Probing the Influence of Amino Acids on Photoluminescence from Carbon Nanotubes Suspended with DNA

The quantitative analysis of amino acid levels in the human organism is required for the early clinical diagnosis of a variety of diseases. In this work the influence of 13 amino acid doping on the photoluminescence (PL) from the semiconducting single-walled carbon nanotubes (SWNTs) suspended with single-stranded DNA (ssDNA) in water has been studied. Amino acid doping leads to the PL enhancement and the strongest increase was found after cysteine doping of the nanotube suspension while addition of other amino acids yielded the significantly smaller effect. The emphasis of cysteine molecules is attributed to presence of the reactive thiol group that turns cysteine into reducing agent that passivates the p-defects on the nanotube sidewall and increases the PL intensity. The reasons of PL enhancement after doping with other amino acids are discussed. The response of nanotube PL to cysteine addition depends on the nanotube aqueous suspension preparation with tip or bath sonication treatment. The enhancement of the emission from different nanotube species after cysteine doping was analyzed too. It was shown that the increase of the carbon nanotube PL at addition of cysteine allows successful monitoring of the cysteine concentration in aqueous solution in the range of 50–1000 μM.     

Interaction of fragmented double-stranded DNA with carbon nanotubes in aqueous solution

Aqueous suspensions of ultrasonically fragmented double-stranded (fds-) DNA and single-walled carbon nanotubes (SWNTs) have been investigated by UV- and IR-absorption, NIR-emission and Raman spectroscopy. According to gel-electrophoresis, the lengths of the polymer fragments were 100–500 base pairs. Analysis of IR and UV data indicates the presence of both double-stranded (ds) and single-stranded (ss)-regions in the fragments. SWNT complex with DNA was revealed by NIR-emission and Raman spectroscopy. It turned out that fds-DNA is less efficient in holding nanotubes in the aqueous solution than ss-DNA. From the UV-data, the character of the helix-coil transition is seen to be like that for fds-DNA off and on nanotube, however, DNA thermostability increased in this latter case. The effective charge density on the DNA sugar-phosphate backbone of the fds-DNA:SWNT hybrid was less than that of DNA alone. Spectroscopic data can be explained by a model in which the formation of hybrids starts due to the interaction between untwisted ss-regions of DNA and the nanotube: the strands wrap on the tube and thus create an ‘anchor’ for the whole polymer. The ds-part of the polymer is located close to the nanotube.     

Efficient water-window X-ray pulse generation from femtosecond-laser-produced plasma by using a carbon nanotube target

We adopt a multiwalled carbon nanotube target to increase the efficiency of water-window and [_]K X-ray pulse conversion from femtosecond-laser-produced plasma. The diameter of the carbon nanotubes is around 30 nm and the length is about 12-m. The X-ray fluence enhancement in the water-window region is sevenfold compared with a conventional carbon plate target. Further enhancement can be expected by optimizing the size of the carbon nanotubes. Soft X-ray pulse duration is 26 ps. It is also found that the [_]K X-ray line emission from the Si substrate of the carbon nanotube target was enhanced. This result indicates that by covering various solid materials with carbon nanotubes, enhanced short [_]K X-ray pulses with the corresponding wavelength can be obtained. These results show that carbon nanotubes are very attractive as a target for femtosecond laser-produced-plasma X-ray sources in single-shot X-ray microscopy and time-resolved X-ray diffraction. PACS 52.50.Jm; 52.38.-r; 52.38.Ph; 68.37.Yz; 78.67.-n     

Pulsed evaporator of an electrodynamic disperse suspension of particles

We consider the technique for obtaining electrodynamic disperse suspension of metal (Al, W, Cu) and dielectric (semiconductor) particles (SiO₂, Al₂O₃, CuO, Cu₂O) and its evaporation with the help of a diffusive electric discharge. The time dependences of current and integrated luminescence intensity in a pulsed electric discharge in a tube containing a film of a substance (Cu) of the electrodynamic disperse suspension are measured.     

Electrocatalytic Oxidation of Nucleic Acids at Electrodes Modified with Nylon and Nitrocellulose Membranes

Electrocatalytic oxidation of guanine in DNA was detected at tin-doped indium oxide electrodes modified with nylon and nitrocellulose polymers. The catalytic oxidation occurs via oxidation at the electrode of the complex Ru(bpy) ₃ ²⁺ to the 3+ state, which is then reduced back to the 2+ state by guanine in DNA (bpy = 2,2-bipyridine). Catalysis is observed as a current enhancement in the cyclic voltammogram of Ru(bpy) ₃ ²⁺ when DNA is immobilized in the film. As seen in solution, the catalytic enhancement in the nitrocellulose film is lower at 800 mM NaCl than without added salt because electrostatic binding of the Ru(bpy) ₃ ²⁺ to the DNA at low salt increases the catalytic rate constant. The cyclic voltammogram of Os(bpy) ₃ ²⁺ , which does not oxidize guanine, exhibits less current in the presence of DNA because binding to the immobilized DNA precludes communication of the metal complex with the electrode. Electrodes modified with poly[C] gave no enhancement; however, catalytic current was observed upon hybridization to poly[G]. Exposure of the poly[C] electrode to random single-stranded DNA gave no catalytic current. Glassy carbon electrodes modified with the membranes behaved in a manner similar to that of the metal oxide electrodes.     

Raman‐induced Kerr effect spectroscopy of single‐wall carbon nanotubes aqueous suspensions in the range 0.1–10 and 100–250 cm−1

Here, we study a low (less than 0.1 µg/ml) concentration aqueous suspension of single‐wall carbon nanotubes (SWNTs) by Raman‐induced Kerr effect spectroscopy (RIKES) in the spectral bands 0.1–10 and 100–250 cm⁻¹. This method is capable of carrying out direct investigation of SWNT hydration layers. A comparison of RIKES spectra of SWNT aqueous suspension and that of milli‐Q water shows a considerable growth in the intensity of low wavenumber Raman modes. These modes in the 0.1–10 cm⁻¹ range are attributed to the rotational transitions of H₂O₂ and H₂O molecules. We explain the observed intensity increase as due to the production of hydrogen peroxide and the formation of a low‐density depletion layer on the water–nanotube interface. A few SWNT radial breathing modes (RBM)are observed (ω_RBM = 118.5, 164.7 and 233.5 cm⁻¹) in aqueous suspension, which allows us to estimate the SWNT diameters (∼2.0, 1.5, and 1 nm, respectively). Copyright © 2011 John Wiley & Sons, Ltd.     

Nonchiral BN Haeckelite nanotubes

A new class of boron-nitrogen (BN) nanotubes composed of tetragons, pentagons, hexagons, heptagons, and octagons is considered. By analogy with carbon nanotubes of the same topological structure, these nanotubes were called Haeckelites. The geometry, energetics, and electronic properties were studied in detail for two regular mutual arrangements of the polygons. It was found that Haeckelite nanotubes are dielectrics with the energy gap E_g = 3.24–4.09 eV. As the nanotube diameter increases, the energy gap E_g decreases, approaching the value for the corresponding planar Haeckelite layer. The ground-state energy of the Haeckelite BN nanotubes is 0.3 eV/atom higher than that of well-known hexagonal BN nanotubes.     

Effects of catalysts on the internal structures of carbon nanotubes and corresponding electron field-emission properties

Using a chemical vapor deposition (CVD) method, multi-walled carbon nanotubes with uniform diameters of approximately 10 nm were synthesized on silicon substrates by the decomposition of acetylene using Fe, Co and Ni as the catalysts. Catalyst effects on the internal structures of the carbon nanotubes were evident in the Fe, Co and Ni catalyzed nanotubes. Although these nanotubes demonstrated similar morphologies, due to the variety of internal structures, the nanotubes synthesized from different catalysts demonstrated various electron field-emission characteristics including turn-on field, threshold field and field enhancement factor. Compared with carbon nanotubes from Ni catalyst, nanotubes from Fe and Co with the same diameters have better field-emission properties. Graphite layers in nanotubes from Fe and Co are much straighter and more parallel to the tube axis with fewer defects. For instance, the turn-on field and threshold field for nanotubes from Ni are 5 V/m and 9 V/m, respectively. These electric fields are much higher than those for nanotubes from Fe, which are 0.35 V/m and 2.8 V/m, respectively. This could be due to the effect of catalysts on the work function of nanotubes, since the catalyst particle usually terminates the free end of the nanotube, and the influence of internal structure on electron transportation along the nanotube axis. Therefore, this study suggests that besides a small diameter, good graphitization (crystallization) is an important prerequisite for a good carbon nanotube emitter. PACS 79.70.+q; 68.37.Lp; 81.07.De     

Specific features of low-frequency vibrational dynamics and low-temperature heat capacity of double-walled carbon nanotubes

A continuous model has been constructed for low-frequency dynamics of a double-walled carbon nanotube. The formation of the low-frequency part of the phonon spectrum of a double-walled nanotube from phonon spectra of its constituent single-walled nanotubes has been considered in the framework of the proposed approach. The influence of the environment on the phonon spectrum of a single double-walled carbon nanotube has been analyzed. A combined method has been proposed for estimating the coefficients of the van der Waals interaction between the walls of the nanotube from the spectroscopic data and the known values of the elastic moduli of graphite. The low-temperature specific heat has been calculated for doublewalled carbon nanotubes, which in the field of applicability of the model (T < 35 K) is substantially less than the sum of specific heats of two individual single-walled nanotubes forming it.     

First principles study of electronic structure and carrier mobility in β-armchair antimony nanotubes

In recent work, we have investigated the structure and stability of β-armchair antimony nanotubes (SbNT) using density functional theory (DFT). We studied electronic properties like electronic band structure, density of states (DOS) and mechanical properties such as stiffness constant, Poisson's ratio, and mechanical strength for these nanotubes. We found that these nanotubes are energetically stable and semiconducting in nature with band-gap varying between 1.32 eV to 1.47 eV. We have also calculated effective mass and carrier mobility for these nanotubes. Furthermore, stiffness constant and mechanical strength of these nanotubes increases with increase in diameter. While, $(4,4)$ nanotube shows anomalously higher strength than other nanotubes. The results of effective mass and carrier mobility for these nanotubes shows that electrons have higher effective mass and therefore lesser mobility than holes for most of the nanotubes. Our calculations show that β-armchair antimony nanotubes (SbNT) could be use in nano-electronics.     

Insertion of Platinum Oxide into Nanotube of Sodium Titanate

A new method for preparing PtO _x -inserted sodium titanate nanotube was reported. By suction of H₂PtCl₆ ethanol solution into the nanotubes first and annealed at 653 K for 3 h afterwards, Pt nanoparticles formed in the nanotubes. The size of Pt nanoparticles is controlled by the dimensions of nanotubes. Some of them are spherical, some are nanorods. XPS and XRD results revealed that during annealing the following complex reaction happened:

$Na_1.1H_0.9Ti_2O_4(OH)_2 + H_2PtCl_6+ O_2 \rightarrow TiO_2(anatase) + PtO_x(x=1,2)+NaCl+ HCl\!\uparrow\!\!.$

     

Characterization of TiO<Subscript>2</Subscript> nanoparticle suspensions for electrophoretic deposition

The rheology of suspensions is critically important for the successful achievement of defect-free TiO₂ deposits by electrophoretic deposition (EPD). The rheological behaviour of TiO₂ nanoparticle suspensions in acetylacetone with and without iodine was investigated over a broad solid-concentration range (0.3–2.5 wt.%) and at different shear rates ( = 10–250 s⁻¹). The influence of these parameters on the quality of TiO₂ films obtained by EPD on stainless steel substrates was assessed. The pure solvent and the 1 wt.% TiO₂ nanoparticles suspension without iodine exhibited shear-thickening flow behaviour. For other concentrations, the suspensions showed shear-thinning behaviour followed by an apparent shear-thickening effect at a critical shear rate (100 s⁻¹). For the suspension with 1 wt.% TiO₂ containing iodine, a shear-thickening flow behaviour was observed over the whole shear rate range investigated. The maximum solids fraction (ϕ_m) was experimentally determined from a linear relationship between solid concentration and viscosity. The estimated value was ϕ_m = 7.94 wt.% for this system. Using a suspension with 1 wt.% concentration, good-quality TiO₂ deposits on stainless steel planar substrates were obtained by EPD at constant voltage condition. The influence of pH on suspension stability was determined in the range pH = 1–9, being pH ≈ 5 the optimal value for this system in terms of EPD results.     

Carbon nanotube bundles and thin layers probed by micro-Raman spectroscopy

Raman spectra of single-wall carbon nanotubes (CNTs) either in the form of micrometer sized bundles or thin layers prepared by dilution and sonication of powders have been compared. We have been able to collect the Raman spectrum of nanotube bundles that are not in touch with the substrate, and therefore not affected by interactions with the substrate surface. This spectrum resulted to be similar to that of the precursor nanotube powders, whereas relevant changes in the Raman spectrum are detected when the diluted powders form very thin layers on either metallic or insulating surfaces, as probed by confocal microraman imaging on well defined areas of the CNTs layers. In the case of thin layers, the intensity of the Raman D band, detected between 1 320 and 1 340 cm^-1 and ascribed to disorder effects, is strongly enhanced. This enhancement occurs independently on the kind of substrate. Received 2 September 2002 Published online 4 February 2003 RID="a" ID="a"e-mail: sangalet@dmf.bs.unicatt.it     

Does the excitation of a plasmon resonance induce a strong chemical enhancement in SERS? On the relation between chemical interface damping and chemical enhancement in SERS

In this contribution, a fundamental new approach is made to explain high enhancement factors in surface-enhanced Raman spectroscopy (SERS) on the basis of chemical enhancement. Usually, high SERS enhancement factors are explained by electromagnetic enhancements due to the excitation of localized surface plasmon resonances and strong near field dipole–dipole coupling. However, very often the corresponding SERS spectra show clear signatures of a chemical enhancement. I propose that this contradiction is easily solved by taking chemical interface damping of the plasmon resonance into account. Chemical interface damping is caused by an electron transfer from the metallic structure into an adsorbate. However, this mechanism is also the basis for chemical enhancement in SERS, i.e., an electron transfers in the lowest unoccupied molecular orbital of the molecule and back to the metal. Hence, if a molecule causes a strong chemical interface damping, the excitation of plasmons is still the key factor for the SERS enhancement. But the reason for this enhancement might be not solely due to electromagnetic fields rather than by a chemical enhancement due to electron transfers from the metal to the molecules.     

Transparent carbon nanotube-based driving electrodes for liquid crystal dispersion display devices

We report the fabrication of transparent rigid or flexible liquid crystal dispersion displays driven by electrodes prepared from coating inert substrates with stable aqueous suspensions of single-walled carbon nanotubes (SWNTs) or multiple-walled carbon nanotubes (MWNTs). The SWNT-coated electrodes exhibit a dense nanotube network with a sheet resistivity ( 25 k) about one decade lower than that of their MWNT counterparts. The electro-optical performance of the SWNT-based devices is at least equivalent to that of an indium tin oxide-based display, whereas those driven by MWNT electrodes operate at slightly higher threshold and saturation voltages. The novel, flexible display devices can be repeatedly bent without any noticeable loss of physical characteristics. PACS 42.79.Kr; 61.46.+w; 81.07.De     

Cation exchange dynamics confined in a synthetic clay mineral

In this work we report X-Ray Diffraction (XRD) and Energy Dispersive X-Ray Spectroscopy (EDS) measurements to investigate the confined cation exchange process in saline aqueous suspensions of a synthetic clay mineral from Lithium-Fluorohectorite to Nickel-Fluorohectorite, as well as the reverse process from Nickel-Fluorohectorite to Lithium-Fluorohectorite and also from Lithium-Fluorohectorite to Sodium-Fluorohectorite. The dynamics of these cation exchanges was followed and it was observed that these processes can be faster than 1 minute. The results are compared to the observations on samples prepared by cation exchange procedures for which the exchange process was performed on the time-scale of months.     

A new class of MO<Subscript>2</Subscript> dioxide nanotubes (M=Si,Ge, Sn,Pb) composed of “square” lattices of atoms: Their structure and energy characteristics

New dioxide nanotubes are described. These nanotubes are rolled up of a “square” lattice of atoms differing from the conventional hexagonal lattice isoelectronic to graphite. The dependence of the strain energy on the nanotube diameter D departs from a 1/D² behavior, and the optimum shape at the same diameter corresponds to “zigzag” tubelenes. Two-layer nanotubes consisting of an MO₂ layer bonded to a carbon nanotube (CNT) are characterized by a considerably lower strain energy, which points to the possibility of using CNTs as a template for the synthesis of such MO₂ nanotubes.     

Effect of hydrogen on the growth and morphology of single wall carbon nanotubes synthesized on a FeMo/MgO catalytic system

Single wall carbon nanotubes were synthesized from thermal pyrolysis of methane on a FeMo/MgO catalyst by radio frequency catalytic chemical vapor deposition (RF-CVD) using argon as a carrier gas. Controlled amounts of hydrogen (H₂/CH₄=0-1 v/v) were introduced in separate experiments along with the carbon source. The properties and morphology of the synthesized single wall carbon nanotubes were monitored by transmission electron microscopy, Raman scattering, and thermogravimetric analysis. The nanotubes with the highest crystallinity were obtained with H₂/CH₄=0.6. By monitoring the Radial Breathing Modes present in the Raman spectra of the single-wall carbon nanotube samples, the variation of the structural and morphological properties of the carbon nanotubes with the flow level of hydrogen, reflect changes of the catalyst systems induced by the presence of hydrogen.     

Ru‐doped TiO2 nanotubes: Improved performance in dye‐sensitized solar cells

In the present work we use a series of Ti–Ru alloys, with minor amounts of Ru (0.01, 0.02, 0.05 and 0.2 at%) to grow anodic self‐organized Ru‐doped TiO₂ nanotube layers. When used in dye‐sensitized solar cells (DSSCs), the nanotube layers with an optimum amount of Ru (0.02 at% Ru in the alloy) show a considerable increase in solar cell efficiency (η = 5.2%) under AM1.5 (100 mW/cm²) conditions compared with non‐doped TiO₂ nanotubes (η = 4.3%).

     

Electrooptic properties of aqueous suspensions of nanotubes based on magnesium hydrosilicate

Nanotubes suspended in a fluid medium have been investigated by the electrooptic method. This method is based on measuring the relative changes in the intensity of light transmitted through a suspension of nanotubes with application of an external electric field. The electrooptic effect (difference in these changes for transmitted light plane-polarized along the external field and perpendicularly to it) is analyzed. For aqueous suspensions of Mg₃Si₂O₅(OH)₄ nanotubes, the field and relaxation dependences of this effect are investigated. An analysis of the results obtained suggests that nanotubes, even when their concentration in water is low, form strong stable aggregates, which, however, can be elongated and enlarged under long-term action of strong rf fields.