Cytotoxicity of carboxyl carbon nanotubes on human embryonic lung fibroblast cells and its mechanism

The wide use in various fields and the great potentials in biomedical applications of carbon nanotubes highlight the need to study their toxicity and biocompatibility for recent years. This work aimed to investigate the cytotoxicity of carbon nanotubes on human embryonic lung fibroblast cells and their inter-related affecting factors. Three carboxyl modified carbon nanotubes, short carboxyl single-walled carbon nanotubes (SWCNTs-COOH), short carboxyl double-walled carbon nanotubes (DWCNTs-COOH) and short carboxyl multi-walled carbon nanotubes (MWCNTs-COOH) were chosen as subjects for the evaluation of carbon nanotubes cytotoxity. Different concentrations of carboxyl carbon nanotubes were incubated with human embryonic lung fibroblast (HELF) cells for 48?h, respectively, and the electron microscopy was used to observe the cell growth and morphology. The results showed that MWCNTs-COOH, which had a better dispersion in water was much more cytotoxic than the other two carbon nanotubes. From Cell Counting Kit-8 assay and acridine orange staining, MWCNTs-COOH could inhibit the cell growth and induce cell apoptosis with a dose–effect relationship and oxidative stress may be one of the mechanisms.     

Adsorption of streptavidin onto single-walled carbon nanotubes: application in fluorescent supramolecular nanoassemblies

We report the solubilization of full-length single-walled carbon nanotubes into a physiological buffer by sonication in presence of streptavidin. Transmission electron microscopy showed that the resultant dispersion was enriched of individual/small ropes of nanotubes. By the analysis of the crystal structure of tetrameric streptavidin and of the tryptophan emission of adsorbed proteins we hypothesized that proteins adsorbed onto SWNT sidewalls through their amine functionalities. Our results suggested using streptavidin as an interlinker between carbon nanotubes and semiconducting nanocrystals. We fabricated a supramolecular luminescent nanoassembly composed of individual or small ropes of full-length single-walled carbon nanotubes decorated with streptavidin-conjugated quantum dots. The luminescent nanoassembly was stably dispersed under physiological conditions and was readily visible by optical fluorescent microscopies.     

Critical oxide thickness for efficient single-walled carbon nanotube growth on silicon using thin SiO2 diffusion barriers

The ability to integrate carbon nanotubes, especially single-walled carbon nanotubes, seamlessly onto silicon would expand their range of applications considerably. Though direct integration using chemical vapor deposition is the simplest method, the growth of single-walled carbon nanotubes on bare silicon and on ultrathin oxides is greatly inhibited due to the formation of a noncatalytic silicide. Using X-ray photoelectron spectroscopy, we show that silicide formation occurs on ultrathin oxides due to thermally activated metal diffusion through the oxide. Silicides affect the growth of single-walled nanotubes more than multi-walled nanotubes due to the increased kinetics at the higher single-walled nanotube growth temperature. We demonstrate that nickel and iron catalysts, when deposited on clean silicon or ultrathin silicon dioxide layers, begin to form silicides at relatively low temperatures, and that by 900 degrees C, all of the catalyst has been incorporated into the silicide, rendering it inactive for subsequent single-walled nanotube growth. We further show that a 4-nm silicon dioxide layer is the minimum diffusion barrier thickness that allows for efficient single-walled nanotube growth.     

Single-Walled Carbon Nanotubes for Flexible Electronics and Sensors

This article reviews the use of electronic quality single-walled carbon nanotubes grown via chemical vapor deposition （CVD） approaches at high temperatures as building blocks for fabricating flexible field-effect devices, such as thin-film transistors （TFTs） and chemical sensors. Dry transfer printing technique is developed for forming films of CVD nanotubes on low-temperature plastic substrates. Examples of TFTs with the use of nanotubes and thin dielectrics and hydrogen sensors with the use of nanotubes decorated with palladium nanoparticles are discussed in detail to demonstrate the promising potentiality of single-walled carbon nanotubes for building high performance flexible devices, which can find applications where traditional devices on rigid substrates are not suitable.     

Direct imaging of single-walled carbon nanotubes in cells

The development of single-walled carbon nanotubes for various biomedical applications is an area of great promise. However, the contradictory data on the toxic effects of single-walled carbon nanotubes highlight the need for alternative ways to study their uptake and cytotoxic effects in cells. Single-walled carbon nanotubes have been shown to be acutely toxic in a number of types of cells, but the direct observation of cellular uptake of single-walled carbon nanotubes has not been demonstrated previously due to difficulties in discriminating carbon-based nanotubes from carbon-rich cell structures. Here we use transmission electron microscopy and confocal microscopy to image the translocation of single-walled carbon nanotubes into cells in both stained and unstained human cells. The nanotubes were seen to enter the cytoplasm and localize within the cell nucleus, causing cell mortality in a dose-dependent manner.     

Binder-free manganese oxide/carbon nanomaterials thin film electrode for supercapacitors

A ternary thin film electrode was created by coating manganese oxide onto a network composed of single-walled carbon nanotubes and single-walled carbon nanohorns. The electrode exhibited a porous structure, which is a promising architecture for supercapacitors applications. The maximum specific capacitances of 357 F/g for total electrode at 1 A/g were achieved in 0.1 M Na(2)SO(4) aqueous solution.     

Novel catalysts, room temperature, and the importance of oxygen for the synthesis of single-walled carbon nanotubes

In this letter, we show for the first time the use of metal oxides as catalysts in the synthesis of single-walled carbon nanotubes (SWCNTs) using laser ablation. Further, SWCNTs have been synthesized at low temperature (down to room temperature), where their nucleation cannot be explained via fullerene nucleation. The data point to a nucleation mechanism previously not identified, that places a stable oxidized ring as the root cause for the growth of SWCNTs.     

Analysis of stress responsive genes induced by single-walled carbon nanotubes in BJ Foreskin cells

Nanotechnology is finding its use as a potential technology in consumer products, defense, electronics, and medical applications by exploiting the properties of nanomaterials. Single-walled carbon nanotubes are novel forms of these nanomaterials with potential for large applications. However, the toxicity studies on this material are not explored in detail and therefore limiting its use. It has been earlier reported that single-walled carbon nanotubes induces oxidative stress and also dictates activation of specific signaling pathway in keratinocytes. The present study explores the effect of single-walled carbon nanotubes on stress genes in human BJ Foreskin cells. The results show induction of oxidative stress in BJ Foreskin cells by single-walled carbon nanotubes and increase in stress responsive genes. The genes included inducible genes like HMOX1, HMOX2, and Cyp1B1. In addition we validated increase for four genes by SWCNT, namely ATM, CCNC, DNAJB4, and GADD45A by RT-PCR. Moreover results of the altered stress related genes have been discussed and that partially explains some of the toxic responses induced by single-walled carbon nanotubes.     

A biocompatible chitosan composite containing phosphotungstic acid modified single-walled carbon nanotubes

Surface modification of carbon nanotubes is crucial for the dispersion and interfacial adhesion of carbon nanotubes in polymer composites. Here we present a novel method to construct single-walled carbon nanotube/chitosan composites using phosphotungstic acid as an anchor reagent to modify single-walled carbon nanotubes. The most direct benefit from this method is that this modification is mild but effective: the induced defects on single-walled carbon nanotubes are negligible based on Raman and transmission electron microscopy observations; and homogeneous dispersion of single-walled carbon nanotubes in chitosan matrices and strong binding between single-walled carbon nanotubes and chitosan are achieved. Moreover, according to the results of tetrazolium-based colorimetric assays in vitro, we demonstrate that the produced phosphotungstic-acid-modified single-walled carbon nanotube/chitosan composites have good biocompatibility. Thus, our study provides a feasible route to fabricate biocompatible composites containing single-walled carbon nanotubes for potential application in bone tissue engineering.     

Covalent functionalization of carbon nanotubes through organometallic reduction and electrophilic attack

Organometallic reagents such as butyllithium are known to covalently functionalize the sidewalls of carbon nanotubes. The function grafted corresponds to the organic part of the alkali compound, while one negative charge is transferred to the nanotube for each function. Carbon nanotubes reduced by organolithium compounds were used here as nucleophilic reactive species through these transferred and delocalized charges. Various halogenated electrophiles in excess were reacted with them in anhydrous conditions. The grafting of the corresponding chemical function onto the carbon nanotubes through a Lewis metathetic exchange reaction was demonstrated by chemical, thermal, and spectroscopic analyses. This synthetic route applied successfully to both single-walled and multi-walled nanotubes and to a series of electrophiles. The extent of functionalization was found to depend on stoechiometries used, although a direct correlation could not be obtained.     

A pilot toxicology study of single-walled carbon nanotubes in a small sample of mice

Single-walled carbon nanotubes are currently under evaluation in biomedical applications, including in vivo delivery of drugs, proteins, peptides and nucleic acids (for gene transfer or gene silencing), in vivo tumour imaging and tumour targeting of single-walled carbon nanotubes as an anti-neoplastic treatment. However, concerns about the potential toxicity of single-walled carbon nanotubes have been raised. Here we examine the acute and chronic toxicity of functionalized single-walled carbon nanotubes when injected into the bloodstream of mice. Survival, clinical and laboratory parameters reveal no evidence of toxicity over 4 months. Upon killing, careful necropsy and tissue histology show age-related changes only. Histology and Raman microscopic mapping demonstrate that functionalized single-walled carbon nanotubes persisted within liver and spleen macrophages for 4 months without apparent toxicity. Although this is a preliminary study with a small group of animals, our results encourage further confirmation studies with larger groups of animals.     

A complete scheme for creating predefined networks of individual carbon nanotubes

We describe and demonstrate a method of creating arrays of patterned, individual, single-walled carbon nanotubes, including the spectroscopic mapping of the array. The process consists of creating networks of nanotubes suspended between silicon pillars, which are then transferred onto other substrates by an innovative process of direct stamping. Raman spectroscopy is used to spatially map and assign the specific properties of the suspended network prior to transfer. This method provides a simple and inexpensive means for deriving nanoscale devices utilizing individually assigned carbon nanotubes in a robust and non-surface-specific technique.     

Raman and electrochemical impedance studies of sol-gel titanium oxide and single walled carbon nanotubes composite films

Titanium oxide grown by a sol-gel route on single-walled carbon nanotubes was studied by Raman and Electrochemical Impedance techniques and compared with mixtures obtained by mechanical grinding. In spite of the superior dispersion of single-walled carbon nanotubes bundles in sol-gel composites, the lost of the small-diameter carbon nanotubes in the oxidizing sol-gel bath was inferred from their Raman spectra and the lower capacitive current of the voltammograms in 0.1 M H2SO4. We proposed proton electrosorption as the main charge storage mechanism for sol-gel composites, favoured by the hydroxylation and n-type conductivity of the oxide, while electrodes based on mixtures were dominated by double-layer charging, developing some pseudocapacitance with potential cycling due to the reversible oxidation of carbon nanotubes. Comparsion with TiO2/Carbon Blacks composites shows the effective role of single-walled carbon nanotubes as templates to control the mesoporous nature of sol-gel composite electrodes.     

Characteristics of multi-walled carbon nanotubes and background aerosols by carbon analysis; particle size and oxidation temperature

Novel carbonaceous nanomaterials such as carbon nanotubes and fullerenes have many beneficial characteristics as industrial materials, but exposure to these nanomaterials also poses health risks. As part of an exposure assessment, we characterized the following carbonaceous nanomaterials, using an aerosol carbon monitor: nine samples of multi-walled carbon nanotubes (MWCNTs), a sample of single-walled carbon nanotubes (SWCNTs), a standard sample of diesel exhaust particles (DEPs), and an ambient particulate matter (APM). The amounts of elemental carbon (EC) determined by the monitor coincided with the mass of MWCNTs calibrated by a microbalance. The carbonaceous nanomaterials were oxidized in three steps of oven temperatures (550, 700 and 920 °C) in this method. The portion of oxidized carbon at each temperature depended on the sample characteristic. We used the monitor to analyze the aerosol samples collected in five stages by a Sioutas cascade impactor (SCI), which collects size-segregated airborne particles having aerodynamic diameters from 6.6 μm to less than 0.25 μm. As MWCNTs aggregate/agglomerate easily, the size was of a good parameter to distinguish the MWCNTs from other materials. Two-dimensional mapping by size and oxidized temperature suggested the origin of the carbonaceous aerosol samples. Based on the results, we reanalyzed our previous data obtained at a factory manufacturing MWCNTs. The characteristics of workplace samples by particle size and carbon analysis were similar to those of MWCNT aerosol particles.     

Solvent-free derivatization of oxidized single-walled carbon nanotubes and nanodiamond with aminobenzo-crown ethers

We report on a one-step amide derivatization of two carbon nanomaterials (CNM) containing carboxylic functional groups, which are oxidized single-walled carbon nanotubes (SWNTs) and nanodiamond (ND), with amino-substituted crown ethers, namely, 4′-aminobenzo-15-crown-5 and 4′-aminobenzo-18-crown-6. The functionalization procedure proposed is based on thermal activation of COOH groups instead of traditional chemical activation, is fast and facile, does not require the use of organic solvents and can be considered as ecologically friendly. The nanohybrids of crown ethers with SWNTs and ND were characterized by means of Fourier-transform infrared and Raman spectroscopy, scanning and transmission electron microscopy, as well as thermogravimetric analysis and solubility tests in toluene and propanol. The approach proposed allows for a facile preparation of crown ether-functionalized SWNTs and ND without contamination with other chemical reagents, solvents and detergents, which might be especially important for a broad spectrum of applications ranging from nanoelectronics to nanomedicine.     

A study of carbon-nanotube-based nanoelectromechanical resonators tuned by shear strain

This paper has investigated, using a classical molecular dynamics simulation method based on the Tersoff-Brenner potential, the resonance-frequency changes of single-walled carbon-nanotube resonators originating from the purely mechanical response of single-walled carbon nanotubes. The tension decreased with increasing rotation angle, so the resonance frequencies could be changed by controlling the rotation angles of the single-walled carbon nanotubes. The resonance frequencies decreased with increasing angle, and when the rotation angle was greater than 60°, the changes were marked. For nanotubes of similar length, the bandwidth for the (3, 3) single-walled carbon nanotube was higher than for the (5, 0) single-walled carbon nanotube. Because properties arising from the shear-strain-induced tension response can affect the electromechanical behavior of carbon nanotubes, the shear-strain-induced tension response should be given serious consideration in the application of embedded carbon nanotubes in nanoelectromechanical systems.     

Removal of nickel ions from water by multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were produced by chemical vapor decomposition using acetylene gas in the presence of Ferrocene catalyst at 800 degrees C, and then oxidized with concentrated nitric acid at 150 degrees C. Both (as-produced and oxidized) CNTs were characterized by TEM, Boehm titration, N2-BET and cation exchange capacity techniques. The adsorption capacity for nickel ions from aqueous solutions increased significantly onto the surface of the oxidized CNTs compared to that on the as-produced CNTs. The effects of adsorption time, solution pH and initial nickel ions concentrations on the adsorption uptake of Ni2+ for both the as-produced and oxidized CNTs were investigated at room temperature. Both Langmuir and Freundlich isotherm models match the experimental data very well. According to the Langmuir model the maximum nickel ions adsorption uptake onto the as-produced and oxidized CNTs were determined as 18.083 and 49.261 mg/g, respectively. Our results showed that CNTs can be used as an effective Ni2+ adsorbent due to the high adsorption capacity as well as the short adsorption time needed to achieve equilibrium.     

Controlled multistep purification of single-walled carbon nanotubes

A controlled and scalable multistep purification method has been developed to remove iron impurity and nonnanotube carbon materials from raw single-walled carbon nanotubes (SWNTs) produced in the HiPco (high-pressure CO) process. In this study, iron nanoparticles, coated by carbon, are exposed and oxidized by multiple step oxidation at increasing temperatures. To avoid catalytic oxidation by iron oxide of carbon nanotubes, the exposed and oxidized iron oxide is deactivated by reaction with C(2)H(2)F(4) or SF(6). The iron fluorides are removed by a Soxhlet extraction with a 6 M HCl solution. The purity and quality of each sample were determined by thermogravimetric analysis (TGA), Raman spectrometry, ultraviolet-visible-near-IR (UV-vis-near-IR) spectrometry, fluorescence spectrometry, and transmission electron microscope (TEM) spectroscopy. The purity and yield of SWNTs are improved due to reduced catalytic activity of the iron oxide. Greater iron oxide removal also resulted from oxidation at higher temperatures.     

Transition of single-walled carbon nanotubes from metallic to semiconducting in field-effect transistors by hydrogen plasma treatment

We report hydrogen plasma treatment results on converting the metallic single-walled carbon nanotubes to semiconducting single-walled carbon nanotubes. We found that the as-grown single-walled carbon nanotubes (SWNTs) can be sorted as three groups which behave as metallic, as-metallic, and semiconducting SWNTs. These three groups have different changes under hydrogen plasma treatment and successive annealing process. The SWNTs can be easily hydrogenated in the hydrogen plasma environment and the as-metallic SWNTs can be transformed to semiconducting SWNTs. The successive annealing process can break the C-H bond, so the conversion is reversible.     

Selection of carbon nanotubes with specific chiralities using helical assemblies of flavin mononucleotide

The chirality of single-walled carbon nanotubes affects many of their physical and electronic properties. Current production methods result in nanotubes of mixed chiralities, so facile extraction of specific chiralities of single-walled carbon nanotubes is an important step in their effective utilization. Here we show that the flavin mononucleotide, a common redox cofactor, wraps around single-walled carbon nanotubes in a helical pattern that imparts efficient individualization and chirality selection. The cooperative hydrogen bonding between adjacent flavin moieties results in the formation of a helical ribbon, which organizes around single-walled carbon nanotubes through concentric pi-pi interactions between the flavin mononucleotide and the underlying graphene wall. The strength of the helical flavin mononucleotide assembly is strongly dependent on nanotube chirality. In the presence of a surfactant, the flavin mononucleotide assembly is disrupted and replaced without precipitation by a surfactant micelle. The significantly higher affinity of the flavin mononucleotide assembly for (8,6)-single-walled carbon nanotubes results in an 85% chirality enrichment from a nanotube sample with broad diameter distribution.