Universal Strategy for Efficient Fabrication of Blood Compatible Surfaces via Polydopamine-Assisted Surface-Initiated Activators Regenerated by Electron Transfer Atom-Transfer Radical Polymerization of Zwitterions

Abstract

Implant and blood-contacting biomaterials are challenged by biofouling and thrombus formation at their interface. Zwitterionic polymer brush coating can achieve excellent hemocompatibility, but the preparation often involves tedious, expensive, and complicated procedures that are designed for specific substrates. Here, we report a facile and universal strategy of creating zwitterionic polymer brushes on variety of materials by polydopamine (PDA)-assisted and surface-initiated activators regenerated by electron transfer atom-transfer radical polymerization (PDA-SI-ARGET-ATRP). A PDA adhesive layer is first dipcoated on a substrate, followed by covalent immobilization of 3-trimethoxysilyl propyl 2-bromo-2-methylpropionate (SiBr, ATRP initiator) on the PDA via condensation. Meanwhile, the trimethoxysilyl group of SiBr also cross-links the PDA oligomers forming stabilized PDA/SiBr complex coating. Finally, SI-ARGET-ATRP is performed in a zwitterionic monomer solution catalyzed by the parts per million level of CuBr2 without deoxygenization. The conveniently fabricated zwitterionic polymer brush coatings are demonstrated to have stable, ultralow fouling, and extremely blood compatible and functionalizable characteristics. This facile, versatile, and universal surface modification strategy is expected to be widely applicable in various advanced biomaterials and devices.

A Uniform and Robust Bioinspired Zwitterion Coating for Use in Blood‐Contacting Catheters with Improved Anti‐Inflammatory and Antithrombotic Properties

“…Previous studies have confirmed that polymeric zwitterion coatings commonly exhibit excellent antifouling properties, because of their ability to strongly bind water molecules, forming highly hydrated layers that can effectively prevent the adhesion of biological agents. [44] In this work, the antifouling performance of a PVC catheter coated with pMPCDA was evaluated by antibacterial adhesion assay, using the pristine PVC catheter as the control. Two kinds of PVC catheter samples were briefly immersed in Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) solutions with a bacterial concentration of 2 × 10 7 colony-forming unit (CFU) mL −1 and then incubated for 24 h. Afterward, the catheter samples were sufficiently washed with PBS and stained with LIVE/DEAD staining agents.…”

Anti-biofouling materials and surfaces based on mussel-inspired chemistry

“…Third, PDA molecules mainly exist as oligomers, and the attached PDA layer may not be very stable under certain application conditions, especially in a polar organic solvent, strong acidic and alkali solutions. 132,135,136 The stability of PDA layers is closely related to the long-term applications of the immobilized hydrophilic polymer coatings. This review offers an overview on the anti-biofouling materials based on the musselinspired chemistry, stimulating the development of new strategies and technologies to overcome the long-standing biofouling challenges.…”

“…131 Likewise, Li et al covalently grafted zwitterionic poly(MPC) polymer brushes on a variety of PDA-coated materials by surfaceinitiated activators regenerated by electron transfer atom-transfer radical polymerization (PDA-SI-ARGET-ATRP). The prepared zwitterionic polymer coatings were demonstrated to have ultralowbiofouling performance, which effectively suppressed the adhesion of proteins and platelets 132.…”

Formation of Various Polymeric Films via Surface‐Initiated ARGET ATRP on Silicon Substrates

“…19 Because of this regenerative catalytic cycle, ARGET ATRP needs no deoxygenating steps for the reaction solutions and it can be proceeded with a very low concentration of a Cu catalyst (at the level of several ppm) under ambient conditions. Along the same line with grafting-from approach, surface-initiated ARGET ATRP (SI-ARGET ATRP) has been successfully applied to a variety of applications including the preparation of low fouling surfaces, 20,21 development of the universal polymer grafting method to fabricate blood compatible surfaces, 22 and the preparation of biocompatible graphene nanosheets. 23 While SI-ARGET ATRP has been widely utilized to prepare functional coatings by grafting polymers from surfaces, there has been little study to investigate systematically the polymer grafting of various monomers over time using the same platform.…”