Studies of DNA-carbon nanotube interactions

Recently a new biomaterial consisting of a DNA-wrapped single-walled carbon nanotube, and known as a DNA/SWNT, has been discovered. The possible applications of this hybrid are varied and range from genomic sequencing to nanoscale electronics to molecular delivery. The realization of these potential applications requires more knowledge about the microscopic properties of this material. In this thesis, I present studies of: the orientation of nucleobases on the nanotube sidewall; the sequence and length dependence of the DNA-nanotube interaction; and solution conditions to manipulate the DNA/SWNT hybrid. The measurement of the UV optical absorbance of DNA/SWNT and the nucleotide absorbance from DNA/SWNT provide the first experimental confirmation that DNA binds to nanotubes through π-stacking. Because the hypochromic absorbance typical of π-stacked structures are expected to occur primarily for DNA dipole transitions that lie along the axis of the optically anisotropic SWNTs, the absorbance changes following binding of DNA to the nanotubes reveals the preferred orientation assumed by each of the four bound nucleotides with respect to the nanotube's long axis. The first observations of pronounced sequence- and length-dependent variations in the binding between ssDNA and SWNTs in aqueous solution are presented. These observations rely on the discovery that there exists a range of DNA lengths able to hybridize with SWNTs that can nevertheless be dissociated at temperatures below the boiling point of water. Quantitative results comparing the isochronal dissociation temperatures and binding energies of DNA/SWNT composed of differing DNA sequences and lengths are given. These results indicate variability and complexity in the binding mechanism responsible for the stability of the hybrid system that transcends simple models based on the sum of independent base-nanotube interactions. Binding energies between a DNA base and nanotube (0.05 to 0.09 eV per base) are similar to stacking energies in the native dsDNA structure (0.04 to 0.08 eV per base), as well as recent computational results (0.09 to 0.13 eV per base). Solution conditions and experiments manipulating the DNA/SWNT, such as removal of bound DNA and the separation of DNA from DNA/SWNTs, are also discussed. These results increase the utility of DNA/SWNTs for researchers in diverse fields.