Crystalline functionalized endohedral C60 metallofullerides.

Endohedral metallofullerenes have been extensively studied since the first experimental observation of La@C60 in a laser-vaporized supersonic beam in 1985. However, most of these studies have focused on metallofullerenes larger than C60 such as (metal)@C82, and there are no reported purified C60-based monomeric metallofullerenes, except for [Li@C60]+(SbCl6)- salt. Pure (metal)@C60 compounds have not been obtained because of their extremely high chemical reactivity. One route to their stabilization is through chemical functionalization. Here we report the isolation, structural determination and electromagnetic properties of functionalized crystalline C60-based metallofullerenes Gd@C60(CF3)5 and La@C60(CF3)5. Synchrotron X-ray single-crystal diffraction reveals that La and Gd atoms are indeed encapsulated in the Ih-C60 fullerene. The HOMO-LUMO gaps of Gd@C60 and La@C60 are significantly widened by an order of magnitude with addition of CF3 groups. Magnetic measurements show the presence of a weak antiferromagnetic coupling in Gd@C60(CF3)3 crystals at low temperatures.

Preparation of small-sized graphene oxide sheets and their biological applications.

By using carbon nanohorns as starting materials, small- and uniform-sized graphene oxide (S-GO) sheets can be prepared in high yields via an oxidation method. The obtained S-GO sheets have a band-like structure with a length of 20-50 nm, a width of 2-10 nm, and a thickness of 0.5-5 nm. S-GO sheets are hydrophilic due to abundant oxygenated groups on the surfaces and edges; hence, this nanomaterial is highly dispersive in aqueous solutions and some hydrophilic organic solvents. Additionally, like other S-GO samples, the S-GO sheets prepared here are strongly fluorescent over the visible light wavelength region. These characteristics underscore the high potential of S-GO sheets for nanomedical and diagnostic applications. In proof-of-concept experiments, the S-GO sheets were conjugated with an arginine-glycine-aspartic acid derivative for tumour-targeting drug delivery applications, and with an immunoglobulin G antibody for immunoassay applications.

Electronic structures of single-walled carbon nanotubes encapsulating ellipsoidal C70.

The molecular orientation of ellipsoidal C(70) in single-walled carbon nanotubes (SWCNTs) depends on the tube diameter (d(t)). Photoluminescence (PL) studies reveal that the fullerene encapsulation effects on the optical transition energy of SWCNTs are significantly different for C(70) and C(60) at d(t) = 1.405-1.431 nm. This indicates that the transition from the "lying" alignment to the "standing" alignment occurs at d(t) ≈ 1.41 nm and the electronic states of SWCNTs are very sensitive to the interspacing between the encapsulated molecules and the SWCNTs. The present findings suggest that the electronic structure of SWCNTs is tunable not only by alternating the encapsulated molecules but also by controlling their molecular orientations, thus paving the way for development of novel SWCNT-based devices.

Strong magnetism observed in carbon nanoparticles produced by the laser vaporization of a carbon pellet in hydrogen-containing Ar balance gas.

Nanometer-scale carbon particles driven by the pulsed-laser vaporization of pelletized pure carbon powder at 1000 °C in a hydrogen-containing environment show anomalous magnetism like a superparamagnet, while the sample prepared in 100% of Ar does not show such magnetism. The observed magnetism was unchanged over months in the ambient. The structure of this nanomaterial resembles the foam of a laundry detergent and transmission electron microscopy indicates a clear corrugated line contrast. On the other hand, a sample without strong magnetism does not give such an image contrast. The x-ray diffraction pattern coincides with that of graphite and no other peak is detected. Thermogravimetry indicates that all samples completely burn out up to approx. 820 °C and no material remains after combustion, indicating that the sample does not contain impurity metals. Magnetization is easily saturated by ∼10,000 G at 280 K with no hysteresis, but the hysteresis appears at 4.2 K. This phenomenon is explained by introducing a crystalline anisotropy which restricts the motion of the magnetic moment and stabilizes the remnant magnetization at zero magnetic field. Magnitudes of the saturation magnetization are in the range of 1-5 emu G g(-1) at 4.2 K, which correspond to 0.002-0.01 Bohr magneton per carbon atom. This concentration may be increased by ten times or more, because only about 4-10% of particles have a magnetic domain in the present samples.

Effect of fullerene encapsulation on radial vibrational breathing-mode frequencies of single-wall carbon nanotubes.

We investigate the effects of C60 fullerene encapsulation on the radial breathing mode (RBM) of semiconducting single-wall carbon nanotubes (SWCNTs) under tunable laser excitations. The changes in the RBM frequencies after C60 insertions show characteristic behavior; higher frequency shifts are observed in the case of smaller diameter tubes (dtor =1.32 nm). The observed frequency shifts are satisfactorily explained by the diameter-dependent interaction between the encapsulated C60 and the host SWCNTs.

Optical band gap modification of single-walled carbon nanotubes by encapsulated fullerenes.

We report optical band gap modifications of single-walled carbon nanotubes upon C60 insertions by using photoluminescence and the corresponding excitation spectroscopy. The shifts in optical transition energies strongly depend on the tube diameter (dt) and the "2n + m" family type, which can be explained by the local strain and the hybridization between the nanotube states and the C60 molecular orbitals. The present results provide possible design rules for nanotube-based heterostructures having a specific type of electronic functionality.

Preparation, photocatalytic activities, and dye-sensitized solar-cell performance of submicron-scale TiO2 hollow spheres.

We prepared submicron-scale spherical hollow particles of anatase TiO2 by using a polystyrene-bead template. The obtained particles were very uniform in size, with a diameter of 490 nm and a shell thickness of 30 nm. The Brunauer-Emmett-Teller surface area measurements revealed a large value of 70 m2/g. The photocatalytic property was investigated by the complete decomposition of gaseous isopropyl alcohol under UV irradiation. It was indicated that the activity of the hollow spheres was 1.8 times higher than that of the conventional P25 TiO2 nanoparticles with a diameter of 30 nm. Furthermore, we fabricated a dye-sensitized solar cell (DSC) using an electrode of the TiO2 hollow spheres, and examined the photovoltaic performance under simulated sunlight. Although the per-area efficiency was rather low (1.26%) because of a low area density of TiO2 on the electrode, the per-weight efficiency was 2.5 times higher than those of the conventional DSCs of TiO2.

Entrapping of exohedral metallofullerenes in carbon nanotubes: (CsC60)n@SWNT nano-peapods.

Exohedral C60-based metallofullerenes, CsC60, have been synthesized and successfully encapsulated into single-wall carbon nanotubes (SWNTs) in high yield by reducing C60 molecules into anions. High-resolution transmission electron microscopy (HRTEM) images and in situ electron energy loss spectroscopy (EELS) indicate that Cs atoms and C60 molecules align within SWNTs as CsC60 exohedral metallofullerenes, and that the formal charge state of encaged CsC60 is expressed as Cs+1C60-1. The present peapods with the exohedral metallofullerenes provide a new insight and the possibility to fine-tune the electronic and transport properties of carbon nanotubes.

End-cap effects on vibrational structures of finite-length carbon nanotubes.

Vibrational structures of C60-related finite-length nanotubes, C(40+20n) and C(42+18n) (1 < or = n < or = 4), in which n is, respectively, the number of cyclic cis- and trans-polyene chains inserted between fullerene hemispheres, are analyzed from density functional theory (DFT) calculations. To illuminate the end-cap effects on their vibrational structures, the corresponding tubes terminated by H atoms C(20n)H20 and C(18n)H18 (1 < or = n < or = 5) are also investigated. DFT calculations show a broad range of vibrational frequencies for the finite-size nanotubes: high-frequency modes (1100-1600 cm(-1)) containing oscillations along tangential directions (tangential modes), medium-frequency modes (700-850 cm(-1)) whose oscillations are located on the edges or end caps, and low-frequency modes (300-600 cm(-1)) involving oscillations along the radial directions (radial modes). Broadening of the calculated frequencies is due to the number of nodes in the standing waves of normal modes in the finite-size tubes. In the capped tubes, calculated vibrational frequencies are insensitive to the number of chains (n), whereas in the uncapped tubes, most vibrational frequencies change significantly with an increase in tube length. The discrepancy in the size dependency is reasonably understood by their C-C bonding networks; the capped tubes have similar bond-length alternation patterns within the polyene chains irrespective of n, whereas the uncapped tubes have various bond-deformation patterns. Thus, DFT calculations illuminate that the edge effects have strong impacts on the vibrational frequencies in the finite-size nanotubes.

Atomic correlation between adjacent graphene layers in double-wall carbon nanotubes.

Atomic correlation between adjacent graphene layers was elucidated for double-wall carbon nanotubes (DWNTs) through a chiral index assignment of two nested nanotubes by high-resolution transmission electron microscopy. Our analysis provides a rather constant diameter difference close to 0.75 nm but no chiral angle correlation between the constituent nanotubes in the concentric DWNTs. The local atomic correlation as a commensurate graphene stacking was repeatedly found in eccentric DWNTs and circumscribed nanotubes, which should lead to elastic deformation and bundling of nanotubes.