Odako growth of dense arrays of single-walled carbon nanotubes attached to carbon surfaces

A novel process is demonstrated whereby dense arrays of single-walled carbon nanotubes (SWNT) are grown directly at the interface of a carbon material or carbon fiber. This growth process combines the concepts of SWNT tip growth and alumina-supported SWNT base growth to yield what we refer to as “odako” growth. In odako growth, an alumina flake detaches from the carbon surface and supports catalytic growth of dense SWNT arrays at the tip, leaving a direct interface between the carbon surface and the dense SWNT arrays. In addition to being a new and novel form of SWNT array growth, this technique provides a route toward future development of many important applications for dense aligned SWNT arrays. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Nanopumping molecules via a carbon nanotube

We demonstrate the feasibility of using a carbon nanotube to nanopump molecules. Molecular dynamics simulations show that the transport and ejection of a C₂₀ molecule via a single-walled carbon nanotube (SWNT) can be achieved by a sustained mechanical actuation driven by two oscillating tips. The optimal condition for nanopumping is found when the tip oscillation frequency and magnitude correlate to form quasi steady-state mechanical wave propagation in the SWNT, so that the energy transfer process is optimal leading to maximal molecular translational motion and minimal rotational motion. Our finding provides a potentially useful mechanism for using an SWNT as a vehicle to deliver large drug molecules.      

Isolation of single-walled carbon nanotube enantiomers by density differentiation

Current methods of synthesizing single-walled carbon nanotubes (SWNTs) result in racemic mixtures that have impeded the study of left- and right-handed SWNTs. Here we present a method of isolating different SWNT enantiomers using density gradient ultracentrifugation. Enantiomer separation is enabled by the chiral surfactant sodium cholate, which discriminates between left- and right-handed SWNTs and thus induces subtle differences in their buoyant densities. This sorting strategy can be employed for simultaneous enrichment by handedness and roll-up vector of SWNTs having diameters ranging from 0.7 to 1.5 nm. In addition, circular dichroism of enantiomer refined samples enables identification of high-energy optical transitions in SWNTs. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

Density functional theory and tight binding-based dynamical studies of carbon metal systems of relevance to carbon nanotube growth

Density functional theory (DFT) and tight binding (TB) models have been used to study systems containing single-walled carbon nanotubes (SWNTs) and metal clusters that are of relevance to SWNT growth and regrowth. In particular, TB-based Monte Carlo (TBMC) simulations at 1000 or 1500 K show that Ni atoms that are initially on the surface of the SWNT or that are clustered near the SWNT end diffuse to the nanotube end so that virtually none of the Ni atoms are located inside the nanotube. This occurs, in part, due to the lowering of the Ni atom energies when they retract from the SWNT to the interior of the cluster. Aggregation of the atoms at the SWNT end does not change the chirality within the simulation time, which supports the application of SWNT regrowth (seeded growth) as a potential route for chirality-controlled SWNT production. DFT-based geometry optimisation and direct dynamics at 2000 K show that Cr and Mo atoms in Cr₅Co₅₀ and Mo₅Co₅₀ clusters prefer to be distributed in the interior of the clusters. Extension of these calculations should deepen our understanding of the role of the various alloy components in SWNT growth.      

Control of aggregate size of polyethyleneimine-coated magnetic nanoparticles for magnetofection

Using magnetic nanoparticles to enhance gene transfection, a recently developed technique termed magnetofection, has been shown to be a powerful technology in gene delivery. The most widely used magnetic nanoparticles in this area are those coated with polyethyleneimine, which is a well known nonviral transfection agent. In this article, we report methods to control the aggregate size of polyethyleneimine-coated magnetite particles. These particles were then used to enhance transfection of green fluorescent protein (GFP) into NIH 3T3 cells in vitro. We find that the aggregate size of the particles has a great effect on their performance in magnetofection, with less aggregated magnetic particles being more effective in enhancing the gene transfection. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users.     

Role of catalysts in the surface synthesis of single-walled carbon nanotubes

We demonstrate the role of catalysts in the surface growth of single-walled carbon nanotubes (SWNTs) by reviewing recent progress in the surface synthesis of SWNTs. Three effects of catalysts on surface synthesis are studied: type of catalyst, the relationship between the size of catalyst particles and carbon feeding rates, and interactions between catalysts and substrates. Understanding of the role of catalysts will contribute to our ability to control the synthesis of SWNTs on various substrates and facilitate the fabrication of nanotube-based devices.      

Effect of nucleases on the cellular internalization of fluorescent labeled DNA-functionalized single-walled carbon nanotubes

Nuclease effects on the cell internalization of single-walled carbon nanotubes (SWNTs) functionalized with fluorescent-labeled DNA in serum containing cell growth media were examined. When Cy3-labeled DNA-functionalized SWNT conjugates (Cy3DNA-SWNTs) were incubated with HeLa cells in a fatal bovine serum (FBS) medium, a high fl uorescence intensity was obtained from the cells, indicative for the high level inclusion of Cy3DNA-SWNTs. However, the fluorescence intensity was remarkably reduced if Cy3DNA-SWNTs were incubated with cells in the FBS-free medium. Further systematic control experiments revealed that Cy3 dye molecules were released from Cy3DNA-SWNT conjugates by nuclease, and the free Cy3 dyes penetrate into HeLa cell with high efficiency. Although the actual amounts of SWNTs internalized in the cells were almost identical for both cells incubated in the FBS-present and FBS-absent media according to the Raman measurements, one should be cautious to determine the degree of SWNT internalization based on the fluorescence intensities especially when the coloring dye molecules were linked to oligonucleotides in nuclease containing media. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Design of a carbon nanotube/magnetic nanoparticle-based peroxidase-like nanocomplex and its application for highly efficient catalytic oxidation of phenols

We report a novel nanotechnology-based approach for the highly efficient catalytic oxidation of phenols and their removal from wastewater. We use a nanocomplex made of multi-walled carbon nanotubes (MWNTs) and magnetic nanoparticles (MNPs). This nanocomplex retains the magnetic properties of individual MNPs and can be effectively separated under an external magnetic field. More importantly, the formation of the nanocomplex enhances the intrinsic peroxidase-like activity of the MNPs that can catalyze the reduction of hydrogen peroxide (H₂O₂). Significantly, in the presence of H₂O₂, this nanocomplex catalyzes the oxidation of phenols with high efficiency, generating insoluble polyaromatic products that can be readily separated from water.      

Synthesis and Ex situ doping of ZnTe and ZnSe nanostructures with extreme aspect ratios

We report synthesis windows for growth of millimeter-long ZnTe nanoribbons and ZnSe nanowires using vapor transport. By tuning the local conditions at the growth substrate, high aspect ratio nanostructures can be synthesized. A Cu-ion immersion doping method was applied, producing strongly p-type conduction in ZnTe and ionic conduction in ZnSe. These extreme aspect ratio wide-bandgap semiconductors have great potential for high density nanostructured optoelectronic circuits.      

Growth of serpentine carbon nanotubes on quartz substrates and their electrical properties

A simple method for high-yield, chemical vapor deposition (CVD) synthesis of serpentine carbon nanotubes, employing quartz substrates and a molecular cluster catalyst, is described. The growth mechanism is analyzed by controlled addition of nanoscale barriers, and by mechanical analysis of the curved sections. The serpentine structures are used to study the electrical transport properties of parallel arrays of identical nanotubes, which show three-terminal conductance that scales linearly with the number of nanotube segments. This article is published with open access at Springerlink.com     

Self-organized growth of complex nanotube patterns on crystal surfaces

The organization of carbon nanotubes into well-defined straight or curved geometries and arrays on surfaces is a critical prerequisite for their integration into nanocircuits and a variety of functional nanosystems. We review the recent development of a new approach to carbon nanotube organization based on self-organized growth directed by well-defined crystal surfaces, or “nanotube epitaxy”. We identify three different modes of surface-directed growth, namely by atomic rows, atomic steps, and nanofacets. Particular emphasis is given here to the combinations of such surface-directed growth with external forces—like those exerted by an electric field or gas flow—for the creation of well-defined complex geometries, including crossbar architectures, serpentines, and coils.      

The dynamics of the nucleation, growth and termination of single-walled carbon nanotubes from in situ Raman spectroscopy during chemical vapor deposition

The dynamics of the chemical vapor deposition (CVD) of single-walled carbon nanotubes (SWNTs) is extracted experimentally using in situ Raman spectroscopy. Nanotubes are grown using a thin film cobalt catalyst and an ethanol precursor in a miniature hot walled reactor with optical access. Raman spectra at room temperature and at the growth temperature are compared for two growth temperatures. The evolution of the G-band, D-band, and radial breathing mode (RBM) is tracked at the growth temperature with time resolution of a few seconds. There are three identifiable phases in the evolution of the Raman signal intensity: an initial exponential increasing phase, a linear growth phase, and a saturation phase. In situ optical spectroscopy thus enables the study of nucleation, steady growth, and deactivation processes to be investigated separately in real time. The evolution curves for all bands (G, D, and RBM), when scaled, collapse onto the same curve, to within experimental uncertainty.      

Polymeric nanomaterials as electrolyte and electrodes in supercapacitors

The energy challenge requires a broad range of options for energy harvesting, storage, and conversion. We have produced polymeric coatings by spraying, to be used as electrolyte and electrodes in a flexible electrochemical double layer capacitor. A thermoplastic polyurethane and a low molecular weight block copolyether were employed with LiClO₄ to prepare solid polymeric electrolytes. Carbon black (CB) and multi-walled carbon nanotubes (MWNTs) were dispersed in the polymer blend electrolyte to produce nanostructured composite electrodes. The conductivities increased with the addition of block copolyether and carbon nanotubes to the electrolyte and electrode, respectively. Scanning electron microscopy (SEM) and atomic force microscope (AFM) images of the nanocomposite electrodes showed nanoagglomerates of CB connected by carbon nanotubes. The solid supercapacitor prepared with these new materials as electrolyte and electrodes showed superior performance to other similar systems. The resulting safe and flexible multilayer device can meet the requirements of modern devices.      

Single-walled carbon nanotube growth with non-iron-group “catalysts” by chemical vapor deposition

Various materials have been found to “catalyze” carbon nanotube growth in chemical vapor deposition (CVD) when they become nano-sized particles. These involve not only metals, such as Pd, Pt, Au, Ag, and Cu, but also semiconductors, such as Si, Ge, and SiC. Alumina and diamond nanoparticles also produce carbon nanotubes. These “catalysts”, which are better called “seeds”, can be categorized into two types: one type forms a eutectic liquid or highly-mobile alloy with carbon, and carbon atoms precipitate from the eutectic alloy; the other type remains as a solid phase and form a carbon surface layer during CVD growth. In this paper, we review recent studies of SWCNT growth with these non-iron-group materials and highlight the mechanisms involved.      

Selective suspension in aqueous sodium dodecyl sulfate according to electronic structure type allows simple separation of metallic from semiconducting single-walled carbon nanotubes

Both density gradient centrifugation and gel electrophoresis have been reported to allow high throughput separation of metallic from semiconducting single-walled carbon nanotubes (SWNTs) when using aqueous sodium dodecyl sulphate (SDS) suspensions. We show here that both methods rely on an initial dispersion-by-sonication step, which is already selective with respect to electronic structure type. The corresponding aqueous SDS “starting” suspensions obtained after sonication and purification by simple centrifugation (70,000 g, 1 h) contain semiconducting SWNTs primarily in the form of small bundles whereas metallic SWNTs are predominantly suspended as individual tubes. Density gradient centrifugation then separates the bundles from the individual tubes on the basis of differences in their overall buoyant densities. Gel electrophoresis separates the longer bundles from the shorter individual tubes on the basis of their different mobilities. We also demonstrate that such starting suspensions can be fractionated according to electronic structure type by even simpler techniques such as size exclusion chromatography or gel filtration, thus opening the way for simple scale-up.      

Bi2S3 nanotubes: Facile synthesis and growth mechanism

Synthesis of tubular nanomaterials has become a prolific area of investigation due to their wide range of applications. A facile solution-based method has been designed to fabricate uniform Bi₂S₃ nanotubes with average size of 20 nm × 160 nm using only bismuth nitrate (Bi(NO₃)₃·5H₂O) and sulfur powder (S) as the reactants and octadecylamine (ODA) as the solvent. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and energy dispersive spectroscopy (EDX) experiments were employed to characterize the resulting Bi₂S₃ nanotubes and the classic rolling mechanism was applied to explain their formation process.      

Proton-resistant quantum dots: Stability in gastrointestinal fluids and implications for oral delivery of nanoparticle agents

Semiconductor quantum dots (QDs) have shown great promise as fluorescent probes for molecular, cellular and in vivo imaging. However, the fluorescence of traditional polymer-encapsulated QDs is often quenched by proton-induced etching in acidic environments. This is a major problem for applications of QDs in the gastrointestinal tract because the gastric (stomach) environment is strongly acidic (pH 1–2). Here we report the use of proton-resistant surface coatings to stabilize QD fluorescence under acidic conditions. Using both hyperbranched polyethylenimine (PEI) and its polyethylene glycol derivative (PEG-grafted PEI), we show that the fluorescence of core shell CdSe /CdS/ ZnS QDs is effectively protected from quenching in simulated gastric fluids. In comparison, amphiphilic lipid or polymer coatings provide no protection under similarly acidic conditions. The proton-resistant QDs are found to cause moderate membrane damage to cultured epithelial cells, but PEGylation (PEG grafting) can be used to reduce cellular toxicity and to improve nanoparticle stability.      

An essay on synthetic chemistry of colloidal nanocrystals

The central goal of synthetic chemistry of colloidal nanocrystals at present is to discover functional materials. Such functional materials should help mankind to meet the tough challenges brought by the rapid depletion of natural resources and the significant increase of population with higher and higher living standards. With this thought in mind, this essay discusses the basic guidelines for developing this new branch of synthetic chemistry, including rational synthetic strategies, functional performance, and green chemistry principles.      

Separation of metallic and semiconducting single-walled carbon nanotubes through fluorous chemistry

Separation of metallic from semiconducting single-walled carbon nanotubes has been a major challenge for some time and some previous efforts have resulted in partial success. We have accomplished the separation effectively by employing fluorous chemistry wherein the diazonium salt of 4-heptadecafluorooc tylaniline selectively reacts with the metallic nanotubes present in the mixture of nanotubes. The resulting fluoroderivative was extracted in perfluorohexane leaving the semiconducting nanotubes in the aqueous layer. The products have been characterized by both Raman and electronic absorption spectroscopy. The method avoids the cumbersome centrifugation step required by some other procedures. This article is published with open access at Springerlink.com