Conspectus The future application of single-walled carbon nanotubes (SWNTs) in electronic (nano)devices is closely coupled to the availability of pure, semiconducting SWNTs and preferably, their defined positioning on suited substrates. Commercial carbon nanotube raw mixtures contain metallic as well as semiconducting tubes of different diameter and chirality. Although many techniques such as density gradient ultracentrifugation, dielectrophoresis, and dispersion by surfactants or polar biopolymers have been developed, so-called conjugated polymer wrapping is one of the most promising and powerful purification and discrimination strategies. The procedure involves debundling and dispersion of SWNTs by wrapping semiflexible conjugated polymers, such as poly(9,9-dialkylfluorene)s (PFx) or regioregular poly(3-alkylthiophene)s (P3AT), around the SWNTs, and is accompanied by SWNT discrimination by diameter and chirality. Thereby, the π-conjugated backbone of the conjugated polymers interacts with the two-dimensional, graphene-like π-electron surface of the nanotubes and the solubilizing alkyl side chains of optimal length support debundling and dispersion in organic solvents. Careful structural design of the conjugated polymers allows for a selective and preferential dispersion of both small and large diameter SWNTs or SWNTs of specific chirality. As an example, with polyfluorenes as dispersing agents, it was shown that alkyl chain length of eight carbons are favored for the dispersion of SWNTs with diameters of 0.8–1.2 nm and longer alkyls with 12–15 carbons can efficiently interact with nanotubes of increased diameter up to 1.5 nm. Polar side chains at the PF backbone produce dispersions with increased SWNT concentration but, unfortunately, cause reduction in selectivity. The selectivity of the dispersion process can be monitored by a combination of absorption, photoluminescence, and photoluminescence excitation spectroscopy, allowing identification of nanotubes with specific coordinates [(n,m) indices]. The polymer wrapping strategy enables the generation of SWNT dispersions containing exclusively semiconducting nanotubes. Toward the applications in electronic devices, until now most applied approach is a direct processing of such SWNT dispersions into the active layer of network-type thin film field effect transistors. However, to achieve promising transistor performance (high mobility and on–off ratio) careful removal of the wrapping polymer chains seems crucial, for example, by washing or ultracentrifugation. More defined positioning of the SWNTs can be accomplished in directed self-assembly procedures. One possible strategy uses diblock copolymers containing a conjugated polymer block as dispersing moiety and a second block for directed self-assembly, for example, a DNA block for specific interaction with complementary DNA strands. Another strategy utilizes reactive side chains for controlled anchoring onto patterned surfaces (e.g., by interaction of thiol-terminated alkyl side chains with gold surfaces). A...
Gel-nanocomposites are rapidly emerging functional advanced materials having widespread applications in materials and biological sciences. Herein, we review syntheses, properties, and applications of various gel-nanocomposites assembled from different metal-based nanoparticles or nanocarbons [fullerene, carbon nanotubes (CNTs), and graphenes] with tailor-made supramolecular (small molecular) or polymeric physical organogels and hydrogels. Dynamic supramolecular self-assembly of gelators prove to be excellent hosts for the incorporation of these dimensionally different nanomaterials. Thus, gel-nanocomposites doped with preformed/in situ synthesized nanoparticles show magnetic or near-infrared-responsive, catalytic or antibacterial properties. Fullerene-based gel-nanocomposites show applications in organic solar cells. Gel-nanocomposites based on CNTs and graphenes and their functionalized (covalent/noncovalent) analogues find interesting properties including electrical conductivity, viscoelasticity, thermal robustness, magnetic, phase-selective, redox and near-infrared radiation sensitive properties. We present appropriate rationale to explain most of these phenomena at the molecular level, which provide useful perspectives for future designs and new spin-offs. Finally, a possible outlook is projected for the design and syntheses of next generation multifunctional gel-nanocomposites, which could be achieved by increasing the complexity of the system upon adding selective nanomaterials with desired properties in a multicomponent mixture following a de novo design in order to take advantage of their individual properties.
Selective detection of nitro-aromatic compounds (NACs) at nanomolar concentration is achieved for the first time in multiple media including water, micelles or in organogels as well as using test strips. Mechanism of interaction of NACs with highly fluorescent p-phenylenevinylene-based molecules has been described as the electron transfer phenomenon from the electron-rich chromophoric probe to the electron deficient NACs. The selectivity in sensing is guided by the pKa of the probes as well as the NACs under consideration. TNP-induced selective gel-to-sol transition in THF medium is also observed through the reorganization of molecular self-assembly and the portable test trips are made successfully for rapid on-site detection purpose.
Environment-friendly management of fruit flies involving pheromones is useful in reducing the undesirable pest populations responsible for decreasing the yield and the crop quality. A nanogel has been prepared from a pheromone, methyl eugenol (ME) using a low-molecular mass gelator. This was very stable at open ambient conditions and slowed down the evaporation of pheromone significantly. This enabled its easy handling and transportation without refrigeration, and reduction in the frequency of pheromone recharging in the orchard. Notably the involvement of the nano-gelled pheromone brought about an effective management of Bactrocera dorsalis, a prevalent harmful pest for a number of fruits including guava. Thus a simple, practical and low cost green chemical approach is developed that has a significant potential for crop protection, long lasting residual activity, excellent efficacy and favorable safety profiles. This makes the present invention well-suited for pest management in a variety of crops.
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