Molecular Nanotube Aggregates of beta- and ggr-Cyclodextrins Linked by Diphenylhexatrienes

Linked by strings of diphenylhexatriene (DPH) molecules, beta- and gamma-cyclodextrins (CDs) can form nanotube aggregates that contain as many as approximately 20 betaCDs (20 nanometers long) or approximately 20 to 35 gammaCDs (20 to 35 nanometers long). Nanotube formation was indicated in solution, by fluorescence anisotropy and light scattering results, and on graphite surfaces, by scanning tunneling microscopy. Tubes were not observed for the smaller alphaCDs. Molecular modeling shows that CD cavity size and the rodlike DPH structure are key factors in nanotube formation. Spectra generated by proton nuclear magnetic resonance indicate the inclusion of DPH in the interior of the CDs and formation of nanotubes in betaCDs and gammaCDs only. The photophysical properties of DPH are affected by its arrangement into a one-dimensional array within the CD nanotube, possibly because of exciton formation.     

Nanocapillarity and Chemistry in Carbon Nanotubes

Open carbon nanotubes were filled with molten silver nitrate by capillary forces. Only those tubes with inner diameters of 4 nanometers or more were filled, suggesting a capillarity size dependence as a result of the lowering of the nanotube-salt interface energy with increasing curvature of the nanotube walls. Nanotube cavities should also be less chemically reactive than graphite and may serve as nanosize test tubes. This property has been illustrated by monitoring the decomposition of silver nitrate within nanotubes in situ in an electron microscope, which produced chains of silver nanobeads separated by high-pressure gas pockets.     

Large-Scale Synthesis of Aligned Carbon Nanotubes

Large-scale synthesis of aligned carbon nanotubes was achieved by using a method based on chemical vapor deposition catalyzed by iron nanoparticles embedded in mesoporous silica. Scanning electron microscope images show that the nanotubes are approximately perpendicular to the surface of the silica and form an aligned array of isolated tubes with spacings between the tubes of about 100 nanometers. The tubes are up to about 50 micrometers long and well graphitized. The growth direction of the nanotubes may be controlled by the pores from which the nanotubes grow.     

An integrated logic circuit assembled on a single carbon nanotube

Single-walled carbon nanotubes (SWCNTs) have been shown to exhibit excellent electrical properties, such as ballistic transport over several hundred nanometers at room temperature. Field-effect transistors (FETs) made from individual tubes show dc performance specifications rivaling those of state-of-the-art silicon devices. An important next step is the fabrication of integrated circuits on SWCNTs to study the high-frequency ac capabilities of SWCNTs. We built a five-stage ring oscillator that comprises, in total, 12 FETs side by side along the length of an individual carbon nanotube. A complementary metal-oxide semiconductor-type architecture was achieved by adjusting the gate work functions of the individual p-type and n-type FETs used.     

Photoconductive coaxial nanotubes of molecularly connected electron donor and acceptor layers

Controlled self-assembly of a trinitrofluorenone-appended gemini-shaped amphiphilic hexabenzocoronene selectively formed nanotubes or microfibers with different photochemical properties. In these nanotubes, which are 16 nanometers in diameter and several micrometers long, a molecular layer of electron-accepting trinitrofluorenone laminates an electron-donating graphitic layer of pi-stacked hexabenzocoronene. The coaxial nanotubular structure allows photochemical generation of spatially separated charge carriers and a quick photoconductive response with a large on/off ratio greater than 10(4). In sharp contrast, the microfibers consist of a charge-transfer complex between the hexabenzocoronene and trinitrofluorenone parts and exhibit almost no photocurrent generation.     

Carbon nanotube quantum resistors

The conductance of multiwalled carbon nanotubes (MWNTs) was found to be quantized. The experimental method involved measuring the conductance of nanotubes by replacing the tip of a scanning probe microscope with a nanotube fiber, which could be lowered into a liquid metal to establish a gentle electrical contact with a nanotube at the tip of the fiber. The conductance of arc-produced MWNTs is one unit of the conductance quantum G0 = 2e2/h = (12.9 kilohms)-1. The nanotubes conduct current ballistically and do not dissipate heat. The nanotubes, which are typically 15 nanometers wide and 4 micrometers long, are several orders of magnitude greater in size and stability than other typical room-temperature quantum conductors. Extremely high stable current densities, J > 10(7) amperes per square centimeter, have been attained.     

Graphite polyhedral crystals

Polyhedral nano- and microstructures with shapes of faceted needles, rods, rings, barrels, and double-tipped pyramids, which we call graphite polyhedral crystals (GPCs), have been discovered. They were found in pores of glassy carbon. They have nanotube cores and graphite faces, and they can exhibit unusual sevenfold, ninefold, or more complex axial symmetry. Although some are giant radially extended nanotubes, Raman spectroscopy and transmission electron microscopy suggest GPCs have a degree of perfection higher than in multiwall nanotubes of similar size. The crystals are up to 1 micrometer in cross section and 5 micrometers in length, and they can probably be grown in much larger sizes. Preliminary results suggest a high electrical conductivity, strength, and chemical stability of GPC.     

Cartwheel architecture of Trichonympha basal body

Centrioles and basal bodies are essential for the formation of cilia, flagella, and centrosomes. They exhibit a characteristic ninefold symmetry imparted by a cartwheel thought to contain rings of SAS-6 proteins. We used cryoelectron tomography to investigate the architecture of the exceptionally long cartwheel of the flagellate Trichonympha. We found that the cartwheel is a stack of central rings that exhibit a vertical periodicity of 8.5 nanometers and is able to accommodate nine SAS-6 homodimers. The spokes that emanate from two such rings associate into a layer, with a vertical periodicity of 17 nanometers on the cartwheel margin. Thus, by using the power of biodiversity, we unveiled the architecture of the cartwheel at the root of the ninefold symmetry of centrioles and basal bodies.     

Boron nitride nanotubes

The successful synthesis of pure boron nitride (BN) nanotubes is reported here. Multi-walled tubes with inner diameters on the order of 1 to 3 nanometers and with lengths up to 200 nanometers were produced in a carbon-free plasma discharge between a BN-packed tungsten rod and a cooled copper electrode. Electron energy-loss spectroscopy on individual tubes yielded B:N ratios of approximately 1, which is consistent with theoretical predictions of stable BN tube structures.     

Synthesis of inorganic fullerene-like molecules

The reaction of [Cp*Fe(eta5-P5)] with Cu(I)Cl in solvent mixtures of CH2Cl2/CH3CN leads to the formation of entirely inorganic fullerene-like molecules of the formula [[Cp*Fe(eta5:eta1:eta1:eta1:eta1:eta1-P5)]12[CuCl]10[Cu2Cl3]5[Cu(CH3CN)2]5] (1) possessing 90 inorganic core atoms. This compound represents a structural motif similar to that of C60: cyclo-P5 rings of [Cp*Fe(eta5-P5)] molecules are surrounded by six-membered P4Cu2 rings that result from the coordination of each of the phosphorus lone pairs to CuCl metal centers, which are further coordinated by P atoms of other cyclo-P5 rings. Thus, five- and six-membered rings alternate in a manner comparable to that observed in the fullerene molecules. The so-formed half shells are joined by [Cu2Cl3]- as well as by [Cu(CH3CN)2]+ units. The spherical body has an inside diameter of 1.25 nanometers and an outside diameter of 2.13 nanometers, which is about three times as large as that of C60.     

Synthesis of large arrays of well-aligned carbon nanotubes on glass

Free-standing aligned carbon nanotubes have previously been grown above 700 degreesC on mesoporous silica embedded with iron nanoparticles. Here, carbon nanotubes aligned over areas up to several square centimeters were grown on nickel-coated glass below 666 degreesC by plasma-enhanced hot filament chemical vapor deposition. Acetylene gas was used as the carbon source and ammonia gas was used as a catalyst and dilution gas. Nanotubes with controllable diameters from 20 to 400 nanometers and lengths from 0. 1 to 50 micrometers were obtained. Using this method, large panels of aligned carbon nanotubes can be made under conditions that are suitable for device fabrication.     

Electrostatic deflections and electromechanical resonances of carbon nanotubes

Static and dynamic mechanical deflections were electrically induced in cantilevered, multiwalled carbon nanotubes in a transmission electron microscope. The nanotubes were resonantly excited at the fundamental frequency and higher harmonics as revealed by their deflected contours, which correspond closely to those determined for cantilevered elastic beams. The elastic bending modulus as a function of diameter was found to decrease sharply (from about 1 to 0.1 terapascals) with increasing diameter (from 8 to 40 nanometers), which indicates a crossover from a uniform elastic mode to an elastic mode that involves wavelike distortions in the nanotube. The quality factors of the resonances are on the order of 500. The methods developed here have been applied to a nanobalance for nanoscopic particles and also to a Kelvin probe based on nanotubes.     

Aligned carbon nanotube arrays formed by cutting a polymer resin--nanotube composite

A simple technique is described here that produces aligned arrays of carbon nanotubes. The alignment method is based on cutting thin slices (50 to 200 nanometers) of a nanotube-polymer composite. With this parallel and well-separated configuration of nanotubes it should be possible to measure individual tube properties and to demonstrate applications. The results demonstrate the nature of rheology, on nanometer scales, in composite media and flow-induced anisotropy produced by the cutting process. The fact that nanotubes do not break and are straightened after the cutting process also suggests that they have excellent mechanical properties.     

Antibody-based bio-nanotube membranes for enantiomeric drug separations

Synthetic bio-nanotube membranes were developed and used to separate two enantiomers of a chiral drug. These membranes are based on alumina films that have cylindrical pores with monodisperse nanoscopic diameters (for example, 20 nanometers). Silica nanotubes were chemically synthesized within the pores of these films, and an antibody that selectively binds one of the enantiomers of the drug was attached to the inner walls of the silica nanotubes. These membranes selectively transport the enantiomer that specifically binds to the antibody, relative to the enantiomer that has lower affinity for the antibody. The solvent dimethyl sulfoxide was used to tune the antibody binding affinity. The enantiomeric selectivity coefficient increases as the inside diameter of the silica nanotubes decreases.     

Fast mass transport through sub-2-nanometer carbon nanotubes

We report gas and water flow measurements through microfabricated membranes in which aligned carbon nanotubes with diameters of less than 2 nanometers serve as pores. The measured gas flow exceeds predictions of the Knudsen diffusion model by more than an order of magnitude. The measured water flow exceeds values calculated from continuum hydrodynamics models by more than three orders of magnitude and is comparable to flow rates extrapolated from molecular dynamics simulations. The gas and water permeabilities of these nanotube-based membranes are several orders of magnitude higher than those of commercial polycarbonate membranes, despite having pore sizes an order of magnitude smaller. These membranes enable fundamental studies of mass transport in confined environments, as well as more energy-efficient nanoscale filtration.     

A Silicon Single-Electron Transistor Memory Operating at Room Temperature

A single-electron memory, in which a bit of information is stored by one electron, is demonstrated at room temperature. The memory is a floating gate metal-oxide-semiconductor transistor in silicon with a channel width ( approximately 10 nanometers) smaller than the Debye screening length of a single electron and a nanoscale polysilicon dot ( approximately 7 nanometers by 7 nanometers) as the floating gate embedded between the channel and the control gate. Storing one electron on the floating gate screens the entire channel from the potential on the control gate and leads to (i) a discrete shift in the threshold voltage, (ii) a staircase relation between the charging voltage and the shift, and (iii) a self-limiting charging process. The structure and fabrication of the memory should be compatible with future ultralarge-scale integrated circuits.     

Self-arrangement of molybdenum particles into cubes

An unusual distribution of particle sizes has been observed following the formation of molybdenum particles by argon ion sputtering. Many of the molybdenum particles produced by sputtering at the threshold pressure for particle formation in the vapor appear to be single crystalline cubes. There are two prominent peaks in the edge length distribution of the cubes, one centered at 4.8 nanometers with a halfwidth of approximately 1.3 nanometers and the other at 17.5 nanometers. The peak for the larger cubes is approximately square and has a total width of 7.0 nanometers. Evidence is presented that the larger cubes are formed by a 3 by 3 by 3 self-arrangement of the smaller cubes, which contain approximately 7000 atoms. Self-arrangement in inorganic structures is normally only observed when the building blocks are atoms, molecules, or clusters of less than 100 atoms.     

DNA-functionalized nanotube membranes with single-base mismatch selectivity

We describe synthetic membranes in which the molecular recognition chemistry used to accomplish selective permeation is DNA hybridization. These membranes contain template-synthesized gold nanotubes with inside diameters of 12 nanometers, and a "transporter" DNA-hairpin molecule is attached to the inside walls of these nanotubes. These DNA-functionalized nanotube membranes selectively recognize and transport the DNA strand that is complementary to the transporter strand, relative to DNA strands that are not complementary to the transporter. Under optimal conditions, single-base mismatch transport selectivity can be obtained.     

Mesoscopic phase coherence in a quantum spin fluid

Mesoscopic quantum phase coherence is important because it improves the prospects for handling quantum degrees of freedom in technology. Here we show that the development of such coherence can be monitored using magnetic neutron scattering from a one-dimensional spin chain of an oxide of nickel (Y2BaNiO5), a quantum spin fluid in which no classical static magnetic order is present. In the cleanest samples, the quantum coherence length is 20 nanometers, which is almost an order of magnitude larger than the classical antiferromagnetic correlation length of 3 nanometers. We also demonstrate that the coherence length can be modified by static and thermally activated defects in a quantitatively predictable manner.     

Tubular graphite cones

We report the synthesis of tubular graphite cones using a chemical vapor deposition method. The cones have nanometer-sized tips, micrometer-sized roots, and hollow interiors with a diameter ranging from about 2 to several tens of nanometers. The cones are composed of cylindrical graphite sheets; a continuous shortening of the graphite layers from the interior to the exterior makes them cone-shaped. All of the tubular graphite cones have a faceted morphology. The constituent graphite sheets have identical chiralities of a zigzag type across the entire diameter, imparting structural control to tubular-based carbon structures. The tubular graphite cones have potential for use as tips for scanning probe microscopy, but with greater rigidity and easier mounting than currently used carbon nanotubes.