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www.rsc.org/annrepa | Annual Reports A

Nanotubes
Karl S. Coleman
DOI: 10.1039/b705543a

This Chapter reviews the literature reported during 2006 on nanotubes.

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Highlights
Highlights include the continued drive to synthesise carbon nanotubes at low temperature, the ability to separate dierent diameter carbon nanotubes (which have very dierent intrinsic electrical properties) by simple dispersion and the use of nanotubes as nanovectors for drug delivery across a cell membrane.

1. Introduction
Carbon nanotubes (CNTs) continue to be the main topic of research in nanotubes. This is reected in the content and scope of this report. CNTs have been shown to have impressive electrical and mechanical properties and have attracted interest and excitement across a broad spectrum of sciences and technologies including engineering, materials, chemistry and biology. Because of these extraordinary properties many potential applications for CNTs have been envisaged ranging from conductive and high strength composites, energy storage, sensors and eld emission devices to nanoscale electronic components such as transistors, diodes, logic gates and bits of memory. This report is divided into four main themes, covering the synthesis, chemistry, biological uses of CNTs and the use of CNTs in polymer composites.

2. Carbon nanotube synthesis

The characteristics of carbon nanotubes (CNTs), which determine their properties, are strongly inuenced by the production method, as well as by the experimental conditions in which the synthesis has been carried out. By choosing appropriate experimental parameters, it is possible to control the type of CNTs synthesised (single-walled vs. multi-walled) and the quality of the material produced (number of defects and the amount of impurities present). The demand for CNTs continues to increase as potential applications are realised therefore it is no surprise that the synthesis of CNTs continues to be an active eld with chemical vapour deposition (CVD) methods or variations of this method continuing to dominate. However, other methods including arc discharge and laser ablation continue to be pursued. The purication of as produced single-walled carbon nanotubes (SWCNTs) has been reviewed.1 The synthesis of multi-walled carbon nanotube (MWCNTs) and SWCNTs by the arc discharge method has been reviewed2 and a comprehensive parametric study on arc discharge in solution has been used to determine optimum conditions for MWCNT growth in water.3 The arc-discharge method has been used to produce
Department of Chemistry, Durham University, South Road, Durham, UK. E-mail: k.s.coleman@durham.ac.uk

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View double-walled carbon nanotubes (DWCNTs) from an iron sulde catalyst with Online chloride as a promoter.4 Carbon black has been used in the arc-discharge method to produce DCWNTs.5 The synthesis of SWCNTs with controlled length and bundle size has been achieved using the arc-discharge method in the presence of CO2.6 Recent advances in laser-based methods for the synthesis of CNTs have also been reviewed,7 with the rst high-yield synthesis of boron-doped single-wall carbon nanotubes from the laser vaporisation of elemental boron doped graphite target described.8 The reaction parameters for the synthesis of CNTs by CVD have been reviewed.9 In CVD methods typically metal catalysts of iron, cobalt or nickel are used to produce carbon nanotubes. However, metal nanoparticles of gold, silver and copper of 3 nm or less in diameter, introduced into CVD ambience immediately after heat treatment at 800950 1C in air, have now been shown to catalyse the production of SWCNTs.10 MWCNTs have been synthesised from the decomposition of acetylene, ethene, methanol and benzene over alkane thiol stabilised gold nanoparticles.11 MWCNTs with single crystals of copper at the tips have been prepared using alkalimetal doped copper catalysts.12 CNTs lled with copper nanowires have been prepared by the CVD of methane over copper microgrids.13 CNTs containing long copper nanowires have been prepared from coal as a carbon source.14 Preformed iron and nickel aerosol nanoparticles, produced by evaporation from resistively heated metal wire, catalyse the formation of either SWCNTs or MWCNTs with alcohols as the carbon precursors. MWCNT synthesis has been initiated by 10 nm sized catalyst particles in the presence of ethanol vapour, while combination of 2.4 nm particles and a decreased alcohol vapour pressure aorded predominately SWCNTs.15 The block copolymer micelle approach has been used to produce metal nanoparticles of iron, cobalt, and nickel with precisely controlled size and spacing which have then be used to synthesise SWCNTs with a narrow size distribution.16 Reversed micelles containing iron and molybdenum ions have been used as precursors of novel catalysts for the gas-phase synthesis of SWCNTs.17 DWCNTs have been selectively synthesised by catalytic chemical vapor deposition of alcohol over iron/cobalt loaded mesoporous silica.18 CVD of acetylene over iron or iron/ cobalt catalysts loaded onto mesoporous silica (MCM-41) produced high quality SCWNTs.19,20 MWCNTs have been synthesised without metal catalysts by the pyrolysis of sucrose in MCM-41 silicate templates.21 A oating catalyst method, using benzene as the carbon source and ferrocene as the catalyst, has been used to prepare both SWCNTs and MWCNTs.22 Aluminium powder has been used as a transition metal catalyst carrier for the CVD growth of well-graphitised MWCNTs.23 High purity MWCNTs consisting of only a few walls have been prepared via the CVD method using a mixture of ethanol and methanol as the carbon source.24 MWCNTs have been synthesised by a CVD method using a mixture a chromium/iron oxide catalyst with natural gas as the carbon source.25 A CVD method in conjunction with radio frequency inductive heating has been shown to aord MWCNTs with smaller external diameters and smaller number of walls when compared to conventional heating.26 Sea urchin shaped nanostructured carbon spheres have been fabricated by the growth of MWCNTs on the surface of hollow carbon spheres.27 MWCNTs have been prepared by a plasma based electron beam generator for the rst time.28 The rapid synthesis of CNTs via inductive heating in a room temperature environment has been demonstrated.29 An electrochemical deposition technique has been employed to produce carbon nanotubes from organic solvents at room

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View temperature with electrodes coated with nickel or iron nanoparticles acting as Online nucleation sites for their formation and growth.30 CNTs lled with nanowires of FeS2 have been prepared in supercritical CS2 at 500 1C from ferrocene.31 A relatively low temperature (590 1C) CVD method using acetylene has been used to produce SWCNTs of narrow diameter distribution by using iron nanoparticles as catalysts whose size was selected with a dierential mobility analyzer.32 A low temperature CVD (450 1C) method involving the decomposition of acetylene over nickel/ molybdenum catalysts on a zeolite support embedded with rare earth oxides has been described.33 Dendrimer templated iron nanoparticles have been used in the low temperature (400 1C) plasma enhanced CVD synthesis of SWCNTs.34,35 Typically CNT syntheses are carried out on insulating substrates but a CVD method has now been used to produce aligned SWCNTs and DWCNTs on conducting metal foils which could be suitable for nanoelectronic applications.36 Laser assisted CVD has been used directly to produce a SWCNT between two electrodes.37 A simple method for the synthesis of horizontally aligned SWCNTs of controllable density on sapphire has been reported.38 Ultra long (500 mm) vertically aligned MWCNTs have ben synthesised using a rapid heating and cooling CVD process.39 The kinetics of CNT synthesis over the popular catalyst combination of cobalt/ molybdenum on MgO has been studied.40 Mechanistic and kinetic studies for CNT formation from CVD using xylene as a carbon feedstock have been reported.41 The chirality (n,m) of SWCNTs, which can determine their properties, can be tailored to some degree by controlling parameters such as temperature, carbon source composition and catalyst support for CVD synthesis over cobalt/molybdenum catalysts.42 C-13 labelled SWCNTs have been prepared.43 A model for the growth of MWCNTs by spray pyrolysis has been proposed.44 Multibranched MWCNTs, perhaps suitable for branched junctions in nanoelectronics, have been synthesised by the pyrolysis of iron(II) phthalocyanine by uctuating the ow of hydrogen carrier gas.45 Pyrolysis of thiophene over nickel nanoparticles aords Y-junction MWCNTs.46 Branched MWCNTs have been synthesised from coal.47 Novel MWCNTs with polygonal cross sections have been prepared by heating ferrocene and oxalic acid in the presence of potassium.48 Rings of bundled SWCNTs have been prepared by decomposing acetylene over a oating iron catalyst at 1100 1C.49 Coiled nitrogen-doped MWNTs have been prepared by the pyrolysis of pyridine and ferrocene.50 The synthesis of coiled CNTs has been reviewed.51 MWCNTs synthesised in the presence of nitrogen have been shown to have a high degree of internal and crystallographic order.52

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3. Chemical modication of carbon nanotubes

Low solubility and the dicult manipulation in common solvents have imposed great limitations to the use of CNTs and as such the chemical modication of carbon nanotubes remains a popular area. It has been used to help dispersion, aid composite formation and to improve biocompatibility or translocation across a cell membrane. The later two topics will be discussed separately. The chemistry of CNTs can be loosely divided into three main categories: the covalent attachment of chemical groups to the surface of the nanotube; the noncovalent adsorption of functional molecules; and the endohedral lling of the inner cavity of the nanotube. The chemistry of carbon nanotubes has been extensively reviewed.53 The applications of soluble carbon nanotubes has been reviewed.54 The role of functionalisation in

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View photovoltaics and biology has been discussed.55 The wettability of aligned carbon Online nanotubes has been reviewed.56 Polypeptide modied MWNTs have been prepared by rst forming aminefunctionalised nanotubes which are then used to initiate the ring-opening polymerisation of gamma-benzyl-L-glutamate N-carboxyanhydride.57 The direct addition of alkane dithiols have been used, in a solvent free method, to chemically modify MWCNTs.58 The density of bundled, isolated and acid treated SWCNTs and MWCNTs has been determined by density gradient centrifugation.59 An alkoxy silane molecule containing an epoxide group (3-glycidoxypropyltrimethoxy silane) has been introduced to the sidewall of MWCNTs.60 SWCNTs undergo DielsAlder cycloaddition reactions in the presence of Cr(CO)6 and high pressure conditions (1.3 GPa).61 SWCNTs have been functionalised with a bioinspired sugar and phosphocholine polymeric structures via a surface-initiated atom transfer radical polymerisation.62 MWCNTs have been covalently assembled on to silicon surfaces using an amidation reaction and probed by scanning electrochemical microscopy, Fig. 1.63 SWCNTs have been successfully modied with various alkyl and peruoroalkyl acyl groups using FriedelCrafts conditions.64 A divergent methodology has been used to prepare polyamidoamine dendrimer modied SWCNTs allowing the number of organic functional groups on the surface of the nanotube to be increased without further damage to the conjugated p-system.65,66 Porphyrins were introduced to the pendent dendrimers and the photophysical properties of the nanoconjugate studied.65 Nanohybrids of SWCNTs with poly(4-vinylpyridine) and zinc porphyrins have been prepared.67 Highly soluble SWCNTs have been functionalised with pyridyl isoxazoline groups which have been used to anchor zinc porphyrin groups to the surface of the nanotube. Steady-state uorescence and nanosecond transient spectroscopy shows an energy transfer quenching of the zinc porphyrin singlet excited state by the nanotubes but no evidence for the occurrence of electron transfer.68 Amide based dendrons introduced to the surface of SWCNTs have been used to template the synthesis of CdS nanoparticles.69 Amine modied MWCNTs have been used as templates to load CdTe quantum dots and Fe3O4 magnetic nanoparticles by an electrostatic self-assembly approach.70 The radical reaction of aryls with SWCNTs has been expanded to now include reaction on water.71 MWCNTs reduced with Li/NH3 have been reacted with a host of alky/aryl iodides to produce highly functionalised and soluble nanotubes.72 Amines have been reacted

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Fig. 1 Covalent assembly of MWCNTs to Si(111) surfaces through a surface amidation reaction. (Reproduced from ref. 63)

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with SWCNTs and acid treated SWCNTs and their interaction studied.73 View Online The treatment of SWCNTs with butyllithium followed by epoxy ethane leads to the introduction of both butyl and hydroxyethyl groups to the nanotube surface.74 SWCNTs have been shortened and poly(ethylene glycol) amine attached.75 Imidazolium based ionic liquids have been covalently attached to MWCNTs with the solubility of the material switchable between solvents by simple anion exchange.76,77 A new reaction sequence for the chemical functionalisation of SWCNTs consisting of the nucleophilic addition of t-BuLi to the sidewalls of the tubes and the subsequent reoxidation of the intermediate to aord t-Bu-SWCNTs has been developed.78 Microwave-assisted 1,3-dipolar cycloaddition of azomethines to MWCNTs has been described. The process was found to be highly ecient, when compared with conventional heating, lowering reaction times form 100 h to only 2 h.79 Microwave-assisted oxidation of SWCNTs in a mixture of nitric and sulfuric acid has aorded highly water soluble nanotubes at concentrations as high as 10 mg/ ml.80 Water soluble SWCNTs have been prepared by treating oxidatively puried nanotubes with molten urea which is believed to introduce amido and ureido groups to the nanotube surface.81 The room temperature ozone oxidation of SWCNTs has been studied and is shown to lead to an irreversible increase in electrical resistance.82 Surface conned reactions have been used to introduce donor (CO2) and acceptor (CO2Et) groups to opposite ends of SWCNTs. The asymmetrically functionalised SWCNTs were shown to exhibit current rectifying behaviour.83 MWCNTs have been coated with polyethyleneimine and the polymer used as a reducing agent for the formation of gold nanoparticles.84 Both SWCNTs and MWCNTs have been coupled to thioglycolic acid capped CdTe nanoparticles through electrostatic interactions to produce photoactive superstructures.85 SWCNTs have been covalently functionalised with conjugated polyacetylenes via an azido cyclisation reaction and have been shown to be soluble in common organic solvents and emit visible light.86 Europium doped Y2O3 nanoparticles have been introduced to the surface of MWCNTs and the material shown to exhibit luminescence in the visible light range.87 The oxidation of semiconducting SWCNTs by H2O2 has been shown, by UV-Vis-NIR spectroscopy, to occur faster than that of metallic SWCNTs allowing the enrichment of metallic SWCNTs in the nal isolated product.88 Amide derivatives of L-alanine and e-caprolactam have been bound to the surface of directly diamidated MWCNTs and SWCNTs.89 Near-edge X-ray absorption ne structure (NEXAFS) has been show to be a useful technique for probing the surface chemistry of functionalised nanotubes.90 STM has been used to image carboxylic acid and amide functionalised SWCNTs.91 DFT calculations have been used to study the electronic properties of diazonium reagent functionalised SWCNTs.92 Using DFT a linear relationship between the reaction energy of CH2/NH/O exo- and endo-addition to armchair SWCNTs has been found.93 Dichlorocarbene functionalised SWCNTs have been the subject of an ab initio study.94 Numerical studies on the eects of sidewall functionalisation on the electrical properties of metallic SWCNTs have been reported.95 Electronic and structural properties of SWCNTs with COOH, NH2, and CONH2 side groups have been investigated using total energy ab initio calculations demonstrating that the SWCNT acts, in all cases studied, as an electron donor.96 The interaction of Vaskas complex has been studied using hybrid quantum mechanics/molecular dynamics calculations.97 First principles density functional pseudopotential calculations have been used to investigate the nature of interactions between SWCNTs and intercalated transition metal metallocene complexes.98 The molecular and electronic

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View structure of one-dimensional crystals of potassium iodide intercalated in SWCNTs Online have been the subject of a theoretical study. Mulliken population analyses indicated that a small amount of charge transfer occurs from the SWCNT to the KI crystal and that the extent of this charge transfer is dependent on the diameter of the conning nanotube.99 Molecular dynamics simulations have been used to study the structural characteristics of water molecules conned in functionalised SWCNTs.100 The interaction of noncovalent molecules with SWCNTs has been reviewed.101 Porphyrins non-covalently bound to SWCNTs have been shown to electronically interact with the nanotube and exhibit charge transfer features, Fig. 2.102 A detailed photophysical study has been carried out on SWCNT/pyrene/porphyrin hybrids.103 The non-covalent adsorption of anionic and cationic naphthalene and pyrene derivatives on SWCNTs has been described and used to assemble thin lms by the layer-by-layer approach.104 Non-covalent interactions between SWCNTs and [60]fullerene-pyrene conjugates have been studied and stable dispersions in organic solvents obtained. An electronic interaction between the SWCNT and [60]fullerenepyrene conjugate was conrmed by time-resolved uorescence data.105 Polycyclic aromatic ammonium salts have been used to solubilise SWCNTs in water.106 MWCNTs have been wrapped and solubilised with pyrene containing poly(phenylacetylene)s.107 Anthracene functionalised copolymers have been used to solubilise SWCNTs and introduce reactive groups to the surface of the polymer-nanotube composite.108 Non-covalent functionalisation of SWCNTs with phthalocyanine compounds, with a surface coverage of 49%, has been achieved.109 It is well known that single stranded DNA (ssDNA) can be used to help disperse or pattern SWCNTs. Typically ssDNA tends to be short, typically under 150 nucleotides, however for particular applications such as patterning the desire is to have the length of ssDNA approaching that of the nanotube. In a bid to achieve this goal the dispersion of SWCNTs by long ssDNA (greater than a thousand nucleotides), produced by a rolling circle amplication method has now been reported.110 The diameter-selective dispersion of SWCNTs has been accomplished through noncovalent complexation of the nanotubes with the water-soluble polymer chitosan.111 MWCNTs have been embedded in polysiloxane shells by the hydrolysis of (3aminopropyl)triethoxysilane adsorbed on the nanotube surface. Gold nanoparticles can be subsequently attached by electrostatic interactions with the protonated amino groups generated.112

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Fig. 2 Representation of SWCNT/porphyrin nanohybrids. M = H2 or Zn, Ar = phenyl. (Reproduced from ref. 102)

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4. Carbon nanotubes in biology

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A growing area of CNT research is in the eld of biomedical materials and devices. Many applications for CNTs have been proposed or are under investigation including biosensors, drug and vaccine delivery vehicles and novel biomaterials (e.g. for use as tissue engineering constructs or scaolds). Developing alongside this area and essential to its growth and future success is that of CNT biocompatibility. Similarly, with the rapid progress of CNT research and the increased exposure of the scientic community to CNTs, and eventually the general public, studies of the toxicology of nanotubes is now coming to the forefront. The biocompatibility of CNTs has been reviewed.113 The respiratory toxicity and health risks of CNTs have been discussed.114,115 The application of carbon nanotubes in biomaterials and biomedical nanotechnology has been reviewed.116 The use of carbon nanotubes as nanovectors for the delivery of therapeutic molecules has been reviewed.117 The prospect of interfacing carbon nanotubes with biological systems for new applications in diagnostics and drug delivery has been reviewed.118 The toxicological and pharmacological prole of carbon nanotube systems has been reviewed.119 Single bilayer membranes of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) have been formed on micron thin-lms of hydrophilised MWCNTs by fusion of small unilamellar vesicles.120 SWCNTs have been wrapped with glycoconjugate polymers containing bioactive sugars.121 The impact of functionalised nanotubes on the cells of the immune system have been assessed. Macrophages and B and T lymphocytes have been shown to uptake the modied nanotubes without aecting cell viability.122 Apatite crystalisation, important for bone growth, on MWCNTs has been studied.123 MWCNTs have been covalently functionalised via 1,3-dipolar cycloaddition reactions with protected amino functions that can be selectively deprotected and modied with the uorescent probe uorescein isothiocyanate (FITC) and the anticancer drug methotrexate (MTX), Fig. 3. The uorescently labelled MTX modied nanotube is able to cross cell membranes.124 SWCNTs have been functionalised with the chelating molecule diethylenetriaminepentaacetic (DTPA) and labeled with an indium (In-111) radiotracer. Intravenous administration followed by radioactivity tracing indicated that the nanotubes were not retained in the reticuloendothelial system organs (liver or spleen) and were rapidly cleared from systemic blood circulation.125 A variety of

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Fig. 3 (a) RNHCH2COOH/(CH2O); (b) hydrazine; (c) FITC; (d) HCl; (e) MTX. R = Boc NH(CH2CH2O)2CH2CH2. (Reproduced from ref. 124).

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View proteins, of dierent size and structure, have been used to solubilise and disperse Online SWCNTs.126 No cytotoxicity was found for MWCNTs, synthesised by catalytic chemical vapour deposition, towards human umbilical vein endothelial cells.127

5. Carbon nanotubes in polymer composites

The unique structure and the resulting exceptional electrical, thermal and mechanical properties of CNTs has made them ideal candidates as advanced llers in nanocomposites. A large part of the CNT-based polymer composites eld is dedicated to exploiting the mechanical properties of CNTs as improved carbon bre replacements, where dramatic improvements in the mechanical properties of the composite can be achieved with exceptionally low loadings. An equally large eort is devoted to developing CNTs as a conductive dispersed phase in an insulating matrix for applications ranging from electronics to automotive and aerospace sectors, such as electrostatic dissipation, electromagnetic interference shielding and transparent conductive coatings. Polymer nanocomposites containing SWCNTs or MWCNTs have been reviewed.128 Recent advances in the science and technology of composites using carbon nanotubes (including other carbon nanostructures) has been reviewed.129 The methods of dispersing carbon nanotubes into polymers to obtain conductive nanocomposites has been reviewed.130 The mechanical reinforcement of polymers using carbon nanotubes has been reviewed.131133 The potential of carbon nanotubes as nanollers in polymers134 and electroactive polymers135,136 has been reviewed. The eects of radiation-induced modications on the thermal stability and phase transition behaviour of composites made of pristine or ion irradiated SWCNTs and poly(3-hexylthiophene) have been reported.137 The importance of the interface between polymer and carbon nanotubes, frictional sliding, on mechanical damping in nanotube reinforced polymer composites has been discussed.138 Composite nanobres of MWCNT/poly(vinyl acetate)139 and MWCNT/polycaprolactone140 have been prepared by electrospinning. A simple method using super critical CO2 has been developed for coating MWCNTs with solvent resistant high molecular weight polymers.141 Water soluble MWCNTs with poly(4-vinylpyridine) or poly(sodium 4-styrenesulfonate) grafted on to the side of the nanotubes have been obtained from the nitroxide radical mediated polymerisation of 4-vinylpyridine and sodium 4-styrenesulfonate.142 Conducting MWCNT networks in an epoxy polymer matrix have been used as in situ sensors for detecting the onset of damage in advanced polymer-based composites.143 The eect of amine functionalised MWCNTs on the mechanical properties of nanotube/expoxy composites has been described.144 MWCNTs covalently functionalised with chlorinated polypropylene have been used as the ller material in polystyrene and poly(vinyl chloride) polymer matrices, Fig. 4.145 A MWCNT/polybenzoxazine nanocomposite has been prepared by the ring-opening polymerisation of benzoxazine with nitric acid oxidised MWCNTs treated with toluene-2,4-diisocyanate (TDI).146 The morphology of poly(p-phenylene sulde)/polyamide 66 blends was found to change upon the addition of acid treated MWCNTs.147 The processing of MWCNT expoxy composites for high-volume production has been studied.148 A nanocomposite of MWCNTs with the biodegradable polymer poly(butylene succinate) (PBS) has been described.149 MWCNTs modied by poly(2-vinylpyridine) have been used to prepare homogenous ultrathin transparent conductive lms.150 SWCNTs functionalised by ferrocene-grafted poly(p-phenyleneethynylene)s have been found to gelate

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Fig. 4 Schematic representation of the covalent binding of polymer to CNTs. (Reproduced from ref. 145)

common organic solvents, such as chloroform, to form a freestanding carbon nanotube organogel.151 Hydrogen bonding has been shown to improve dispersion of acid treated SWCNTs in copolymers of styrene and vinyl phenol.152 MWCNTs with dithioester groups on their surface have been used as reversible additionfragmentation chain transfer (RAFT) agents to graft polymer chains of highly reactive groups on to the surface of nanotubes.153 A physical vapour deposition method has been used to achieve periodic polyethylene oligomer patterning on individual SWCNTs and MWCNTs perpendicular to the nanotube axes.154 Electrical bistability and memory has been observed in MWCNT/poly(3-hexyl thiophene).155 The electrical and thermal conduction mechanisms in expoxy composites containing SWCNTs or MWCNTs have been evaluated.156 The morphology, mechanical and electrical properties of poly(urea urethane) nanocomposites containing MWCNTs have been reported.157 Rubber composites containing MWCNTs irradiated with near-infrared light show a reversible photomechanical actuation response which is directly related to the degree of uniaxial alignment of the nanotubes in the matrix.158 Controlled polymer solution crystallisation has been used to synthesise polymer single crystal-CNT (both SWCNT and MWCNT) hybrid materials with lamellar crystals periodically spaced along the entire length of the nanotube.159 SWCNTs and uorinated SWCNTs have been incorporated into polyisobutylene with the later showing an increase in hardness of 847% over the starting polymer matrix. This is one of the largest increases in strength observed in a

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View polymer SWCNT composite.160 The mechanical properties of acid treated Online MWCNTs/poly(methyl methacrylate) composites have been improved by the addition of amine-terminated poly(ethylene oxide) which is thought to enhance the interfacial adhesion between the polymer matrix and the nanotubes.161 SWCNTs have been successfully integrated within a lyotropic hexagonal liquid crystal (Triton X).162 Poly(acrylic acid) has been grafted on to the surface of MWCNTs, to form water soluble nanotubes, by a two-step gamma irradiation technique.163 The eective elastic properties of expoxy based carbon nanotube composites has been modelled.164

6. Nanotubes other than carbon

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Single-wall boron nitride nanotubes samples synthesised by laser vaporisation of a hexagonal BN target under a nitrogen atmosphere have been studied by Raman spectroscopy.165 Ultrathin crystalline corundum-type In2O3 nanotubes derived from orthorhombic InOOH have been synthesised.166 Bismuth subcarbonate nanotubes with diameters of 3 to 5 nm have been synthesised from bismuth citrate and have been shown to exhibit antibacterial properties.167 Pure rutile TiO2 nanotubes have been prepared using a sacricial carbon nanotube template.168 Tensile tests and buckling experiments of individual WS2 nanotubes have been carried out in a highresolution scanning electron microscope.169 The use of highly ordered transparent TiO2 nanotube arrays in dye-sensitised solar cells has been described.170 Urchin-like nanostructures consisting of high-density spherical nanotube radial arrays of vanadium oxide have been synthesised by a simple chemical route using an ethanolic solution of vanadium tri-isopropoxide and alkylamine hexadecylamine.171 SiO2 nanotubes have been synthesised using a sacricial carbon nanobre template by hydrolysis of tetraethyl orthosilicate.172 A solvent and template free route for the synthesis of inorganic WC nanotubes from the thermal decomposition of W(CO)6 in the presence of magnesium has been reported.173 Well-faceted hexagonal ZnO nanotubes have been synthesised by a simple hydrothermal and aging process without any catalysts or templates.174

Abbreviations
CNT CVD DFT DWCNT MTX MWCNT ssDNA STM SWCNT carbon nanotube chemical vapour deposition density functional theory double-walled carbon nanotube methotrexate multi-walled carbon nanotube single stranded DNA scanning tunneling microscopy single-walled carbon nanotube

References
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