A systematic study on the use of 9,9-dialkylfluorene homopolymers (PFs) for large-diameter semiconducting (sc-) single-walled carbon nanotube (SWCNT) enrichment is the focus of this report. The enrichment is based on a simple three-step extraction process: (1) dispersion of as-produced SWCNTs in a PF solution; (2) centrifugation at a low speed to separate the enriched sc-tubes; (3) filtration to collect the enriched sc-SWCNTs and remove excess polymer. The effect of the extraction conditions on the purity and yield including molecular weight and alkyl side-chain length of the polymers, SWCNT concentration, and polymer/SWCNT ratio have been examined. It was observed that PFs with alkyl chain lengths of C10, C12, C14, and C18, all have an excellent capability to enrich laser-ablation sc-SWCNTs when their molecular weight is larger than ∼10 000 Da. More detailed studies were therefore carried out with the C12 polymer, poly(9,9-di-n-dodecylfluorene), PFDD. It was found that a high polymer/SWCNT ratio leads to an enhanced yield but a reduced sc-purity. A ratio of 0.5-1.0 gives an excellent sc-purity and a yield of 5-10% in a single extraction as assessed by UV-vis-NIR absorption spectra. The yield can also be promoted by multiple extractions while maintaining high sc-purity. Mechanistic experiments involving time-lapse dispersion studies reveal that m-SWCNTs have a lower propensity to be dispersed, yielding a sc-SWCNT enriched material in the supernatant. Dispersion stability studies with partially enriched sc-SWCNT material further reveal that m-SWCNTs : PFDD complexes will re-aggregate faster than sc-SWCNTs : PFDD complexes, providing further sc-SWCNT enrichment. This result confirms that the enrichment was due to the much tighter bundles in raw materials and the more rapid bundling in dispersion of the m-SWCNTs. The sc-purity is also confirmed by Raman spectroscopy and photoluminescence excitation (PLE) mapping. The latter shows that the enriched sc-SWCNT sample has a narrow chirality and diameter distribution dominated by the (10,9) species with d = 1.29 nm. The enriched sc-SWCNTs allow a simple drop-casting method to form a dense nanotube network on SiO2/Si substrates, leading to thin film transistors (TFTs) with an average mobility of 27 cm(2) V(-1) s(-1) and an average on/off current ratio of 1.8 × 10(6) when considering all 25 devices having 25 μm channel length prepared on a single chip. The results presented herein demonstrate how an easily scalable technique provides large-diameter sc-SWCNTs with high purity, further enabling the best TFT performance reported to date for conjugated polymer enriched sc-SWCNTs.
Boron nitride nanotubes (BNNTs) exhibit a range of properties that are as compelling as those of carbon nanotubes (CNTs); however, very low production volumes have prevented the science and technology of BNNTs from evolving at even a fraction of the pace of CNTs. Here we report the high-yield production of small-diameter BNNTs from pure hexagonal boron nitride powder in an induction thermal plasma process. Few-walled, highly crystalline small-diameter BNNTs (∼5 nm) are produced exclusively and at an unprecedentedly high rate approaching 20 g/h, without the need for metal catalysts. An exceptionally high cooling rate (∼10(5) K/s) in the induction plasma provides a strong driving force for the abundant nucleation of small-sized B droplets, which are known as effective precursors for small-diameter BNNTs. It is also found that the addition of hydrogen to the reactant gases is crucial for achieving such high-quality, high-yield growth of BNNTs. In the plasma process, hydrogen inhibits the formation of N2 from N radicals and promotes the creation of B-N-H intermediate species, which provide faster chemical pathways to the re-formation of a h-BN-like phase in comparison to nitridation from N2. We also demonstrate the fabrication of macroscopic BNNT assemblies such as yarns, sheets, buckypapers, and transparent thin films at large scales. These findings represent a seminal milestone toward the exploitation of BNNTs in real-world applications.
Advances in the synthesis and scalable manufacturing of single-walled carbon nanotubes (SWCNTs) remain critical to realizing many important commercial applications. Here we review recent breakthroughs in the synthesis of SWCNTs and highlight key ongoing research areas and challenges. A few key applications that capitalize on the properties of SWCNTs are also reviewed with respect to the recent synthesis breakthroughs and ways in which synthesis science can enable advances in these applications. While the primary focus of this review is on the science framework of SWCNT growth, we draw connections to mechanisms underlying the synthesis of other 1D and 2D materials such as boron nitride nanotubes and graphene.
A series of vancomycin-modified nanoparticles were developed and employed in magnetic confinement assays to isolate a variety of Gram-positive and Gram-negative bacteria from aqueous solution. We determined that the orientation/architecture of vancomycin on the surface of the nanoparticles and the overall surface coverage is critical in mediating fast and effective interactions between the nanoparticle and the pathogen cell wall surface and only one orientation/architecture in a series of modified nanoparticles leads to the efficient and reproducible capture of several important pathogenic bacteria. Interestingly, as the nanoparticles increase in diameter (from approximately 50 to 2800 nm), it is necessary to incorporate a long linker between the nanoparticle surface and the vancomycin moiety in order for the surface bound probe to efficiently confine Gram-positive bacteria. Finally, we also determined that the time required for efficient labeling and subsequent magnetic confinement significantly decreases as the size of the nanoparticle and the vancomycin surface coverage on the nanoparticle increases. As disease detection technologies transition to "lab-on-a-chip" based platforms it is necessary to develop strategies to effectively and inexpensively preconcentrate cells from large volume to volumes more amenable to these types of microfluidic devices. These small molecule-modified superparamagnetic nanoparticles can provide a means by which this can be accomplished.
Clusters of iron oxide nanoparticles encapsulated in a pH-responsive hydrogel are synthesized and studied for their ability to alter the T 2 -relaxivity of protons. Encapsulation of the clusters with the hydrophilic coating is shown to enhance the transverse relaxation rate by up to 85% compared to clusters with no coating. With the use of pH-sensitive hydrogel, difficulties inherent in comparing particle samples are eliminated and a clear increase in relaxivity as the coating swells is demonstrated. Agreement with Monte Carlo simulations indicates that the lower diffusivity of water inside the coating and near the particle surface leads to the enhancement. This demonstration of a surface-active particle structure opens new possibilities in using similar structures for nanoparticle-based diagnostics using magnetic resonance imaging.
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