Single-wall carbon nanotubes modified with organic dyes: Synthesis, characterization and potential cytotoxic effects

This work deals with the covalent functionalization of single-wall carbon nanotubes (SWNTs) with phenosafranine (PS) and Nile Blue (NB) dyes. These dyes can act as photosensitizers in energy and electron transfer reactions, with a potential to be applied in photodynamic therapy. Several changes in the characteristic Raman vibrational features of the dyes suggest that a covalent modification of the nanotubes with the organic dyes occurs. Specifically, the vibrational modes assigned to the NH(2) moieties of the dyes are seen to disappear in the SWNT-dye nanocomposites, corroborating the bond formation between amine groups in the dyes and carboxyl groups in the oxidized nanotubes. The X-ray absorption (XANES) data also show, that the intense band at 398.6 eV attributed to 1s -> 2p pi* transition of the nitrogen of the aromatic PS ring, is shifted due to the bonding with the carbonic structure of the SWNTs. The cytotoxicity data of dyes-modified SWNT composites in the presence and absence of light shows that the SWNT-NB (4 mu g/mL) composite presents a good photodynamic effect, namely a low toxicity in the dark, higher toxicity in the presence of light and also a reduced dye photobleaching by auto-oxidation. (C) 2010 Elsevier B.V. All rights reserved.

Charge-transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E(laser) = 1.17 eV suggest that a charge-transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright (C) 2010 John Wiley & Sons, Ltd.

Single wall carbon nanotubes loaded with Pd and NiPd nanoparticles for H2 sensing at room temperature

Pd and bimetallic Ni50Pd50 nanoparticles protected by polyvinylpyrrolidone (PVP) have been synthesized by the reduction-by-solvent method and deposited on single wall carbon nanotubes (SWCNTs) to be tested as H2 sensors. The SWCNTs were deposited by drop casting from different suspensions. The Pd nanoparticles-based sensors show a very reproducible performance with good sensitivity and very low response times (few seconds) for different H2 concentrations, ranging from 0.2% to 5% vol. H2 in air at atmospheric pressure. The influence of the metal nanoparticle composition, the quality of SWCNTs suspension and the metal loading have been studied, observing that all these parameters play an important role in the H2 sensor performance. Evidence for water formation during the H2 detection on Pd nanoparticles has been found, and its repercussion on the behaviour of the assembled sensors is discussed. The sensor preparation procedure detailed in this work has proven to be simple and reproducible to prepare cost-effective and highly efficient H2 sensors that perform very well under real application conditions.

Single-wall carbon nanotube interactions with copper-oxamato building block of molecule-based magnets probed by resonance Raman spectroscopy

The electronic interactions between the [Cu(opba)]2- anions (where opba is orthophenylenebis (oxamato)) and single-wall carbon nanotubes (SWCNTs) were investigated by resonance Raman spectroscopy. The opba can form molecular magnets, and the interactions of opba with SWCNTs can produce materials with very different magnetic/electronic properties. It is observed that the electronic interaction shows a dependence on the SWCNT diameter independent of whether they are metallic or semiconducting, although the interaction is stronger for metallic tubes. The interaction also is dependent on the amount of complex that is probably adsorbed on the carbon surface of the SWCNTs. Some charge transfer can be also occurring between the metallic complex and the SWCNTs. Copyright (c) 2012 John Wiley & Sons, Ltd.

Electrochemical behaviour of different redox probes on single wall carbon nanotube buckypaper-modified electrodes

In the present work, the electrochemical properties of single-walled carbon nanotube buckypapers (BPs) were examined in terms of carbon nanotubes nature and preparation conditions. The performance of the different free-standing single wall carbon nanotube sheets was evaluated via cyclic voltammetry of several redox probes in aqueous electrolyte. Significant differences are observed in the electron transfer kinetics of the buckypaper-modified electrodes for both the outer- and inner-sphere redox systems. These differences can be ascribed to the nature of the carbon nanotubes (nanotube diameter, chirality and aspect ratio), surface oxidation degree and type of functionalities. In the case of dopamine, ferrocene/ferrocenium, and quinone/hydroquinone redox systems the voltammetric response should be thought as a complex contribution of different tips and sidewall domains which act as mediators for the electron transfer between the adsorbate species and the molecules in solution. In the other redox systems only nanotube ends are active sites for the electron transfer. It is also interesting to point out that a higher electroactive surface area not always lead to an improvement in the electron transfer rate of various redox systems. In addition, the current densities produced by the redox reactions studied here are high enough to ensure a proper electrochemical signal, which enables the use of BPs in sensing devices.

Comparisons of diffusive and viscous contributions to transport coefficients of light gases in single-walled carbon nanotubes

We examine here the relative importance of different contributions to transport of light gases in single walled carbon nanotubes, using methane and hydrogen as examples. Transport coefficients at 298 K are determined using molecular dynamics simulation with atomistic models of the nanotube wall, from which the diffusive and viscous contributions are resolved using a recent approach that provides an explicit expression for the latter. We also exploit an exact theory for the transport of Lennard-Jones fluids at low density considering diffuse reflection at the tube wall, thereby permitting the estimation of Maxwell coefficients for the wall reflection. It is found that reflection from the carbon nanotube wall is nearly specular, as a result of which slip flow dominates, and the viscous contribution is small in comparison, even for a tube as large as 8.1 nm in diameter. The reflection coefficient for hydrogen is 3-6 times as large as that for methane in tubes of 1.36 nm diameter, indicating less specular reflection for hydrogen and greater sensitivity to atomic detail of the surface. This reconciles results showing that transport coefficients for hydrogen and methane, obtained in simulation, are comparable in tubes of this size. With increase in adsorbate density, the reflection coefficient increases, suggesting that adsorbate interactions near the wall serve to roughen the local potential energy landscape perceived by fluid molecules.

Enhancement of hydrogen physisorption on single-walled carbon nanotubes resulting from defects created by carbon bombardment

The defect effect on hydrogen adsorption on single-walled carbon nanotubes (SWNTs) has been studied by using extensive molecular dynamics simulations and density functional theory (DFT) calculations. It indicates that the defects created on the exterior wall of the SWNTs by bombarding the tube wall with carbon atoms and C-2 dimers at a collision energy of 20 eV can enhance the hydrogen adsorption potential of the SWNTs substantially. The average adsorption energy for a H-2 molecule adsorbed on the exterior wall of a defected (10,10) SWNT is similar to 150 meV, while that for a H-2 molecule adsorbed on the exterior wall of a perfect (10,10) SWNT is similar to 104 meV. The H-2 sticking coefficient is very sensitive to temperature, and has a maximum value around 70 to 90 K. The electron density contours, the local density of states, and the electron transfers obtained from the DFT calculations clearly indicate that the H-2 molecules are all physisorbed on the SWNTs. At temperatures above 200 K, most of the H-2 molecules adsorbed on the perfect SWNT are soon desorbed, but the H-2 molecules can still remain on the defected SWNTs at 300 K. The detailed processes of H-2 molecules adsorbing on and desorbing from the (10,10) SWNTs are demonstrated.

RuSe Electrocatalysts and Single Wall Carbon Nanohorns Supports for the Oxygen Reduction Reaction

Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.

Label-free Detection of Microcystin-LR in Waters Using Real-Time Potentiometric Biosensors Based on Single-Walled Carbon Nanotubes Imprinted Polymers

Microcystin-LR (MC-LR) is a dangerous toxin found in environmental waters, quantified by high performance liquid chromatography and/or enzyme-linked immunosorbent assays. Quick, low cost and on-site analysis is thus required to ensure human safety and wide screening programs. This work proposes label-free potentiometric sensors made of solid-contact electrodes coated with a surface imprinted polymer on the surface of Multi-Walled Carbon NanoTubes (CNTs) incorporated in a polyvinyl chloride membrane. The imprinting effect was checked by using non-imprinted materials. The MC-LR sensitive sensors were evaluated, characterized and applied successfully in spiked environmental waters. The presented method offered the advantages of low cost, portability, easy operation and suitability for adaptation to flow methods.

Effects of polymer-coated multi-wall carbon nanotubes on mouse RAW 264.7 macrophages

Surface characteristics (area, chemical reactivity) play an important role in cell response to nanomaterials. The aim of this study was to evaluate the oxidative and inflammatory effects of multi−wall carbon nanotubes (MWCNT) uncoated (P0) or coated with carboxylic polyacid or polystyrene polybutadiene polymetacrylate of methyl polymers (P1 and P2 respectively) on murine macrophages (RAW 264.7 cell line). Carbon black nanoparticles (CB, diameter 95 nm) and crocidolite fibers (diameter: 80 nm, length: < 10 μm) were used as controls. Surface functional groups present on MWCNTs were analyzed by Knudsen flow reactor. The amount of acidic sites was P1> P0> P2, for basic sites was P0> P1>> P2 and for oxidizable sites was P0> P2> P1. In contact with cells, P2 formed smaller aggregates than P0 and P1, which were of similar size. Optical microscopy showed the formation of vacuoles after exposure only to P0, P1 and crocidolite. Incubation of cells with P0, P1 and crocidolite fibers induced a significant and similar decrease in metabolic activity, whereas P2 and CB had no effect. Cell number and membrane permeability were unmodified by incubation with the different particles. Incubation of macrophages with P0, P1 and crocidolite induced a dose− and time−dependent increase in mRNA expression of oxidative stress marker (HO−1, GPX1) and inflammatory mediators (TNF−a, MIP−2). No such responses were observed with P2 and CB. In conclusion, MWCNT coated with a carboxylic polyacid polymer exerted similar oxidative and inflammatory effects to uncoated MWCNT. By contrast, no such effects were observed with MWCNT coated with a polystyrene−based polymer. This kind of coating could be useful to decrease MWCNT toxicity.

Single-walled carbon nanotubes functionalized with sodium hyaluronate enhance bone mineralization

The aim of this study was to evaluate the effects of sodium hyaluronate (HY), single-walled carbon nanotubes (SWCNTs) and HY-functionalized SWCNTs (HY-SWCNTs) on the behavior of primary osteoblasts, as well as to investigate the deposition of inorganic crystals on titanium surfaces coated with these biocomposites. Primary osteoblasts were obtained from the calvarial bones of male newborn Wistar rats (5 rats for each cell extraction). We assessed cell viability using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide assay and by double-staining with propidium iodide and Hoechst. We also assessed the formation of mineralized bone nodules by von Kossa staining, the mRNA expression of bone repair proteins, and the deposition of inorganic crystals on titanium surfaces coated with HY, SWCNTs, or HY-SWCNTs. The results showed that treatment with these biocomposites did not alter the viability of primary osteoblasts. Furthermore, deposition of mineralized bone nodules was significantly increased by cells treated with HY and HY-SWCNTs. This can be partly explained by an increase in the mRNA expression of type I and III collagen, osteocalcin, and bone morphogenetic proteins 2 and 4. Additionally, the titanium surface treated with HY-SWCNTs showed a significant increase in the deposition of inorganic crystals. Thus, our data indicate that HY, SWCNTs, and HY-SWCNTs are potentially useful for the development of new strategies for bone tissue engineering.

Structure of single-wall peptide nanotubes: in situ flow aligning X-ray diffraction

The structure of single wall peptide nanotubes is presented for the model surfactant-like peptide A6K. Capillary flow alignment of a sample in the nematic phase at high concentration in water leads to oriented X-ray diffraction patterns. Analysis of these, accompanied by molecular dynamics simulations, suggests the favourable self-assembly of antiparallel peptide dimers into beta-sheet ribbons that wrap helically to form the nanotube wall.

Electronic transport properties of ascorbic acid and nicotinamide adsorbed on single-walled carbon nanotubes

Ab initio simulations of carbon nanotubes interacting with ascorbic acid and nicotinamide are reported. The electronic transport properties of these systems are studied using a combination of density functional theory and non-equilibrium Green`s functions methods. The adsorptions of both molecules are observed to depend strongly on their functionalization. The interaction through the appropriate functionalized species modifies the structural and electronic properties of the original system, resulting in a chemisorption regime. Changes in the electronic transport properties are also observed, with reductions on the total electronic transmission probabilities. Nevertheless, when the molecules interact through the pristine form, a physisorption interaction is observed with insignificant structural and electronic transport changes. (c) 2011 Elsevier B.V. All rights reserved.

Tight-binding model for carbon nanotubes from ab initio calculations

Here we present a parametrized tight-binding (TB) model to calculate the band structure of single-wall carbon nanotubes (SWNTs). On the basis of ab initio calculations we fit the band structure of nanotubes of different radii with results obtained with an orthogonal TB model to third neighbors, which includes the effects of orbital hybridization by means of a reduced set of parameters. The functional form for the dependence of these parameters on the radius of the tubes can be used to interpolate appropriate TB parameters for different SWNTs and to study the effects of curvature on their electronic properties. Additionally, we have shown that the model gives an appropriate description of the optical spectra of SWNTs, which can be useful for a proper assignation of SWNTs` specific chirality from optical absorption experiments.