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A new method was used to measure the fraction of semiconducting nanotubes in various as-grown or processed single-walled carbon nanotube (SWCNT) samples. SWCNT number densities were compared in images from near-IR photoluminescence (semiconducting species) and AFM (all species) to compute the semiconducting fraction. The results show large variations among growth methods and effective sorting by density gradient ultracentrifugation. This counting-based method provides important information about SWCNT sample compositions that can guide controlled growth methods and help calibrate bulk characterization techniques.

The spillover phenomenon, which essentially involves transfer of H from a metal catalyst to a graphitic receptor, has been considered promising for efficient hydrogen storage. An open question about the spillover mechanism is how a H atom binds to graphene instead of forming the thermodynamically preferred H(2). Using ab initio calculations, we show that the catalyst saturation provides a way to the adsorption of hydrogen on the receptor by increasing the H chemical potential to a spillover favorable range. Although it is energetically unfavorable for the spillover to occur on a pristine graphene surface, presence of a phase of hydrogenated graphene facilitates the spillover by significantly improving the C-H binding. We show that thermodynamic spillover can occur, both from the free-standing and from the receptor-supported clusters. Further, the computed energy barrier of the motion of a H from the catalyst to the hydrogenated graphene is small (0.7 eV) and can be overcome at operational temperatures.

Ultrasmall copper nanoparticles are produced by N,N,N',N'-tetramethyl-p-phenylenediamine (TMPDA) reduction of aqueous Cu(2+) on a hydrophobically immobilized sodium dodecylbenzenesulfonate (SDBS) surfactant template in the presence of sodium citrate at room temperature. Single-walled carbon nanotubes (SWNTs) act as a scaffold controlling the size of the SDBS micelle, which in turn confines a limited number of copper ions near the nanotube surface. TMPDA reduction forms copper nanoparticles as confirmed by X-ray photoelectron spectroscopy and electron diffraction, whose size was determined by atomic force microscopy and transmission electron microscopy to be approximately 2 nm. Particles formed in the absence of the SWNT immobilizer range from 2 to 150 nm.

Growth of high quality, vertically aligned single-walled carbon nanotubes (carpets) is achieved using a rapid insertion hot filament chemical vapor deposition (HF-CVD) technique. The effect of the substrate morphology on growth is explored by comparing carpets grown on epitaxially polished MgO substrates to those grown on "as-cut", macroscopically rough MgO substrates. Depending on the substrate morphology, we observe differences in both the overall carpet morphology as well as the diameter distribution of nanotubes grown in the carpet based on optical measurements. In addition, we explore the role of water in the growth of carpets on MgO and the conventional Al2O3 coated Si substrates. We find that the addition of a small amount of water is beneficial to the growth rates of the SWNT carpets, enhancing the growth rates by up to eight times.

The formation and stability of bimetallic catalyst particles, in the framework of carbon nanotube growth, is studied using the Bozzolo-Ferrante-Smith (BFS) method for alloys. Monte Carlo-Metropolis simulations with the BFS method are utilized in order to predict and study equilibrium configurations for nanoscale catalyst particles which are directly relevant to the catalyst state prior to growth of carbon nanotubes. At the forefront of possible catalyst combinations is the popular Fe-Mo bimetallic catalyst, which we have recently studied experimentally. We explain our experimental results, which indicate that the growth observed is dependent on the order of co-catalyst deposition, in the straightforward interpretation of BFS strain and chemical energy contributions toward the formation of Fe-Mo catalyst prior to growth. We find that the competition between the formation of metastable inner Mo cores and clusters of surface-segregated Mo atoms in Fe-Mo catalyst particles influences catalyst formation, and we investigate the role of Mo concentration and catalyst particle size in this process. Finally, we apply the same modeling approach to other prominent bimetallic catalysts and suggest that this technique can be a powerful tool to understand and manipulate catalyst design for highly efficient carbon nanotube growth.

Near-infrared fluorescence videomicroscopy has been used to study simultaneously the translational and rotational diffusion of individual semiconducting single-walled carbon nanotubes (SWCNTs) in aqueous suspension. Analysis of translational trajectories revealed diffusion coefficient values from approximately 0.3 to 6 microm(2)/s. The nanotube lengths deduced from these values ranged between approximately 130 nm and 6 microm. From the minor bending motions observed in individual nanotubes several micrometers in length, we confirmed that the shorter SWCNTs of primary interest here can be considered to be rigid rods under normal conditions. Because the nanotubes act as highly rigid, photostable, steady, and anisotropic fluorophores, it was possible to monitor their rotational reorientations through fluctuations in emission intensity under linearly polarized excitation. The magnitudes of observed orientational fluctuations varied substantially among individual nanotubes. These magnitudes correlated strongly with translational diffusion coefficient, reflecting the length dependence of both types of motions. Combined translational and rotational measurements also revealed the influence of local environment on nanotube mobility.

Films of the molybdenum-iron nanocluster [H x PMo 12O 40 subsetH 4Mo 72Fe 30(O 2CMe) 15O 254(H2O) 68] (FeMoC) were generated on gold via the self-assembly technique using two divergent routes. The first route entails the self-assembly of unfunctionalized FeMoC onto a preprepared carboxyl-terminated SAM on gold. The second route involves the preparation of thiol-terminated functionalized FeMoC clusters, which are then allowed to self-assemble onto bare gold surfaces. Monolayer films of FeMoC clusters are attained via both routes, with the second route requiring shorter immersion times (2 days) than the first route (6 days). Multilayer films of FeMoC are formed via the second route for immersion times longer than 2 days. Characterization of these films using optical ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy confirm the self-assembly of the clusters on the surfaces.

An efficient new method is demonstrated for measuring length distributions of semiconducting single-walled carbon nanotubes (SWCNTs) through analysis of their highly polarized photoluminescence when aligned by shear flows. Instrumentation and procedures are developed to characterize nanotube lengths in bulk suspensions with rapid data acquisition and interpretation. Applying the method with spectrally resolved SWCNT emission provides the first measurements of (n,m)-specific length distributions. A positive correlation is found between average length and nanotube diameter, although this correlation is weaker following extensive sample centrifugation. Intense sonication shortened all nanotube species and had the strongest effect on those with small diameters. The new method should provide a useful alternative to atomic force microscopy for characterizing SWCNT lengths.

Scaffolds play a pivotal role in the tissue engineering paradigm by providing temporary structural support, guiding cells to grow, assisting the transport of essential nutrients and waste products, and facilitating the formation of functional tissues and organs. Single-walled carbon nanotubes (SWNTs), especially ultra-short SWNTs (US-tubes), have proven useful for reinforcing synthetic polymeric scaffold materials. In this article, we report on the in vivo biocompatibility of US-tube reinforced porous biodegradable scaffolds in a rabbit model. US-tube nanocomposite scaffolds and control polymer scaffolds were implanted in rabbit femoral condyles and in subcutaneous pockets. The hard and soft tissue response was analyzed with micro-computed tomography (micro CT), histology, and histomorphometry at 4 and 12 weeks after implantation. The porous US-tube nanocomposite scaffolds exhibited favorable hard and soft tissue responses at both time points. At 12 weeks, a three-fold greater bone tissue ingrowth was seen in defects containing US-tube nanocomposite scaffolds compared to control polymer scaffolds. Additionally, the 12 week samples showed reduced inflammatory cell density and increased connective tissue organization. No significant quantitative difference in polymer degradation was observed among the various groups; qualitative differences between the two time points were consistent with expected degradation due to the progression of time. Although no conclusions can be drawn from the present study concerning the osteoinductivity of US-tube nanocomposite scaffolds, the results suggest that the presence of US-tubes may render nanocomposite scaffolds bioactive assisting osteogenesis.

A new class of water-soluble C60 transfecting agents has been prepared using Hirsch-Bingel chemistry and assessed for their ability to act as gene-delivery vectors in vitro. In an effort to elucidate the relationship between the hydrophobicity of the fullerene core, the hydrophilicity of the water-solubilizing groups, and the overall charge state of the C60 vectors in gene delivery and expression, several different C60 derivatives were synthesized to yield either positively charged, negatively charged, or neutral chemical functionalities under physiological conditions. These fullerene derivatives were then tested for their ability to transfect cells grown in culture with DNA carrying the green fluorescent protein (GFP) reporter gene. Statistically significant expression of GFP was observed for all forms of the C60 derivatives when used as DNA vectors and compared to the ability of naked DNA alone to transfect cells. However, efficient in vitro transfection was only achieved with the two positively charged C60 derivatives, namely, an octa-amino derivatized C60 and a dodeca-amino derivatized C60 vector. All C60 vectors showed an increase in toxicity in a dose-dependent manner. Increased levels of cellular toxicity were observed for positively charged C60 vectors relative to the negatively charged and neutral vectors. Structural analyses using dynamic light scattering and optical microscopy offered further insights into possible correlations between the various derivatized C60 compounds, the C60 vector/DNA complexes, their physical attributes (aggregation, charge) and their transfection efficiencies. Recently, similar Gd@C60-based compounds have demonstrated potential as advanced contrast agents for magnetic resonance imaging (MRI). Thus, the successful demonstration of intracellular DNA uptake, intracellular transport, and gene expression from DNA using C60 vectors suggests the possibility of developing analogous Gd@C60-based vectors to serve simultaneously as both therapeutic and diagnostic agents.

We present a robust method for synthesis of aligned, single-walled carbon nanotube (CNT) "flying carpets" from nanostructured alumina flakes. Roll-to-roll e-beam deposition is utilized to produce the flakes, and hot filament chemical vapor deposition is utilized to grow dense, aligned carbon nanotubes from the flakes with remarkably high CNT yields. The flakes are captured inside a mesh cage and freely suspended in the gas flow during growth. Optical characterization indicates the presence of high quality, small diameter single-walled carbon nanotubes.

Carbon nanotubes (CNTs) have been grown using Fe, Co, Ni, and Co/Fe spin-on-catalyst (SOC) systems, involving the metal salt dispersed with a spin-on-glass precursor. During initial growth runs (CH4/H2/900 degrees C), the CNT yield followed the order Co-SOC > Fe-SOC >> Ni-SOC. The Fe catalysts produced the longest nanotubes at the expense of a larger average CNT diameter and broader diameter distribution than the Co-SOC system. A series of Co/Fe-SOCs were prepared where as the atomic percentage of Co is increased nucleation of CNT increases but the CNT length decreases. The linear relationship between the diameter and length of CNTs grown from the Co/Fe-SOC suggests that slow growth is beneficial with respect to control over CNT diameter. After initial CNT growth, the original samples were subjected to additional growth runs. Four individual reactions were observed in the Fe-SOC and binary Co/Fe-SOC: regrowth (amplification), double growth (a second CNT growing from a previously active catalyst), CNT etching, and nucleation from initially inactive catalysts (new growth). CNT etching was observed for the mixed catalyst systems (Co/Fe-SOC) but not for either Fe-SOC or Co-SOC. During the regrowth experiments, CNTs were observed that were not present after the initial growth run (and were not as a result of amplification or double growth). Thus, catalysts, which were initially inactive toward nucleation of CNTs in the original growth run, are capable of becoming activated when placed back into the furnace and submitted to regrowth under identical conditions.

Oxidation of graphite may be carried out by reaction with meta-chloroperoxybenzoic acid to yield graphite epoxide. Scanning tunneling microscopy (STM) showed that the functionalization occurs at the edges rather than on the basal plane of the graphite. Quantification of the epoxide content is possible through the deepoxidation reaction using MeReO3/PPh3.

The fluorescence spectra of individual semiconducting single-walled carbon nanotubes embedded in polymer films were measured during the application of controlled stretching and compressive strains. Nanotube band gaps were found to shift in systematic patterns that depend on the (n,m) structural type and are in excellent agreement with the predictions of theoretical models. Loss of nanotube-host adhesion was revealed by abrupt irregularities in plots of spectral shift vs strain.

Single-walled carbon nanotubes (SWNTs) were functionalized by direct fluorination and subsequent reaction with 6-aminohexanoic acid for water-soluble carboxylic acid functionalized SWNTs (AHA-SWNTs). Both of the compounds were used as precursors to attach SWNTs to APTES coated silicon surfaces. AHA-SWNTs in aqueous solution were reacted with APTES self-assembled monolayers (SAMs) with coupling reagents N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) and N-hydroxysuccinimide (NHS). The surface coverage is a function of concentration of AHA-SWNTs, solvent and coupling method. While for the fluorinated SWNTs (F-SWNTs), direct addition of F-SWNTs to preformed APTES SAMs at 90 degrees C shows essentially no reaction, in contrast to the one-pot reaction of F-SWNTs with APTES molecules in the presence of SWNTs on a silicon substrate. This reaction route provides a convenient method to attach SWNTs to silicon surfaces.

Far-field near-infrared fluorescence microscopy of single-walled carbon nanotubes (SWNTs) has been hampered by the diffraction limit to resolution. A new analysis method is presented that allows subwavelength (

Nanotechnology offers many opportunities for enhanced diagnostic and therapeutic medicine against cancer and other diseases. In this review, the special properties that result from the nanoscale size of quantum dots, metal colloids, superparamagnetic iron oxide, and carbon-based nanostructures are reviewed and interpreted against a background of the structural and electronic detail that gives rise to their nanotechnologic behavior. The detection and treatment of cancer is emphasized, with special attention paid to the biologic targeting of the disease. The future of nanotechnology in cancer research and clinical practice is projected to focus on 'theranostic' nanoparticles that are both diagnostic and therapeutic by design.

The reaction between fluorinated single-wall carbon nanotubes (F-SWNTs) and branched (M(w) = 600, 1800, 10000, and 25000 Da) or linear (M(w) = 25000 Da) polyethyleneimine (PEI) yields the covalent attachment of the polymer to the sidewalls of the nanotubes. The resulting PEI-functionalized SWNTs (PEI-SWNTs) were characterized by solid-state (13)C NMR, Raman spectroscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy, atomic force microscopy, transmission electron microscopy, and thermal gravimetric analysis studies. As expected, the number of polymer molecules per SWNT is larger for low molecular weight PEI than for high molecular weight PEI. However, above 1800 Da, the number of polymer molecules per SWNT does not vary as much. This is supported by Raman spectral data that shows the D:G ratio is relatively insensitive of the molecular weight for M(w) > 1800 Da. The PEI-SWNTs are shown to have solubility in aqueous media of up to 0.4 mg x mL(-1). Solid-state (13)C NMR shows the presence of carboxylate substituents that have been attributed to carbamate formation as a consequence of the reversable CO(2) absorption to the primary amine substituents of the PEI. Desorption of CO(2) is accomplished by heating under argon at 75 degrees C, while the dependence of the quantity of CO(2) absorbed on temperature and the molecular weight of the PEI is reported. Under the conditions investigated the maximum absorption of 9.2% w/w is observed for PEI(25000)-SWNT at 27 degrees C. The possible CO(2) absorption applications of the PEI-SWNTs is discussed.

A new kind of carbon foam, which is based on the welding of single-walled carbon nanotubes, is built in a computer simulation. Its precisely defined architecture and all atomic positions allow one to perform detailed theoretical analysis of the properties. Such foam is as light as 19 of steel, while its stiffness is similar and nearly isotropic, and it represents a strong three-dimensional material with various possible applications. Furthermore, its nanoporous structure is accessible to molecular hydrogen and the potential surface analysis indicates that it should be an excellent hydrogen storage medium. Importantly, such foam is a feasible structure that can be produced based on the known tube/fullerene welding techniques.

Single walled carbon nanotubes (SWNTs) may be made soluble in a range of organic solvents without sidewall functionalization via their reduction by Na/Hg amalgam in the presence of dibenzo-18-crown-6. The [Na(dibenzo-18-crown-6)]n[SWNT] complex has been characterized by UV-Visible, Raman, and AFM and is consistent with no additional sidewall functionalization as compared with raw SWNTs, while MALDI-MS shows the presence of the [Na(dibenzo-18-crown-6)]+ ion. Solubility is greatest in CH2Cl2 and DMF being comparable to surfactant dispersed SWNTs, however, measurable solubilities are also observed in hexane, toluene, and alcohols. Reaction with alkyl halides (bromohexane, 1-iodododecane) yields alkyl functionalized SWNTs (i.e., C6H11-SWNTs and C12H25-SWNTs) with an C(SWNT):alkyl ratio (ca. 40:1) significantly lower than that observed by the analogous reaction of alkyl halides with reduced SWNTs formed by the Billups method in liquid ammonia.

Single-nanotube photometry was used to measure the product of absorption cross section and fluorescence quantum yield for 12 (n,m) structural species of semiconducting single-walled carbon nanotubes in aqueous SDBS suspension. These products ranged from 1.7 to 4.5 x 10(-19) cm(2)/C atom, generally increasing with optical band gap as described by the energy gap law. The findings suggest fluorescent quantum yields of approximately 8% for the brightest, (10,2) species and introduce the empirical calibration factors needed to deduce quantitative (n,m) distributions from bulk fluorimetric intensities.

We report the formation of a fullerene-peptide conjugate via the incorporation of a fullerene substituted phenylalanine derivative, "Bucky amino acid" (Baa), to a cationic peptide, which acts as a passport for intracellular delivery, enabling transport of a range of sequences into HEK-293, HepG2, and neuroblastoma cells where the peptides in the absence of the fullerene amino acid cannot enter the cell. Delivery of the fullerene species to either the cytoplasm or nucleus of the cell is demonstrated. Fullerene peptides based on the nuclear localization sequence (NLS), H-Baa-Lys(FITC)-Lys-Lys-Arg-Lys-Val-OH, can actively cross over the cell membrane and accumulate significantly around the nucleus of HEK-293 and neuroblastoma cells, while H-Baa-Lys(FITC)-Lys8-OH accumulates in the cytoplasm. Cellular studies show that the uptake for the anionic peptide Baa-Lys(FITC)Glu4Gly3Ser-OH is greatly reduced in comparison with the cationic fullerene peptides of the same concentration. The hydrophobic nature of the fullerene assisting peptide transport is suggested by the effect of gamma-cyclodextrin (CD) in lowering the efficacy of transport. These data suggest that the incorporation of a fullerene-based amino acid provides a route for the intracellular delivery of peptides and as a consequence the creation of a new class of cell penetrating peptides.

A series of [60]fullerene-substituted phenylalanine (Baa) and lysine derivatives have been prepared by the condensation of 1,2-(4'-oxocyclohexano)fullerene with the appropriately protected (4-amino)phenylalanine and lysine, respectively. Conversion of the imine to the corresponding amine is achieved by di-acid catalyzed hydroboration. The reduction of the imine is not accompanied by hydroboration of the fullerene cage. The [70]fullerene phenylalanine derivative has also been prepared as have the di-amino acid derivatives. The compounds were characterized by MALDI-TOF mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry. 1H and 13C NMR spectroscopy allowed the observation of diastereomers. Fullerene-substituted peptides may be synthesized on relatively large scale by solid-phase peptide synthesis. The presence of the C60-substituted amino acid in a peptide has a significant effect on the secondary structures and self-assembly properties of peptides as compared to the native peptide. The antioxidant assay of Baa and a Baa-derived anionic peptide was determined to be significantly more potent than Trolox.

Single-walled carbon nanotubes have been functionalized and the specific surface areas of the functionalized nanotubes measured. Contrary to expectations, functionalization leads to a decrease in specific surface area compared to that of the unfunctionalized nanotubes. Treatment with a concentrated 1:1 nitric/sulfuric acid mixture followed by high-temperature baking at 1000 degrees C was found to increase the specific surface area of the nanotubes. For the unfunctionalized SWNTs, this treatment increases the specific surface area (SSA) by 20%. In the case of SWNTs functionalized by n-butyl groups the increase in the SSA was nearly 2-fold with the value increasing from 410 (drying at 110 degrees C) to 770 m2/gm (acid and bake treatment followed by drying at 110 degrees C). For the ozonized SWNTs, the SSA increases more than 3-fold from 381 (drying at 110 degrees C) to 1068 m2/gm (acid and bake treatment followed by drying at 110 degrees C). SEM images indicate that the nanotubes rebundle in the solid state with an average bundle size of 10-30 nm. AFM studies show that the ozonized tubes have been cut to short bundles after ozonolysis. Hydrogen uptake studies carried out on the baked ozonized tubes led to a 3 wt % hydrogen uptake at 77 K and 30 bar.

Epoxidation of single-walled carbon nanotubes (SWNTs) may be carried out by the reaction of SWNTs with either trifluorodimethyldioxirane or 3-chloroperoxybenzoic acid; the resulting O-SWNTs are spectroscopically similar to those formed by ozonolysis. Quantification of the epoxide substituents is possible through the catalytic de-epoxidation reaction using MeReO3/PPh3 and the 31P NMR spectroscopy. The de-epoxidation methodology may be used to determine that wet air oxidation is preferable to either acid or O2/SF6 purification. We have demonstrated that previously assumed "pure" SWNTs are actually "doped" to a level of at least 1 oxygen per 250 carbon atoms.

The synthetic conditions for the isolation of the iron-molybdenum nanocluster FeMoC [HxPMo12O40 [subset]H4Mo72Fe30(O2CMe)15O254(H2O)98], along with its application as a catalyst precursor for VLS growth of SWNTs have been studied. As-prepared FeMoC is contaminated with the Keplerate cage [H4Mo72Fe30(O2CMe)15O254(H2O)98] without the Keggin [HxPMo12O40]n- template, however, isolation of pure FeMoC may be accomplished by Soxhlet extraction with EtOH. The resulting EtOH solvate is consistent with the replacement of the water ligands coordinated to Fe being substituted by EtOH. FeMoC-EtOH has been characterized by IR, UV-vis spectroscopy, MS, XPS and 31P NMR. The solid-state 31P NMR spectrum for FeMoC-EtOH (delta-5.3 ppm) suggests little effect of the paramagnetic Fe3+ centers in the Keplerate cage on the Keggin ion's phosphorous. The high chemical shift anisotropy, and calculated T1 (35 ms) and T2 (8 ms) values are consistent with a weak magnetic interaction between the Keggin ion's phosphorus symmetrically located within the Keplerate cage. Increasing the FeCl2 concentration and decreasing the pH of the reaction mixture optimizes the yield of FeMoC. The solubility and stability of FeMoC in H2O and MeOH-H2O is investigated. The TGA of FeMoC-EtOH under air, Ar and H2 (in combination with XPS) shows that upon thermolysis the resulting Fe : Mo ratio is highly dependent on the reaction atmosphere: thermolysis in air results in significant loss of volatile molybdenum components. Pure FeMoC-EtOH is found to be essentially inactive as a pre-catalyst for the VLS growth of single-walled carbon nanotubes (SWNTs) irrespective of the substrate or reaction conditions. However, reaction of FeMoC with pyrazine (pyz) results in the formation of aggregates that are found to be active catalysts for the growth of SWNTs. Activation of FeMoC may also be accomplished by the addition of excess iron. The observation of prior work's reported growth of SWNTs from FeMoC is discussed with respect to these results.

We report a study on Dielectrophoresis Field Flow Fractionation of Single-Wall Carbon Nanotubes (SWNTs). SWNTs, individually suspended in 1% SDBS solution, were separated by type when they passed a dielectrophoresis field flow fractionation device where 1 MHz AC voltage was supplied and the field strength was well below 1 V per mum. Furthermore, we uniquely observed enrichment of semiconductive SWNTs based on their band gap. In addition to Raman spectrum, UV-vis absorption and NIR fluorescence spectra were used for solution samples for characterization.

Gadolinium-based carbon nanostructures are poised to make a significant impact as advanced contrast agents (CAs) for magnetic resonance imaging (MRI) in medicine. This paper reviews and forecasts gadonanotubes as synthons for the design of high-performance MRI CA probes with efficacies up to 100 times greater than current clinical CAs. This level of performance is vital for achieving the goal of cellular and molecular imaging with MRI. These new materials will be useful for in vivo MRI applications as circulating drug nanocapsules because of their low toxicities, extremely high relaxivities, and potential for cellular targeting and induced cell death by magnetic hyperthermia.