Gating of Water Flow Induced by Bending of a Carbon Nanotube

The ON-OFF state transition of the water transport induced by the structural bending of a carbon nanotube is studied by molecule dynamics simulation. The water permeation through a bent carbon nanotube shows excellent gating property with a threshold bending angle of about 14.6°. We also investigate the water density distribution inside the nanochannel to illustrate the mechanism.     

Water alignment and proton conduction inside carbon nanotubes

First-principles molecular dynamics simulations have been carried out to investigate the structure, electronic properties, and proton conductivity of water confined inside single-walled carbon nanotubes. The simulations predict the formation of a strongly connected one-dimensional hydrogen-bonded water wire resulting in a net electric dipole moment directed along the nanotube axis. An excess proton injected into the water wire is found to be significantly stabilized, relative to the gas phase, due to the high polarizability of the carbon nanotube.     

碳纳米管阵列水渗透性质的研究

碳纳米管阵列组成的碳纳米管分子膜在生物学分子器件等方面有重要应用. 本文利用分子动力学方法计算研究水分子对(11, 11)碳纳米管阵列的渗透过程. 结果发现, 只有当阵列间隙面积大于57.91 Ų时, 水分子才能进入阵列间隙中, 并揭示了碳管内部、阵列间隙内水分子结构随相邻碳管间距变化的演化趋势以及管内外水分子电偶极矩的分布特性.     

Long fine single-wall carbon nanotube growth by Nano-spin-threading: model schematics and simulations

We have investigated model schematics for a long fine single-wall carbon nanotube growth inside a larger diameter nanotube. Our proposed schematics are as follows: fullerenes are encapsulated into the nano-channel connected with fullerene storage tank; and then a inner nanotube grows via fullerene coalescence under 1200 °C in the nano-channel. Then the grown carbon nanotube is extracted from the nano-channel by mechanical control. We have investigated fullerene mergence inside single-wall carbon nanotube using classical molecular dynamics simulations based on the Tersoff–Brenner potential and the Lennard–Jones potential. During fullerene-encapsulating, since the fullerenes naturally have the kinetic energies due to the suction force and can be also accelerated by external force fields to improve the fullerene encapsulation rate, they can be migrated toward the other side of the nano-channel with kinetic energies. Our molecular dynamics simulations showed that the structural relaxation of dynamically free atoms affected on the growth of inner carbon nanotube rather than the Stone-Wales transformations. Since the broken bonds make the structural relaxation during merging to be easily achieved from the migration of carbon atoms or carbon chains, the inner nanotube grows via the re-bonding-reactions of dynamically free carbon atoms or chains as well as the Stone-Wales transformations. We could conclude that the growth rate of the inner CNT could be increased when bond-breakings between carbon atoms of fullerenes were easily achieved.     

Modeling on ion rejection using membranes comprising ultra-small radii carbon nanotubes

In this paper, we investigate the complete ion rejection using carbon nanotube membranes comprising ultra-small radii nanotubes. Three acceptance radii for a water molecule, a sodium ion and a chloride ion are determined assuming the continuous approximation. Given the acceptance radii, we may confine the scope of the nanotube radius so that only water molecules can pass through but the heavier sodium and chloride ions are repulsed from the nanotube ends. We assume that the collective motion of water molecules inside a sufficiently long nanotube is driven by atomic vibrations so that classical phonon theory might be used to deduce the average water transit time inside the nanotube for ion rejection. We predict that for carbon nanotube membranes comprising nanotubes of radii lying between 3.4 and 3.9 ?, only water molecules will pass through, and sodium and chloride ions will not, which together using phonon theory, we deduce that the smaller the nanotube radius, the lower the average water transit time and the higher the efficiency of the membrane for ion rejection purposes. The present theoretical approach has the merit of rapid computational times and indicates those nanotube radii where future experimental work might be focussed.     

First-principles simulations of chemical reactions in an HCl molecule embedded inside a C or BN nanotube induced by ultrafast laser pulses

We show by first-principles simulations that ultrafast laser pulses induce different chemical reactions in a molecule trapped inside a nanotube. A strong laser pulse polarized perpendicular to the tube axis induces a giant bond stretch of an encapsulated HCl molecule in semiconducting carbon nanotube or in a BN nanotube. Depending on the initial orientation of the HCl molecule, the subsequent laser-induced dynamics is different: either complete disintegration or rebonding of the HCl molecule. Radial motion of the nanotube is always observed and a vacancy appears on the tube wall when the HCl is perpendicular to the tube axis. Those results are important to analyze confined nanochemistry and to manipulate molecules and nanostructures encapsulated in organic and inorganic nanotubes.     

Hexagonal silicon nanotube confined inside a carbon nanotube: A first-principles study

We studied the stability, geometrical structures and electronic energy band of hexagonal silicon nanotube (SiNT) confined inside carbon nanotubes based on first-principle calculations. The results show that the encapsulating process of SiNT is exothermic in (9,9) carbon nanotube while endothermic in (8,8) and (7,7) carbon nanotubes. When the SiNT is inserted into (9,9) carbon nanotube, the insertion energy is about 0.09 eV. Energy band of SiNT@(9,9) nanotube is not distorted greatly compared with the superposition of bands of isolated SiNT and (9,9) carbon nanotube. Especially, a parabolic band occurs near the Fermi level of energy band in SiNT@(7,7) nanotube. Such a band could be a nearly free electronic state originating from carbon nanotube. Moreover, we discuss the variation of total energy as the SiNT rotates around its axis inside carbon nanotubes.     

Model estimation of the polarization forces generated by a moving point charge in carbon nanotubes

Two models of polarization forces generated inside a carbon nanotube by a moving point charge are considered. In the first model, carbon atoms are replaced by equivalent spherical dielectrics; in the second model, the carbon nanotube is replaced by a homogeneous hollow dielectric tube.     

Effect of molecular structure on fluid transport through carbon nanotubes

We perform molecular dynamics simulations to study the transport of geometrically modified water models through channels of carbon nanotube (CNT) membranes. We use two modifications to an existing water model (extended simple point charge SPC/E) as representative surrogates of molecular fluids: (1) bent model (model B) in which the HOH angle is varied while keeping the dipole moment constant by adjusting the OH bond length and (2) modified bent model (model MB) in which the HOH angle changes without any change in OH bond length thereby changing the dipole moment. Interestingly, we find that the fluid transport is a nonmonotonic function of the bond angle for both fluid models. This observed trend is not anticipated based on the fluid density as a function of the bond angle inside and outside of the nanotube channel. However, the average residence time of transmitted molecules through the channel provides an approximately inverse linear correlation with the observed flux, independent of the fluid model. Based on these correlations, we have developed an empirical design parameter connecting fluid transport through CNTs as a function of average occupancy (number of fluid molecules inside the nanotube) and the average residence time. Our results suggest that transport through carbon nanotubes can be sensitive to small changes in the structure of fluid molecules that can potentially be utilised for mixture separation.     

Dynamic mechanism for encapsulating two HIV replication inhibitor peptides with carbon nanotubes

Encapsulation of biomolecules inside a carbon nanotube(CNT) has attracted great interest because it could enable the delivery of nanoscale pharmaceutical drugs with CNT-based devices.Using a molecular dynamics simulation,we investigate the dynamic process by which human immunodeficiency virus(HIV) replication inhibitor peptides(HRIPs) are encapsulated in a water solution contained inside a CNT.The van der Waals attraction between the HRIPs and the CNT and the root-mean-square deviation are used to analyse the evolution of the encapsulation.It is found that the interaction between the HRIPs and the CNT is the main driving force for the encapsulation process,which does not cause an obvious conformational change to the HRIPs.     

Effect of Vibration on Water Transport through Carbon Nanotubes

We study the response of water permeation properties through a carbon nanotube on the time-dependent mechanical signals. It is found that there is a critical frequency of vibrating fc （about 1333 GHz） which plays a significant role in the water permeation properties. The total water flow, the net flux, the number of hydrogen bonds and the dipole flipping frequency of the single-file water chain inside the nanotube are almost unchanged for the frequency of vibrating f 〈 fc. Simulation results show that the nanotube can be effectively resistant to the mechanical noise. Such excellent effect of noise screening is attributed to the exceptional property of water molecules connected by strong hydrogen bonds with each other and forming a one-dimensional water chain inside the nanotube. Our findings are important for the understanding of why biological systems can achieve accurate information transfer in an environment full of fluctuations.     

Water transportation across narrow channel of nanometer dimension

Since the discovery of the carbon nanotube and aquaporin, the study of the transportation of water across nanochannels has become one of the hot subjects. When the radius of a nanochannel is only about one nanometer or a little larger, water confined in those nanoscale channels usually exhibits dynamics different from those in bulk system, such as the wet–dry transition due to the confinement, concerted hydrogen-bond orientations and flipping, concerted motion of water molecules, and strong interactions with external charges. Those dynamics correlate with the unique behavior of the water transportation across the channels, such as the extra-high permeability, excellent on–off gating behavior with response to the external mechanical and electrical signals and noises, enhancement by structure outside the channel, directional transportation driven by charges close to a channel or electric field. In this article, we review some of the recent progress on the study of the water molecules inside those narrow nanochannels.     

Asymmetry of the water flux induced by the deformation of a nanotube

The behavior of nano-confined water is expected to be fundamentally different from the behavior of bulk water.At the nanoscale,it is still unclear whether water flows more easily along the convergent direction or the divergent one,and whether a hourglass shape is more convenient than a funnel shape for water molecules to pass through a nanotube.Here,we present an approach to explore these questions by changing the deformation position of a carbon nanotube.The results of our molecular dynamics simulation indicate that the water flux through the nanotube changes significantly when the deformation position moves away from the middle region of the tube.Different from the macroscopic level,we find water flux asymmetry(water flows more easily along the convergent direction than along the divergent one),which plays a key role in a nano water pump driven by a ratchet-like mechanism.We explore the mechanism and calculate the water flux by means of the Fokker-Planck equation and find that our theoretical results are well consistent with the simulation results.Furthermore,the simulation results demonstrate that the effect of deformation location on the water flux will be reduced when the diameter of the nanochannel increases.These findings are helpful for devising water transporters or filters based on carbon nanotubes and understanding the molecular mechanism of biological channels.     

Electron microscope vualization of muliphase fluids contained in closed carbon nanotubes

Aqueous multiphase fluids trapped in closed multiwall carbon nanotubes are visualized with high resolution using transmission electron microscopy (TEM). The hydrothermally synthesized nanotubes have inner diameter of 70 nm and wall thickness 20 nm, on average. The nanotubes are hydrophilic due to oxygen groups attached on their wall surfaces. Segregated liquid inclusions contained in the nanotubes under high pressure can be mobilized by heating. A resistive heating stage is utilized to heat a thin membrane inside a nanotube, causing the membrane to evaporate slowly and eventually pinch off. Focused electron beam heating is employed as a second means of thermal stimulation, which results in localized heating. With the latter method, gas/liquid interface motion is observed inside the thin channel of a carbon nanotube. Experiments like the ones presented herein may help understand the dynamics of fluids contained in nanoscale channels.     

单壁碳纳米管受限空间内水的分布

碳纳米管管腔作为分子物质的纳米通道,其储存或输送水的能力具有重要研究价值.为了研究碳纳米管管腔受限空间对水分子团簇结构和分布的影响,本文采用分子动力学方法探究了管径、手性和温度对单壁碳纳米管管腔内水的结构和分布的影响.结果表明:在常温下,管径尺寸范围为1.018—1.253 nm的单壁碳纳米管管内易形成有序的多元环水结构,此范围以外碳纳米管管内难以形成水的有序结构;且随着管径尺寸增大,多元环水呈现由三元环至六元环的结构变化;范德瓦耳斯势分布分析表明,在上述管径范围内,水分子趋向于贴近碳纳米管管壁分布而形成水的有序结构.对比管径尺寸差别较小的碳纳米管,其手性对多元环水结构影响不大.多元环水结构的稳定性表现出温度依赖性,管径较大的碳纳米管内的多元环水的有序结构更易随温度升高而消失.     

Nano watermill driven by revolving charge

A novel nanoscale watermill for the unidirectional transport of water molecules through a curved single-walled carbon nanotube(SWNT) is proposed and explored by molecular dynamics simulations. In this nanoscale system, a revolving charge is introduced to drive a water chain confined inside the SWNT, the charge and the tube together serving as a nano waterwheel and nano engine. A resonance-like phenomenon is found, and the revolving frequency of the charge plays a key role in pumping the water chain. The water flux across the SWNT increases with respect to the revolving frequency of the external charge and it reaches its maximum when the frequency is 4 THz. Correspondingly, the number of hydrogen bonds in the water chain inside the SWNT decreases dramatically as the frequency increases from 4 THz to 25 THz. The mechanism behind the resonance phenomenon has been investigated systematically. Our findings are helpful for the design of nanoscale fluidic devices and energy converters.     

Single-Walled Carbon Nanotubes Acting as Controllable Transport Channels

The motion and equilibrium distribution of water molecules adsorbed inside neutral and negatively charged singlewalled carbon nanotubes (SWNTs) have been studied using molecular dynamics simulations (MDSs) at room temperature based on CHARMM (Chemistry at HARvard Molecular Mechanics) potential parameters. We find that water molecules have a conspicuous electropism phenomenon and regular tubule patterns inside and outside the charged tube wall. The analyses of the motion behaviour of water molecules in the radial and axial directions show that by charging the SWNT, the adsorption efficiency is greatly enhanced, and the electric field produced by the charged SWNTs prevents water molecules from flowing out of the nanotube. However, water molecules can travel through the neutral SWNT in a fluctuating manner. This indicates that by electrically charging and uncharging the SWNTs, one can control the adsorption and transport behaviour of polar molecules in SWNTs for using as a stable storage medium or long transport channels. The transport velocity can be tailored by changing the charge on the SWNTs, which may have a further application as modulatable transport channels.     

Molecular dynamics investigation into the electric charge effect on the operation of ion-based carbon nanotube oscillators

The fabrication of nanoscale oscillators working in the gigahertz (GHz) range and beyond has now become the focal center of interest to many researchers. Motivated by this issue, this paper proposes a new type of nano-oscillators with enhanced operating frequency in which both the inner core and outer shell are electrically charged. To this end, molecular dynamics (MD) simulations are performed to investigate the mechanical oscillatory behavior of ions, and in particular chloride ion, tunneling through electrically charged carbon nanotubes (CNTs). It is assumed that the electric charges with similar sign and magnitude are evenly distributed on two ends of nanotube. The interatomic interactions between carbon atoms and van der Waals (vdW) interactions between ion and nanotube are respectively modeled by Tersoff-Brenner and Lennard-Jones (LJ) potential functions, whereas the electrostatic interactions between ion and electric charges are modeled by Coulomb potential function. A comprehensive study is conducted to get an insight into the effects of different parameters such as sign and magnitude of electric charges, nanotube radius, nanotube length and initial conditions (initial separation distance and velocity) on the oscillatory behavior of chloride ion-charged CNT oscillators. It is shown that, the chloride ion frequency inside negatively charged CNTs is lower than that inside positively charged ones with the same magnitude of electric charge, while it is higher than that inside uncharged CNTs. It is further observed that, higher frequencies are generated at higher magnitudes of electric charges distributed on the nanotube.     

Hard X-radiation emitted by a charged particle moving in a carbon nanotube

We consider the radiation emitted by a charged particle propagating inside a single-layer carbon nanotube and interacting without delay with the screened charges of the nuclei of carbon atoms. It is shown, for example, that a beam of positrons with an energy of around 1 GeV and a divergence of some 10⁻⁴ rad is captured by the nanotube and emits hard X-rays with an energy of about 0.3 MeV in the direction of its propagation. The theoretical results obtained allow one to consider carbon nanotubes as a new source of hard X-radiation.     

Spontaneous decay of excited atomic states near a carbon nanotube

The spontaneous decay process of an excited atom placed inside or outside a carbon nanotube is analyzed. Calculations have been performed for various achiral nanotubes. The effect of the nanotube surface is shown to increase the atomic spontaneous decay rate by up to 6 orders of magnitude compared with that of the same atom in vacuum. This increase is associated with nonradiative decay via surface excitations in the nanotube.