Overcoming the "coffee-stain" effect by compositional Marangoni-flow-assisted drop-drying.

Attempts at depositing uniform films of nanoparticles by drop-drying have been frustrated by the "coffee-stain" effect due to convective macroscopic flow into the contact line. Here, we show that uniform deposition of nanoparticles in aqueous suspensions can be attained easily by drying the droplet in an ethanol vapor atmosphere. This technique allows the particle-laden water droplets to spread on a variety of surfaces such as glass, silicon, mica, PDMS, and even Teflon. Visualization of droplet shape and internal flow shows initial droplet spreading and strong recirculating flow during spreading and shrinkage. The initial spreading is due to a diminishing contact angle from the absorption of ethanol from the vapor at the contact line. During the drying phase, the vapor is saturated in ethanol, leading to preferential evaporation of water at the contact line. This generates a surface tension gradient that drives a strong recirculating flow and homogenizes the nanoparticle concentration. We show that this method can be used for depositing catalyst nanoparticles for the growth of single-walled carbon nanotubes as well as to manufacture plasmonic films of well-spaced, unaggregated gold nanoparticles.

Diameter-dependent solubility of single-walled carbon nanotubes.

We study the solubility and dispersibility of as-produced and purified HiPco single-walled carbon nanotubes (SWNTs). Variation in specific operating conditions of the HiPco process are found to lead to significant differences in the respective SWNT solubilities in oleum and surfactant suspensions. The diameter distributions of SWNTs dispersed in surfactant solutions are batch-dependent, as evidenced by luminescence and Raman spectroscopies, but are identical for metallic and semiconducting SWNTs within a batch. We thus find that small diameter SWNTs disperse at higher concentration in aqueous surfactants and dissolve at higher concentration in oleum than do large-diameter SWNTs. These results highlight the importance of controlling SWNT synthesis methods in order to optimize processes dependent on solubility, including macroscopic processing such as fiber spinning, material reinforcement, and films production, as well as for fundamental research in type selective chemistry, optoelectronics, and nanophotonics.

Templated growth of graphenic materials.

A novel strategy is proposed for the topologically controlled synthesis of extended graphenic sheets by additively reacting carbon into a pre-existing graphene sheet which is on top of a templating substrate. This concept is implemented and demonstrated using chemical vapor deposition (CVD). Novel morphological features observed in this study suggest unusual aspects of the CVD growth process. CVD results demonstrate the basic soundness of the synthesis strategy but highlight the sensitivity of the process to certain types of disruption and the need for alternative forms of embodiment.

Antenna chemistry with metallic single-walled carbon nanotubes.

We show that, when subjected to microwave fields, surfactant-stabilized single-walled carbon nanotubes (SWNTs) develop polarization potentials at their extremities that readily drive electrochemical reactions. In the presence of transition metal salts with high oxidation potential (e.g., FeCl3), SWNTs drive reductive condensation to metallic nanoparticles with essentially diffusion-limited kinetics in a laboratory microwave reactor. Using HAuCl4, metallic particles and sheaths deposit regioselectively at the SWNT tips, yielding novel SWNT-metal composite nanostructures. This process is shown to activate exclusively metallic SWNTs; a degree of diameter selectivity is observed using acceptors with different oxidation potentials. The reaction mechanism is shown to involve Fowler-Nordheim field emission in solution, where electric fields concentrate at the SWNT tips (attaining approximately 10(9) V/m) due to the SWNT high aspect ratio (approximately 1000) and gradient compression in the insulating surfactant monolayer. Nanotube antenna chemistry is remarkably simple and should be useful in SWNT separation and fractionation processes, while the unusual nanostructures produced could impact nanomedicine, energy harvesting, and synthetic applications.

Selective photochemical functionalization of surfactant-dispersed single wall carbon nanotubes in water.

Ultraviolet (UV) irradiation of single wall carbon nanotubes (SWCNTs) individually dispersed in surfactants leads to diameter and type-selective photohydroxylation of the nanotubes. Photohydroxylation of first semiconductor and then small diameter metallic SWCNTs was confirmed after 254 nm UV irradiation in acidic, neutral, and basic aqueous solutions at ambient and elevated temperatures. The increased oxygen content of the SWCNTs after UV irradiation, as detected by X-ray photoelectron spectroscopy, suggests that SWCNTs were hydroxylated by reaction with water. Attenuated total reflectance Fourier transform infrared analysis provides evidence of hydroxyl functional groups on their surface. This photochemical reaction is impeded by molecular oxygen and appears to involve a reactive intermediate generated in the vicinity of semiconducting SWCNTs. This represents a noncontaminating selective reaction in the liquid phase that uses an intrinsic property of the tubes.

Synthesis of high aspect-ratio carbon nanotube "flying carpets" from nanostructured flake substrates.

We present a robust method for synthesis of aligned, single-walled carbon nanotube (CNT) "flying carpets" from nanostructured alumina flakes. Roll-to-roll e-beam deposition is utilized to produce the flakes, and hot filament chemical vapor deposition is utilized to grow dense, aligned carbon nanotubes from the flakes with remarkably high CNT yields. The flakes are captured inside a mesh cage and freely suspended in the gas flow during growth. Optical characterization indicates the presence of high quality, small diameter single-walled carbon nanotubes.

Brownian dynamics simulations of single-wall carbon nanotube separation by type using dielectrophoresis.

We theoretically investigate the separation of individualized metallic and semiconducting single-wall carbon nanotubes (SWNTs) in a dielectrophoretic (DEP) flow device. The SWNT motion is simulated by a Brownian dynamics (BD) algorithm, which includes the translational and rotational effects of hydrodynamic, Brownian, dielectrophoretic, and electrophoretic forces. The device geometry is chosen to be a coaxial cylinder because it yields effective flow throughput, the DEP and flow fields are orthogonal to each other, and all the fields can be described analytically everywhere. We construct a flow-DEP phase map showing different regimes, depending on the relative magnitudes of the forces in play. The BD code is combined with an optimization algorithm that searches for the conditions that maximize the separation performance. The optimization results show that a 99% sorting performance can be achieved with typical SWNT parameters by operating in a region of the phase map where the metallic SWNTs completely orient with the field, whereas the semiconducting SWNTs partially flow-align.

Stable luminescence from individual carbon nanotubes in acidic, basic, and biological environments.

Aqueous surfactant suspensions of single walled carbon nanotubes (SWNTs) are very sensitive to environmental conditions. For example, the photoluminescence of semiconducting SWNTs varies significantly with concentration, pH, or salinity. In most cases, these factors restrict the range of applicability of SWNT suspensions. Here, we report a simple strategy to obtain stable and highly luminescent individualized SWNTs at pH values ranging from 1 to 11, as well as in highly saline buffers. This strategy relies on combining SWNTs previously suspended in sodium dodecylbenzene sulfonate (SDBS) with biocompatible poly(vinyl pyrrolidone) (PVP), which can be polymerized in situ to entrap the SWNT-SDBS micelles. We present a model that accounts for the photoluminescence stability of these suspensions based on PVP morphological changes at different pH values. Moreover, we demonstrate the effectiveness of these highly stable suspensions by imaging individual luminescent SWNTs on the surface of live human embryonic kidney cells (HEK cells).

Carbon nanotube-enhanced thermal destruction of cancer cells in a noninvasive radiofrequency field.

BACKGROUND: Single-walled carbon nanotubes (SWNTs) have remarkable physicochemical properties that may have several medical applications. The authors have discovered a novel property of SWNTs-heat release in a radiofrequency (RF) field-that they hypothesized may be used to produce thermal cytotoxicity in malignant cells. METHODS: Functionalized, water-soluble SWNTs were exposed to a noninvasive, 13.56-megahertz RF field, and heating characteristics were measured with infrared thermography. Three human cancer cell lines were incubated with various concentrations of SWNTs and then treated in the RF field. Cytotoxicity was measured by fluorescence-activated cell sorting. Hepatic VX2 tumors in rabbits were injected with SWNTs or with control solutions and were treated in the RF field. Tumors were harvested 48 hours later to assess viability. RESULTS: The RF field induced efficient heating of aqueous suspensions of SWNTs. This phenomenon was used to produce a noninvasive, selective, and SWNT concentration-dependent thermal destruction in vitro of human cancer cells that contained internalized SWNTs. Direct intratumoral injection of SWNTs in vivo followed by immediate RF field treatment was tolerated well by rabbits bearing hepatic VX2 tumors. At 48 hours, all SWNT-treated tumors demonstrated complete necrosis, whereas control tumors that were treated with RF without SWNTs remained completely viable. Tumors that were injected with SWNTs but were not treated with RF also were viable. CONCLUSIONS: The current results suggested that SWNTs targeted to cancer cells may allow noninvasive RF field treatments to produce lethal thermal injury to the malignant cells. Now, the authors are developing SWNTs coupled with cancer cell-targeting agents to enhance SWNT uptake by cancer cells while limiting uptake by normal cells.

Single wall carbon nanotube amplification: en route to a type-specific growth mechanism.

With the desire to mass produce any specific n,m type of single wall carbon nanotube (SWNT) from a small sample of the same material, we disclose here the preliminary work directed toward that goal. The ultimate protocol would involve taking a single n,m-type nanotube sample, cutting the nanotubes in that sample into many short nanotubes, using each of those short nanotubes as a template for growing much longer nanotubes of the same type, and then repeating the process. The result would be an amplification of the original tube type: a parent SWNT serving as the prolific progenitor of future identical SWNT types. As a proof-of-concept, we use here a short SWNT seed as a template for vapor liquid solid (VLS) amplification growth of an individual long SWNT. The original short SWNT seed was a polymer-wrapped SWNT, end-carboxylated, and further tethered with Fe salts at its ends. The Fe salts were to act as the growth catalysts upon subsequent reductive activation. Deposition of the short SWNT-Fe tipped species upon an oxide surface was followed by heating in air to consume the polymer wrappers, then reducing the Fe salts to Fe(0) under a H2-rich atmosphere. During this heating, the Fe(0) can etch back into the short SWNT so that the short SWNT acts as a template for new growth to a long SWNT that occurs upon introduction of C2H4 as a carbon source. Analysis indicated that the templated VLS-grown long SWNT had the same diameter and surface orientation as the original short SWNT seed, although amplifying the original n,m type remains to be proven. This study could pave the way for an amplified growth process of SWNTs en route to any n,m tube type synthesis from a starting sample of pure nanotubes.

Mammalian pharmacokinetics of carbon nanotubes using intrinsic near-infrared fluorescence.

Individualized, chemically pristine single-walled carbon nanotubes have been intravenously administered to rabbits and monitored through their characteristic near-infrared fluorescence. Spectra indicated that blood proteins displaced the nanotube coating of synthetic surfactant molecules within seconds. The nanotube concentration in the blood serum decreased exponentially with a half-life of 1.0 +/- 0.1 h. No adverse effects from low-level nanotube exposure could be detected from behavior or pathological examination. At 24 h after i.v. administration, significant concentrations of nanotubes were found only in the liver. These results demonstrate that debundled single-walled carbon nanotubes are high-contrast near-infrared fluorophores that can be sensitively and selectively tracked in mammalian tissues using optical methods. In addition, the absence of acute toxicity and promising circulation persistence suggest the potential of carbon nanotubes in future pharmaceutical applications.

Efficient transfer of a VA-SWNT film by a flip-over technique.

A transfer of a VA-SWNT film onto a conductive surface has been achieved using a novel "flip-over" technique. The top surface of a VA-SWNT film was covered by entangled bundles in an as-grown sample. When a VA-SWNT film was flipped over, an optically flat surface consisting of the tips of very well aligned, clean bundles from the bottom of the film are exposed while the top of the film is well contacted to the substrate. Thus, we expect this technique to provide us with means to prepare carbon nanotube electrodes for device applications such as super capacitors, thermo-electric devices, fuel cells, and field emission filaments.

Dielectrophoresis field flow fractionation of single-walled carbon nanotubes.

We report a study on Dielectrophoresis Field Flow Fractionation of Single-Wall Carbon Nanotubes (SWNTs). SWNTs, individually suspended in 1% SDBS solution, were separated by type when they passed a dielectrophoresis field flow fractionation device where 1 MHz AC voltage was supplied and the field strength was well below 1 V per mum. Furthermore, we uniquely observed enrichment of semiconductive SWNTs based on their band gap. In addition to Raman spectrum, UV-vis absorption and NIR fluorescence spectra were used for solution samples for characterization.

Isotropic-nematic phase transition of single-walled carbon nanotubes in strong acids.

We present the first quantitative assessment of the maximum amount of nanotubes that can exist in the isotropic phase () of single-walled carbon nanotubes (SWNTs) in Brønsted-Lowry acids. We employ a centrifugation technique in conjunction with UV-vis-nIR spectroscopy to quantify , which is also the critical concentration of the isotropic-nematic transition of SWNTs in strong acids. Centrifugation of biphasic dispersions of SWNTs, that is, acid dispersions consisting of an isotropic phase in equilibrium with an ordered nematic liquid crystalline phase, results in a clear phase separation, where the isotropic phase is supernatant. Dilution of the isotropic phase with a known amount of acid followed by UV-vis-nIR absorbance measurements yields , that is, the maximum concentration of SWNTs that can exist in the isotropic phase in a given acid for a given SWNTs' length distribution. At low SWNT concentration (below 200 ppm) in superacids, light absorbance in the range from 400 to 1400 nm scales linearly with concentration. This Beer's law behavior yields calibration curves for measuring SWNTs' concentration in acids. We find that the critical concentration of the isotropic-nematic transition increases with acid strength in accordance with the previously proposed sidewall protonation mechanism for dispersing SWNTs in acids.