Engineering molecular chains in carbon nanotubes.

A range of mono- and bis-functionalised fullerenes have been synthesised and inserted into single-walled carbon nanotubes. The effect of the size and shape of the functional groups of the fullerenes on the resultant 1D arrays formed within the nanotubes was investigated by high resolution transmission electron microscopy and X-ray diffraction. The addition of non-planar, sterically bulky chains to the fullerene cage results in highly ordered 1D structures in which the fullerenes are evenly spaced along the internal nanotube cavity. Theoretical calculations reveal that the functional groups interact with neighbouring fullerene cages to space the fullerenes evenly within the confines of the nanotube. The addition of two functional groups to opposite sides of the fullerene cages results in a further increase in the separation of the fullerene cages within the nanotubes at the cost of lower nanotube filling rates.

Electronic structure of carbon nanotubes with ultrahigh curvature.

The electronic and the vibrational structure of carbon nanotubes with ultrahigh curvature was systematically studied by resonance Raman scattering, high-resolution transmission electron microscopy (HRTEM), molecular dynamics, and ab initio DFT calculations. The ultrahigh curvature tubes were grown inside commercial HiPco tubes after filling the latter with the small but carbon-rich molecule ferrocene. TEM showed partial filling of the outer tubes with inner tubes and mobility of the latter in the electron beam. The smallest analyzed tube was of (5,0) chirality and had a DFT determined diameter of 0.406 nm and a radial breathing mode frequency of 570 cm(-1). For all inner tubes which had transitions in the visible spectral range, transition energies and RBM frequencies were determined with a resonance width of only 45 meV. Experimentally determined transition energies revealed dramatic deviations up to several electronvolts compared to tight-binding calculations and a significant family spread of more than 2 eV but were in agreement with many electron contribution corrected extended tight-binding results and with results from DFT calculations.

Controlling intermolecular spin interactions of La@C(82) in empty fullerene matrices.

The ESR properties and crystal structures of solid-state La@C(82) in empty fullerene matrices were investigated by changing the concentration of La@C(82) and the species of an empty fullerene matrix: C(60), C(70), C(78)(C(2v)(3)), C(82)(C(2)) and C(84)(D(2d)(4)). The rotational correlation time of La@C(82) molecules tended to be shorter when La@C(82) is dispersed in larger fullerene matrices because large C(2n) molecules provide more space for La@C(82) molecules for rotating. La@C(82) dispersed in a hcp-C(82) matrix showed the narrowest hyperfine structure (hfs) due to the ordered nature of La@C(82) molecules in the C(82) crystal. On the other hand, in a C(60) matrix, La@C(82) molecules formed clusters because of the large different solubility, which leads to the ESR spectra being broad sloping features due to strong dipole-dipole and exchange interactions.

Molecular Imaging Cellular SPIO Uptake with Nonlinear Optical Microscopy.

We report a novel application to demonstrate and visualize the selective binding of lipids in cells of the reticuloendothelial system to super paramagnetic iron oxide (SPIO) nanoparticles. Ten New Zealand White rabbits that were experimentally injected intravenously with SPIO and five controls were investigated with vibrational microspectroscopy based on surface-enhanced coherent anti-Stokes Raman scattering (SECARS) microscopy. Marked cellular intensity enhancements in hepatic Kupffer cells and melanomacrophages of spleen have been observed in the range of 2850-2875 cm-1 in SPIO-injected animals but not in controls. The enhancements are related to the selective association of lipid molecules in cells of the reticuloendothelial system to uptaken SPIO, which can uniquely be visualized with SECARS microscopy.

Polyarene-functionalized fullerenes in carbon nanotubes: towards controlled geometry of molecular chains.

Mechanisms for controlling the assembly of molecular arrays in carbon nanotubes via alteration of the size and geometry of the functional groups attached to the molecules inserted into the nanotubes are studied. As model compounds, a series of structurally related fullerenes functionalized with polyaryl groups (C(60)X, where X is a polyaryl group) of various lengths are synthesized to explore this effect. These molecules are inserted into single-walled carbon nanotubes (SWNTs) under mild conditions to prevent their decomposition and to form C(60)X@SNWT structures. The molecular chains thus formed are studied by high-resolution transmission electron microscopy, X-ray diffraction, and Raman spectroscopy, revealing that the functional groups increase the interfullerene separation proportionally with the size of X. However, the functional groups themselves appear to adopt various orientations with respect to each other and exhibit intermolecular pi-pi interactions within the cavities of the carbon nanotubes. All these effects create a distribution of observed interfullerene separations in nanotubes, which are examined by theoretical simulations and interpreted in terms of molecular geometries and intermolecular interactions.

Dynamics of carbon nanotube growth from fullerenes.

The growth of double-walled carbon nanotubes from peapods was studied. The transformation was monitored by the decrease of fullerene Raman lines, the growth of inner tube Raman lines, and the development of X-ray diffraction patterns. A visual check of the growth process by HRTEM provided additional information. From the difference in time constants for the bleaching of fullerene Raman lines and for the growth of nanotube Raman lines, the existence of an intermediate phase was concluded that was eventually observed in X-ray diffraction and HRTEM. Time constants for the growth of large diameter inner tubes were up to a factor two larger than for small diameter inner tubes. The results fully support the fullerene coalescence growth model triggered by Stone-Wales transformations.

Diaphanospondylodysostosis (DSD): confirmation of a recessive disorder with abnormal vertebral ossification and nephroblastomatosis.

We report on four patients from three families, with similar radiological findings: absent (or severely delayed) ossification of vertebral bodies and associated anomalies. The babies were stillborn or died soon after birth of respiratory insufficiency. Two patients are sibs (female and male) born to first cousin Malian parents. The two others were non-consanguineous. This perinatally lethal entity comprises short neck, short wide thorax, and normally shaped limbs. Associated, inconstant anomalies are myelomeningocele, cystic kidneys with nephrogenic rests (in the sibs), and cleft palate. Radiologically, the hallmarks are absence of ossification of the vertebral bodies and sacrum, abnormal position of the vertebral pedicles, which are lamellar and angulated, ribbon-like ribs reduced in number, narrow pelvis, upward widening of the iliac wings, and unusual tilt of the ischiopubic rami, contrasting with the normal appendicular skeleton. Maroteaux briefly described one of the patients in the 2002 edition of "Maladies osseuses de l'enfant" and three sibs with similar renal and radiological findings were reported in 2003 in this Journal. Combined with the latter cases, these four new patients allow delineation of a specific lethal AR syndrome with ossification defect of the axial skeleton and renal dysplasia. We propose to name this entity diaphanospondylodysostosis.

Raman spectroscopy of fullerenes and fullerene-nanotube composites.

The discovery of fullerenes in 1985 opened a completely new field of materials research. Together with the single-wall carbon nanotubes (SWCNTs) discovered later, these curved carbon networks are a playground for pure as well as applied science. We present a review of Raman spectroscopy of fullerenes, SWCNTs and composite materials. Beginning with pristine C(60), we discuss intercalated C(60) compounds and polymerized C(60), as well as higher and endohedral fullerenes. Concerning SWCNTs, we show how the diameter distribution can be obtained from the Raman spectra and how doping modifies the spectra. Finally, the Raman response of C(60) encapsulated into SWCNTs (C(60) peapods) is discussed.