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Adsorption of volatile organic compounds onto carbon nanotubes, carbon nanofibers, and high-surface-area graphites.

The adsorption of different alkanes (linear and cyclic), aromatics, and chlorohydrocarbons onto different nonmicroporous carbons--multiwalled carbon nanotubes (CNTs), carbon nanofibers (CNFs), and high-surface-area graphites (HSAGs)--is studied in this work by inverse gas chromatography (IGC). Capacity of adsorption was derived from the isotherms of adsorption, whereas thermodynamic properties (enthalpy of adsorption, surface free energy characteristics) have been determined from chromatographic retention data. HSAGs present the highest adsorption capacity, followed by CNTs and CNFs (although CNTs present an intermediate surface area between the two HSAG studied). Among the different adsorbates tested, benzene exhibits the highest adsorption capacity, and the same trend is observed in the enthalpy of adsorption. From surface free energy data, enthalpies of adsorption of polar compounds were divided into dispersive and specific contributions. The interactions of cyclic (benzene and cyclohexane) and chlorinated compounds (trichloroethylene, tetrachloroethylene, and chloroform) with the surfaces are mainly dispersive over all the carbons tested, CNTs being the material with the highest dispersive contribution, as was deduced also from the entropy parameter. Adsorption parameters were correlated with morphological and chemical properties of the materials.

Journal Article↗

[Research developments of Raman scattering of carbon nanotubes].

Carbon nanotubes is a new one-dimension carbon material. With novel structural, electronic and mechanical properties, carbon nanotubes constitute' an important form of carbon that may find applications in many fields. Raman scattering is an important measurement method for the carbon nanotubes, especially for single-walled carbon nanotubes (SWNTs). The tube configuration can be studied in detail using Raman spectroscopy. Theoretical calculations predicated that SWNTs have 15 or 16 Raman active vibrational modes; the exact number depends on the symmetry of the tubes but is independent of its diameter. Also, the wavenumber of radius breathing mode (RMB) is inverse proportional to the radius of SWNTs by means of Raman spectroscopy. The recent progress of Raman scattering of carbon nanotubes is reviewed in this paper. The characteristic and vibrational theory of carbon nanotubes are presented. The potential application of carbon nanotubes is also briefly described.

Nanotubes, Carbon↗

DNA-assisted dispersion and separation of carbon nanotubes.

Carbon nanotubes are man-made one-dimensional carbon crystals with different diameters and chiralities. Owing to their superb mechanical and electrical properties, many potential applications have been proposed for them. However, polydispersity and poor solubility in both aqueous and non-aqueous solution impose a considerable challenge for their separation and assembly, which is required for many applications. Here we report our finding of DNA-assisted dispersion and separation of carbon nanotubes. Bundled single-walled carbon nanotubes are effectively dispersed in water by their sonication in the presence of single-stranded DNA (ssDNA). Optical absorption and fluorescence spectroscopy and atomic force microscopy measurements provide evidence for individually dispersed carbon nanotubes. Molecular modelling suggests that ssDNA can bind to carbon nanotubes through pi-stacking, resulting in helical wrapping to the surface. The binding free energy of ssDNA to carbon nanotubes rivals that of two nanotubes for each other. We also demonstrate that DNA-coated carbon nanotubes can be separated into fractions with different electronic structures by ion-exchange chromatography. This finding links one of the central molecules in biology to a technologically very important nanomaterial, and opens the door to carbon-nanotube-based applications in biotechnology.

Biotechnology↗

The mechanism of water diffusion in narrow carbon nanotubes.

Carbon nanotubes show exceptional physical properties that render them promising candidates as building blocks for nanostructured materials. Many ambitious applications, ranging from gene therapy to membrane separations, require the delivery of fluids, in particular aqueous solutions, through the interior of carbon nanotubes. To foster these and other applications, it is necessary to understand the thermodynamic and transport properties of water confined within long narrow carbon nanotubes. Previous theoretical work considered either short carbon nanotubes or short periods of time. By conducting molecular dynamics simulations in the microcanonical ensemble for water confined in infinitely long carbon nanotubes of diameter 1.08 nm, we show here that confined water molecules diffuse through a fast ballistic motion mechanism for up to 500 ps at room temperature. By comparing the results obtained for the diffusion of water to those obtained for the diffusion of a reference Lennard-Jones fluid, we prove here that long-lasting hydrogen bonds are responsible for the ballistic diffusion of water clusters in narrow carbon nanotubes, as opposed to spatial mismatches between pore-fluid and fluid-fluid attractive interactions which, as shown previously by others, are responsible for the concerted motion of simple fluids in molecular sieves. Additionally we prove here for the first time that, despite the narrow diameter of the carbon nanotubes considered which may suggest the existence of single-file diffusion, when the trajectories of confined water are studied at time scales in excess of 500 ps, a Fickian-type diffusion mechanism prevails. Our results are important for designing nano fluidic apparatuses to develop, for example, novel drug-delivery devices.

Capillary Action↗

Synthesis of carbon nanotubes.

Carbon nanotubes play a fundamental role in the rapidly developing field of nanoscience and nanotechnology because of their unique properties and high potential for applications. In this article, the different synthesis methods of carbon nanotubes (both multi-walled and single-walled) are reviewed. From the industrial point of view, the chemical vapor deposition method has shown advantages over laser vaporization and electric arc discharge methods. This article also presents recent work in the controlled synthesis of carbon nanotubes with ordered architectures. Special carbon nanotube configurations, such as nanocoils, nanohorns, bamboo-shaped and carbon cylinder made up from carbon nanotubes are also discussed.

Crystallization↗

Dispersion and solubilization of carbon nanotubes.

Carbon nanotubes are generally insoluble in any solvents, resulting in their poor processability for many proposed potential applications. Several strategies have been developed to introduce carbon nanotubes into solvent systems, including dispersion and suspension under special experimental conditions and the chemical modification and functionalization. The well-dispersed and solubilized carbon nanotubes make it possible to characterize and study the carbon nanotubes by using solution-based techniques, to realize some of the unique properties of the nanotubes, and to carry out further chemical transformations. In this review, recent development in the experimental methods for the dispersion and solubilization of carbon nanotubes will be summarized and discussed.

Biocompatible Materials↗

Defects in carbon nanotubes.

Carbon nanotubes are quasi one-dimensional nanostructures with unique eletrical prroperties that make them prime candidates for molecular electronics, which is certainly a most promising direction in nanotechnology. Early theoretical works predicted that the electronic properties of "ideal" carbon nanotubes depend on their diameter and chirality. However, carbon nanotubes are probably not as perfect as they were once thought to be. Defects such as pentagons, heptagons, vacancies, or dopant are found to modify drastically the electronic properties of these nanosystems. Irradiation processes can lead to interesting, highly defective nanostructures and also to the coalescence of nanotubes within a rope. The introduction of defects in the carbon network is thus an interesting way to tailor its intrinsic properties, to create new potential nanodevices. The aim of the present Acount is to investigate theoretically the effects of different types of defects on the electronic properties of carbon nanotubes, and to propose new potential applications in nanoelectronics.

Journal Article↗

Respiratory toxicity of multi-wall carbon nanotubes.

Carbon nanotubes focus the attention of many scientists because of their huge potential of industrial applications, but there is a paucity of information on the toxicological properties of this material. The aim of this experimental study was to characterize the biological reactivity of purified multi-wall carbon nanotubes in the rat lung and in vitro. Multi-wall carbon nanotubes (CNT) or ground CNT were administered intratracheally (0.5, 2 or 5 mg) to Sprague-Dawley rats and we estimated lung persistence, inflammation and fibrosis biochemically and histologically. CNT and ground CNT were still present in the lung after 60 days (80% and 40% of the lowest dose) and both induced inflammatory and fibrotic reactions. At 2 months, pulmonary lesions induced by CNT were characterized by the formation of collagen-rich granulomas protruding in the bronchial lumen, in association with alveolitis in the surrounding tissues. These lesions were caused by the accumulation of large CNT agglomerates in the airways. Ground CNT were better dispersed in the lung parenchyma and also induced inflammatory and fibrotic responses. Both CNT and ground CNT stimulated the production of TNF-alpha in the lung of treated animals. In vitro, ground CNT induced the overproduction of TNF-alpha by macrophages. These results suggest that carbon nanotubes are potentially toxic to humans and that strict industrial hygiene measures should to be taken to limit exposure during their manipulation.

Administration, Inhalation↗

Conformational selectivity of peptides for single-walled carbon nanotubes.

Carbon nanotubes show promising prospects for applications ranging from molecular electronics to ultrasensitive biosensors. An important aspect to understanding carbon nanotube properties is their interactions with biomolecules such as peptides and proteins, as these interactions are important in our understanding of nanotube interactions with the environment, their use in cellular systems, as well as their interface with biological materials for medical and diagnostic applications. Here we report the sequence and conformational requirements of peptides for high-affinity binding to single-walled carbon nanotubes (SWNTs). A new motif, X(1)THX(2)X(3)PWTX(4), where X(1) is G or H, X(2) is H or D or null, X(3) is null or R, and X4 is null or K, was identified from two classes of phage-displayed peptide libraries. The high affinity binding of the motif to SWNTs required constrained conformations which were achieved through either the extension of the amino acid sequence (e.g., LLADTTHHRPWT) or the addition of a constrained disulfide bond (e.g., CGHPWTKC). This motif shows specific high-affinity to the currently studied SWNTs, compared to previously reported peptides. The conformations of the identified peptides in complex with SWNTs were also characterized with a variety of biophysical methodologies including CD, fluorescence, NMR spectroscopy, and molecular modeling.

Amino Acid Sequence↗

Biomolecular applications of carbon nanotubes.

Carbon nanotubes are a significant addition to the emerging field of nanotube biotechnology. The biocompatibility, high structural integrity, and unique electronic and mechanical properties of carbon nanotubes complement or surpass those of self-assembled lipid nanotubes, peptide nanotubes, and template-synthesised nanotubes (metals, polymers, semiconductors, and carbons). Carbon nanotubes are candidates for a range of biomolecular applications that is likely to widen considerably in the future.

Journal Article↗

Molecular electronics with carbon nanotubes.

Carbon nanotubes have unique properties that make them a most promising system on which to base molecular electronics. We briefly review the electrical characteristics of carbon nanotubes, and then focus on carbon nanotube field-effect transistors (CNTFETs). Procedures by which hole-transport, electron-transport and ambipolar CNTFETs can be fabricated are presented, and their electrical characteristics are discussed and compared with those of Si MOSFETs. Ways to fabricate arrays of CNTFETs are also demonstrated, and electron and hole CNTFETs are integrated to form complementary logic circuits.

Journal Article↗

Soluble carbon nanotubes.

Carbon nanotubes have attracted great interdisciplinary interest because of their unique structure and properties. However, carbon-nanotube research is challenged by several problems, such as: i) mass production of material, ii) control of length, diameter, and chirality, and iii) manipulation for use in diverse technological fields. Issues regarding the synthesis and purification as well as the functionalization and solubilization of carbon nanotubes are relevant topics in this rapidly growing field. In this paper, covalent and noncovalent approaches to functionalized and solubilized nanotubes are examined in detail, with particular emphasis on the change of properties that accompany the chemical modification.

Journal Article↗

High brightness electron beam from a multi-walled carbon nanotube.

Carbon nanotubes can act as electron sources with very rigid structures, making them particularly interesting for use as point electron sources in high-resolution electron-beam instruments. Promising results have been reported with respect to some important requirements for such applications: a stable emitted current and a long lifetime. Two parameters of an electron source affect the resolution of these instruments: the energy spread of the emitted electrons and a parameter called the reduced brightness, which depends on the angular current density and the virtual source size. Several authors have measured a low energy spread associated with electron emission. Here we measure the reduced brightness, and find a value that is more than a factor of ten larger than provided by state-of-the-art electron sources in electron microscopes. In addition, we show that an individual multi-walled carbon nanotube emits most current into a single narrow beam. On the basis of these results, we expect that carbon nanotube electron sources will lead to a significant improvement in the performance of high-resolution electron-beam instruments.

Journal Article↗

Sorption of 243Am(III) to multiwall carbon nanotubes.

Carbon nanotubes have attracted great interest in multidisciplinary study since their discovery. Herein, radionuclide 243Am(III) sorption to uncapped multiwall carbon nanotubes (MWCNTs) was carried out at 20+/-2 degrees C in 0.01 and 0.1 M NaClO4 solutions. Effects of 243Am(III) solution concentration, ionic strength, and pH on 243Am(III) sorption to MWCNTs were also investigated. The sorption is strongly dependent on pH values and weakly dependent on the ionic strength in the experimental conditions. The results show that MWCNTs can adsorb 243Am(III) with extraordinarily high efficiency by forming very stable complexes. Chemisorption or chemicomplexation is the main mechanism of 243Am(III) sorption on the surface of MWCNTs. MWCNTs can be a promising candidate for the preconcentration and solidification of 243Am(III) or its analogue lanthanides and actinides from large volumes of aqueous solution, as required for remediation purposes, and perhaps also as a sorbent for the removal of heavy metal ions from the industry wastewater.

Actinoid Series Elements↗

pH-dependent electron-transport properties of carbon nanotubes.

Carbon nanotube electrochemical transistors integrated with microfluidic channels are utilized to examine the effects of aqueous electrolyte solutions on the electron-transport properties of single isolated carbon nanotubes. In particular, pH and concentration of supporting inert electrolytes are examined. A systematic threshold voltage shift with pH is observed while the transconductance and subthreshold swing remain independent of pH and concentration. Decreasing pH leads to a negative shift of the threshold voltage, indicating that protonation does not lead to hole doping. Changing the type of contact metal does not alter the observed pH response. The pH-dependent charging of SiO2 substrate is ruled out as the origin based on measurements with suspended nanotube transistors. Increasing the ionic strength leads to reduced pH response. Contributions from possible surface chargeable chemical groups are considered.

Electric Conductivity↗

Controlled growth of carbon nanotubes.

Carbon nanotubes have extraordinary mechanical and electronic properties and hold great promise for future applications. The most important aspects of this structure are its low density, high aspect ratio, one dimensionality, high mechanical strength and high electrical and thermal conductivity. We present a short, state-of-the-art account of tailored nanotube growth. To provide these properties in real devices there exists a need for producing nanotubes on substrates. The challenge in the creation of mesoscale nanotube-based architectures and tailored nanotube networks consisting of thousands of tubes in a predefined order is obviously great. Currently, chemical vapour deposition (CVD) appears to be the most powerful method for achieving such required structures. We describe our work on a new synthesis method, based on catalytic CVD using mainly gas-phase catalyst delivery. Gas-phase catalyst delivery allows us to assemble single-walled and multi-walled carbon nanotubes in predetermined multiple orientations on substrates to build one- to three-dimensional architectures. We are able to control, to a large extent, the types of nanotubes produced, their lengths, locations and their orientations. The ability to make mesoscale architectures with nanotubes should lead us to develop applications in areas such as nano-electromechanical systems.

Biocompatible Materials↗

Electrically excited, localized infrared emission from single carbon nanotubes.

Carbon nanotube field-effect transistors (CNTFETs) produce band gap derived infrared emission under both ambipolar and unipolar transport conditions. We demonstrate here that heterogeneities/defects in the local environment of a CNTFET perturb the local potentials and, as a result, the characteristic bias dependent motion of the ambipolar light emission. Such defects can also introduce localized infrared emission due to impact excitation by carriers accelerated by a voltage drop at the defect. The correlation of the change in the motion of the ambipolarlight emission and of the stationary electroluminescence with the electrical characteristics of the CNTFETs shows that stationaryelectroluminescence can identify "environmental defects" in carbon nanotubes and help evaluate their influence on electrical transport and device operation. A number of different defects are studied involving local dielectric environment changes (partially polymer-covered nanotubes), nanotube-nanotube contacts in looped nanotubes, and nanotube segments close to the electronic contacts. Random defects due to local charging are also observed.

Electrochemistry↗

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↗