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Phototriggered functionalization of hierarchically structured polymer brushes

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Queensland University of Technology ePrints Archive
Keywords
  • Acrylic Monomers
  • Copolymers
  • Dendrimers
  • Ethylene
  • Ethylene Glycol
  • Free Radical Reactions
  • Grafting (Chemical)
  • Mass Spectrometry
  • Medical Applications
  • Organic Polymers
  • Polymerization
  • Polymers
  • Proteins
  • Secondary Ion Mass Spectrometry
  • Surface Plasmon Resonance
  • X Ray Photoelectron Spectroscopy
  • Biofunctionalization
  • Biomedical Applications
  • Biotinylated Antibodies
  • Oligo(Ethylene Glycol) Methacrylate
  • Polymer Architecture
  • Surface Architectures
  • Surface Initiated Atom Transfer Radical Polymerization (Si Atrp)
  • Time Of Flight Secondary Ion Mass Spectrometry
  • Atom Transfer Radical Polymerization
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Abstract

The precise design of bioactive surfaces, essential for the advancement of many biomedical applications, depends on achieving control of the surface architecture as well as on the ability to attach bioreceptors to antifouling surfaces. Herein, we report a facile avenue toward hierarchically structured antifouling polymer brushes of oligo(ethylene glycol) methacrylates via surface-initiated atom transfer radical polymerization (SI-ATRP) presenting photoactive tetrazole moieties, which permitted their functionalization via nitrile imine-mediated tetrazole-ene cyclocloaddition (NITEC). A maleimide-functional ATRP initiator was photoclicked to the side chains of a brush enabling a subsequent polymerization of carboxybetaine acrylamide to generate a micropatterned graft-on-graft polymer architecture as evidenced by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Furthermore, the spatially resolved biofunctionalization of the tetrazole-presenting brushes was accessed by the photoligation of biotin-maleimide and subsequent binding of streptavidin. The functionalized brushes bearing streptavidin were able to resist the fouling from blood plasma (90% reduction with respect to bare gold). Moreover, they were employed to demonstrate a model biosensor by immobilization of a biotinylated antibody and subsequent capture of an antigen as monitored in real time by surface plasmon resonance. © 2015 American Chemical Society.

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