We report a new nonwrapping approach to noncovalent engineering of carbon nanotube surfaces by short, rigid functional conjugated polymers, poly(aryleneethynylene)s. Our technique not only enables the dissolution of various types of carbon nanotubes in organic solvents, which represents the first example of solubilization of carbon nanotubes via pi-stacking without polymer wrapping, but could also introduce numerous neutral and ionic functional groups onto the carbon nanotube surfaces.

Homogeneous carbon nanotube/polymer composites were fabricated using noncovalently functionalized, soluble single-walled carbon nanotubes (SWNTs). These composites showed dramatic improvements in the electrical conductivity with very low percolation threshold (0.05–0.1 wt % of SWNT loading). By significantly improving the dispersion of SWNTs in commercial polymers, we show that only very low SWNT loading is needed to achieve the conductivity levels required for various electrical applications without compromising the host polymer’s other preferred physical properties and processability. In contrast to previous techniques, our method is applicable to various host polymers and does not require lengthy sonication.

Using nanometer thick tunneling barriers with specifically attached cytochrome c, the electron-transfer rate constant was studied as a function of the SAM composition (alkane versus terthiophene), the omega-terminating group type (pyridine, imidazole, nitrile), and the solution viscosity. At large electrode-reactant separations, the pyridine terminated alkanethiols exhibit an exponential decline of the rate constant with increasing electron-transfer distance. At short separations, a plateau behavior, analogous to systems involving -COOH terminal groups to which cytochrome c can be attached electrostatically, is observed. The dependence of the rate constant in the plateau region on system properties is investigated. The rate constant is insensitive to the mode of attachment to the surface but displays a significant viscosity dependence, change with spacer composition (alkane versus terthiophene), and nature of the solvent (H(2)O versus D(2)O). Based on these findings and others, the conclusion is drawn that the charge-transfer rate constant at short distance is determined by polarization relaxation processes in the structure, rather than the electron tunneling probability or large-amplitude conformational rearrangement (gating). The transition in reaction mechanism with distance reflects a gradual transition between the tunneling and frictional mechanisms. This conclusion is consistent with data from a number of other sources as well.