Detecting and quantifying oxygen functional groups on graphite nanofibers by fluorescence labeling of surface species

The ability to quantify functional groups on graphitic carbon nanofiber (GCNF) surfaces and to covalently attach ligands chemoselectively will aid in the development of functionalized GCNFs and potentially other carbon nanomaterials for applications in nanotechnology. Herein, we report the identification and quantification of functional groups on the surface of GCNFs using fluorescence labeling of surface species (FLOSS). Using reactions that are selective for specific functional groups and fluorescent dyes containing the dansyl group, surface aldehyde/ketone, carboxyl, and hydroxyl groups were identified and quantified in their total and relative amounts by FLOSS. Oxygen-containing functionality that was detected by FLOSS on nitric acid-oxidized GCNFs totaled approximately 2.5% of surface carbon, present as 0.9% aldehyde/ketone, 1.2% carboxyl groups on average, and 0.4% hydroxyl groups. The amounts of oxygen-containing functional groups on as-produced and demineralized GCNFs were much lower, amounting to no more than 0.05% of aldehyde/ketone groups on demineralized GCNFs and 0.3% of these groups on as-produced fibers. The FLOSS method has revealed information about the fiber surface that is not accessible by other methods, while also providing insight into the chemical reactivities of functional groups that can be used as sites for the attachment of ligands to give covalently functionalized materials.