N$_{3}^{-}$ azide anion confined inside finite-size carbon nanotubes

In this work, the confinement of an N\(_{3}^{-}\) azide anion inside finite-size single-wall zigzag and armchair carbon nanotubes of different diameters has been studied by wave function and density functional theory. Unrelaxed and relaxed interaction energies have been computed, resulting in a favorable interaction between the guest and host system. In particular, the largest interaction has been observed for the confinement in an armchair (5,5) carbon nanotube, for which a natural population analysis as well as an investigation based on the molecular electrostatic potential has been carried out. The nature of the interaction between the two fragments appears to be mainly electrostatic, favored by the enhanced polarizability of the nanotube wall treated as a finite system and passivated by hydrogen atoms. The results obtained are promising for possible applications of this complex as a starting point for the stabilization of larger polynitrogen compounds, suitable as a high-energy density material.     

Effect of chirality,length and diameter of carbon nanotubes on the adsorption of 20 amino acids: a molecular dynamics simulation study

We carried out molecular dynamics simulations to study the adsorption of all the 20 amino acids (AAs; aromatic, polar and non-polar) on the surface of chiral, zigzag and armchair single-walled carbon nanotubes. The adsorption was occurring in all systems. In the aromatic AAs, the π–π stacking and the semi-hydrogen bond formation cause a strong interaction with the carbon nanotubes (CNTs). We also investigated the chirality, length and diameter dependencies on adsorption energies. We found that all AAs have more tendency to adsorption on the chiral and zigzag CNTs over the armchair. The results show that increasing both the diameter and the length causes the enhancement of the adsorption energy. But, the effect of the length is more than of the diameter. For example, the adsorption energy of Trp on the surface of CNT (4,1), with 2 nm length, is 20.4 kcal/mol. When the length of CNT becomes twice, the adsorption energy increases by 24 ± 0.3%. But by doubling the diameter, the adsorption energy increased only by 9.8 ± 0.25%.     

DFT studies of COOH tip-functionalized zigzag and armchair single wall carbon nanotubes

Structure and energy calculations of pristine and COOH-modified model single wall carbon nanotubes (SWCNTs) of different length were performed at B3LYP/6-31G* level of theory. From 1 to 9 COOH groups were added at the end of the nanotube. The differences in structure and energetics of partially and fully functionalized SWCNTs at one end of the nanotube are observed. Up to nine COOH groups could be added at one end of (9,0) zigzag SWCNT in case of full functionalization. However, for (5,5) armchair SWCNT, the full functionalization was impossible due to steric crowding and rim deformation. The dependence of substituent attachment energy on the number of substituents at the carbon nanotube rim was observed.     

First-principles investigation of the interaction of gold and palladium with armchair carbon nanotube

In this paper, we investigate the adsorption mechanisms at the interface between carbon nanotubes and metal electrodes that can influence the Schottky barrier (SB). We developed a theoretical model based on the first-principles density functional theory for the interaction of an armchair single-wall carbon nanotube (SWNT) with either Au(111) or Pd(111) surface. We considered the side-wall contact by modelling the full SWNT as well as the end-contact geometry using the graphene ribbon model to mimic the contact with very large diameter nanotubes. Strong interaction has been found for the Pd–SWNT interface where the partial density of states (DOS) shows that d-orbitals of palladium are dominant at the Fermi energy so that the hybrid Pd-orbitals have the correct symmetry to overlap with π-electrons and form covalent bonds. The SWNT can only be physisorbed on the gold surface for which the contribution to the DOS of the d-orbitals is very low. Moreover, the filling of antibonding states makes the Au–SWNT bond unstable. The average and ‘atom to atom’ energy barriers at the interface have been evaluated. The matching of open-edge carbon dimers with metal lattice in the end-contact geometry is more likely for large diameter SWNTs and this makes lower the SB at the interface.     

Carbon doped boron phosphide nanotubes: A computational study

A computational study based on density functional theory (DFT) calculations has been performed to investigate the properties of the electronic structure of carbon doped boron phosphide nanotube (C-doped BPNT). Pristine and the C-doped structures of two representative (6,0) zigzag and (4,4) armchair BPNTs have been investigated. At first, the geometries of the structures have been allowed to relax by optimization. Subsequently, NMR parameters have been calculated in the optimized structures. The results indicated that the influence of C-doping was more significant on the geometries of the zigzag model than the armchair one. The difference of band gap energies between the pristine and C-doped armchair BPNT was larger than the zigzag model. Significant differences of NMR parameters of those nuclei directly contributed to the C-doping atoms have been observed.     

Translational dynamic friction analysis of double-walled carbon nanotubes

Conflicting results on the effects of commensurability, overlap area, helicity and end configuration of double-walled carbon nanotubes (DWCNTs) on translational intertube friction have been reported. We perform molecular dynamics simulations on DWCNTs with different commensurabilities, overlap areas, helicities and end configurations to analyse the intertube friction behaviour and clarify these results. It is found that commensurability and overlap area play an insignificant role, while the atomic configurations of nanotube ends play a dominant role: armchair, normal and reconstructed zigzag ends contribute little to intertube friction; while the irregular ends with dangling atoms greatly increase the friction force. This end effect may also explain the role of helicity in the intertube friction. Implications of the end effect on experimental observations are also discussed.     

Injectable nanocomposites of single-walled carbon nanotubes and biodegradable polymers for bone tissue engineering

We have investigated the dispersion of single-walled carbon nanotubes (SWNTs) and functionalized SWNTs (F-SWNTs) in the unsaturated, biodegradable polymer poly(propylene fumarate) (PPF) and examined the rheological properties of un-cross-linked nanocomposite formulations as well as the electrical and mechanical properties of cross-linked nanocomposites. F-SWNTs were produced from individual SWNTs by a diazonium-based method and dispersed better than unmodified SWNTs in both un-cross-linked and cross-linked PPF matrix. Cross-linked nanocomposites with F-SWNTs were superior to those with unmodified SWNTs in terms of their mechanical properties. Specifically, nanocomposites with 0.1 wt % F-SWNTs loading resulted in a 3-fold increase in both compressive modulus and flexural modulus and a 2-fold increase in both compressive offset yield strength and flexural strength when compared to pure PPF networks, whereas the use of 0.1 wt % SWNTs gained less than 37% mechanical reinforcement. These extraordinary mechanical enhancements considered together with Raman scattering and sol fraction measurements indicate strong SWNT-PPF interactions and increased cross-linking densities resulting in effective load transfer. With enhanced mechanical properties and capabilities of in situ injection and cross-linking, these SWNT/polymer nanocomposites hold significant implications for the fabrication of bone tissue engineering scaffolds.     

Molecular dynamics simulation of melting and crystallization processes of polyethylene clusters confined in armchair single-walled carbon nanotubes

The confined interaction is important to understand the melting and crystallization of polymers within single-wall carbon tube (SWNT). However, it is difficult for us to observe this interaction. In the current work, the structures and behaviors of melting and crystallization for polyethylene (PE) clusters confined in armchair single-walled carbon nanotubes ((n,n)-SWNTs) are investigated and examined based on molecular dynamics (MD) simulations. The nonbonded energies, structures, Lindemman indices, radial density distributions, and diffusion coefficients are used to demonstrate the features of melting phase transition for PE clusters confined in (n,n)-SWNTs. The chain end-to-end distance (R _n) and chain end-to-end distribution are used to examine the flexibility of the PE chain confined in SWNT. The global orientational order parameter (P₂) is employed to reveal the order degree of whole PE polymer. The effect of polymerization degree on melting temperature and the influence of SWNT chirality on structure of PE cluster are examined and discussed. Results demonstrate that within the confined environment of SWNT, PE clusters adopt novel co-axial crystalline layer structure, in which parallel chains of each layer are approximately vertical to tube axis. The disordered-ordered transformation of PE chains in each layer is an important structural feature for crystallization of confined PE clusters. SWNTs have a considerable effect on the structures and stabilities of the confined PE clusters.     

The influence of the carbon nanotube on the structural and dynamical properties of cholesterol cluster

We have performed the molecular dynamics simulations for the free cholesterol cluster and the same cluster located near the carbon nanotube. We have found that the cholesterol molecules quite evenly cover the surface of single walled armchair (10, 10) carbon nanotube, forming the molecular layer. Moreover, the characteristic alignment of cholesterol molecules within the layer (along the nanotube) is observed. The comparison of the structural and dynamical observable characterizing cholesterol molecule is presented and discussed, both for the cluster with and without the presence of the nanotube.     

Methane storage in homogeneous armchair open-ended single-walled boron nitride nanotube triangular arrays: a grand canonical Monte Carlo simulation study

The physisorption of methane in homogeneous armchair open-ended SWBNNT triangular arrays was evaluated using grand canonical ensemble Monte Carlo simulation for tubes 11.08, 13.85, 16.62, and 19.41 ? [(8,8), (10,10), (12,12), and (14,14), respectively] in diameter, at temperatures of 273, 298, 323, and 373 K, and at fugacities of 0.5-9.0 Mpa. The intermolecular forces were modeled using the Lennard-Jones potential model. The absolute, excess, and delivery adsorption isotherms of methane were calculated for the various boron nitride nanotube arrays. The specific surface areas and the isosteric heats of adsorption, Q(st), were also studied, different isotherm models were fitted to the simulated adsorption data, and the model parameters were correlated. According to the results, it is possible to reach 108% and 140% of the US Department of Energy's target for CH(4) storage (180 v/v at 298 K and 35 bar) using the SWBNNT array with nanotubes 16.62 and 19.41 ? in diameter, respectively, as adsorbent. The results show that for a van der Waals gap of 3.4 ?, there is no interstitial adsorption except for arrays containing nanotubes with diameters of >15.8 ?. Multilayer adsorption starts to occur in arrays containing nanotubes with diameters of >16.62 ?, and the minimum pressure required for multilayer adsorption is 1.0 MPa. A brief comparison of the methane adsorption capacities of single-walled carbon and boron nitride nanotube arrays was also performed.     

Hydrogen adsorption capacities of multi-walled boron nitride nanotubes and nanotube arrays: a grand canonical Monte Carlo study

Hydrogen adsorption in multi-walled boron nitride nanotubes and their arrays was studied using grand canonical Monte Carlo simulation. The results show that hydrogen storage increases with tube diameter and the distance between the tubes in multi-walled boron nitride nanotube arrays. Also, triple-walled boron nitride nanotubes present the lowest level of hydrogen physisorption, double-walled boron nitride nanotubes adsorb hydrogen better when the diameter of the inner tube diameter is sufficiently large, and single-walled boron nitride nanotubes adsorb hydrogen well when the tube diameter is small enough. Boron nitride nanotube arrays adsorb hydrogen, but the percentage of adsorbed hydrogen (by weight) in boron nitride nanotube arrays is rather similar to that found in multi-walled boron nitride nanotubes. Also, when the Langmuir and Langmuir-Freundlich equations were fitted to the simulated data, it was found that multi-layer adsorptivity occurs more prominently as the number of walls and the tube diameter increase. However, in single-walled boron nitride nanotubes with a small diameter, the dominant mechanism is monolayer adsorptivity.     

The interaction between nerve cells and carbon nanotube networks made by CVD process investigation

In this research we investigate neuroblastoma cells cultivated on single-walled carbon nanotubes networks made by CVD method on silicon substrates. The complex analysis of grown cells made by atomic force, electron microscopy and Raman spectroscopy was carried out and the effect of nanotube growth process on proliferation factor was investigated. It is shown that despite of a weak decrease in proliferation, cell morphology remains unchanged and no physical or chemical interaction between carbon nanotubes and cells is observed. The results of the research can be used to investigate the interaction between conductive nano- materials and cells for the development of neural replacement implants. Also they can be useful in bio-electronic interface investigation of signal propagation in neurons.     

Can trans-polyacetylene be formed on single-walled carbon-doped boron nitride nanotubes?

Recently, the grafting of polymer chains onto nanotubes has attracted increasing attention as it can potentially be used to enhance the solubility of nanotubes and in the development of novel nanotube-based devices. In this article, based on density functional theory (DFT) calculations, we report the formation of trans-polyacetylene on single-walled carbon-doped boron nitride nanotubes (BNNTs) through their adsorption of a series of C(2)H(2) molecules. The results show that, rather than through [2 + 2] cycloaddition, an individualmolecule would preferentially attach to a carbon-doped BNNT via "carbon attack" (i.e., a carbon in the C(2)H(2) attacks a site on the BNNT). The adsorption energy gradually decreases with increasing tube diameter. The free radical of the carbon-doped BNNT is almost completely transferred to the carbon atom at the end of the adsorbed C(2)H(2) molecule. When another C(2)H(2) molecule approaches the carbon-doped BNNT, it is most energetically favorable for this C(2)H(2) molecule to be adsorbed at the end of the previously adsorbed C(2)H(2) molecule, and so on with extra C(2)H(2) molecules, leading to the formation of polyacetylene on the nanotube. The spin of the whole system is always localized at the tip of the polyacetylene formed, which initiates the adsorption of the incoming species. The present results imply that carbon-doped BNNT is an effective "metal-free" initiator for the formation of polyacetylene.     

Conjugates between photosystem I and a carbon nanotube for a photoresponse device

Photosystem I (PS I) is a large pigment–protein complex embedded in the thylakoid membranes that performs light-driven electron transfer across the thylakoid membrane. Carbon nanotubes exhibit excellent electrical conductivities and excellent strength and stiffness. In this study, we generated PSI–carbon nanotube conjugates dispersed in a solution aimed at application in artificial photosynthesis. PS I complexes in which a carbon nanotube binding peptide was introduced into the middle of the PsaE subunit were conjugated on a single-walled carbon nanotube, orienting the electron acceptor side to the nanotube. Spectral and photoluminescence analysis showed that the PS I is bound to a single-walled carbon nanotube, which was confirmed by transmission electron microscopy. Photocurrent observation proved that the photoexcited electron originated from PSI and transferred to the carbon nanotube with light irradiation, which also confirmed its orientated conjugation. The PS I–carbon nanotube conjugate will be a useful nano-optoelectronic device for the development of artificial systems.     

Computational study of Au_4 cluster on a carbon nanotube with and without defects using QM/MM methodology

We use ONIOM (QM/MM) methodology to carry out geometry calculations in a 4-atom nanocluster supported by an (8, 8) armchair carbon nanotube with and without defects employing LSDA/SDD for the QM system and UFF for MM. In two particular cases, defects were added in the carbon nanotube wall. These defects are a double oxygenated vacancy (Vac(2)O(2)) and a double vacancy but without oxygen which creates two pentagons and an octagon. Our results show how geometries using QM/MM and energies calculations carried out with QM, change on both the gold nanocluster and the carbon nanotube. In addition, an application of ONIOM methodology in a comparative study to predict behavior of structures as hybrid materials based in carbon nanotubes combined with gold nanoclusters is shown. In this work we examine geometry changes on both the gold nanocluster and the carbon nanotube. A comparison is made with the binding energy resulting values as well as with the orbital energies such as the frontier orbitals HOMO and LUMO.     

Zwitterionic polymers exhibiting high resistance to nonspecific protein adsorption from human serum and plasma

This study examined six different polymer and self-assembled monolayer (SAM) surface modifications for their interactions with human serum and plasma. It was demonstrated that zwitterionic polymer surfaces are viable alternatives to more traditional surfaces based on poly(ethylene glycol) (PEG) as nonfouling surfaces. All polymer surfaces were formed using atom transfer radical polymerization (ATRP) and they showed an increased resistance to nonspecific protein adsorption compared to SAMs. This improvement is due to an increase in the surface packing density of nonfouling groups on the surface, as well as a steric repulsion from the flexible polymer brush surfaces. The zwitterionic polymer surface based on carboxybetaine methacrylate (CBMA) also incorporates functional groups for protein immobilization in the nonfouling background, making it a strong candidate for many applications such as in diagnostics and drug delivery.     

Density functional theory study of epoxy polymer chains adsorbing onto single-walled carbon nanotubes: electronic and mechanical properties

We performed first principles calculations based on density functional theory (DFT) to investigate the effect of epoxy monomer content on the electronic and mechanical properties of single-walled carbon nanotubes (SWCNTs). Our calculation results reveal that interfacial interaction increases with increasing numbers of epoxy monomers on the surface of SWCNTs. Furthermore, density of states (DOS) results showed no orbital hybridization between the epoxy monomers and nanotubes. Mulliken charge analysis shows that the epoxy polymer carries a positive charge that is directly proportional to the number of monomers. The Young’s modulus of the nanotubes was also studied as a function of monomer content. It was found that, with increasing number of monomers on the nanotubes, the Young’s modulus first decreases and then approaches a constant value. The results of a SWCNT pullout simulation suggest that the interfacial shear stress of the epoxy/SWCNT complex is approximately 68 MPa. These results agreed well with experimental results, thus proving that the simulation methods used in this study are viable.     

Water transport through carbon nanotubes with defects

Non-equilibrium molecular dynamics simulations are performed to investigate how changing the number of structural defects in the wall of a (7,7) single-walled carbon nanotube (CNT) affects water transport and internal fluid dynamics. Structural defects are modelled as vacancy sites (missing carbon atoms). We find that, while fluid flow rates exceed continuum expectations, increasing numbers of defects lead to significant reductions in fluid velocity and mass flow rate. The inclusion of such defects causes a reduction in the water density inside the nanotubes and disrupts the nearly frictionless water transport commonly attributed to CNTs.     

Simple benzene derivatives adsorption on defective single-walled carbon nanotubes: a first-principles van der Waals density functional study

We have investigated the interaction between open-ended zig-zag single-walled carbon nanotube (SWCNT) and a few benzene derivatives using the first-principles van der Waals density functional (vdW-DF) method, involving full geometry optimization. Such sp ²-like materials are typically investigated using conventional DFT methods, which significantly underestimate non-local dispersion forces (vdW interactions), therefore affecting interactions between respected molecules. Here, we considered the vdW forces for the interacting molecules that originate from the interacting π electrons of the two systems. The ?0.54 eV adsorption energy reveals that the interaction of benzene with the side wall of the SWCNT is typical of the strong physisorption and comparable with the experimental value for benzene adsorption onto the graphene sheet. It was found that aromatics are physisorbed on the sidewall of perfect SWCNTs, as well as at the edge site of the defective nanotube. Analysis of the electronic structures shows that no orbital hybridization between aromatics and nanotubes occurs in the adsorption process. The results are relevant in order to identify the potential applications of noncovalent functionalized systems.

Atomistic Simulations of Uniaxial Tensile Behaviors of Single-walled Carbon Nanotubes

Atomistic simulations, using the second-generation reactive empirical bond order (REBO) potential, are performed to investigate the uniaxial tensile behaviors of single-walled carbon nanotubes (SWCNTs). It is found that the effect of the nanotube diameters on the elastic modulus, the tensile strength and the stress vs. strain relation of SWCNTs is small yet noticeable. However, the effect of the degree of helicity is significant.