Semireduction of Alkynes Using Formic Acid with Reusable Pd-Catalysts.

The treatment of PdCl2 with K2CO3 and HCO2H in dioxane gives black precipitates, which are an effective catalyst for the semireduction of alkynes to alkenes using formic acid as a reductant. Even 0.05 mol % Pd promoted the reduction reaction of tolane in high yield with high selectivity.

Not nanocarbon but dispersant induced abnormality in lysosome in macrophages in vivo.

The properties of nanocarbons change from hydrophobic to hydrophilic as a result of coating them with dispersants, typically phospholipid polyethylene glycols, for biological studies. It has been shown that the dispersants remain attached to the nanocarbons when they are injected in mice and influence the nanocarbons' biodistribution in vivo. We show in this report that the effects of dispersants also appear at the subcellular level in vivo. Carbon nanohorns (CNHs), a type of nanocarbon, were dispersed with ceramide polyethylene glycol (CPEG) and intravenously injected in mice. Histological observations and electron microscopy with energy dispersive x-ray analysis revealed that, in liver and spleen, the lysosome membranes were damaged, and the nanohorns formed a complex with hemosiderin in the lysosomes of the macrophages. It is inferred that the lysosomal membrane was damaged by sphigosine generated as a result of CPEG decomposition, which changed the intra lysosomal conditions, inducing the formation of the CPEG-CNH and hemosiderin complex. For comparison, when glucose was used instead of CPEG, neither the nanohorn­hemosiderin complex nor lysosomal membrane damage was found. Our results suggest that surface functionalization can control the behavior of nancarbons in cells in vivo and thereby improve their suitability for medical applications.

Carboxylation of thin graphitic sheets is faster than that of carbon nanohorns.

Globular aggregates of carbon nanohorns (CNHs) often contain graphite-like thin sheets (GLSs), and providing different functions to CNHs and GLSs would expand the possible applications of the CNH-GLS aggregates. We show that the GLS edges can be carboxylated selectively by immersing the aggregates in an aqueous solution of H2O2 at room temperature for 1 hour. The presence of carboxyl groups was confirmed by temperature-programmed desorption mass spectroscopy measurements, and their amounts were evaluated using thermogravimetric analysis. The preferential carboxylation of GLSs at their edges was evidenced, after the carboxyl groups were reacted with Pt-ammine complexes, by electron microscopic observation of the Pt atoms at the GLS edges. Since few holes in CNH walls were opened by the short-period H2O2 treatment, there was little carboxylation of CNHs.

Decoration of carbon nanohorns with palladium and platinum nanoparticles.

Carbon nanohorns (CNHs) have been decorated with palladium and platinum nanoparticles, which are prepared in-situ, with the aid of sodium dodecyl sulphate (SDS), by the self-regulated reduction of palladium acetate and chloroplatinic acid, respectively. The latter acts as a reducing agent for the metal ions, while at the same time, aids the solubilisation of CNHs. The soluble in polar media nanoPd-CNH and nanoPt-CNH hybrid materials have been characterised and morphologically evaluated by complementary microscopy, thermal and analytical techniques such as transmission electron microscopy, energy dispersive X-ray spectroscopy, dynamic light scattering, thermogravimetric analysis, UV-VIS-NIR and Raman spectroscopy. Finally, the nanoPd-CNH and nanoPt-CNH hybrid materials have been tested in catalysis toward the formation of carbon-carbon bond in Heck, Suzuki and Stille reactions.

(Terpyridine)copper(II)-carbon nanohorns: metallo-nanocomplexes for photoinduced charge separation.

New metallo-nanostructured materials of carbon nanohorns (CNHs), within the family of elongated carbon nanotubes, have been prepared by the coordination of copper(II)-2,2':6',2' '-terpyridine (Cu(II)tpy) with oxidized carbon nanohorns (CNHs-COOH). The resulted CNHs-COO-Cu(II)tpy metallo-nanocomplexes have been characterized by diverse analytical spectroscopic tools and cyclic and differential pulse voltammetry. Scanning transmission electron microscopy (STEM), dynamic light scattering (DLS), and energy dispersive X-ray spectroscopy (EDX) measurements have been employed to probe the morphological characteristics and particle-size distribution of CNHs-COO-Cu(II)tpy as well as to investigate the elemental composition of the metallo-nanocomplex. Steady-state and time-resolved fluorescence emission studies have shown efficient fluorescence quenching, suggesting that electron transfer occurs from the singlet excited state of Cu(II)tpy to CNHs. Photoexcitation of Cu(II)tpy resulted in the one-electron reduction of nanohorns with a simultaneous one-electron oxidation of the Cu(II)tpy unit (CNHs(*-)-COO-(Cu(II)tpy)*+) as revealed by transient absorption measurements. The charge-separated state of CNHs(*-)-COO-(Cu(II)tpy)*+ has been confirmed with the aid of an electron mediator, such as hexyl-viologen dication (HV2+) and an electron-hole shifter in polar solvents.

High-Power Abiotic Direct Glucose Fuel Cell Using a Gold-Platinum Bimetallic Anode Catalyst.

We developed a high-power abiotic direct glucose fuel cell system using a Au-Pt bimetallic anode catalyst. The high power generation (95.7 mW cm-2) was attained by optimizing operating conditions such as the composition of a bimetallic anode catalyst, loading amount of the metal catalyst on a carbon support, ionomer/carbon weight ratio when the catalyst was applied to the anode, glucose and KOH concentrations in the fuel solution, and operating temperature and flow rate of the fuel solution. It was found that poly(N-vinyl-2-pyrrolidone)-stabilized Au80Pt20 nanoparticles (mean diameter 1.5 nm) on a carbon (Ketjen Black 600) support function as a highly active anode catalyst for the glucose electrooxidation. The ionomer/carbon weight ratio also greatly affects the cell properties, which was found to be optimal at 0.2. As for the glucose concentration, a maximum cell power was derived at 0.4-0.6 mol dm-3. A high KOH concentration (4.0 mol dm-3) was preferable for deriving the maximum power. The cell power increased with the increasing flow rate of the glucose solution up to 50 cm3 min-1 and leveled off thereafter. At the optimal condition, the maximum power density and corresponding cell voltage of 58.2 mW cm-2 (0.36 V) and 95.7 mW cm-2 (0.34 V) were recorded at 298 and 328 K, respectively.

Controlling the incorporation and release of C60 in nanometer-scale hollow spaces inside single-wall carbon nanohorns.

We succeeded in large-scale preparation of single-wall carbon nanohorns (SWNH) encapsulating C60 molecules in a liquid phase at room temperature using a "nano-precipitation" method, that is, complete evaporation of the toluene from a C60-SWNH-toluene mixture. The C60 molecules were found to occupy 6-36% of the hollow space inside the SWNH, depending on the initial quantity of C60. We showed that the C60 in C60@SWNHox was quickly released in toluene, and the release rate decreased by adding ethanol to toluene. Numerical analysis of the release profiles indicated that there were fast and slow release processes. We consider that the incorporation quantity and the release rate of C60 were controllable in/from SWNHs because SWNHs have large diameters, 2-5 nm.

Ultrastructural localization of intravenously injected carbon nanohorns in tumor.

Nanocarbons have many potential medical applications. Drug delivery, diagnostic imaging, and photohyperthermia therapy, especially in the treatment of tumors, have attracted interest. For the further advancement of these application studies, the microscopic localization of nanocarbons in tumor tissues and cells is a prerequisite. In this study, carbon nanohorns (CNHs) with sizes of about 100 nm were intravenously injected into mice having subcutaneously transplanted tumors, and the CNHs in tumor tissue were observed with optical and electron microscopy. In the tumor tissue, the CNHs were found in macrophages and endothelial cells within the blood vessels. Few CNHs were found in tumor cells or in the region away from blood vessels, suggesting that, under these study conditions, the enhanced permeability of tumor blood vessels was not effective for the movement of CNHs through the vessel walls. The CNHs in normal skin tissue were similarly observed. The extravasation of CNHs was not so obvious in tumor but was easily found in normal skin, which was probably due to their vessel wall structure difference. Proper understanding of the location of CNHs in tissues is helpful in the development of the medical uses of CNHs.

Benzyne cycloaddition onto carbon nanohorns.

A facile approach for the covalent functionalization of carbon nanohorns (CNHs) based on the benzyne cycloaddition reaction is presented. The benzynes were in situ generated from either anthranilic acid by decomposition of the internal benzenediazonium-2-carboxylate or from 2-(trimethylsilyl)-phenyl triflate by fluoride ion attack at the silicon atom followed by displacement of the trimethylsilyl group under mild conditions. Moreover, the functionalization reaction was tested and performed under conventional conditions as well as under microwave irradiation. Modified CNHs possessing fused rings onto their graphitic skeleton were fully characterized by means of complementary spectroscopic techniques, thermogravimetric analysis, electron microscopy and light scattering. Moreover, Sonogashira coupling with propargyl alcohol followed by condensation with thioctic acid, to the iodo-modified CNHs obtained from the cycloaddition reaction of 2-amino-5-iodobenzoic acid with CNHs, resulted in the preparation of a new CNH-based material in which endocyclic disulfides are extended from the fused rings onto CNHs. The latter moieties were used to immobilize gold nanoparticles, furnishing the CNH-Au(nano) hybrid material, in which the former were identified with the aid of UV-Vis and EDX spectroscopy.

Microwave-assisted functionalization of carbon nanohorns via [2+1] nitrenes cycloaddition.

The microwave-assisted functionalization of carbon nanohorns (CNHs) via [2+1] nitrenes cycloaddition, providing well dispersible hybrid materials possessing aziridino-rings covalently grafted onto the graphitic network of CNHs, was accomplished, while condensation of hydroxy-functionalized CNHs with thioctic acid, furnishing an endocyclic disulfide bond extended from the aziridino-rings, allowed the stabilization of Au nanoparticles.

Highly efficient field emission from carbon nanotube-nanohorn hybrids prepared by chemical vapor deposition.

Electrically conductive carbon nanotubes (CNTs) with high aspect ratios emit electrons at low electric fields, thus applications to large-area field emission (FE) devices with CNT cathodes are attractive to save energy consumption. However, the poor dispersion and easy bundling properties of CNTs in solvents have hindered this progress. We have solved these problems by growing single-walled CNTs (SWNTs) on single-walled carbon nanohorn (SWNH) aggregates that have spherical forms with ca. 100-nm diameters. In the obtained SWNT-SWNH hybrids (NTNHs), the SWNTs diameters were 1-1.7 nm and the bundle diameters became almost uniform, that is, less than 10 nm, since the SWNTs were separated by SWNH aggregates. We also confirmed that a large-area FE device with NTNH cathodes made by screen printing was highly and homogeneously bright, suggesting the success of the hybrid strategy.

Biodistribution and ultrastructural localization of single-walled carbon nanohorns determined in vivo with embedded Gd2O3 labels.

Single-walled carbon nanohorns (SWNHs) are single-graphene tubules that have shown high potential for drug delivery systems. In drug delivery, it is essential to quantitatively determine biodistribution and ultrastructural localization. However, to date, these determinations have not been successfully achieved. In this report, we describe for the first time a method that can achieve these determinations. We embedded Gd(2)O(3) nanoparticles within SWNH aggregates (Gd(2)O(3)@SWNHag) to facilitate detection and quantification. Gd(2)O(3)@SWNHag was intravenously injected into mice, and the quantities of Gd in the internal organs were measured by inductively coupled plasma atomic emission spectroscopy: 70-80% of the total injected material accumulated in liver. The high electron scattering ability of Gd allows detection with energy dispersive X-ray spectroscopy and facilitates the ultrastructural localization of individual Gd(2)O(3)@SWNHag with transmission electron microscopy. In the liver, we found that the Gd(2)O(3)@SWNHag was localized in Kupffer cells but were not observed in hepatocytes. In the Kupffer cells, most of the Gd(2)O(3)@SWNHag was detected inside phagosomes, but some were in another cytoplasmic compartment that was most likely the phagolysosome.

Enhancement of in vivo anticancer effects of cisplatin by incorporation inside single-wall carbon nanohorns.

Cisplatin (CDDP) was incorporated inside single-wall carbon nanohorns with holes opened (SWNHox) by a nanoprecipitation method that involved dispersion of CDDP and SWNHox in a solvent followed by the solvent evaporation. The incorporated CDDP quantity increased from the previously reported value of 15 to 46%, and the total released quantity of CDDP also increased from 60 to 100% by changing the solvent from dimethylformamide to water. Concurrently, in vitro anticancer efficiency of CDDP@SWNHox increased to 4-6 times greater than that of the intact CDDP. In vivo, CDDP@SWNHox intratumorally injected to transplanted tumors of mice suppressed the tumor growth more than the intact CDDP. We observed that CDDP@SWNHox adhered to the cell surfaces in vitro and stayed within the tumor tissues in vivo. Therefore, we think that the CDDP released from SWNHox realized high concentrations locally at the cells in vitro and in the tissues in vivo and could efficiently attack the tumor cells. We also found that SWNHox itself had an in vivo anticancer effect, which might increase the anticancer activities of CDDP@SWNHox.

In situ observation of carbon-nanopillar tubulization caused by liquidlike iron particles.

The tubulization process of amorphous carbon nanopillars was observed in situ by transmis-sion electron microscopy. Amorphous carbon nanopillars were transformed into graphitic tubules by annealing at 650-900 degrees C in the presence of iron nanoparticles. A molten catalyst nanoparticle penetrated an amorphous carbon nanopillar, dissolving it, and leaving a graphite track behind. An iron nanoparticle moved with its shape changing like an earthworm. We concluded that the tubulization mechanism is a solid-(quasiliquid)-solid mechanism where the carbon phase transformation is a kind of liquid phase graphitization of amorphous carbon catalyzed by liquefied metal-carbon alloy nanoparticles.

Energy-filtered electron diffraction and high-resolution electron microscopy on short-range ordered structure in GaAs(0.5)Sb(0.5).

Characteristic intensity distribution of diffuse scattering in III-V alloy semiconductor GaAs(0.5)Sb(0.5) epitaxially grown was observed by the energy-filtered electron diffraction method with [110] incidence. The diffuse scattering situates at the one-third positions between the fundamental reflections extending parallel to the q002 direction in the reciprocal space. A high-resolution electron microscope image shows weak contrast modulation corresponding to the diffuse scattering. The image processed with the Fourier transform by selecting the diffuse scattering and a fundamental reflection shows small regions consisting of bright dots being elongated along the (111) planes and aligning on the (002) planes, which are considered to result from the ordering of As and Sb during the growth process. The effect of including the fundamental reflection for imaging the ordered regions in the image processing method is also discussed. Finally, based on the results obtained by energy-filtered electron diffraction and high-resolution electron microscopy, a simple structure model for the short-range ordered structure in GaAs(0.5)Sb0.5 is proposed.