Multimodal biomedical imaging with asymmetric single-walled carbon nanotube/iron oxide nanoparticle complexes

Magnetic iron oxide nanoparticles and near-infrared (NIR) fluorescent single-walled carbon nanotubes (SWNT) form heterostructured complexes that can be utilized as multimodal bioimaging agents. Fe catalyst-grown SWNT were individually dispersed in aqueous solution via encapsulation by oligonucleotides with the sequence d(GT)15, and enriched using a 0.5 T magnetic array. The resulting nanotube complexes show distinct NIR fluorescence, Raman scattering, and visible/NIR absorbance features, corresponding to the various nanotube species. AFM and cryo-TEM images show DNA-encapsulated complexes composed of a approximately 3 nm particle attached to a carbon nanotube on one end. X-ray diffraction (XRD) and superconducting quantum interference device (SQUID) measurements reveal that the nanoparticles are primarily Fe2O3 and superparamagnetic. The Fe2O3 particle-enriched nanotube solution has a magnetic particle content of approximately 35 wt %, a magnetization saturation of approximately 56 emu/g, and a magnetic relaxation time scale ratio (T1/T2) of approximately 12. These complexes have a longer spin-spin relaxation time (T2 approximately 164 ms) than typical ferromagnetic particles due to the smaller size of their magnetic component while still retaining SWNT optical signatures. Macrophage cells that engulf the DNA-wrapped complexes were imaged using magnetic resonance imaging (MRI) and NIR mapping, demonstrating that these multifunctional nanostructures could potentially be useful in multimodal biomedical imaging.     

Employing Raman spectroscopy to qualitatively evaluate the purity of carbon single-wall nanotube materials

Carbon single-wall nanotubes (SWNTs) have highly unique electronic, mechanical and adsorption properties, making them interesting for a variety of applications. Raman spectroscopy has been demonstrated to be one of the most important methods for characterizing SWNTs. For example, Raman spectroscopy may be employed to differentiate between metallic and semi-conducting nanotubes, and may also be employed to determine SWNT diameters and even the nanotube chirality. Single-wall carbon nanotubes are generated in a variety of ways, including arc-discharge, laser vaporization and various chemical vapor deposition (CVD) techniques. In all of these methods, a metal catalyst must be employed to observe SWNT formation. Also, all of the current synthesis techniques generate various non-nanotube carbon impurities, including amorphous carbon, fullerenes, multi-wall nanotubes (MWNTs) and nano-crystalline graphite, as well as larger micro-sized particles of graphite. For any of the potential nanotube applications to be realized, it is, therefore, necessary that purification techniques resulting in the recovery of predominantly SWNTs at high-yields be developed. It is, of course, equally important that a method for determining nanotube wt.% purity levels be developed and standardized. Moreover, a rapid method for qualitatively measuring nanotube purity could facilitate many laboratory research efforts. This review article discusses the application of Raman spectroscopy to rapidly determine if large quantities of carbon impurities are present in nanotube materials. Raman spectra of crude SWNT materials reveal tangential bands between 1500-1600 cm(-1), as well as a broad band at approximately 1350 cm(-1), attributed to a convolution of the disorder-induced band (D-band) of carbon impurities and the D-band of the SWNTs themselves. Since the full-width-at-half-maximum (FWHM) intensity of the various carbon impurity D-bands is generally much broader than that of the nanotube D-band, an indication of the SWNT purity level may be obtained by simply examining the line-width of the D-band. We also briefly discuss the effect of nanotube bundling on SWNT Raman spectra. Finally, sections on employing Raman spectroscopy, and Raman spectroscopy coupled with additional techniques, to identify the separation and possible isolation of a specific nanotube within purified SWNT materials is provided. Every SWNT can be considered to be a unique molecule, with different physical properties, depending on its (n, m) indices. The production of phase-pure (n, m) SWNTs may be essential for some nanotube applications.     

Label-free detection of DNA hybridization using pyrene-functionalized single-walled carbon nanotubes: effect of chemical structures of pyrene molecules on DNA sensing performance

We investigate the effect of functional groups of pyrene molecules on the electrical sensing performance of single-walled carbon nanotubes (SWNTs) based DNA biosensor, in which pyrenes with three different functional groups of carboxylic acid (Py-COOH), aldehyde (Py-CHO) and amine (Py-NH2) are used as linker molecules to immobilize DNA on the SWNT films. UV/Visible absorption spectra results show that all of the pyrene molecules are successfully immobilized on the SWNT surface via pi-pi stacking interaction. Based on fluorescence analysis, we show that the amide bonding of amine terminated DNA via pyrene containing carboxylic groups is the most efficient to immobilize DNA on the nanotube film. The electrical detection results show that the conductance of Py-COOH modified SWNT film is increased upon DNA immobilization, followed by further increase after hybridization of target DNAs. It indicates that the pyrene molecules with carboxylic acid groups play an important role to achieve highly efficient label-free detection by nondestructive and specific immobilization of DNAs.     

Chemical optimization of self-assembled carbon nanotube transistors

We present the improvement of carbon nanotube field effects transistors (CNTFETs) performances by chemical tuning of the nanotube/substrate and nanotube/electrode interfaces. Our work is based on a method of selective placement of individual single walled carbon nanotubes (SWNTs) by patterned aminosilane monolayer and its use for the fabrication of self-assembled nanotube transistors. This method brings a relevant solution to the problem of systematic connection of self-organized nanotubes. The aminosilane monolayer reactivity can be used to improve carrier injection and doping level of the SWNT. We show that the Schottky barrier height at the nanotube/metal interface can be diminished in a continuous fashion down to an almost ohmic contact through these chemical treatments. Moreover, sensitivity to 20 ppb of triethylamine is demonstrated for self-assembled CNTFETs, thus opening new prospects for gas sensors taking advantages of the chemical functionality of the aminosilane used for assembling the CNTFETs.     

SWNT-DNA and SWNT-polyC hybrids: AFM study and computer modeling

Hybrids of carbon single-walled nanotubes (SWNT) with fragmented single or double-stranded DNA (fss- or fds-DNA) or polyC were studied by Atom Force Microscopy (AFM) and computer modeling. It was found that fragments of the polymer wrap in several layers around the nanotube, forming a strand-like spindle. In contrast to the fss-DNA, the fds-DNA also forms compact structures near the tube surface due to the formation of self-assembly structures consisting of a few DNA fragments. The hybrids of SWNT with wrapped single-, double- or triple strands of the biopolymer were simulated, and it was shown that such structures are stable. To explain the reason of multi-layer polymeric coating of the nanotube surface, the energy of the intermolecular interactions between different components of polyC was calculated at the MP2/6-31++G** level as well as the interaction energy in the SWNT-cytosine complex.     

DNA-linker-induced surface assembly of ultra dense parallel single walled carbon nanotube arrays

Ultrathin film preparations of single-walled carbon nanotube (SWNT) allow economical utilization of nanotube properties in electronics applications. Recent advances have enabled production of micrometer scale SWNT transistors and sensors but scaling these devices down to the nanoscale, and improving the coupling of SWNTs to other nanoscale components, may require techniques that can generate a greater degree of nanoscale geometric order than has thus far been achieved. Here, we introduce linker-induced surface assembly, a new technique that uses small structured DNA linkers to assemble solution dispersed nanotubes into parallel arrays on charged surfaces. Parts of our linkers act as spacers to precisely control the internanotube separation distance down to <3 nm and can serve as scaffolds to position components such as proteins between adjacent parallel nanotubes. The resulting arrays can then be stamped onto other substrates. Our results demonstrate a new paradigm for the self-assembly of anisotropic colloidal nanomaterials into ordered structures and provide a potentially simple, low cost, and scalable route for preparation of exquisitely structured parallel SWNT films with applications in high-performance nanoscale switches, sensors, and meta-materials.     

Influence of surface chemistry on inkjet printed carbon nanotube films

Carbon nanotube ink chemistry and the proper formulation are crucial for direct-write printing of nanotubes. Moreover, the correct surface chemistry of the self-assembled monolayers that assist the direct deposition of carbon nanotubes onto the substrate is equally important to preserve orientation of the printed carbon nanotubes. We report that the successful formulation of two single walled carbon nanotube (SWNT) inks yields a consistent, homogenous printing pattern possessing the requisite viscosities needed for flow through the microcapillary nozzles of the inkjet printer with fairly modest drying times. The addition of an aqueous sodium silicate allows for a reliable method for forming a uniform carbon nanotube network deposited directly onto unfunctionalized surfaces such as glass or quartz via inkjet deposition. Furthermore, this sodium silicate ingredient helps preserve applied orientation to the printed SWNT solution. Sheet resistivity of this carbon nanotube ink formula printed on quartz decreases as a function of passes and is independent of the substrate. SWNTs were successfully patterned on Au. This amine-based surface chemistry dramatically helps improve the isolation stabilization of the printed SWNTs as seen in the atomic force microscopy (AFM) image. Lastly, using our optimized SWNT ink formula and waveform parameters in the Fuji materials printer, we are able to directly write/print SWNTs into 2D patterns. Dried ink pattern expose and help orient roped carbon nanotubes that are suspended in ordered arrays across the cracks.     

Mono-dispersed single-wall carbon nanotubes formed in channels of zeolite crystal: Production, optical and electrical transport properties

Carbon nanotube materials can now be produced in macroscopic quantities. However, the raw material has a disordered structure and unsorted size, which restrict investigations of both the properties and applications of the nanotubes. In this paper, an alternative approach to the synthesis of mono-sized and parallel-aligned single wall carbon nanotubes (SWCNs) is reported. The SWCNs are formed in 1 nm-sized channels of aluminophosphate zeolite crystallites by pyrolysis of tripropylamine molecules. As verified by tunnel electron microscopy and micro-Raman scattering, the SWNT is of zigzag structure. Electrical transport properties of the SWNT are measured in the temperature range of 0·3K∼300K. The temperature-dependent dc conductivity shows that the SWNT is an intrinsic semiconductor with a narrow band-gap of 52 meV. The well-aligned and mono-sized SWCNs allow us to make more controlled characterization as well as open a door to potential nano-technological application for the novel electronic nanotube system.     

Photovoltaic device performance of single-walled carbon nanotube and polyaniline films on n-Si: device structure analysis

In this paper, we explore the use of two organic materials that have been touted for use as photovoltaic (PV) materials: inherently conducting polymers (ICPs) and carbon nanotubes (CNTs). Due to these materials' attractive features, such as environmental stability and tunable electrical properties, our focus here is to evaluate the use of polyaniline (PANI) and single wall carbon nanotube (SWNT) films in heterojunction diode devices. The devices are characterized by electron microscopy (film morphology), current-voltage characteristics (photovoltaic behavior), and UV/visible/NIR spectroscopy (light absorption). We have found that both PANI and SWNT can be utilized as photovoltaic materials in a simple bilayer configuration with n-type Silicon: n-Si/PANI and n-Si/SWNT. It was our aim to determine how photovoltaic performance was affected utilizing both PANI and SWNT layers in multilayer devices: n-Si/PANI/SWNT and n-Si/SWNT/PANI. The short-circuit current density increased from 4.91 mA/cm(2) (n-Si/PANI) to 12.41 mA/cm(2) (n-Si/PANI/SWNT), while an increase in power conversion efficiency by ~91% was also observed. In the case of n-Si/SWNT/PANI and its corresponding device control (n-Si/SWNT), the short-circuit current density was decreased by an order of magnitude. The characteristics of the device were affected by the architecture and the findings have been attributed to the more effective transport of holes from the PANI to SWNT and less effective transport of holes from PANI to SWNT in the respective multilayer devices.     

Polyethylene crystallization nucleated by carbon nanotubes under shear

Polyethylene crystallization under shear has been studied in the presence of single-wall, few-wall, and multiwall carbon nanotubes (SWNT, FWNT, and MWNT). Polyethylene crystal d-spacings for (110) and (200) planes in polyethylene/carbon nanotubes (CNT) are smaller than in the control polyethylene without CNT and the polymer chain is oriented along the CNT axis. The single-wall carbon nanotube templated polyethylene crystals do not redissolve in boiling xylenes; instead, the chain morphology transforms to an amorphous conformation but remains oriented along the nanotube axis. SWNT crystal peaks were also observed in polyethylene/SWNT fibers.     

Tuning the conductance of single-walled carbon nanotubes by ion irradiation in the Anderson localization regime

Carbon nanotubes are a good realization of one-dimensional crystals where basic science and potential nanodevice applications merge. Defects are known to modify the electrical resistance of carbon nanotubes; they can be present in as-grown carbon nanotubes, but controlling their density externally opens a path towards the tuning of the electronic characteristics of the nanotube. In this work, consecutive Ar+ irradiation doses are applied to single-walled nanotubes (SWNTs) producing a uniform density of defects. After each dose, the room-temperature resistance versus SWNT length (R(L)) along the nanotube is measured. Our data show an exponential dependence of R(L) indicating that the system is within the strong Anderson localization regime. Theoretical simulations demonstrate that mainly di-vacancies contribute to the resistance increase induced by irradiation, and that just a 0.03% of di-vacancies produces an increase of three orders of magnitude in the resistance of a SWNT of 400 nm length.     

Microwave‐Assisted Regeneration of Single‐Walled Carbon Nanotubes from Carbon Fragments

Direct growth of chirality‐controlled single‐walled carbon nanotubes (SWNTs) with metal catalyst free strategy, like cloning or epitaxial growth, has suffered from the low efficiency. The underlying problem is the activation of seed edge. Here an unexpectedly efficient microwave‐assisted pathway to regenerate SWNTs from carbon fragments on SiO₂/Si substrate is demonstrated via Raman spectroscopy and atomic force microscope (AFM) characterization. In this attempt, microwave irradiation provides fast heating to remove polar groups bonded to carbon nanotubes and reduce the spontaneous closure of tubes’ open ends. The survived SWNT and carbon fragments connected to it after plasma treatment are simply microwaved and then they serve as the template for regeneration. Scanning electron microscope and AFM characterizations indicate that the efficiency of the regeneration can reach 100%. And the regenerated SWNT has been proved without any change in chirality compared to the original SWNT. Electrical measurements on regenerated carbon nanotube films indicate 1 and 2 times increase in on/off ratio and on‐state current respectively than original carbon nanotube films obtained from solution‐phase separation, confirming the improvement of SWNT's quality. The microwave‐assisted regeneration is found to be highly effective and would be applied to improve the cloning efficiency of carbon nanotubes potentially.     

A Field Effect Transistor Fabricated with Metallic Single-Walled Carbon Nanotubes

We report novel transport properties of the individual single-walled carbon nanotube (SWNT) field effect transistors (FETs) decorated with the protein (streptavidin)-coated nanoparticles. Upon adsorption of the protein-coated nanoparticles at the metal-nanotube contact, the metallic SWNT devices abruptly exhibit a p-type semiconducting behavior. In the case of semiconducting SWNT devices, the adsorptions of protein-coated nanoparticles make the gating more effective, resulting in a far suppressed off-state leakage current as well as an enhanced on-state p-channel current. Through the ab initio electronic structure calculations, it is suggested that such an apparent metal-semiconductor transition may be due to the intervening charged species in the contact area, originated from the surface of the proteins. Noting the separation of the semiconducting nanotubes from metallic ones would be a formidable task; we suggest that the device concept here could be another breakthrough for the nanotube-based electronic devices, in which the nanotubes are not necessarily semi-conducting.     

Charge-transfer interaction in single-walled carbon nanotubes with tetrathiafulvalene and their applications

We observed that single-walled carbon nanotube (SWNT) was aligned in the presence of TTF This alignment was induced by a specific interaction between SWNT and tetrathiafulvalene (TTF), a well-known organic donor. The interaction between the two molecules can be explained by a charge-transfer, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The binding energies of S (2P1/2) and S (2P3/2) were shifted from 163.0 eV and 164.1 eV to 163.9 eV and 165.1 eV, respectively. In Raman spectra of the SWNT-TTF, three peaks of SWNT in radial breathing mode were also upshifted by 4-5 cm(-1). The charge-transfer interaction also contributed in modifying the electronic structure of SWNT and furthermore enhanced the electrical conductivity of SWNT. A more conductive thin film was fabricated using the SWNT-TTF Four-probe measurement revealed that the surface resistance of the SWNT-TTF film was reduced to 4.359 omega at room temperature while that of SWNT film was 6.894 omega. These results enable carbon nanotubes to be utilized more for practically for industrial applications in fabricating peculiar nano-sized building blocks.     

气相沉积生长单壁纳米碳管束

采用流动催化热解碳氢化合物方法制备出具有一定取向的单壁纳米碳管束。研究了单壁纳米碳管束的生长过程,发现单壁纳米碳管的生长过程是在气流飘浮单个催化剂颗粒中完成。这与热解碳氢化合物制备定向的多壁纳米碳管在基体催化上生长过程有所不同。根据单壁纳米碳管生长过程,推测出单壁纳米碳管束生长速度的数量级为10^-5m/s。     

Separation of single-walled carbon nanotubes by use of ionic liquid-aided capillary electrophoresis

This paper presents a simple, highly efficient method for analyzing single-walled carbon nanotube (SWNT) bundles based on (1) ultrasound-assisted solubilization/dispersion of SWNTs in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, (2) encapsulation of the nanotubes in sodium dodecyl sulfate micelles, and (3) analysis by capillary electrophoresis. The process by which SWNTs disperse in the ionic liquid was studied by Raman spectroscopy. No degradation of SWNTs was observed under mild sonication conditions. The shape and position changes observed in the Raman spectral bands for the nanotubes are ascribed to debundling and interaction with the ionic liquid. Separation of solubilized SWNTs was accomplished by using a 50 mM formic acid solution at pH 2.0 as background electrolyte and a potential of -10 kV. Under these conditions, separation was completed within only 4 min. Eighteen peaks for SWNTs were identified in the analysis of commercial SWNT bundles. The two types of bundles studied exhibited distinct, highly characteristic electrophoretic profiles which could be used to control SWNTs purity.     

Polymeric nanocomposites of functionalized carbon nanotubes synthesized in supercritical CO2

A novel method to synthesize single-wall carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) nanocomposite by in-situ polymerization in supercritical CO2 is presented. The surfaces of the SWNT bundles were first functionalized with amino ethyl methacrylate (AEMA) followed by co-polymerization with methyl methacrylate. Supercritical fluid enhanced the diffusivity of monomer and facilitated the growth of tethered PMMA chains near the entanglement area and the interstitial space of the SWNT bundles. Partial debundling and disentanglement of the SWNT bundles and an enhanced dispersion in the polymer matrix were observed under SEM and TEM. After the removal of the polymer matrix physically attached to the nanotubes, it is found that the nanotubes were covered by tethered PMMA chains, which were a few nanometers in thickness. This work creates a route for improving impregnation and dispersion in SWNT composites; the same process can be extended to other vinyl polymers.     

Optical absorption of DNA-carbon nanotube structures

We measured the UV optical absorption of single-stranded DNA bound to single-walled carbon nanotubes (DNA/SWNT). The nucleotide absorbance from DNA/SWNT provides the first experimental confirmation that DNA binds to nanotubes through pi-stacking. Because the hypochromic absorbance typical of pi-stacked structures are expected to occur primarily for DNA dipole transitions that lie along the axis of the optically anisotropic SWNTs, the absorbance changes following binding of DNA to nanotubes reveal the preferred orientation assumed by each of the four bound nucleotides with respect to the nanotube's long axis.     

The geometrical effect of single walled carbon nanotube network transistors on low frequency noise characteristics

The noise characteristics of randomly networked single walled carbon nanotubes grown directly by plasma enhanced chemical vapor deposition with field effect transistor. Geometrical complexity due to the large number of tube-tube junctions in the nanotube network is expected to be one of the key factors for the noise power of 1/f dependence. We investigated low frequency noise as a function of channel length (2-10 microm) and found that increased with longer channel length. Percolational behaviors of nanotube network that differs from ordinary semiconducting and metallic materials can be characterized by a geometrical picture with electrical homo- and hetero-junctions. Fixed nanotube density provides a test conditions to evaluate the contributions of junctions as a noise center. Hooge's empirical law is applied to investigate the low frequency noise characteristics of single walled carbon nanotube random network transistors. The noise power shows the dependence of the transistor channel length. It is understood that nanotube/nanotube junctions act as a noise center. However, the differences induced by channel length in the noise power are observed as not so significant. We conclude that tolerance of low frequency noise is important property for SWNT networks as an electronic device application.     

Optically active single-walled carbon nanotubes

The optical, electrical and mechanical properties of single-walled carbon nanotubes (SWNTs) are largely determined by their structures, and bulk availability of uniform materials is vital for extending their technological applications. Since they were first prepared, much effort has been directed toward selective synthesis and separation of SWNTs with specific structures. As-prepared samples of chiral SWNTs contain equal amounts of left- and right-handed helical structures, but little attention has been paid to the separation of these non-superimposable mirror image forms, known as optical isomers. Here, we show that optically active SWNT samples can be obtained by preferentially extracting either right- or left-handed SWNTs from a commercial sample. Chiral 'gable-type' diporphyrin molecules bind with different affinities to the left- and right-handed helical nanotube isomers to form complexes with unequal stabilities that can be readily separated. Significantly, the diporphyrins can be liberated from the complexes afterwards, to provide optically enriched SWNTs.