Aqueous two-phase extraction has recently been demonstrated as a new method to separate single-wall carbon nanotubes (SWCNTs). In this work, we determined that the mechanism of separation is driven by the hydrophobicity of the surfactant, or combination of surfactants, at the SWCNT surface. This knowledge allowed us to develop a simple approach for obtaining highly enriched single-chirality suspensions in only 1 or 2 steps. These results were obtained by strategically combining multiple surfactants with different diameter-dependent binding affinities for SWCNTs and salts that readjust the surfactant structure within the mixed micelle surrounding the SWCNTs. The procedure is successfully applied to SWCNTs from different sources (CoMoCAT and HiPco) with various diameter distributions (from 0.53 to 1.2 nm). Each separation step is characterized by optical absorption, resonant Raman, and photoluminescence excitation spectroscopies. By determining the SWCNT sorting mechanism, we were able to develop a new set of parameters that separated another chirality.

Single-file transport of water into carbon nanotubes is experimentally demonstrated for the first time through the splitting of the radial breathing mode (RBM) vibration in Raman spectra of bile salt solubilized tubes when both empty (closed) and water-filled (open-ended) tubes are present. D2O filling is observed for a wide range of diameters, d, down to very thin tubes [e.g., (5,3) tube, d=0.548  nm] for which only a single water molecule fits in the cross section of the internal nanotube channel. The shift in RBM frequency upon filling is found to display a very complex dependence on nanotube diameter and chirality, in support of a different yet well-defined ordering and orientation of water molecules at room temperature. Large shifts of the electronic transitions are also observed.

Asymmetric dye molecules have unusual optical and electronic properties. For instance, they show a strong second-order nonlinear optical (NLO) response that has attracted great interest for potential applications in electro-optic modulators for optical telecommunications and in wavelength conversion of lasers. However, the strong Coulombic interaction between the large dipole moments of these molecules favours a pairwise antiparallel alignment that cancels out the NLO response when incorporated into bulk materials. Here, we show that by including an elongated dipolar dye (p,p'-dimethylaminonitrostilbene, DANS, a prototypical asymmetric dye with a strong NLO response) inside single-walled carbon nanotubes (SWCNTs), an ideal head-to-tail alignment in which all electric dipoles point in the same sense is naturally created. We have applied this concept to synthesize solution-processible DANS-filled SWCNTs that show an extremely large total dipole moment and static hyperpolarizability (β0 = 9,800 × 10(-30) e.s.u.), resulting from the coherent alignment of arrays of ∼70 DANS molecules.