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.

Immobilization of Catalysts of Biological Interest on Porous Oxidized Silicon Surfaces

The present paper deals with the immobilization of redox mediators and proteins onto protected porous silicon surfaces to obtain their direct electrochemical reactions and to retain their bioactivities. This paper shows that MP-11 and viologens are able to establish chemical bonds with 3-aminopropyltriethoxylsilane-modified porous silicon surface. The functionalization of the surfaces have been fully characterized by energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS) to examine the immobilization of these mediators onto the solid surface. Amperometric and open circuit potential measurements have shown the direct electron transfer between glucose oxidase and the electrode in the presence of the viologen mediator covalently linked to the 3-aminopropyltriethoxylsilane (APTES)-modified porous silicon surfaces.

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.

Electrochemical Evidence of Strong Electronic Interaction of PtRu on Carbon Nanotubes with High Density of Defects

We show that carbon nanotubes (CNTs) with high density of defects can present a strong electronic interaction with nanoparticles of Pt-Ru with average particle size of 3.5 +/- 0.8 nm. Depending on the Pt-Ru loading on the CNTs, CO and methanol oxidation reactions suggest there is a charge transfer between Pt-Ru that in turn provokes a decrease in the electronic interaction taking place between Ru and Pt in the PtRu alloy. The CO stripping potentials were observed at about 0.65 and 0.5 V for Pt-Ru/CNT electrodes with Pt-Ru loadings of 10 and 20, and 30 wt %, respectively. (C) 2008 The Electrochemical Society. [DOI: 10.1149/1.2990222] All rights reserved.

Composite electrode of carbon nanotubes and vitreous carbon for electron field emission

In this work, the electron field emission behaviour of electrodes formed by carbon nanotubes (CNTs) grown onto monolithic vitreous carbon (VCarbon) substrates with microcavities is presented. Scanning electron microscopy was used to characterize the microstructure of the films. Tungsten probes, stainless steel sphere, and phosphor electrodes were employed in the electron field emission study. The CNT/VCarbon composite represents a route to inexpensive excellent large area electron emission cathodes with fields as low as 2.1 V mu m(-1). In preliminary lifetime tests for a period of about 24 h at an emission current of about 4 mA cm(-2), there is an onset degradation of the emission current of about 28%, which then stabilizes. Electron emission images of the composites show the cavity of the samples act as separate emission sites and predominantly control the emission process. The emission of CNTs/VCarbon was found to be stable for several hours. (c) 2008 American Institute of Physics.

Organic molecule assembled between carbon nanotubes: A highly efficient switch device

We report a highly efficient switch built from an organic molecule assembled between single-wall carbon nanotube electrodes. We theoretically show that changes in the distance between the electrodes alter the molecular conformation within the gap, affecting in a dramatic way the electronic and charge transport properties, with an on/off ratio larger than 300. This opens up the perspective of combining molecular electronics with carbon nanotubes, bringing great possibilities for the design of nanodevices.

Spin filtering and disorder-induced magnetoresistance in carbon nanotubes: Ab initio calculations

Nitrogen-doped carbon nanotubes can provide reactive sites on the porphyrin-like defects. It is well known that many porphyrins have transition-metal atoms, and we have explored transition-metal atoms bonded to those porphyrin-like defects inN-doped carbon nanotubes. The electronic structure and transport are analyzed by means of a combination of density functional theory and recursive Green's function methods. The results determined the heme B-like defect (an iron atom bonded to four nitrogens) is the most stable and has a higher polarization current for a single defect. With randomly positioned heme B defects in nanotubes a few hundred nanometers long, the polarization reaches near 100%, meaning they are effective spin filters. A disorder-induced magnetoresistance effect is also observed in those long nanotubes, and values as high as 20 000% are calculated with nonmagnectic eletrodes.

Transport properties of single vacancies in nanotubes

We present density of states and electronic transport calculations of single vacancies in carbon nanotubes. We confirm that the defect reconstructs into a pentagon and a nonagon, following the removal of a single carbon atom. This leads to the formation of a dangling bond. Finally, we demonstrate that care must be taken when calculating the density of states of impurities in one-dimensional systems in general. Traditional treatments of these systems using periodic boundary conditions leads to the formation of minigaps even in the limit of large unit cells.

First-principles study of the adsorption of atomic and molecular hydrogen on BC(2)N nanotubes

The adsorption of atomic and molecular hydrogen on armchair and zigzag boron carbonitride nanotubes is investigated within the ab initio density functional theory. The adsorption of atomic H on the BC(2)N nanotubes presents properties which are promising for nanoelectronic applications. Depending on the adsorption site for the H, the Fermi energy moves toward the bottom of the conduction band or toward the top of the valence band, leading the system to exhibit donor or acceptor characteristics, respectively. The H(2) molecules are physisorbed on the BC(2)N surface for both chiralities. The binding energies for the H(2) molecules are slightly dependent on the adsorption site, and they are near to the range to work as a hydrogen storage medium.

Nanostructured Films Based on Carbon Nanotubes and Cobalt for the Electrocatalytic Reduction of H(2)O(2)

This paper presents the fabrication of a nanothick Co-modified film electrochemically synthesized on layer-by-layer (LbL) structures made with dendrimer polyamidoamine/carbon nanotubes (PAMAM/CNT), and its electrocatalytic properties toward H(2)O(2) reduction. Scanning electron microscopy indicated the formation of a homogeneous, 14 nm thick Co film. The porous nature of the PAMAM/CNT LbL film allowed the electrolyte access to the bottom of the electrode, generating a homogenous Co electrodeposit. In addition, the nanostructure based on Co-modified PAMAM/CNT LbL exhibited high electrocatalytic activity for H(2)O(2) reduction when compared to the Co-free PAMAM/CNT LbL film, which demonstrates the suitability of the system studied for biosensing. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3602200] All rights reserved.

Strong reduction of V(4+) amount in vanadium oxide/hexadecylamine nanotubes by doping with Co(2+) and Ni(2+) ions: Electron paramagnetic resonance and magnetic studies

In this work we present a complete characterization and magnetic study of vanadium oxide/hexadecylamine nanotubes (VO(x)/Hexa NT's) doped with Co(2)+ and Ni(2+) ions. The morphology of the NT's has been characterized by transmission electron microscopy, while the metallic elements have been quantified by the instrumental neutron activation analysis technique. The static and dynamic magnetic properties were studied by collecting data of magnetization as a function of magnetic field and temperature and by electron paramagnetic resonance. At difference of the majority reports in the literature, we do not observe magnetic dimers in vanadium oxide nanotubes. Also, we observed that the incorporation of metallic ions (Co(2+), S = 3/2 and Ni(2+), S = 1) decreases notably the amount of V(4+) ions in the system, from 14-16% (nondoped case) to 2%-4%, with respect to the total vanadium atoms (fact corroborated by XPS experiments) anyway preserving the tubular nanostructure. The method to decrease the amount of V(4+) in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3580252]

Autocatalysis in the open circuit interaction of alcohol molecules with oxidized Pt surfaces

We studied the open circuit interaction of methanol and ethanol with oxidized platinum electrodes using in situ infrared spectroscopy. For methanol, it was found that formic acid is the main species formed in the initial region of the transient and that the steep decrease of the open circuit potential coincides with an explosive increase in the CO(2) production, which is followed by an increase in the coverage of adsorbed CO. For ethanol, acetaldehyde was the main product detected and only traces of dissolved CO(2) and adsorbed CO were found after the steep potential decay. In both cases, the transients were interpreted in terms of (a) the emergence of sub-surface oxygen in the beginning of the transient, where the oxide content is high, and (b) the autocatalytic production of free platinum sites for lower oxide content during the steep decay of the open circuit potential.

Aging and calorie restriction modulate yeast redox state, oxidized protein removal, and the ubiquitin-proteasome system

The ubiquitin-proteasome system governs the half-life of most cellular proteins. Calorie restriction (CR) extends the maximum life span of a variety of species and prevents oxidized protein accumulation. We studied the effects of CR on the ubiquitin-proteasome system and protein turnover in aging Saccharomyces cerevisiae. CR increased chronological life span as well as proteasome activity compared to control cells. The levels of protein carbonyls, a marker of protein oxidation, and those of polyubiquitinated proteins were modulated by CR. Controls, but not CR cells, exhibited a significant increase in oxidized proteins. In keeping with decreased proteasome activity, polyubiquitinated proteins were increased in young control cells compared to time-matched CR cells, but were profoundly decreased in aged control cells despite decreased proteasomal activity. This finding is related to a decreased polyubiquitination ability due to the impairment of the ubiquitin-activating enzyme in aged control cells, probably related to a more oxidative microenvironment. CR preserves the ubiquitin-proteasome system activity. Overall, we found that aging and CR modulate many aspects of protein modification and turnover. (C) 2011 Elsevier Inc. All rights reserved.

Effect of Simvastatin on the Generation of Autoantibodies Against Oxidized LDL and Progression of Atherosclerosis in Rabbits

Oxidized Low-Density Lipoproteins (oxLDL) and autoantibodies against oxLDL are important in the development of atherosclerotic lesions. Statins are efficacious in the control of dyslipidemia and prevention of atherosclerosis; however, many questions concerning the mechanism of action of such drugs remain unknown. This work investigated the effect of simvastatin on generation of autoantibodies against oxLDL and development of atherosclerosis in rabbits. The animals were divided into three groups: control, hypercholesterolemic, and hypercholesterolemic simvastatin (3.0 mg simvastatin/ kg body weight). Concentrations of autoantibodies against oxLDL were determined on days 0,30 and 60 of the experiment and the atherosclerotic lesions were evaluated at the end of the study. Simvastatin reduced intimal proliferation in the thoracic region, prevented arterial calcification and inhibited the generation of autoantibodies against oxLDL. In conclusion, daily administration of simvastatin slows down atherosclerotic lesion development in rabbits with induced hypercholesterolemia and inhibition on generation of autoantibodies against oxLDL contributes to the cardioprotective effect observed.

Modeling volatile organic compounds (voc`s) adsorption onto cup-stacked carbon nanotubes (cscnt) using the linear driving force model

Modeling volatile organic compounds (voc`s) adsorption onto cup-stacked carbon nanotubes (cscnt) using the linear driving force model. Volatile organic compounds (VOC`s) are an important category of air pollutants and adsorption has been employed in the treatment (or simply concentration) of these compounds. The current study used an ordinary analytical methodology to evaluate the properties of a cup-stacked nanotube (CSCNT), a stacking morphology of truncated conical graphene, with large amounts of open edges on the outer surface and empty central channels. This work used a Carbotrap bearing a cup-stacked structure (composite); for comparison, Carbotrap was used as reference (without the nanotube). The retention and saturation capacities of both adsorbents to each concentration used (1, 5, 20 and 35 ppm of toluene and phenol) were evaluated. The composite performance was greater than Carbotrap; the saturation capacities for the composite was 67% higher than Carbotrap (average values). The Langmuir isotherm model was used to fit equilibrium data for both adsorbents, and a linear driving force model (LDF) was used to quantify intraparticle adsorption kinetics. LDF was suitable to describe the curves.