Functionalization of single-walled carbon nanotubes "on water"

Single-walled carbon nanotubes (SWNTs) are exfoliated and functionalized into small bundles and individuals by vigorous stirring "on water" in the presence of a substituted aniline and an oxidizing agent. This is an example of an "on water" reaction that leads to functionalized SWNTs, and it represents a "green", or environmentally friendly, process. A variety of reaction conditions were explored. The products were analyzed with Raman, UV-vis-NIR, and X-ray photoelectron spectroscopies, atomic force and transmission electron microscopies, and thermogravimetric analysis.     

Gromov hyperbolicity through decomposition of metric spaces

We study the hyperbolicity of metric spaces in the Gromov sense. We deduce the hyperbolicity of a space from the hyperbolicity of its “building block components”. These results are valuable since they simplify notably the topology of the space and allow to obtain global results from local information. We also study how the punctures and the decomposition of a Riemann surface in Y-pieces and funnels affect the hyperbolicity of the surface.     

Gromov hyperbolicity through decomposition of metrics spaces II

In this article we study the hyperbolicity in the Gromov sense of metric spaces. We deduce the hyperbolicity of a space from the hyperbolicity of its “building block components,” which can be joined following an arbitrary scheme. These results are especially valuable since they simplify notably the topology and allow to obtain global results from local information. Some interesting theorems about the role of punctures and funnels on the hyperbolicity of Riemann surfaces can be deduced from the conclusions of this article.     

Electrons are transported through phenylene-ethynylene oligomer monolayers via localized molecular orbitals

We report excellent correlations between the first negative threshold potentials (V(TH)s) for electric conduction, electrochemical potentials, and computed lowest unoccupied molecular orbital energies in a series of phenylene-ethynylene oligomers bearing a sulfur-based anchoring unit and different electroactive substituents on the central benzene ring. The theoretical and electrochemical results strongly suggest that the peaks observed in the i-V curves have a true molecular origin and are associated with distinct unoccupied molecular levels of the compounds that are strongly localized on the central ring (except for compound I). This localization might account for the existence of a long-lived radical-anion state that permits lateral electron hopping and leads to charge trapping and storage.     

NanoCell electronic memories

NanoCells are disordered arrays of metallic islands that are interlinked with molecules between micrometer-sized metallic input/output leads. In the past, simulations had been conducted showing that the NanoCells may function as both memory and logic devices that are programmable postfabrication. Reported here is the first assembly of a NanoCell with disordered arrays of molecules and Au islands. The assembled NanoCells exhibit reproducible switching behavior and two types of memory effects at room temperature. The switch-type memory is characteristic of a destructive read, while the conductivity-type memory features a nondestructive read. Both types of memory effects are stable for more than a week at room temperature, and bit level ratios (0:1) of the conductivity-type memory have been observed to be as high as 10(4):1 and reaching 10(6):1 upon ozone treatment, which likely destroys extraneous leakage pathways. Both molecular electronic and nanofilamentary metal switching mechanisms have been considered, though the evidence points more strongly toward the latter. The approach here demonstrates the efficacy of a disordered nanoscale array for high-yielding switching and memory while mitigating the arduous task of nanoscale patterning.     

Synthesis of planar poly(p-phenylene) derivatives for maximization of extended π-conjugation

Described is the synthesis of a ladder polymer with a poly(p-phenylene) (PPP) backbone. The main PPP backbone was synthesized via palladium-catalyzed coupling of an arylbis(boronic ester) with an aryl dibromide. Imine bridges, formed by exposure of the polymer to trifluoroacetic acid, are used to force the consecutive units into planarity. The bridging units are sp² hybridized thus allowing for greater π-electron flow between the consecutive phenyl units by lowering the band gap between the hydroquinoidal and the quinoidal forms of the phenylene backbone. When the bridges are n-dodecyl substituted, the fully planar structures (with Mn < 5 000) are soluble in hot chlorobenzene from which flexible free standing films can be cast. The n-butyl substituted polymers and the higher molecular weight n-dodecyl substituted polymers are soluble in CH₂Cl₂/trifluoroacetic acid mixtures. The optical spectra of the planar systems are compared to that of the parent nonplanarized polymers, some analogous planar oligomers, and oligo(p-phenylenes).