Facile deposition of [60]fullerene and carbon nanotubes on ITO electrode by electrochemical oxidative polymerization of ethylenedioxythiophene

It was found that [60]fullerene encapsulated in p-sulfonatocalix[8]arene and single-walled carbon nanotubes (SWNTs) solubilized by sodium dodecylsulfate can be readily deposited on the ITO electrode by electrochemical oxidative polymerization of ethylenedioxythiophene (EDOT) without chemical modification of these carbon clusters. The driving force for the deposition is an electrostatic interaction between the anionic complexes and the cationic charges of poly(EDOT) formed in the oxidative polymerization process. The surface morphology was thoroughly characterized by scanning electron micrograph: the [60]fullerene/poly(EDOT) film is covered by nano-particles with 20-100 nm diameters whereas the SWNTs/poly(EDOT) film is covered by nanorods with several microm length and ca. 100 nm diameter. The results indicate that the anionic complexes act as nuclei for the polymer growth in the oxidation polymerization. Interestingly, when these modified ITO electrodes were photoirradiated, the appearance of a photocurrent wave was observed. The action spectra showed that the photoexcited energy of [60]fullerene or SWNTs is efficiently collected by the electroconductive poly(EDOT) film and transferred to the ITO electrode.     

Synthesis of pyrene and benzo[a]pyrene adducts at the exocyclic amino groups of 2'-deoxyadenosine and 2'-deoxyguanosine by a palladium-mediated C-N bond-formation strategy

Single-electron oxidation of the carcinogenic hydrocarbon benzo[a]pyrene (BaP) is thought to result in a radical cation intermediate and this species has been proposed to cause alkylation at the nitrogens of the purine nucleobases. Although several different nucleoside adducts have been isolated as arising from this mode of metabolic activation, there are no selective, total syntheses of the stable exocyclic amino group adducts formed by the single-electron oxidation of any hydrocarbon with the purine 2'-deoxynucleosides to date. In this paper we disclose the synthesis of the model adducts N(6)-(1-pyrenyl)-2'-deoxyadenosine and N(2)-(1-pyrenyl)-2'-deoxyguanosine as well as the first synthesis of the carcinogen-linked nucleoside derivatives N(6)-(6-benzo[a]pyrenyl)-2'-deoxyadenosine and N(2)-(6-benzo[a]pyrenyl)-2'-deoxyguanosine via a palladium-mediated C-N bond formation. Two different coupling strategies were attempted: coupling of an aryl bromide with a suitably protected nucleoside and the coupling of an arylamine with a suitable halonucleoside. The former had somewhat limited applicability in that only N(6)-(1-pyrenyl)-2'-deoxyadenosine was prepared by this method; on the other hand, the latter was more general. However, there are noteworthy differences in the amination reactions at the C-6 and C-2 positions. Reactions at the C-6 resulted in the competing formation of a 1:2 amine-nucleoside adduct in addition to the desired monoaryl nucleoside. Such a dimer formation was not observed at the C-2. The C-2 adducts, however, displayed an interesting conformational behavior.     

O6-(benzotriazol-1-yl)inosine derivatives: easily synthesized, reactive nucleosides

A novel class of O6-(benzotriazol-1-yl)inosine as well as the corresponding 2'-deoxy derivatives can be conveniently prepared by a reaction between sugar-protected or -unprotected inosine or 2'-deoxyinosine nucleosides and 1H-benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphate (BOP). The reaction appears to proceed via a nucleoside phosphonium salt, and in the absence of any additional nucleophile, the released 1-hydroxybenzotriazole undergoes reaction with the formed phosphonium salt leading to the requisite O6-(benzotriazol-1-yl)inosine or 2'-deoxyinosine derivatives. Isolation and characterization of the phosphonium salt as well as analysis by 31P{1H} NMR appear to be consistent with this reaction pathway. The resulting O6-(benzotriazol-1-yl)inosine derivatives are effective as electrophilic nucleosides, undergoing facile reactions with a variety of nucleophiles such as alcohols, phenols, amines, and a thiol. Unusual and challenging nucleoside derivatives such as an aryl-bridged dimer, a nucleoside-amino acid conjugate, and a nucleoside-nucleoside dimer have also been synthesized from the O6-(benzotriazol-1-yl)-2'-deoxyinosine derivative. Finally, a fully protected DNA building block, the O6-(benzotriazol-1-yl)-2'-deoxyinosine 5'-O-DMT 3'-O-phosphoramidite, has been prepared and a preliminary evaluation of its use for DNA modification has been performed. Results from these studies indicate several important facts: A single, simple methodological approach provides a class of stable, isolable ribo and 2'-deoxyribonucleoside derivatives that possess excellent reactivity for SNAr chemistry with a wide range of nucleophiles. Also, a benzotriazolyl nucleoside phosphoramidite appears to be a suitable reagent for incorporation into DNA for purposes of site-specific DNA modification.     

Inclusion of cut and as-grown single-walled carbon nanotubes in the helical superstructure of schizophyllan and curdlan (beta-1,3-glucans)

We have found that single-chain schizophyllan and curdlan (s-SPG and s-curdlan, respectively) can dissolve as-grown and cut single-walled carbon nanotubes (ag-SWNTs and c-SWNTs, respectively) in aqueous solution. The vis-NIR spectra of the composites suggest that c-SWNTs are dissolved as a bundle, whereas ag-SWNTs exist as one or only a few pieces in the tubular hollow constructed by the helical structure inherent to these beta-1,3-glucans. EDX and CLSM measurements and TEM observation established that the distribution map of these polysaccharides overlaps well with the image of SWNTs, indicating that these two components form a composite. Very interestingly, when c-SWNTs were dissolved with the aid of s-SPG or s-curdlan in water, a clear periodical structure with inclined stripes, as detected by AFM, appeared on the fibrous composite surface. Because this periodical structure has never been recognized for the composites with other water-soluble polymers, one can regard that s-SPG or s-curdlan wraps c-SWNTs constructing a helically twined structure. High-resolution TEM observation of an ag-SWNTs/s-SPG composite gave a clearer image in that two s-SPG chains twine one ag-SWNT and the helical motif is right-handed. When this sample was subjected to the AFM measurement, the composite showed the 2-3 nm height. This height implies that one piece of ag-SWNT is included in the s-SPGs helical structure. As a summary, it has been established that beta-1,3-glucans such as s-SPG and s-curdlan not only dissolve SWNTs but also create a novel superstructure on the surface.     

Release of N(2) from the carbon nanotubes via high-temperature annealing

Nitrogen (N)-doped carbon nanotubes (CNTs) were heated to 1000 degrees C under an ultrahigh vacuum. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) reveal three different N structures; graphitelike, pyridine-like, and molecular N(2). The vibrationally resolved XANES peaks of N(2) were first observed, suggesting the existence of molecular N(2) as intercalated and trapped forms. The annealing process can decrease the average N content from 6.3 at. % to 3.3 at. %, mainly by releasing molecular N(2). Electron energy-loss spectroscopy (EELS) confirms that the annealing releases molecular N(2) from the CNTs.     

Green-emissive transparent BaSi2O5:Eu film phosphor on quartz glass created by a sputtering thermal diffusion process

Eu²⁺-doped BaSi₂O₅ film phosphors on quartz substrates are fabricated by radio-frequency magnetron sputtering thermal diffusion. The BaSi₂O₅: Eu²⁺ phosphor crystals have some preferred orientations that are lattice-spacing matched with the crystallized β- SiO₂ crystals, and they show pore and grain boundary-free morphology with a rod-like shape fused into the crystallized β- SiO₂ crystals. The BaSi₂O₅: Eu²⁺ film phosphor has a high transparency, with a transmittance of about 30% in visible light. The BaSi₂O₅: Eu²⁺ film phosphor shows 510 nm green emission from the f–d transition of the Eu²⁺ ions, and in particular the best sample shows a green photoluminescence brightness of about 5% of a BaSi₂O₅: Eu²⁺ powder phosphor screen. These excellences in optical properties can be explained by less optical scattering at pores or grain boundaries, and less reflection at the continuously index-changed interface.     

Fabrication of low OH loss holey fibers with varying air hole sizes and their optical properties

We experimentally investigate a flexible fabrication technique for low OH and transmission losses holey fibers with a Ge-doped core and air holes in a silica cladding region. Versatile holey fibers of different size, pitch, and shape of air holes were achieved by controlling the temperature and heating time of the holey fiber preform. In addition, we suppress the OH loss of less than ∼0.323 dB/km at 1383 nm. After fabricating holey fibers, we measure their optical properties including cut-off wavelength, mode field diameter, splicing loss, dispersion, bending loss, and polarization dependent loss based on the size of air holes. The total transmission loss was measured to be ∼0.226 dB/km at 1550 nm by improving the fabrication process. After fabricating optical patch cord based on holey fibers, we measured the long-term stability of the fabricated holey fiber by using the temperature cycling technique for 24 and obtained low power fluctuation of 0.2 dB. We achieve the high quality holey fiber with a low bending loss of ∼0.04 dB/turn under a bending radius of 2.5 mm at 1550 nm. We also obtain a tunable band rejection filter with a number of bending turns.     

Josephson-vortex-flow terahertz emission in layered high-Tc superconducting single crystals

We report on the successful terahertz emission (0.6-1 THz) that is continuous and tunable in its frequency and power, by driving Josephson vortices in resonance with the collective standing Josephson plasma modes excited in stacked Bi2Sr2CaCu2O8+x intrinsic Josephson junctions. Shapiro-step detection was employed to confirm the terahertz-wave emission. Our results provide a strong feasibility of developing long-sought solid-state terahertz-wave emission devices.     

Nonane droplet combustion with and without buoyant convection: Flame structure, burning rate and extinction in air and helium

The burning and extinction characteristics of isolated small nonane droplets are examined in a buoyant convective environment and in an environment with no external axial convection (as created by doing experiments at low gravity) to promote spherical droplet flames. The ambience is air and a mixture of 30%O₂/70%He to assess the influence of soot formation. The initial droplet diameter (D_o) ranges from 0.4 to 0.95 mm. Measurements are reported of the extinction diameter and time to extinction, and of the evolution of droplet diameter, flame diameter, soot shell diameter, burning rate, and broadband radiative emissions.In a buoyancy-free environment for air larger droplets burn slower than smaller droplets for the range of D_o examined, which is attributed to the influence of soot. In the presence of a buoyant flow in air, no influence of D_o is observed on the burning rate while the buoyant flames are still heavily sooting. The effect of D_o is believed to be due to a combination of dominance of the nonluminous, nonsooting, portion of the buoyant flame around the forward half of the droplet on heat transport and the secondary role of the luminous wake portion of the flame. In a non-sooting helium inert at low gravity, no effect of D_o is found on the evolution of droplet diameter.Flame extinction is observed only in the 30%O₂/70%He ambience. For all of the observations, extinction appears to occur before the disappearance of the droplet which is then followed by a period of evaporation. The extinction diameter and time to extinction increases with D_o and an empirical correlation is presented for these two variables.     

Misalignment tolerance analysis and fabrication for highly efficient parallel optical-electrical convertor module

A compact, highly efficient, and passively assembled parallel optical-electrical convertor module (POECM) for active optical cable application is proposed. This paper presents our POECM structure, optical design simulation results, fabrication process, and data transmission test results, in sequence. The POECM has a compact size of \(18.5\hbox {mm} \times 10\hbox {mm} \times 2.8\hbox {mm}\) . We confirm a data rate of total throughput at 21.6 Gbps ( \(5.4\hbox {Gbps} \times 4\) channels) with a bit error rate of less than \(10^{-12}\) .