Rigid versus Flexible Ligands on Carbon Nanotubes for the Enhanced Sensitivity of Cobalt Ions

Carbon nanotubes have shown great promise in the fabrication of ultracompact and highly sensitive chemical and biological sensors. Additional chemical functionalization schemes can controllably improve selectivity of the carbon nanotube-based sensors; however, the exact transduction mechanism is still under debate. In this article we detail the synthesis and selective response of single-walled carbon nanotubes (SWNTs) functionalized with polyazomethine (PAM) polymer toward the application of a specific trace metal ion detector. The response of the polymer system was compared to shape persistent macrocycle (MAC) comprised of identical ion coordination ligands. While ion detection with rigid MAC/SWNT chemiresistor was comparable to bare SWNT, flexible PAM offers significant SWNT signal amplification, allowing for picomolar detection of Co<sup>2+</sup> ions with both selectivity and a fast response. We hypothesized that rearrangement of the flexible PAM on the SWNT network is a sensing mechanism which allows for ultrasensitive detection of metal ions. The electron transfer and polymer rearrangement on the SWNT were studied by a combination of optical spectroscopy and electrical measurementsultimately allowing for a better understanding of fundamental mechanisms that prompt device response.