An ionic liquid supported CeO_2 nanoparticles-carbon nanotubes composite-enhanced electrochemical DNA-based sensor for the detection of Pb^(2+)

An electrochemical sensor incorporating a signal enhancement for the determination of lead （II） ions （Pb2＋） was designed on the basis of the thrombin-binding aptamer （TBA） as a molecular recog- nition element and ionic liquid supported cerium oxide （CeO2） nanoparticles-carbon nanotubes compo- site modification. The composite comprises nanoparticles CeO2, multi-waU carbon nanotubes （MWNTs） and hydrophobic room temperature ionic liquid （RTIL） 1-ethyl-3-methylimidazolium tetrafluoroborate （EMIMBF4）. The electrochemical sensors were fabricated by immersing the CeOa-MWNTs-EMIMBF4 modified glassy carbon electrode （GCE） into the solution of TBA probe. In the presence of Pb2＋, the TBA probe could form stable G-quartet structure by the specific binding interactions between Pb2＋ and TBA. The TBA-bound Pb2＋ can be electrochemically reduced, which provides a readout signal for quantitative detection of Pb2＋. The reduction peak current is linearly related to the concentration of Pb2＋ from 1.0 ＊ 10-8 M to 1.0 ＊ 105 M with a detection limit of 5 ＊ 109 M. This work demonstrates that the CeOz-MWNTs-EMIMBF4 nanocomposite modified GCE provides a promising platform for immobi- lizing the TBA probe and enhancing the sensitivity of the DNA-based sensors.

Variational principles for buckling and vibration of MWCNTs modeled by strain gradient theory

Variational principles for the buckling and vibration of multi-walled carbon nanotubes （MWCNTs） are established with the aid of the semi-inverse method. They are used to derive the natural and geometric boundary conditions coupled by small scale parameters. Hamilton＇s principle and Rayleigh＇s quotient for the buckling and vibration of the MWCNTs are given. The Rayleigh-Ritz method is used to study the buckling and vibration of the single-walled carbon nanotubes （SWCNTs） and double-walled carbon nanotubes （DWCNTs） with three typical boundary conditions. The numerical results reveal that the small scale parameter, aspect ratio, and boundary conditions have a profound effect on the buckling and vibration of the SWCNTs and DWCNTs.

Toluene Sensing Properties of P4VP/Multi-Walled Carbon Nanotubes Multi-Layer Film Sensors

Abstract--Poly4-vinylphenol （P4VP）/multi-wan carbon nanotubes （MWNTs） multi-layer sensitive films were deposited on interdigitated electrodes by airbrush technology to detect toluene vapor at room temperature. The surface and section morphologies of the multi-layer films were observed by a scanning electron microscope （SEM）. It is found that the resistance of the sensor increases when it is exposed to toluene vapor and the response has a good linearity with the concentration of toluene. The results show that the P4VP/MWNTs three-layer film sensors have better sensing properties compared with the two-layer film sensors. The related sensing mechanism is studied in detail.

Ordered SnO nanoparticles in MWCNT as a functional host material for high-rate lithium-sulfur battery cathode

Lithium-sulfur battery has become one of the most promising candidates for next generation batteries, and it is still restricted due to the low sulfur conductivity, large volume expansion and severe polysulfide shuttling. Herein, we present a novel hybrid electrode with a ternary nanomaterial based on sulfur-impregnated multiwalled carbon nanotubes filled with ordered tin-monoxide nanoparticles （MWCNT-SnO/S）. Using a dry plasma reduction method, a mechanically robust material is prepared as a cathode host material for lithium-sulfur batteries. The MWCNT-SnO/S electrode exhibits high conductivity, good ability to capture polysulfides, and small volume change during a repeated charge-discharge process. In situ transmission electron microscopy and ultraviolet-visible absorption results indicate that the MWCNT-SnO host efficiently suppresses volume expansion during lithiation and reduces polysulfide dissolution into the electrolyte. Furthermore, the ordered SnO nanoparticles in the MWCNTs facilitate fast ion/electron transfer during the redox reactions by acting as connective links between the walls of the MWCNTs. The MWCNT-SnO/S cathode with a high sulfur content of 70 wt.% exhibits an initial discharge capacity of 1,682.4 mAh·g^-1 at 167.5 m·g^-1 （0.1 C rate） and retains a capacity of 530.1 mAh·g^-1 at 0.5 C after 1,000 cycles with nearly 100% Coulombic efficiency. Furthermore, the electrode exhibits the high capacity even at a high current rate of 20 C.

An effective poly（p-phenylenevinylene） polymer adhesion route toward three-dimensional nitrogen-doped carbon nanotube/reduced graphene oxide composite for direct electrocatalytic oxygen reduction

Heteroatom-doped nanocarbons have excellent potential for use in the oxygen reduction reaction （ORR）. However, construction of three-dimensional （3D） N-doped carbon materials with good electrocatalytic performance remains a challenge. Herein, a poly（p-phenylenevinylene） （PPV）-precursor adhesion route was developed for construction of 3D N-doped reduced graphene oxide-PPV calcined-carbon nanotubes （N-RGO-PPV（c）-CNTs）. In the synthesis, the PPV- precursor plays the role of a ＂glue＂ for strong adhesion of the RGO and CNTs. At high temperature, PPV can undergo transformation from the glassy state to a viscous state. Thus, the N-RGO-PPV（c）-CNT composite with multi-porous structure and ridge-like folded graphene flakes could be formed during nitridation at high temperature, which was favorable for production of more active sites for the ORR. As an ORR catalyst, the N-RGO-PPV（c）-CNT composites exhibited superior catalytic activity in alkaline electrolyte. The obtained onset potential （Eonset） of 0.92 V and catalytic current density of 5.7 mA·cm^-2 at 0.6 V （vs. RHE） are comparable to those of the 20% Pt/C composite （0.98 V and 5.2 mA·cm^-2）. The electron transfer number for the N-RGO-PPV（c）-CNT catalyst was about 3.99, which is close to that of the 20% Pt/C （4.01） catalyst. Notably, the optimal N-RGO-PPV（c）-CNT catalyst shows better durability and methanol tolerance than commercial 20% Pt/C. The good performance of the N-RGO-PPV（c）-CNT catalyst for the ORR may be attributed to the synergistic effects of the unique 3D structure for effective mass-transfer, the effective N-doping for production of more active sites, and the good contact between the RGO and CNTs for easy charge-transfer.

Near-infrared light-activated cancer cell targeting and drug delivery with aptamer-modified nanostructures

Stimuli-activated targeted delivery systems for highly accurate treatment of tumors have received considerable attention in recent years. Herein, we reveal a light-activable cancer-targeting strategy that uses a complementary DNA sequence to hybridize and mask sgc8 aptamers conjugated onto photothermal agents such as gold nanorods or single-walled carbon nanotubes （SWNTs）. Upon exposure to near-infrared （NIR） laser, localized photothermal heating of the surface of those nano-agents results in dehybridization of the double-stranded DNA and uncaging of the aptamer sequence to allow specific cancer-cell targeting. Utilizing doxorubicin-loaded SWNTs as a model system, targeted drug delivery to cancer cells activated by NIR light was achieved. This work demonstrates the concept of NIR-activable tumor-targeting delivery systems with controllable cancer-cell binding to potentially enable highly specific and efficient cancer therapy.

Comparative study of gel-based separated arcdischarge, HiPCO, and CoMoCAT carbon nanotubes for macroelectronic applications

Due to their excellent electrical properties and compatibility with room-temperature deposition/printing processing, high-purity single-walled semiconducting carbon nanotubes hold great potential for macroelectronic applications such as in thin-film transistors and display back-panel electronics. However, the relative advantages and disadvantages of various nanotubes for macroelectronics remains an open issue, despite the great significance. Here in this paper, we report a com- parative and systematic study of three kinds of mainstream carbon nanotubes （arc-discharge, HiPCO, CoMoCAT） separated using low-cost gel-based column chromatography for thin-film transistor applications, and high performance transistors--which satisfy the requirements for transistors used in active matrix organic light-emitting diode displays--have been achieved. We observe a trade-off between transistor mobility and on/off ratio depending on the nanotube diameter. While arc-discharge nanotubes with larger diameters lead to high device mobility, HiPCO and CoMoCAT nanotubes with smaller diameters can provide high on/off ratios （〉 106） for transistors with comparable dimensions. Furthermore, we have also compared gel-based separated nanotubes with nanotubes separated using the density gradient ultracentrifuge （DGU） method, and find that gel-separated nanotubes can offer purity and thin-film transistor performance as good as DGU-separated nanotubes. Our approach can serve as the critical foundation for future carbon nanotube-based thin-film macroelectronics.

Improving Thermal and Flame Retardant Properties of Epoxy Resin with Organic NiFe-Layered Double Hydroxide-Carbon Nanotubes Hybrids

To improve the dispersion of carbon nanotubes （CNTs） and flame retardancy of layered double hydroxide （LDH） in epoxy resin （EP）, organic nickel-iron layered double hydroxide （ONiFe-LDH-CNTs） hybrids were assembled through co-precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe-LDH-CNTs nano- composites containing 4 wt% of ONiFe-LDH-CNTs with different ratios of ONiFe-LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy （TEM）. The results revealed a coexistence of exfoliated and intercalated ONiFe-LDH- CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe-LDH-CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe-LDH and synergistic effect between ONiFe-LDH and CNTs.

Metal-film-assisted ultra-clean transfer of single-walled carbon nanotubes

Transfer printing of nanomaterials onto target substrates has been widely used in the fabrication of nanodevices, but it remains a challenge to fully avoid contamination introduced in the transfer process. Here we report a metal-film- assisted method to realize an ultra-clean transfer of single-walled carbon nanotubes （SWCNTs） mediated by poly（methyl methacrylate） （PMMA）. The amount of PMMA residue can be greatly reduced due to its strong physical adhesion to the metal film, leading to ultra-clean surfaces of both the SWCNTs and the substrates. This metal-film-assisted transfer method is efficient, nondestructive, and scalable. It is also suitable for the transfer of graphene and other nanostructures. Furthermore, the relatively low temperature employed allows this technique to be compatible with nanomaterial-based flexible electronics.

Improved photoconductive properties of composite nanofibers based on aligned conjugated polymer and single-walled carbon nanotubes

We successfully address the challenge of aligning single-walled carbon nanotubes （SWNTs） and conjugated polymer chains in composite nanofibers for enhancing their opto-electrical properties. A pore-filling template strategy has been developed to prepare such nanocomposites from SWNTs and poly（para-phenylene vinylene） （PPV） chains, with both species well-oriented aligned along the pore axis. Addition of the SWNTs leads to a remarkable increase in photocurrent of four orders of magnitude as compared to equivalent pristine PPV nanofibers. Further analysis indicates that the strong photocurrent enhancement is not simply an effect of alignment, but additionally benefits from alignment-enhanced interaction of polymer chains with SWNTs, as supported by density functional theory （DFT） calculations.

Scanning electron microscopy imaging of single-walled carbon nanotubes on substrates

Scanning electron microscopy （SEM） plays an indispensable role in nanoscience and nanotechnology because of its high efficiency and high spatial resolution in characterizing nanomaterials. Recent progress indicates that the contrast arising from different conductivities or bandgaps can be observed in SEM images if single-walled carbon nanotubes （SWCNTs） are placed on a substrate. In this study, we use SWCNTs on different substrates as model systems to perform SEM imaging of nanomaterials. Substantial SEM observations are conducted at both high and low acceleration voltages, leading to a comprehensive understanding of the effects of the imaging parameters and substrates on the material and surface-charge signals, as well as the SEM imaging. This unified picture of SEM imaging not only furthers our understanding of SEM images of SWCNTs on a variety of substrates but also provides a basis for developing new imaging recipes for other important nanomaterials used in nanoelectronics and nanophotonics.

High-strength composite yarns derived from oxygen plasma modified super-aligned carbon nanotube arrays

Spinning carbon nanotube （CNT） yarns from super-aligned carbon nanotube （SACNT） arrays is a promising approach to fabricate high-strength fibers. However the reported tensile strengths of the as-prepared fibers are far below that of an individual CNT. It is therefore still a challenge to improve their mechanical strengths. Here we report that the tensile strengths and Young＇s moduli can be further improved to 2.2 GPa and 200 GPa respectively, if we first treat the SACNT array with oxygen plasma by using a reactive ion etching （RIE） facility, then dry spin yarns from it and make composite fibers with polyvinyl alcohol. According to the experimental results obtained using scanning electron microscopy （SEM）, Raman spectroscopy and X-ray photoelectron spectroscopy （XPS）, the improvement is attributed to the oxygen RIE process, as it can create functional groups on the outer walls of CNTs and thus improve the interaction between the CNTs and the polymer molecules.

Highly selective sorting of semiconducting single wall carbon nanotubes exhibiting light emission at telecom wavelengths

Single wail carbon nanotubes （SWNTs） are known for their exceptional electronic properties. However, most of the synthesis methods lead to the production of a mixture of carbon nanotubes having different chiralities associated with metallic （m-SWNTs） and semiconducting （s-SWNTs） characteristics. For application purposes, effective methods for separating these species are highly desired. Here, we report a protocol for achieving a highly selective separation of s-SWNTs that exhibit a fundamental optical transition centered at 1,550 nm. We employ a polymer assisted sorting approach, and the influence of preparation methods on the optical and transport performances of the separated nanotubes is analyzed. As even traces of m-SWNTs can critically affect performances, we aim to produce samples that do not contain any detectable fraction of residual m-SWNTs.

Rayleigh scattering studies on inter-layer interactions in structure-defined individual double-wall carbon nanotubes

Although the inter-layer coupling in layered materials has attracted considerable interest due to its importance in determining physical properties of two- dimensional systems, studies on the inter-layer coupling in one-dimensional systems have so far been limited. Double-wall carbon nanotubes （DWCNTs） are one of the most fundamental and ideal model systems to study the interqayer coupling in one-dimensional systems. In this work, Rayleigh scattering spectroscopy and transmission electron microscopy are used to characterize the electronic transition between inner-and outer-nanotubes of the exactly same individual DWCNT. We find that the interqayer coupling is strong, leading to downshifts in most of the optical transition energies （up to -0.2 eV） compared to isolated CNTs. We also find that the presence of metallic tubes lead to stronger shifts. The inter-layer screening of Coulomb interactions is one of the key factors in explaining the observed results.

Single-walled carbon nanotube networks for ethanol vapor sensing applications

Networks of pristine high quality single walled carbon nanotubes （SWNTs）, the SWNTs after Ar-plasma treatment （from 2 to 12 rain） and carbon nanobuds （CNBs） have been tested for ethanol vapor sensing. It was found that the pristine high quality SWNTs do not exhibit any ethanol sensitivity, while the introduction of defects in the tubes results in the appearance of the ethanol sensitivity. The CNB network showed ethanol sensitivity without plasma treatment. Both CNB and low defect （after 3 min treatment） SWNT networks exhibit significant drift in the resistance baseline, while heavily plasma-treated （9 min） SWNTs exhibited high ethanol vapor sensitivity without the baseline change. The mechanisms of the ethanol sensitivity and stability after the plasma irradiation are attributed to the formation of sensitive dangling bonds in the SWNTs and formation of defect channels facilitating access of the ethanol vapor to all parts of the bundled nanotubes.

Spontaneous twisting of a collapsed carbon nanotube

We study the collapsing and subsequent spontaneous twisting of a carbon nanotube by in situ transmission electron microscopy （TEM）. A custom-sized nanotube is first created in the microscope by selectively extracting shells from a parent multi-walled tube. The few-walled, large-diameter daughter nanotube is driven to collapse via mechanical stimulation, after which the ribbon-like collapsed tube spontaneously twists along its long axis. In situ diffraction experiments fully characterize the uncollapsed and collapsed tubes. The experimental observations and associated theoretical analysis indicate that the origin of the twisting is compressive strain.

Direct discrimination between semiconducting and metallic single-walled carbon nanotubes with high spatial resolution by SEM

Single-walled carbon nanotube （SWCNT） films with a high density exhibit broad functionality and great potential in nanodevices, as SWCNTs can be either metallic or semiconducting in behavior. The films greatly benefit from characterization technologies that can efficiently identify and group SWCNTs based on metallic or semiconducting natures with high spatial resolution. Here, we developed a facile imaging technique using scanning electron microscopy （SEM） to discriminate between semiconducting and metallic SWCNTs based on black and white colors. The average width of the single-SWCNT image was reduced to -9 nm, -1/5 of previous imaging results. These achievements were attributed to reduced surface charging on the SiOdSi substrate under enhanced accelerating voltages. With this identification technique, a CNT transistor with an on/off ratio of 〉10s was fabricated by identifying and etching out the white metallic SWCNTs. This improved SEM imaging technique can be widely applied in evaluating the selective growth and sorting of SWCNTs.

Carbon Xerogel-supported Iron as a Catalyst in Combustion Synthesis of Carbon Fibrous Nanostructures

The catalytically assisted self-propagating high-temperature synthesis of carbon fibrous nanostructures, where the iron-doped colloidal carbon xerogel is proposed as a catalyst system, was examined. The carbon xerogel was prepared through carbonization of an iron doped organic xerogel at temperatures ranging from 600 to 1050℃. The reaction between calcium carbide and hexachloroethane in the presence of sodium azide is exothermic enough to proceed at a high temperature, self-sustaining regime. The combustion reactions of those mixtures enriched with iron-doped carbon xerogels were conducted in a stainless steel reactor---calorimetric bomb under an initial pressure of 1 MPa of argon. Scanning electron microscopy analysis of the combustion products revealed low yield of various type of carbon fibers （presumably nanotubes）, which grew via the tip-growth mechanism. The fibrous nanostructures were found in the vicinity of the spot of ignition, while in the outer and cooler area of the reactor, dusty products with soot-like morphology dominated. No significant correlation between the pyrolysis temperature of the carbon xerogel and the morphology of the obtained carbon fibrous nanostructures was observed.

Radial deformation of single-walled carbon nanotubes on quartz substrates and the resultant anomalous diameter-dependent reaction selectivity

Owing to the unique conjugated structure, the chemical-reaction selectivity of single-walled carbon nanotubes （SWNTs） has attracted great attention. By utilizing the radial deformation of SWNTs caused by the strong interactions with the quartz lattice, we achieve an anomalous diameter-dependent reaction selectivity of quartz lattice-oriented SWNTs in treatment with iodine vapor; this is distinctly different from the widely reported and well accepted higher reaction activity in small-diameter tubes compared to large-diameter tubes. The radial deformation of SWNTs on quartz substrate is verified by detailed Raman spectroscopy and mappings in both G-band and radial breathing mode. Due to the strong interaction between SWNTs and the quartz lattice, large-diameter tubes present a larger degree of radial deformation and more delocalized partial electrons are distributed at certain sidewall sites with high local curvature. It is thus easier for the carbon--carbon bonds at these high-curvature sites on large-diameter tubes to break down during reaction. This anomalous reaction activity offers a novel approach for selective removal of small-band^aD large-diameter tubes.

Local synthesis of carbon nanotubes for direct integration in Si microsystems——design considerations

The integration of nanomaterials such as carbon nanotubes （CNTs） into microsystems is highly desirable, in order to make use of the unique nanomaterial properties in real devices. However, the CNTtomicrosystem integration is challenging to implement in a manufacturable, cost effective industrial process. This paper presents our work towards a process for making complete, integrated CMOS / MEMS systems with integrated CNT. We demonstrate the feasibility of the process, using roomtemperature process ing, lowcost equipment and consumables, and electrical control with automation possibilities. CNTs are directly integrated at the desired positions in the Si microsystem, forming closed Si / CNT / Si circuits. We explore different designs with the aim to obtain uniform and welldefined CNT synthesis conditions, and show that simplified designs can perform comparably to more complex ones. The Si / CNT / Si circuits obtained can show rectifying （Schottky like） or nearohmic behavior. Gas sensing possibilities are demonstrated, indicating the possibility of monitoring aging/ fermenting of food. Functionalization of CNTs is demon strated, using thermal evaporation of Sn and Pd, opening for selective and sensitive sensors for various gases and ana lytes. Detailed microscopic characterization of the obtained CNTs are presented.