Hydrogen‐bond networks in finite ice nanotubes

An exhaustive analysis of all H‐bond networks for finite elements of ice nanotubes formed by up to 32 water molecules (3,660,732 configurations in total) is performed. The results constitute a unique database and demonstrate the H‐bond network formation and changes with the growth of the ice nanotube. The statistical analysis shows that H‐bonds can be classified according to their structural positions, and there are remarkable dependencies of the cooperativity energy and bond lengths on the system's morphology. The study of low‐energy configurations supports the conclusion about the ferroelectric order in ice nanotubes with odd numbers of water molecules in the ring. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Melting behavior of water in cylindrical pores: carbon nanotubes and silica glasses

We report a study of the effects of confinement in multi-walled carbon nanotubes and mesoporous silica glasses (SBA-15) on the solid structure and melting of both H(2)O and D(2)O ice, using differential scanning calorimetry, dielectric relaxation spectroscopy, and neutron diffraction. Multi-walled nanotubes of 2.4, 3.9 and 10 nm are studied, and the SBA-15 studied has pores of mean diameter 3.9 nm; temperatures ranging from approximately 110 to 290 K were studied. We find that the melting point is depressed relative to the bulk water for all systems studied, with the depression being greater in the case of the silica mesopores. These results are shown to be consistent with molecular simulation studies of freezing in silica and carbon materials. The neutron diffraction data show that the cubic phase of ice is stabilized by the confinement in carbon nanotubes, as well as in silica mesopores, and persists up to temperatures of about 240 K, above which there is a transition to the hexagonal ice structure.     

Confined water inside single-walled carbon nanotubes: global phase diagram and effect of finite length

Studies on confined water are important not only from the viewpoint of scientific interest but also for the development of new nanoscale devices. In this work, we aimed to clarify the properties of confined water in the cylindrical pores of single-walled carbon nanotubes (SWCNTs) that had diameters in the range of 1.46 to 2.40 nm. A combination of x-ray diffraction (XRD), nuclear magnetic resonance, and electrical resistance measurements revealed that water inside SWCNTs with diameters between 1.68 and 2.40 nm undergoes a wet-dry type transition with the lowering of temperature; below the transition temperature T(wd), water was ejected from the SWCNTs. T(wd) increased with increasing SWCNT diameter D. For the SWCNTs with D = 1.68, 2.00, 2.18, and 2.40 nm, T(wd) obtained by the XRD measurements were 218, 225, 236, and 237 K, respectively. We performed a systematic study on finite length SWCNT systems using classical molecular dynamics calculations to clarify the effect of open ends of the SWCNTs and water content on the water structure. It was found that ice structures that were formed at low temperatures were strongly affected by the bore diameter, a = D - σ(OC), where σ(OC) is gap distance between the SWCNT and oxygen atom in water, and the number of water molecules in the system. In small pores (a < 1.02 nm), tubule ices or the so-called ice nanotubes (ice NTs) were formed irrespective of the water content. On the other hand, in larger pores (a > 1.10 nm) with small water content, filled water clusters were formed leaving some empty space in the SWCNT pore, which grew to fill the pore with increasing water content. For pores with sizes in between these two regimes (1.02 < a < 1.10 nm), tubule ice also appeared with small water content and grew with increasing water content. However, once the tubule ice filled the entire SWCNT pore, further increase in the water content resulted in encapsulation of the additional water molecules inside the tubule ice. Corresponding XRD measurements on SWCNTs with a mean diameter of 1.46 nm strongly suggested the presence of such a filled structure.     

Self-metallization of photocatalytic porphyrin nanotubes

Porphyrin nanotubes represent a new class of nanostructures for which the molecular building blocks can be altered to control their structural and functional properties. Nanotubes containing tin(IV) porphyrins are photocatalytically active and can reduce metal ions from aqueous solution. The metal is deposited selectively onto tube surfaces, producing novel composite nanostructures that have potential applications as nanodevices. Two examples presented here are nanotubes with a continuous gold wire in the core and a gold ball at the end and nanotubes coated with platinum nanoparticles mainly on their outer surfaces. The latter are capable of photocatalytic reduction of water to hydrogen.     

Miniature organic transistors with carbon nanotubes as quasi-one-dimensional electrodes

As the dimensions of electronic devices approach those of molecules, the size, geometry, and chemical composition of the contact electrodes play increasingly dominant roles in device functions. It is shown here that single-walled carbon nanotubes (SWNT) can be used as quasi-one-dimensional (1D) electrodes to construct organic field effect transistors (FET) with molecular scale width ( approximately 2 nm) and channel length (1-3 nm). An important feature owing to the quasi-1D electrode geometry is the favorable gate electrostatics that allows for efficient switching of ultra-short organic channels. This affords room temperature conductance modulation by orders of magnitude for organic transistors that are only several molecules in length, with switching characteristics superior to similar devices with lithographically patterned metal electrodes. With nanotubes, covalent carbon-carbon bonds could be utilized to form contacts to molecular materials. The unique geometrical, physical, and chemical properties of carbon nanotube electrodes may lead to various interesting molecular devices.     

The role of activation energy and reduced viscosity on the enhancement of water flow through carbon nanotubes

Molecular dynamics simulations are carried out to study the pressure driven fluid flow of water through single walled carbon nanotubes. A method for the calculation of viscosity of the confined fluid based on the Eyring theory of reaction rates is proposed. The method involves the calculation of the activation energy directly from the molecular dynamics trajectory information. Computations are performed using this method to study the effect of surface curvature on the confined fluid viscosity. The results indicate that the viscosity varies nonlinearly with the carbon nanotube diameter. It is concluded that the reason behind the observed enhancement in the rate of fluid flow through carbon nanotubes could be the nonlinear variation of viscosity.     

Conductance switching in diarylethenes bridging carbon nanotubes

The recently reported photoswitching of diarylethene derivative molecules bridging carbon nanotube (CNT) contacts is theoretically analyzed. The short lifetime of the lowest unoccupied molecular orbital (LUMO) indicates that neither the open nor closed form of the molecule can be photoexcited into a charge-neutral excited state for any appreciable length of time preventing photochromic ring opening. Analysis of the highest occupied molecular orbital (HOMO) and LUMO lifetimes also suggests that photoexcitation results in oxidation of the molecules. This either reduces the quantum yield of photochromic ring closing, or it gives rise to the possibility of oxidative ring closing. Analysis of the resistance values and energy levels indicates that the HOMO energy levels of the closed isomers relevant for transport must lie within a few k(B)T of the CNT Fermi level. For armchair contacts, the change in resistance with isomer or substituent group is the result of shifts in the energy level of the molecular HOMO. The coupling of the molecular HOMO to the CNT contacts is insensitive to the isomer type or substituent group. For zigzag CNTs, the conductance is dominated by surface states at the Fermi level on the cut ends of the CNTs so that the conductance is relatively insensitive to the isomer type, and the conductance switching ratio is low. Multiple bridging molecules can interact coherently, resulting in energy splitting, shifting, and interference that cause a nonlinear change in conductance with increasing numbers of molecules. Instead of a factor of 3 increase in conductance expected for three independent channels, a factor of 10(3) increase in conductance is obtained for three bridging molecules.     

A density-functional theory of hydrogen adsorption on indium nitride nanotubes

First-principles calculations based on density functional theory (DFT) are used to study the chemisorption properties of one, two, and four hydrogen atoms on the zigzag and armchair single-walled InN nanotubes (InNNTs).The results indicate that the H atom is strongly bounded to the exterior wall of (4, 4) InNNTs compared with the (7, 0) InNNTs, while the chemisorption energies corresponding to the most stable configuration of H₂ dissociation and a single H atom are found to be–3.85 and–3.26 eV, respectively. Furthermore, the effect of the hydrogen storage on the geometries and electronic properties of related InN nanotubes were also discussed. The computed density of states (DOS) indicates that the energy gap of the zigzag and armchair InN nanotubes on hydrogen adsorptions are significantly decreased which can increase the electrical conductance of the tubes. Therefore, InN nanotubes due to the high binding energy can be used for hydrogen storage.     

Ferroelectric mobile water

In molecular dynamics simulations single-domain ferroelectric water is produced under ordinary ambient conditions utilizing carbon nanotubes open to a water reservoir. This ferroelectric water diffuses while keeping its proton-ordered network intact. The mobile/immobile water transitions and the step-wise changes in net polarization of water are observed to occur spontaneously. The immobile water becomes mobile by transforming into the single-domain ferroelectric water. Our general notion of relating a more highly ordered structure with a lower temperature has so far restricted researchers' attention to very low temperatures when experimenting on proton-ordered phases of water. The present study improves our general understanding of water, considering that the term 'ferroelectric water' has so far practically stood for 'ferroelectric ice,' and that single-domain ferroelectric water has not been reported even for the ice nanotubes.     

Electronic transport in Z-junction carbon nanotubes

In this paper, the electronic transport in different Z-shape carbon nanotubes containing double knee junction structures on the same tube is studied. One consists of (5,5)-(9,0)-(5,5) double knee nano-metal-metal-metal junctions and another consists (6,6)-(10,0)-(6,6) double knee nano-metal-semiconductor-metal junctions. With the nearest-neighbor pi-orbital tight-binding model, quantum conductances of these double knee junctions are calculated using the Landauer formula. The interesting conductance curves are provided to exhibit a potential application in the arena of molecular electronics.     

Thermodynamics of water entry in hydrophobic channels of carbon nanotubes

Experiments and computer simulations demonstrate that water spontaneously fills the hydrophobic cavity of a carbon nanotube. To gain a quantitative thermodynamic understanding of this phenomenon, we use the recently developed two phase thermodynamics method to compute translational and rotational entropies of confined water molecules inside single-walled carbon nanotubes and show that the increase in energy of a water molecule inside the nanotube is compensated by the gain in its rotational entropy. The confined water is in equilibrium with the bulk water and the Helmholtz free energy per water molecule of confined water is the same as that in the bulk within the accuracy of the simulation results. A comparison of translational and rotational spectra of water molecules confined in carbon nanotubes with that of bulk water shows significant shifts in the positions of the spectral peaks that are directly related to the tube radius.     

Self-assembly and proton conductance of organic nanotubes from pillar[5]arenes

Organic nanotubes have been assembled from pillar[5]arenes 1 and 2. Compound 1 gelates organic solvents through the formation of tubular fibers which are evidenced by TEM and XRD experiments, while 2 assembles into two different channels under the template effect of water wires. In addition, the water wires in the nanotubes of 2 can be under selective proton conductance. The results described herein represent a new strategy for building tubular structures.     

Dynamics of water confined in single- and double-wall carbon nanotubes

Using high-resolution quasielastic neutron scattering, we investigated the temperature dependence of single-particle dynamics of water confined in single- and double-wall carbon nanotubes with the inner diameters of 14+/-1 and 16+/-3 A, respectively. The temperature dependence of the alpha relaxation time for water in the 14 A nanotubes measured on cooling down from 260 to 190 K exhibits a crossover at 218 K from a Vogel-Fulcher-Tammann law behavior to an Arrhenius law behavior, indicating a fragile-to-strong dynamic transition in the confined water. This transition may be associated with a structural transition from a high-temperature, low-density (<1.02 gcm(3)) liquid to a low-temperature, high-density (>1.14 gcm(3)) liquid found in molecular dynamics simulation at about 200 K. However, no such dynamic transition in the investigated temperature range of 240-195 K was detected for water in the 16 A nanotubes. In the latter case, the dynamics of water simply follows a Vogel-Fulcher-Tammann law. This suggests that the fragile-to-strong crossover for water in the 16 A nanotubes may be shifted to a lower temperature.     

Interactions between polymers and carbon nanotubes: a molecular dynamics study

We used force-field-based molecular dynamics to study the interaction between polymers and carbon nanotubes (CNTs). The intermolecular interaction energy between single-walled carbon nanotubes and polymers was computed, and the morphology of polymers adsorbed to the surface of nanotubes was investigated. Furthermore, the "wrapping" of nanotubes by polymer chains was examined. It was found that the specific monomer structure plays a very important role in determining the strength of interaction between nanotubes and polymers. The results of our study suggest that polymers with a backbone containing aromatic rings are promising candidates for the noncovalent binding of carbon nanotubes into composite structures. Such polymers can be used as building blocks in amphiphilic copolymers to promote increased interfacial binding between the CNT and a polymeric matrix.     

Molecular dynamics simulation of pressure-driven water flow in silicon-carbide nanotubes

Many properties of silicon carbide (SiC) nanotubes, such as their high mechanical strength and resistance to corrosive environments, are superior to those of their carboneous counterparts, namely, carbon nanotubes (CNTs) and, therefore, SiC nanotubes can be a viable alternative to CNTs in a variety of applications. We employ molecular dynamics simulations to examine flow of water in SiC nanotubes and to study the differences and similarities with the same phenomenon in the CNTs. The simulations indicate that SiC nanotubes always provide larger flow enhancements than those reported for the CNTs. Moreover, a given flow enhancement in SiC nanotubes requires an applied pressure gradient that is at least an order of magnitude smaller than the corresponding value in a CNT of the same size.     

Radiowave dielectric investigation of water confined in channels of carbon nanotubes

Structure and dynamics of water confined in channels of diameter of few nanometer in size strongly differ from the ones of water in the bulk phase. Here, we present radiowave dielectric relaxation measurements on water-filled single-walled carbon nanotubes, with the aim of highlighting some aspects on the molecular electric dipole organization of water responding to high spatial confinement in a hydrophobic environment. The observed dielectric spectra, resulting into two contiguous relaxation processes, allow us to separate the confined water in the interior of the nanotubes from external water, providing support for the existence in the confinement region of water domains held together by hydrogen bonds. Our results, based on the deconvolution of the dielectric spectra due to the presence of a bulk and a confined water phase, furnish a significantly higher Kirkwood correlation factor, larger than the one of water in bulk phase, indicating a strong correlation between water molecules inside nanotubes, not seen in bulk water.     

Graphite-incorporated MoS2 nanotubes: a new coaxial binary system

Graphite-filled MoS2 nanotubes were synthesized by pyrolizing propylene inside MoS2 nanotubes prepared by a template-assisted technique. The large coaxial nanotubes were constituted of graphite sheets inserted between the MoS2 layers, forming the outer part, and coaxial multiwall carbon nanotubes intercalated with MoS2 inside. High-resolution electron microscopy (HREM) and electron energy loss spectroscopy techniques along with molecular dynamics simulation and quantum mechanical calculations were used to characterize the samples. The one-dimensional structures exhibit diverse morphologies such as long straight and twisted nanotubes with several structural irregularities. The interplanar spacing between the MoS2 layers was found to increase from 6.3 to 7.4 A due to intercalation with carbon. Simulated HREM images revealed the presence of mechanical strains in the carbon-intercalated MoS2 layers as the reason for obtaining these twisted nanostructures. The mechanism of formation of carbon-intercalated MoS2 tubular structures and their stability and electronic properties are discussed. Our results open up the possibility of using MoS2 nanotubes as templates for the synthesis of new one-dimensional binary-phase systems.     

Hydrogen adsorption in defected carbon nanotubes

Recently there has been lot of interest in the development of hydrogen storage in various systems for the large-scale application of fuel cells, mobiles and for automotive uses. Hectic materials research is going on throughout the world with various adsorption mechanisms to increase the storage capacity. It was observed that physisorption proves to be an effective way for this purpose. Some of the materials in this race include graphite, zeolite, carbon fibers and nanotubes. Among all these, the versatile material carbon nanotube (CNT) has a number of favorable points like porous nature, high surface area, hollowness, high stability and light weight, which facilitate the hydrogen adsorption in both outer and inner portions. In this work we have considered armchair (5,5), zig zag (10,0) and chiral tubes (8,2) and (6,4) with and without structural defects to study the physisorption of hydrogen on the surface of carbon nanotubes using DFT calculations. For two different H₂ configurations, adsorption binding energies are estimated both for defect free and defected carbon nanotubes. We could observe larger adsorption energies for the configuration in which the hydrogen molecular axis perpendicular to the hexagonal carbon ring than for parallel to C–C bond configuration corresponding to the defect free nanotubes. For defected tubes the adsorption energies are calculated for various configurations such as molecular axis perpendicular to a defect site octagon and parallel to C–C bond of octagon and another case where the axis perpendicular to hexagon in defected tube. The adsorption binding energy values are compared with defect free case. The results are discussed in detail for hydrogen storage applications.     

Acyclic cucurbit[n]uril molecular containers selectively solubilize single-walled carbon nanotubes in water

Making single-walled carbon nanotubes (SWNTs) soluble in water is a challenging first step to use their remarkable electronic and optical properties in a variety of applications. We report that acyclic cucurbit[n]uril molecular containers 1 and 2 selectively solubilize small-diameter and low chiral angle SWNTs. The selectivity is tunable by increasing the concentration of the molecular containers or by adjusting the ionic strength of the solution. Even at a concentration 1000 times lower than typically required for surfactants, the molecular containers render SWNTs soluble in water. Molecular mechanics simulations suggest that these C-shaped acyclic molecules complex the SWNTs such that a large portion of nanotube sidewalls are exposed to the external environment. These "naked" nanotubes fluoresce upon patching the exposed surface with sodium dodecylbenzene sulfonate.     

Helical rosette nanotubes with tunable stability and hierarchy

The design of nanostructured materials with tunable dimensions and properties that maintain their structural integrity under physiological conditions is a major challenge in biomedical engineering and nanomedicine. Helical rosette nanotubes (HRN) are a new class of materials produced through a hierarchical self-assembly process of low molecular weight synthetic organic modules in water. Here, we describe a synthetic strategy to tune their stability and hierarchy by preorganization of the self-assembling units, control of net charge per unit of nanotube surface area, amphiphilicity, and number of H-bonds per self-assembling module, and through peripheral steric (de)compression. Using these criteria, HRNs with tunable stability and hierarchical architecture were produced from self-assembling modules that (a) persist as individual molecules in solution, (b) self-assemble into HRN but denature at high temperature (<85 degrees C), (c) self-assemble into HRN whose structural integrity persists even in boiling water (>95 degrees C), and (d) self-assemble into well-dispersed short nanotubes, long nanotubes, ribbons, or superhelices. Given the biocompatibility, synthetic accessibility, and chemical and physical tunability of these materials, numerous applications in biomedical engineering, materials science, and nanoscience and technology are envisioned.