Microscopic structure and collapse of depletion-induced gels in vesicle-polymer mixtures.

We present the behavior of depletion-induced gels for vesicle-polymer mixtures when the ratio of the polymer radius of gyration to the mean vesicle radius is 0.09 and 0.27. As the polymer concentration increases, density gradients build up and an interface is developed between a highly turbid vesicle-rich phase and a polymer-rich phase. Increasing the polymer concentration further forms a gel (CP=0.3 and 0.1 wt% for Rg/a approximately 0.09 and 0.27, respectively), which subsequently collapses. This collapse is characterized by a slow initial rising for a finite delay time, a rapid collapse, and a slow final compaction to an equilibrium height. However, we observe a remarkably different polymer concentration dependence on the collapse rate. Unlike other colloidal gels, we find that the delay time for the vesicle collapse decreases with increasing polymer concentration. We show that this behavior can be accounted for by considering the permeability for solvent backflow, which is directly related to the characteristic pore area of the gel obtained using confocal microscopy.

Colloid dynamics in semiflexible polymer solutions.

We investigate the dynamics of monodisperse colloidal polystyrene particles suspended in solutions of the semiflexible polymer filamentous actin, over a range of filament lengths that either exceed or are substantially less than the particle radius. The filament length is controlled by the capping protein gelsolin, and particle surface chemistries that minimize the adsorption of filaments are used. The particle dynamics are measured on short time scales using diffusing wave spectroscopy. A sharp transition in the initial particle diffusivity marks the expected shift from a dilute to a tightly entangled polymer network as the filament average length increases. In both the dilute and entangled regimes, the measured particle dynamics are compared with the theories of rodlike and semiflexible polymer solution rheology using the generalized Stokes-Einstein relationship. In the dilute limit, the particle dynamics are in good agreement with theory. However, in the tightly entangled regime, the particle response is consistent with polymer depleted near the surfaces of the particles. The magnitude of the depletion layer thickness depends strongly on particle size and weakly on filament length. This behavior is in agreement with nonlocal entropic repulsions and the loss of conformational entropy associated with rodlike molecules near impenetrable particles. These results illustrate the use of microrheology as a method to investigate local structure and dynamics in colloid-polymer solutions.

Electronic durability of flexible transparent films from type-specific single-wall carbon nanotubes.

The coupling between mechanical flexibility and electronic performance is evaluated for thin films of metallic and semiconducting single-wall carbon nanotubes (SWCNTs) deposited on compliant supports. Percolated networks of type-purified SWCNTs are assembled as thin conducting coatings on elastic polymer substrates, and the sheet resistance is measured as a function of compression and cyclic strain through impedance spectroscopy. The wrinkling topography, microstructure and transparency of the films are independently characterized using optical microscopy, electron microscopy, and optical absorption spectroscopy. Thin films made from metallic SWCNTs show better durability as flexible transparent conductive coatings, which we attribute to a combination of superior mechanical performance and higher interfacial conductivity.

Separation of empty and water-filled single-wall carbon nanotubes.

The separation of empty and water-filled laser ablation and electric arc synthesized nanotubes is reported. Centrifugation of these large-diameter nanotubes dispersed with sodium deoxycholate using specific conditions produces isolated bands of empty and water-filled nanotubes without significant diameter selection. This separation is shown to be consistent across multiple nanotube populations dispersed from different source soots. Detailed spectroscopic characterization of the resulting empty and filled fractions reveals that water filling leads to systematic changes to the optical and vibrational properties. Furthermore, sequential separation of the resolved fractions using cosurfactants and density gradient ultracentrifugation reveals that water filling strongly influences the optimal conditions for metallic and semiconducting separation.

Carbon nanotubes: measuring dispersion and length.

Advanced technological uses of single-walled carbon nanotubes (SWCNTs) rely on the production of single length and chirality populations that are currently only available through liquid-phase post processing. The foundation of all of these processing steps is the attainment of individualized nanotube dispersions in solution. An understanding of the colloidal properties of the dispersed SWCNTs can then be used to design appropriate conditions for separations. In many instances nanotube size, particularly length, is especially active in determining the properties achievable in a given population, and, thus, there is a critical need for measurement technologies for both length distribution and effective separation techniques. In this Progress Report, the current state of the art for measuring dispersion and length populations, including separations, is documented, and examples are used to demonstrate the desirability of addressing these parameters.

Tailored distribution of single-wall carbon nanotubes from arc plasma synthesis using magnetic fields.

We report a method for tuning the distribution of single-wall carbon nanotubes (SWCNTs) produced by the anodic arc production method via the application of nonuniform magnetic fields to the gap region during synthesis. Raman, ultraviolet-visible-near-infrared absorbance and near-infrared fluorescence spectroscopies were used to characterize samples together with scanning electron microscopy. Application of the nonuniform magnetic field 0.2-2 kG results in a broadening of the diameter range of SWCNTs produced toward decreased diameters, with substantial fractions of produced SWCNTs being of small diameter, less than ∼1.3 nm, at the highest field. The ability to tune production of the arc production method may allow for improvement in achievable SWCNT properties.