Gd2@C79N: isolation, characterization, and monoadduct formation of a very stable heterofullerene with a magnetic spin state of S = 15/2.

The dimetallic endohedral heterofullerene (EHF), Gd(2)@C(79)N, was prepared and isolated in a relatively high yield when compared with the earlier reported heterofullerene, Y(2)@C(79)N. Computational (DFT), chemical reactivity, Raman, and electrochemical studies all suggest that the purified Gd(2)@C(79)N, with the heterofullerene cage, (C(79)N)(5-) has comparable stability with other better known isoelectronic metallofullerene (C(80))(6-) cage species (e.g., Gd(3)N@C(80)). These results describe an exceptionally stable paramagnetic molecule with low chemical reactivity with the unpaired electron spin density localized on the internal diatomic gadolinium cluster and not on the heterofullerene cage. EPR studies confirm that the spin state of Gd(2)@C(79)N is characterized by a half-integer spin quantum number of S = 15/2. The spin (S = ½) on the N atom of the fullerene cage and two octet spins (S = 7/2) of two encapsulated gadoliniums are coupled with each other in a ferromagnetic manner with a small zero-field splitting parameter D. Because the central line of Gd(2)@C(79)N is due to the Kramer's doublet with a half-integer spin quantum number of S = 15/2, this relatively sharp line is prominent and the anisotropic nature of the line is weak. Interestingly, in contrast with most Gd(3+) ion environments, the central EPR line (g = 1.978) is observable even at room temperature in a toluene solution. Finally, we report the first EHF derivative, a diethyl bromomalonate monoadduct of Gd(2)@C(79)N, which was prepared and isolated via a modified Bingel-Hirsch reaction.

Transport in carbon nanotube field-effect transistors tuned using low energy electron beam exposure.

We have studied the effect of low energy (30 keV) electron beam exposure on carbon nanotube field-effect transistors, using an electron beam lithography system to provide spatially controlled dosage. We show that reversible tuning of the transport behavior is possible when a backgate potential is applied during exposure. n-type behavior can be obtained by electron beam exposure of a device with positive gate bias, while ambipolar behavior can be obtained via negative gate bias. The observed transport behavior is relatively stable in time. We propose possible mechanisms for the observed phenomena and suggest directions for further research.

Specific vectorial immobilization of oligonucleotide-modified yeast cytochrome C on carbon nanotubes.

Iso-1-cytochrome c from the yeast Saccharomyces cerevisiae (YCC) contains a surface cysteine residue, Cys102, that is located opposite to the lysine-rich side containing the exposed heme edge, which is the docking site for enzymes. Site-specific vectorial immobilization of YCC via Cys102 on single-walled carbon nanotubes (SWNT) thus provides a selective interface between nanoscopic electronic devices and complex enzymes. We have achieved this by modification of Cys102 with an oligonucleotide (dT(18)). Atomic force microscopy, fluorescence imaging, and cyclic voltammetry show the specific adsorption of YCC, modified with dT(18), on the SWNT sidewall with retention of its native properties. Pretreatment of the SWNT with Triton-X405 blocks the nonspecific binding of untreated YCC but does not interfere with binding of the oligonucleotide-modified YCC.

Electrochemistry at single-walled carbon nanotubes: the role of band structure and quantum capacitance.

We present a theoretical description of the kinetics of electrochemical charge transfer at single-walled carbon nanotube (SWNT) electrodes, explicitly taking into account the SWNT electronic band structure. SWNTs have a distinct and low density of electronic states (DOS), as expressed by a small value of the quantum capacitance. We show that this greatly affects the alignment and occupation of electronic states in voltammetric experiments and thus the electrode kinetics. We model electrochemistry at metallic and semiconducting SWNTs as well as at graphene by applying the Gerischer-Marcus model of electron transfer kinetics. We predict that the semiconducting or metallic SWNT band structure and its distinct van Hove singularities can be resolved in voltammetry, in a manner analogous to scanning tunneling spectroscopy. Consequently, SWNTs of different atomic structure yield different rate constants due to structure-dependent variations in the DOS. Interestingly, the rate of charge transfer does not necessarily vanish in the band gap of a semiconducting SWNT, due to significant contributions from states which are a few k(B)T away from the Fermi level. The combination of a nanometer critical dimension and the distinct band structure makes SWNTs a model system for studying the effect of the electronic structure of the electrode on electrochemical charge transfer.

Individual single-walled carbon nanotubes as nanoelectrodes for electrochemistry.

We demonstrate the use of individual single-walled carbon nanotubes (SWNTs) as nanoelectrodes for electrochemistry. SWNTs were contacted by nanolithography, and cyclic voltammetry was performed in aqueous solutions. Interestingly, metallic and semiconducting SWNTs yielded similar steady-state voltammetric curves. We clarify this behavior through a model that considers the electronic structure of the SWNTs. Interfacial electron transfer to the SWNTs is observed to be very fast but can nonetheless be resolved due to the nanometer critical dimension of SWNTs. These studies demonstrate the potential of using a SWNT as a model carbon nanoelectrode for electrochemistry.

Raman spectroscopic investigation of H2, HD, and D2 physisorption on ropes of single-walled, carbon nanotubes.

We have observed the S- and Q-branch Raman spectra of H2, HD, and D2 adsorbed at 85 K and pressures up to 8 atm on single-walled, carbon nanotubes (SWNT). Comparative data for H2 on graphite and C60 were also collected. Frequency-downshifted and upshifted features were observed in the Q-branch spectra of H2 on C60 and SWNT. These shifts are small and are therefore inconsistent with charge transfer. An H2-surface potential with van der Waals and electrostatic terms was developed and used to estimate the shifts in the frequency of the Q(0) transition of H2 adsorbed in two types of sites. These calculations corroborate the experimental findings and indicate physisorption in multiple sites of the SWNT ropes.