Copper-free click biofunctionalization of silicon nitride surfaces via strain-promoted alkyne-azide cycloaddition reactions

Langmuir. 2012 Jun 12;28(23):8651-63. doi: 10.1021/la300921e. Epub 2012 May 29.

Abstract

Cu-free "click" chemistry is explored on silicon nitride (Si(3)N(4)) surfaces as an effective way for oriented immobilization of biomolecules. An ω-unsaturated ester was grafted onto Si(3)N(4) using UV irradiation. Hydrolysis followed by carbodiimide-mediated activation yielded surface-bound active succinimidyl and pentafluorophenyl ester groups. These reactive surfaces were employed for the attachment of bicyclononyne with an amine spacer, which subsequently enabled room temperature strain-promoted azide-alkyne cycloaddition (SPAAC). This stepwise approach was characterized by means of static water contact angle, X-ray photoelectron spectroscopy, and fluorescence microscopy. The surface-bound SPAAC reaction was studied with both a fluorine-tagged azide and an azide-linked lactose, yielding hydrophobic and bioactive surfaces for which the presence of trace amounts of Cu ions would have been problematic. Additionally, patterning of the Si(3)N(4) surface using this metal-free click reaction with a fluorescent azide is shown. These results demonstrate the ability of the SPAAC as a generic tool for anchoring complex molecules onto a surface under extremely mild, namely ambient and metal-free, conditions in a clean and relatively fast manner.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkynes / chemistry*
  • Azides / chemistry*
  • Click Chemistry
  • Dicyclohexylcarbodiimide / chemistry
  • Esters
  • Fluorescent Dyes
  • Fluorine / chemistry
  • Green Chemistry Technology
  • Hydrophobic and Hydrophilic Interactions
  • Lactose / chemistry
  • Microscopy, Fluorescence
  • Photoelectron Spectroscopy
  • Silicon Compounds / chemistry*
  • Succinimides / chemistry
  • Surface Properties
  • Ultraviolet Rays
  • Water

Substances

  • Alkynes
  • Azides
  • Esters
  • Fluorescent Dyes
  • Silicon Compounds
  • Succinimides
  • Water
  • Fluorine
  • Dicyclohexylcarbodiimide
  • Lactose
  • N-hydroxysuccinimide
  • silicon nitride