Abstract: The liquid crystal morphologies of symmetrical diacy phosphatidylcholine liposomes examined in this research study were found to be dependent on saturated hydrocarbon chain length. Both powder X-ray diffraction and synchrotron mid-IR spectromicroscopy indicate that phosphatidylcholines with short hydrocarbon tails (i.e. ten and twelve carbons) are more likely to form unilamellar liposomes while those with long hydrocarbon tails (i.e. eighteen and twenty carbons) are more likely to form multilamellar liposomes. Hydrocarbon chain lengths of fourteen and sixteen represent a transitional zone between these two liquid crystal morphologies. The FTIR spectra where a shoulder develops on the peak at wavenumber 1750 cm(-1) particularly highlights the change in the packing of adjacent molecules in the transitional zone.
Abstract: Synchrotron infrared radiation has been successfully coupled through an infrared (IR) microscope to a thin-cavity external reflectance cell to study the diffusion controlled redox of a ferrocyanide solution. Excellent signal-to-noise ratios were achieved even at aperture settings close to the diffraction limit. Comparisons of noise levels as a function of aperture size demonstrate that this can be attributed to the high brilliance of synchrotron radiation relative to a conventional thermal source. Time resolved spectroscopic studies of diffusion controlled redox behavior have been measured and compared to purely electrochemical responses of the thin-cavity cell. Marked differences between the two measurements have been explained by analyzing diffusion in both the axial (linear) and radial dimensions. Whereas both terms contribute to the measured current and charge, only species that originate in the volume element above the electrode and diffuse in the direction perpendicular to the electrode surface are interrogated by IR radiation. Implications for the use of ultramicroelectrodes and synchrotron IR (SIR) to study electrochemical processes in the submillisecond time domain are discussed.
Abstract: The interaction of O(2) with gold foil and gold nanoparticles grown by thermal deposition on TiO(2)(110) was studied by in situ ambient pressure X-ray photoelectron spectroscopy at room temperature. No spontaneous dissociation of O(2) was observed either on Au foil or on Au nanoparticles up to 1 Torr of O(2). X-ray irradiation, however, is very effective in promoting gold oxidation on both surfaces in the presence of O(2). Our results help reconcile recent conflicting experimental observations regarding the activation of molecular oxygen, which is a crucial issue in Au catalyzed oxidation reactions.
Abstract: We introduce a new technique for measurement of the thermal conductivity of ultrathin films of single-walled carbon nanotubes (SWNTs) utilizing IR radiation as heat source and the SWNT film as thermometer. The technique is applied to study the temperature dependence of the thermal conductivity of an as-prepared SWNT film obtained in the electric arc discharge process and a film of purified SWNTs prepared by vacuum filtration. The interplay between thermal and electrical transport in SWNT networks is analyzed in relation to the type of intertube junctions and the possibility of optimizing the thermal and electrical properties of SWNT networks for specific applications is discussed.
Abstract: C(60).C(8)H(8) and C(70).C(8)H(8) are prototypes of rotor-stator cocrystals. We present infrared and Raman spectra of these materials and show how the rotor-stator nature is reflected in their vibrational properties. We measured the vibrational spectra of the polymer phases poly(C(60)C(8)H(8)) and poly(C(70)C(8)H(8)) resulting from a solid-state reaction occurring on heating. On the basis of the spectra, we propose a connection pattern for the fullerene in poly(C(60)C(8)H(8)), where the symmetry of the C(60) molecule is D(2h). On illuminating the C(60).C(8)H(8) cocrystal with green or blue light, a photochemical reaction was observed leading to a product similar to that of the thermal polymerization.
Abstract: In this study we present direct sidewall functionalization of single-walled nanotubes, carried out via two different dissolving metal reduction methods. A modified Birch reduction scheme and a novel synthetic route were applied to form carbanion complexes on the surface of the nanotubes in liquid NH3 and tetrahydrofuran, respectively. The carbanion complex was reacted with a series of alkyl and aryl halogenides resulting in the corresponding SWNT derivatives. We determined the chemical composition and the thermal stability of the functionalized nanotubes by thermogravimetry/mass spectrometry and pyrolysis-gas chromatography. Characteristic decomposition peaks, observed in the temperature range of 350-600 degrees C, suggest the formation of covalent derivatives upon functionalization that is also supported by Raman spectroscopic studies. The influence of the functional groups and the type of nanotubes on the thermal stability, as well as the relationship between the functional group content and the intensity of the Raman D peak are discussed.
Abstract: The photoresponse in the electrical conductivity of a single-walled carbon nanotube (SWNT) film is dramatically enhanced when the nanotube film is suspended in vacuum. We show here that the change in conductivity is bolometric (caused by heating of the SWNT network). Electron-phonon interactions lead to ultrafast relaxation of the photoexcited carriers, and the energy of the incident infrared (IR) radiation is efficiently transferred to the crystal lattice. It is not the presence of photoexcited holes and electrons, but a rise in temperature, that results in a change in resistance; thus, photoconductivity experiments cannot be used to support the band picture over the exciton model of excited states in carbon nanotubes. The photoresponse of suspended SWNT films is sufficiently high that they may function as the sensitive element of an IR bolometric detector.
Abstract: Cubane (C8H8) and fullerene (C60) are famous cage molecules with shapes of platonic or archimedean solids. Their remarkable chemical and solid-state properties have induced great scientific interest. Both materials form polymorphic crystals of molecules with variable orientational ordering. The idea of intercalating fullerene with cubane was raised several years ago but no attempts at preparation have been reported. Here we show that C60 and similarly C70 form high-symmetry molecular crystals with cubane owing to topological molecular recognition between the convex surface of fullerenes and the concave cubane. Static cubane occupies the octahedral voids of the face-centred-cubic structures and acts as a bearing between the rotating fullerene molecules. The smooth contact of the rotor and stator molecules decreases significantly the temperature of orientational ordering. These materials have great topochemical importance: at elevated temperatures they transform to high-stability covalent derivatives although preserving their crystalline appearance. The size-dependent molecular recognition promises selective formation of related structures with higher fullerenes and/or substituted cubanes.
