Attaching molecules to chlorinated and brominated amorphous carbon substrates via Grignard reactions.

Amorphous carbon thin films are an attractive material because they provide a chemically robust surface that has been utilized in biomolecule array, biosensor, and bioelectronic applications. These thin films are particularly versatile because they are deposited at room temperature, making them readily integrated with other materials and devices. Here we present an alternative means of functionalizing carbon substrates based on Grignard chemistry. First, the amorphous carbon substrates are halogenated with a solution-based, radical-initiated halogenation reaction using PX5 (X = Br or Cl). Next, the halogenated surfaces are modified via the formation of a carbon-carbon bond between the surface and the Grignard reagents employed. Alkyl-, perfluoroalkyl-, and poly(ethylene glycol)-Grignard reagents were chosen to show the utility of this reaction scheme in functionalizing carbon surfaces to withstand oxidation and provide a hydrophobic and/or biocompatible substrate.