Jin Miyawaki

Preparation of Nitrogen-Doped Graphene Sheets by a Combined Chemical and Hydrothermal Reduction of Graphene Oxide

Nitrogen-doped graphene sheets were prepared through a hydrothermal reduction of colloidal dispersions of graphite oxide in the presence of hydrazine and ammonia at pH of 10. The effect of hydrothermal temperature on the structure, morphology, and surface chemistry of as-prepared graphene sheets were investigated though XRD, N(2) adsorption, solid-state (13)C NMR, SEM, TEM, and XPS characterizations. Oxygen reduction and nitrogen doping were achieved simultaneously under the hydrothermal reaction. Up to 5% nitrogen-doped graphene sheets with slightly wrinkled and folded feature were obtained at the relative low hydrothermal temperature. With the increase of hydrothermal temperature, the nitrogen content decreased slightly and more pyridinic N incorporated into the graphene network. Meanwhile, a jellyfish-like graphene structure was formed by self-organization of graphene sheets at the hydrothermal temperature of 160 °C. Further increase of the temperature to 200 °C, graphene sheets could self-aggregate into agglomerate particles but still contained doping level of 4 wt % N. The unique hydrothermal environment should play an important role in the nitrogen doping and the jellyfish-like graphene formation. This simple hydrothermal method could provide the synthesis of nitrogen-doped graphene sheets in large scale for various practical applications.

Toxicity of Single-Walled Carbon Nanohorns

We extensively investigated in vitro and in vivo the toxicities of as-grown single-walled carbon nanohorns (SWNHs), a tubular nanocarbon containing no metal impurity. The SWNHs were found to be a nonirritant and a nondermal sensitizer through skin primary and conjunctival irritation tests and skin sensitization test. Negative mutagenic and clastogenic potentials suggest that SWNHs are not carcinogenic. The acute peroral toxicity of SWNHs was found to be quite low--the lethal dosage for rats was more than 2000 mg/kg of body weight. Intratracheal instillation tests revealed that SWNHs rarely damaged rat lung tissue for a 90-day test period, although black pigmentation due to accumulated nanohorns was observed. While further toxicological assessments, including chronic (repeated dose), reproductive, and developmental toxicity studies, are still needed, yet the present results strongly suggest that as-grown SWNHs have low acute toxicities.

Light-assisted oxidation of single-wall carbon nanohorns for abundant creation of oxygenated groups that enable chemical modifications with proteins to enhance biocompatibility.

We show that light-assisted oxidation with hydrogen peroxide effectively and rapidly opens holes in carbon nanohorn walls and, more importantly, creates abundant oxygenated groups such as carboxylic groups at the hole edges. These oxygenated groups reacted with the protein bovine serum albumin. The obtained conjugates were highly dispersed in phosphate-buffered saline and were taken up by cultured mammalian cells via an endocytosis pathway.

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.

A simple determination method of the absolute adsorbed amount for high pressure gas adsorption

Abstract A new determination method of the absolute adsorbed amount is proposed. The present method, which is called the buoyancy-mediated (BM) method, is simpler than the adsorbed volume mapping (AVM) method [Chem. Phys. Lett., 321 (2000) 342]. If there are data of the experimental surface excess mass up to the high pressure region, the BM method coincides with the AVM method. In the case of methane adsorption on pitch-based activated carbon fiber (ACF: P-5), the obtained volume of the adsorbed layer is from 0.84 to 20 ml/g. The isosteric heat of adsorption from the absolute adsorption isotherms is in the range of 19 to 25 kJ/mol, which almost coincides with the value calculated from grand canonical Monte-Carlo simulation.

Pore structure analysis of activated carbon fiber by microdomain-based model

The pore structures of commercial pitch and PAN-based activated carbon fibers (ACFs) were investigated. The pore size and pore size distribution of pitch-based ACFs were measured by nitrogen adsorption isotherms and 129Xe NMR spectroscopy and compared with each other. Scanning tunneling microscopy showed that the ACFs were composed of spherical microdomain units the size of a few nanometers. The activation mechanism of ACFs was considered and explained by novel hypothesis; the concept of microdomain structure of ACFs was considered and explained to overcome limitation of the conventional fractal hypothesis. Whereas micropores were generated on each microdomain, the origin of mesopores was interdomain pores, resulting from the microdomain hypothesis.

Two-Dimensional Materials as Emulsion Stabilizers: Interfacial Thermodynamics and Molecular Barrier Properties

A new application for two-dimensional (2D) materials is emulsification, where they can serve as ultrathin platelike interfacial stabilizers in two-liquid systems. We present a first detailed thermodynamic analysis of atomically thin 2D materials at organic-aqueous liquid-liquid interfaces and derive expressions for the transfer free energies of emulsion stabilization that account for material geometry, van der Waals transparency or opacity, and variable hydrophobicity. High mass potency is shown to be an intrinsic property of the 2D geometry, which at the atomically thin limit places every atom in contact with both liquid phases, resulting in unit atom efficiency. The thermodynamic model successfully predicts that graphene oxide but not pristine graphene has a favorable hydrophobic-hydrophilic balance for oil-water emulsion stabilization. Multilayer tiling is predicted to occur by the passivation of droplet surface patches left uncovered by packing inefficiencies in the first monolayer, and complete multilayer coverage is confirmed by cryogenic scanning electron microscopy. The molecular barrier function of graphene interfacial films causes a significant suppression of dispersed-phase evaporation rates with potential applications in controlled release. Finally, these emulsions can be used as templates for creating solid graphene foams or graphene microsacks filled with lipophilic cargos. Emerging 2D materials are promising as dispersants or emulsifiers where high mass potency and multifunctional properties are desired.

Structural features of polyacrylonitrile-based carbon fibers

The structural changes as functions of spinning conditions and heat treatments were investigated with respect to the structural feature of PAN-based carbon fibers by scanning tunneling microscopy (STM). The distinct granule structure on the cross section of both high tensile strength and high modulus carbon fibers was observed by SEM, while slender granule-shape domain on the longitudinal surface was revealed by STM. A structure model was proposed, which depicted that the PAN-based carbon fiber was a heterogeneous structure composed of aggregated mesostructural domains. These domains were closely arranged into spiral form along fiber axis, allowing the fibers have high strength and good elongation. The initial shape and size of domains was determined by the precursor composition and spinning conditions and also strongly depended on the heat-treated temperature and stretching conditions. The smaller or slender domain, the higher tensile strength obtained for fibers. We expect that the PAN-based carbon fiber with better performance should be produced by optimizing the size and shape of these domains.

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.

Histological assessments for toxicity and functionalization-dependent biodistribution of carbon nanohorns

Single-walled carbon nanohorns (SWNHs) intravenously administered to mice did not show severe toxicity during a 26-week test period, which was confirmed by normal gross appearance, normal weight gain and the lack of abnormality in the tissues on histological observations of the mice. SWNH biodistribution was influenced by chemical functionalization. Accumulation of SWNH in the lungs reduced as SWNH hydrophilicity increased; however, the most hydrophilic SWNHs modified with bovine serum albumin (BSA) were most likely to be trapped in the lungs, suggesting that the BSA moiety enhanced macrophage phagocytosis in the lungs. Clearance of some of the hydrophobic SWNHs from the lungs was observed, the mechanism of which is briefly discussed.