiated atom transfer radical polymerization. The effects of grafting composition and charge bias variations on blood compatibility of poly(TMA-co-SA)-grafted surface were reported. The protein adsorption on different poly(TMA-co-SA)-grafted surfaces from human plasma protein (fibrinogen, HSA, and γ-globulin) solutions was evaluated using an enzyme-linked immunosorbent assay. Blood platelet adhesion and time measurements on plasma clotting were conducted to determine the platelet activation on the grafted surface. It was found that the protein resistance and anti-blood cell adhesion of prepared surface can be precisely controlled by controlling the charge balance of TMA/SA compositions. In addition, different charge bias variations on the poly(TMA-co-SA)-grafted surface would induce electrostatic interactions between plasma proteins and prepared surfaces which lead to adsorptions of interfacial protein and blood cells, plasma clotting, and blood cell hemolysis. Results from this study suggest that the hemocompatility of mixed charged poly(TMA-co-SA)-grafted surface depends on the charge bias level. This provides a great potential for designing biomaterial with unique surface chemical structure which could be used in contact with human blood.