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At least 19 recordsLinked to original sources
PubMed2006

Debundling of single-walled nanotubes by dilution: observation of large populations of individual nanotubes in amide solvent dispersions.

Large-scale debundling of single-walled nanotubes has been demonstrated by dilution of nanotube dispersions in the solvent N-methyl-2-pyrrolidone (NMP). At high concentrations some very large (approximately 100 s of micrometers) nanotube aggregates exist that can be removed by mild centrifugation. By measurement of the absorbance before and after centrifugation as a function of concentration the relative aggregate and dispersed nanotube concentrations can be monitored. No aggregates are observed below CNT approximately 0.02 mg/mL, suggesting that this can be considered the nanotube dispersion limit in NMP. After centrifugation, the dispersions are stable against sedimentation and further aggregation for a period of weeks at least. Atomic force microscopy (AFM) studies on deposited films reveal that the bundle diameter distribution decreases dramatically as concentration is decreased. Detailed data analysis suggests the presence of an equilibrium bundle number density and that the dispersions self-arrange themselves to always remain close to the dilute/semidilute boundary. A population of individual nanotubes is always observed that increases with decreasing concentration until almost 70% of all dispersed objects are individual nanotubes at a concentration of 0.004 mg/mL. The number density of individual nanotubes peaks at a concentration of approximately 10(-2) mg/mL. Both the mass fraction and the partial concentration of individual nanotubes can also be measured and behave in similar fashion. Comparison of the number density and partial concentration also of individual nanotubes reveals that the individual nanotubes have average molar masses of approximately 700,000 g/mol. The presence of individual nanotubes in NMP dispersion was confirmed by photoluminescence spectroscopy. Concentration dependence of the photoluminescence intensity confirms that the AFM measurements reflect the diameter distributions in situ. In addition, Raman spectroscopy confirms the presence of large quantities of individual nanotubes in the deposited films. Finally, the nature of the solvent properties required for dispersion are discussed.

Amides↗
PubMed2002

Scanning probe microscopy installed with nanotube probes and nanotube tweezers.

We have developed well-controlled processes for the growth and manipulation of carbon nanotubes. The relatively thin multiwalled nanotubes were prepared with high purity by arc discharge with a high gas temperature. In the manipulation of nanotubes, the first crucial process is to prepare a nanotube array, so-called nanotube cartridge. We have found the alternated current electrophoresis of nanotubes by which nanotubes are aligned at the knife-edge of a disposal razor. The second important process is to transfer a nanotube from the nanotube cartridge onto a substrate in a scanning electron microscope. Using this method, we have developed nanotube probes and nanotube tweezers that operate in a scanning probe microscope (SPM). The nanotube probes have been applied for observation of biological samples and industrial samples to clarify their advantages. The nanotube tweezers have been demonstrated for their motion in scanning electron microscope and operated to carry a nanomaterial in a SPM.

DNA↗
PubMed2005

Cytotoxicity assessment of some carbon nanotubes and related carbon nanoparticle aggregates and the implications for anthropogenic carbon nanotube aggregates in the environment.

Nanotechnology and nanomaterials have become the new frontier world-wide over the past few years and prospects for the production and novel uses of large quantities of carbon nanotubes in particular are becoming an increasing reality. Correspondingly, the potential health risks for these and other nanoparticulate materials have been of considerable concern. Toxicological studies, while sparse, have been concerned with virtually uncharacterized, single wall carbon nanotubes, and the conclusions have been conflicting and uncertain. In this research we performed viability assays on a murine lung macrophage cell line to assess the comparative cytotoxicity of commercial, single wall carbon nanotubes (ropes) and two different multiwall carbon nanotube samples; utilizing chrysotile asbestos nanotubes and black carbon nanoaggregates as toxicity standards. These nanotube materials were completely characterized by transmission electron microscopy and observed to be aggregates ranging from 1 to 2 microm in mean diameter, with closed ends. The cytotoxicity data indicated a strong concentration relationship and toxicity for all the carbon nanotube materials relative to the asbestos nanotubes and black carbon. A commercial multiwall carbon nanotube aggregate exhibiting this significant cell response was observed to be identical in structure to multiwall carbon nanotube aggregates demonstrated to be ubiquitous in the environment, and especially in indoor environments, where natural gas or propane cooking stoves exist. Correspondingly, preliminary epidemiological data, although sparse, indicate a correlation between asthma incidence or classification, and exposure to gas stoves. These results suggest a number of novel epidemiological and etiological avenues for asthma triggers and related respiratory or other environmental health effects, especially since indoor number concentrations for multiwall carbon nanotube aggregates is at least 10 times the outdoor concentration, and virtually all gas combustion processes are variously effective sources. These results also raise concerns for manufactured carbon nanotube aggregates, and related fullerene nanoparticles.

Adolescent↗
PubMed2005

Binding and condensation of plasmid DNA onto functionalized carbon nanotubes: toward the construction of nanotube-based gene delivery vectors.

Carbon nanotubes (CNTs) constitute a class of nanomaterials that possess characteristics suitable for a variety of possible applications. Their compatibility with aqueous environments has been made possible by the chemical functionalization of their surface, allowing for exploration of their interactions with biological components including mammalian cells. Functionalized CNTs (f-CNTs) are being intensively explored in advanced biotechnological applications ranging from molecular biosensors to cellular growth substrates. We have been exploring the potential of f-CNTs as delivery vehicles of biologically active molecules in view of possible biomedical applications, including vaccination and gene delivery. Recently we reported the capability of ammonium-functionalized single-walled CNTs to penetrate human and murine cells and facilitate the delivery of plasmid DNA leading to expression of marker genes. To optimize f-CNTs as gene delivery vehicles, it is essential to characterize their interactions with DNA. In the present report, we study the interactions of three types of f-CNTs, ammonium-functionalized single-walled and multiwalled carbon nanotubes (SWNT-NH3+; MWNT-NH3+), and lysine-functionalized single-walled carbon nanotubes (SWNT-Lys-NH3+), with plasmid DNA. Nanotube-DNA complexes were analyzed by scanning electron microscopy, surface plasmon resonance, PicoGreen dye exclusion, and agarose gel shift assay. The results indicate that all three types of cationic carbon nanotubes are able to condense DNA to varying degrees, indicating that both nanotube surface area and charge density are critical parameters that determine the interaction and electrostatic complex formation between f-CNTs with DNA. All three different f-CNT types in this study exhibited upregulation of marker gene expression over naked DNA using a mammalian (human) cell line. Differences in the levels of gene expression were correlated with the structural and biophysical data obtained for the f-CNT:DNA complexes to suggest that large surface area leading to very efficient DNA condensation is not necessary for effective gene transfer. However, it will require further investigation to determine whether the degree of binding and tight association between DNA and nanotubes is a desirable trait to increase gene expression efficiency in vitro or in vivo. This study constitutes the first thorough investigation into the physicochemical interactions between cationic functionalized carbon nanotubes and DNA toward construction of carbon nanotube-based gene transfer vector systems.

Cations↗
PubMed2005

Atomic nanotube welders: boron interstitials triggering connections in double-walled carbon nanotubes.

Here we demonstrate that the incorporation of boron (B) atoms between double-walled carbon nanotubes (DWNTs) during thermal annealing (1400-1600 degrees C) results in covalent nanotube "Y" junctions, DWNT coalescence, and the formation of flattened multiwalled carbon nanotubes (MWNTs). These processes occur via the merging of adjacent tubes, which is triggered by B interstitial atoms. We observe that B atom interstitials between DWNTs are responsible for the rapid establishment of covalent connections between neighboring tubes (polymerization), thereby resulting in the fast annealing of the carbon cylinders with B atoms embedded in the newly created carbon nanotube network. Once B is in the lattice, tube faceting (polygonization) starts to occur, and the electronic properties are expected to change dramatically. Therefore, B atoms indeed act as atomic nanotube fusers (or welders), and this process could now be used in assembling novel electronic nanotube devices, nanotube networks, carbon nanofoams and heterojunctions exhibiting p-type electronic properties.

Boron↗
PubMed2005

Flow-induced planar assembly of parallel carbon nanotubes and crossed nanotube junctions.

We report the in-situ assembly of carbon nanotubes by chemical vapor deposition of hydrocarbon precursor (a solution of ferrocene dissolved in isopropyl alcohol). We utilized the vapor stream inside the reaction chamber to comb carbon nanotubes along the same direction and obtained two-dimensional (planar) assembly of nanotubes with tunable distributions. When the carbon source was flowing at a relatively higher rate of approximately 0.2 ml/min, most of nanotubes were driven along the vapor flow direction during their growth process and formed a thin freestanding mat featured with a parallel arrangement, whereas a lower flowing rate (approximately 0.05 ml/min) only resulted in random spider-web structures consisting of crossed nanotube junctions with a variety of configurations (e.g., "+", "Y", "T" shapes and twists). The measured direction-dependent electrical resistance of these two assemblies was in agreement with respective structures, which was anisotropic for parallel nanotubes and nearly isotropic for random networks. Such large-area planar carbon nanotube arrays with controlled orientation and various junction configurations will facilitate the design and fabrication of electronic and mechanical devices.

Carbon↗
PubMed2003

Carbon nanotube purification: preparation and characterization of carbon nanotube paste electrodes.

Paste electrodes have been constructed using single-wall carbon nanotubes mixed with mineral oil. The electrochemical behavior of such electrodes prepared with different percentages of carbon nanotubes has been compared with that of graphite paste electrodes and evaluated with respect to the electrochemistry of ferricyanide with cyclic voltammetry. Carbon nanotubes were purified by a treatment with concentrated nitric acid, then oxidized in air. In addition, electrochemical pretreatments were carried out to increase the selectivity of carbon nanotube electrodes. Performances of carbon nanotube paste and carbon paste electrodes were evaluated by studying such parameters as current peak, deltaEp, anodic and cathodic current ratio, and charge density toward several different electroactive molecules. Data interpretation based on the carbon nanotubes and carbon surface area is presented. Carbon nanotube paste and carbon paste electrodes were tested as H2O2 and NADH probes, and several analytical parameters were evaluated. The oxidative behavior of dopamine was examined at these electrodes. The two-electron oxidation of dopamine to dopaminequinone showed an excellent reversibility in cyclic voltammetry that was significantly better than that observed at carbon paste electrodes.

Journal Article↗
PubMed2005

Aligned arrays of nanotubes and segmented nanotubes on substrates fabricated by electrodeposition onto nanorods.

We describe an electrochemical-based approach to create vertically aligned nanotube arrays on substrates. Initially, nanoporous anodic alumina films are used as templates to electrodeposit nanorods, and then the alumina templates are removed and nanotube arrays are electrodeposited using the nanorod arrays as templates. We have used this approach to fabricate gold nanotube arrays using nickel nanorods as templates. By anodizing the ends of the nickel nanorods before gold electrodeposition, no deposition occurs at the ends of the rods, resulting in open-ended nanotubes. In addition, we have used layered nickel-gold nanorods as templates to create gold nanostructure arrays with alternating segments of filled and empty nanotubes. This approach is versatile and may be used to electrodeposit a wide range of nanotube materials with good control over the nanotube dimensions.

Journal Article↗
PubMed2006

Novel nanotube-on-insulator (NOI) approach toward single-walled carbon nanotube devices.

We present a novel nanotube-on-insulator (NOI) approach for producing high-yield nanotube devices based on aligned single-walled carbon nanotubes. First, we managed to grow aligned nanotube arrays with controlled density on crystalline, insulating sapphire substrates, which bear analogy to industry-adopted silicon-on-insulator substrates. On the basis of the nanotube arrays, we demonstrated registration-free fabrication of both top-gated and polymer-electrolyte-gated field-effect transistors with minimized parasitic capacitance. In addition, we have developed a way to transfer these aligned nanotube arrays to flexible substrates successfully. Our approach has great potential for high-density, large-scale integrated systems based on carbon nanotubes for both micro- and flexible electronics.

Journal Article↗
PubMed2001

Formation of ordered ice nanotubes inside carbon nanotubes.

Following their discovery, carbon nanotubes have attracted interest not only for their unusual electrical and mechanical properties, but also because their hollow interior can serve as a nanometre-sized capillary, mould or template in material fabrication. The ability to encapsulate a material in a nanotube also offers new possibilities for investigating dimensionally confined phase transitions. Particularly intriguing is the conjecture that matter within the narrow confines of a carbon nanotube might exhibit a solid-liquid critical point beyond which the distinction between solid and liquid phases disappears. This unusual feature, which cannot occur in bulk material, would allow for the direct and continuous transformation of liquid matter into a solid. Here we report simulations of the behaviour of water encapsulated in carbon nanotubes that suggest the existence of a variety of new ice phases not seen in bulk ice, and of a solid-liquid critical point. Using carbon nanotubes with diameters ranging from 1.1 nm to 1.4 nm and applied axial pressures of 50 MPa to 500 MPa, we find that water can exhibit a first-order freezing transition to hexagonal and heptagonal ice nanotubes, and a continuous phase transformation into solid-like square or pentagonal ice nanotubes.

Journal Article↗
PubMed2006

Synthesis and photoluminescence of Y2O3:RE3+ (RE=Eu, Tb, Dy) porous nanotubes templated by carbon nanotubes.

Y2O3:RE3+(RE=Eu, Tb, Dy) porous nanotubes were first synthesized using carbon nanotubes as template. The morphology of the coated precursors and porous Y2O3:Eu3+ nanotubes was determined by scanning electron Microscopy (SEM) and transmission electron microscopy (TEM). It was found that the coating of precursors on carbon nanotubes (CNTs) is continuous and the thickness is about 15 nm, after calcinated, the Y2O3:Eu3+ nanotubes are porous with the diameter size in the range of 50-80 nm and the length in micrometer scale. X-ray diffraction (XRD) patterns confirmed that the samples are cubic phase Y2O3 and the photoluminescence studies showed that the porous rare earth ions doped nanotubes possess characteristic emission of Eu3+, Tb3+, and Dy3+. This method may also provide a novel approach to produce other inorganic porous nanotubes used in catalyst and sensors.

Dysprosium↗
PubMed2004

Nanotube molecular transporters: internalization of carbon nanotube-protein conjugates into Mammalian cells.

The interactions between various functionalized carbon nanotubes and several types of human cancer cells are explored. We have prepared modified nanotubes and have shown that these can be derivatized in a way that enables attachment of small molecules and of proteins, the latter through a novel noncovalent association. The functionalized carbon nanotubes enter nonadherent human cancer cells as well as adherent cell lines (CHO and 3T3) and by themselves are not toxic. While the fluoresceinated protein streptavidin (MW approximately 60 kD) by itself does not enter cells, it readily enters cells when complexed to a nanotube-biotin transporter and exhibits dose-dependent cytotoxicity. The uptake pathway is consistent with adsorption-mediated endocytosis. The use of carbon nanotubes as molecular transporters could be exploited for various cargos. The biocompatibility and unique physical, electrical, optical, and mechanical properties of nanotubes provide the basis for new classes of materials for drug, protein, and gene delivery applications.

Animals↗
PubMed2005

Simultaneous targeted immobilization of anti-human IgG-coated nanotubes and anti-mouse IgG-coated nanotubes on the complementary antigen-patterned surfaces via biological molecular recognition.

Introduction of self-assembly in nanometer-sized building blocks is expected to accomplish bottom-up fabrications in a more reproducible, efficient, and economic manner; however, it is necessary to selectively place multiple types of nano-building blocks (e.g., metal nanotubes and semiconductor nanotubes) at specific locations on surfaces with high precision and reproducibility for more complex nanometer-scale device assemblies. Biological molecular recognition such as antibody-antigen bindings may be suitable to use in the building-block assembly since nature always assembles materials with complex functions and structures at room temperature reproducibly. Our approach is to immobilize antibody-coated nanotubes at specific complementary binding positions patterned on surfaces. To demonstrate this hypothesis, two types of nanotubes coated with different antibodies were anchored selectively onto their complementary antigen areas, patterned by tips of atomic force microscope (AFM). Because those nanotubes can be coated by various metals and semiconductors with controlled morphologies, this outcome opens the possibility to accomplish the proposed unconventional device fabrication methodology that antibody nanotubes coated with different types of metals/semiconductors can be self-assembled on antigen-patterned surfaces via biological molecular recognition.

Animals↗
PubMed2003

Individual single-walled nanotubes and hydrogels made by oxidative exfoliation of carbon nanotube ropes.

Single-walled carbon nanotubes were oxidized by a technique previously developed for the oxidation of graphite to graphite oxide (GO). This process involves treatment with concentrated H(2)SO(4) containing (NH(4))(2)S(2)O(8) and P(2)O(5), followed by H(2)SO(4) and KMnO(4). Oxidation results in complete exfoliation of nanotube ropes to yield individual oxidized tubes that are 40-500 nm long. The C:O:H atomic ratio of vacuum-dried oxidized nanotubes is approximately 2.7:1.0:1.2. XPS and IR spectra show evidence for surface O-H, C=O, and COOH groups. The oxidized nanotubes slowly form viscous hydrogels at unusually low concentration (>or=0.3 wt %), and this behavior is attributed to the formation of a hydrogen-bonded nanotube network. The oxidized tubes bind readily to amine-coated surfaces, on which they adsorb as smooth and dense monolayer films. Thin films of the oxidized nanotubes show ohmic current-voltage behavior, with resistivities in the range of 0.2-0.5 Omega-cm.

Journal Article↗
PubMed2003

Nanotube electronics: large-scale assembly of carbon nanotubes.

Nanoscale electronic devices made from carbon nanotubes, such as transistors and sensors, are much smaller and more versatile than those that rely on conventional microelectronic chips, but their development for mass production has been thwarted by difficulties in aligning and integrating the millions of nanotubes required. Inspired by biomolecular self-assembly processes, we have created chemically functionalized patterns on a surface, to which pre-grown nanotubes in solution can align themselves in huge numbers. This method allows wafer-scale fabrication of millions of carbon-nanotube circuits with single-nanotube precision, and may enable nanotube-based devices, such as computer chips and high-density sensor arrays, to be produced industrially.

Journal Article↗
PubMed2004

Computational studies of carbon nanotube-hydrocarbon bond strengths at nanotube ends: effect of link heteroatom and hydrocarbon structure.

Semiempirical and density functional electronic structure theory methods were used to study SWNT-X--R bond strengths, where the single-walled carbon nanotube (SWNT) had an armchair or zigzag structure, the link heteroatom X was O, N(H), or S and the hydrocarbon chain R was CH(2)CH(3), CH(OH)CH(3), CHCH(2), or CH(CF(3))CH(3). In all systems the hydrocarbon was bonded to the end of the nanotube. The SWNT-X--R bond (that is, the bond joining the link atom to the hydrocarbon) is more than 0.4 eV stronger for armchair than for zigzag nanotubes with the same diameters, irrespective of whether O, N, or S are used as link atoms or whether OH, C==C, or CF(3) groups are present in the hydrocarbon chain. This raises the possibility for selective manipulation of armchair/zigzag nanotubes using a variety of link atoms and hydrocarbon structures. The SWNT-O--CH(CF(3))CH(3) bond is weaker than the SWNT-O--CH(2)CH(3) bond (for both armchair and zigzag nanotubes), while inclusion of a double bond in the ethyl chain increases the bond strengths. Also, SWNT-S--CH(2)CH(3) and SWNT-N(H)--CH(2)CH(3) bonds are stronger than SWNT-O--CH(2)CH(3) bonds.

Journal Article↗
PubMed2004

Layer-by-layer assembled multilayer films of titanate nanotubes, Ag- or Au-loaded nanotubes, and nanotubes/nanosheets with polycations.

Aqueous suspensions of hydrothermally synthesized titanate nanotubes and poly(diallyldimethylammonium chloride) (PDDA) have been employed to fabricate multilayer films on various substrates in a layer-by-layer fashion. Atomic force microscopy displays the dense coverage of the substrate surface by the nanotubes. UV-vis absorption spectroscopy confirms the consecutive growth of PDDA/nanotube layer pairs. Single crystalline Ag and Au nanoparticles with narrow size distribution spatially correlating with the nanotubes have been obtained by treating the nanotubes with AgNO(3) or HAuCl(4) aqueous solution followed by chemical reduction. The noble metal nanoparticles show a strong surface plasmon absorption band. A multilayer film construction of the noble-metal-loaded nanotubes has also been achieved. This process has been further extended to the heteroassembly of nanotubes/nanosheets in different layer sequences.

Journal Article↗
PubMed2006

The formation of low-dimensional inorganic nanotube crystallites in carbon nanotubes.

The filling of carbon nanotubes, which vary in diameter and morphology, is directly observed by molecular dynamics computer simulation with a potential model which thermodynamically favors a four-coordinate bulk crystal structure. Inorganic nanotube (INT) structures form which are based on percolating hexagonal nets. For small carbon nanotube diameters the filling is shown to proceed via an "internal wetting" mechanism, which depends on the internal carbon nanotube area rather than the free volume. Both single- and double-walled INTs are predicted to form. The atomistic formation mechanisms are discussed and an intermediate structure identified. The INT structures, including the observed intermediate, are discussed by reference to a simple energy landscape. The formation energetics are discussed in terms of a simple analytical model which combines the INT strain energy and the tube-tube interactions. An effective phase diagram, which predicts the INT morphologies as a function of carbon nanotube diameter, is derived and discussed with respect to the analytical model.

Journal Article↗