Synthesis and Characterization of Antifouling Poly(N-acryloylaminoethoxyethanol) with Ultralow Protein Adsorption and Cell Attachment

Abstract

Rational design of effective antifouling polymers is challenging but important for many fundamental and applied applications. Herein we synthesize and characterize an N-acryloylaminoethoxyethanol (AAEE) monomer, which integrates three hydrophilic groups of hydroxyl, amide, and ethylene glycol in the same material. AAEE monomers were further grafted and polymerized on gold substrates to form polyAAEE brushes with well-controlled thickness via surface-initiated atomic transfer radical polymerization (SI-ATRP), with particular attention to a better understanding of the molecular structure-antifouling property relationship of hydroxyl-acrylic-based polymers. The surface hydrophilicity and antifouling properties of polyAAEE brushes as a function of film thickness are studied by combined experimental and computational methods including surface plasmon resonance (SPR) sensors, atomic force microscopy (AFM), cell adhesion assay, and molecular dynamics (MD) simulations. With the optimal polymer film thicknesses (∼10-40 nm), polyAAEE-grafted surfaces can effectively resist protein adsorption from single-protein solutions and undiluted human blood plasma and serum to a nonfouling level (i.e., <0.3 ng/cm(2)). The polyAAEE brushes also highly resist mammalian cell attachment up to 3 days. MD simulations confirm that the integration of three hydrophilic groups induce a stronger and closer hydration layer around polyAAEE, revealing a positive relationship between surface hydration and antifouling properties. The molecular structure-antifouling properties relationship of a series of hydroxyl-acrylic-based polymers is also discussed. This work hopefully provides a promising structural motif for the design of new effective antifouling materials beyond traditional ethylene glycol-based antifouling materials.

Salt-Responsive Zwitterionic Polymer Brushes with Tunable Friction and Antifouling Properties

“…30 Upon formation of the initiator monolayer, the ATRP procedure for grafting polymer brushes was the same to that used for polymer brushes on silica wafer. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 measurements were performed using an Axis Ultra DLD spectrometer (Kratos Analytical).…”

Modulation of Living Cell Behavior with Ultra‐Low Fouling Polymer Brush Interfaces

“…Several recent studies dealing with ultra‐low fouling surface–cell interactions focused on a specific application without aiming to generalize the observed surface–cell effects 4,18–21. Some complex surface–cell relationships have been recently reported—the ultra‐low fouling surface wettability (or hydrophilicity),22,23 hydration and layer thickness,24–26 zwitterionization,27 and charge, and the presence of various functional groups28 have been shown to influence cellular behavior. The differentiation of stem cells was investigated in dependence on surface hydrophilicity and zwitterionization of the coating 29.…”

A survey of state-of-the-art surface chemistries to minimize fouling from human and animal biofluids

“…25B vs. 25D). ] 170 As was already the situation for other types of brush ( poly(L-serine), 60 poly-SBMA, 120 polyCBAA, 135 and polyHPMA/polyHEMA 166,167vide supra), there also existed for antifouling polyAAEE coatings an optimal range of polymer thickness (∼10-40 nm). Recently (in 2014), Zheng's group reported a longer, OEG version of HEAAthe N-acryloylaminoethoxyethanol (AAEE) monomer shown in Fig.…”