Multiwalled carbon nanotubes in alfalfa and wheat: toxicology and uptake

Data on the bioavailability and toxicity of carbon nanotubes (CNTs) in the environment, and, in particular, on their interactions with vascular plants, are limited. We investigated the effects of industrial-grade multiwalled CNTs (75 wt% CNTs) and their impurities on alfalfa and wheat. Phytotoxicity assays were performed during both seed germination and seedling growth. The germinations of both species were tolerant of up to 2560 mg l⁻¹ CNTs, and root elongation was enhanced in alfalfa and wheat seedlings exposed to CNTs. Remarkably, catalyst impurities also enhanced root elongation in alfalfa seedlings as well as wheat germination. Thus the impurities, not solely the CNTs, impacted the plants. CNT internalization by plants was investigated using electron microscopy and two-dimensional Raman mapping. The latter showed that CNTs were adsorbed onto the root surfaces of alfalfa and wheat without significant uptake or translocation. Electron microscopy investigations of internalization were inconclusive owing to poor contrast, so Fe₃O₄-functionalized CNTs were prepared and studied using energy-filter mapping of Fe₃O₄. CNTs bearing Fe₃O₄ nanoparticles were detected in the epidermis of one wheat root tip only, suggesting that internalization was possible but unusual. Thus, alfalfa and wheat tolerated high concentrations of industrial-grade multiwalled CNTs, which adsorbed onto their roots but were rarely taken up.     

Tailoring the diameter of single-walled carbon nanotubes for optical applications

Single-walled carbon nanotubes (SWCNTs) with specific diameters are required for various applications particularly in electronics and photonics, since the diameter is an essential characteristic determining their electronic and optical properties. In this work, the selective growth of SWCNTs with a certain mean diameter is achieved by the addition of appropriate amounts of CO₂ mixed with the carbon source (CO) into the aerosol (floating catalyst) chemical vapor deposition reactor. The noticeable shift of the peaks in the absorption spectra reveals that the mean diameters of the as-deposited SWCNTs are efficiently altered from 1.2 to 1.9 nm with increasing CO₂ concentration. It is believed that CO₂ acts as an etching agent and can selectively etch small diameter tubes due to their highly curved carbon surfaces. Polymer-free as-deposited SWCNT films with the desired diameters are used as saturable absorbers after stamping onto a highly reflecting Ag-mirror using a simple dry-transfer technique. Sub-picosecond mode-locked fiber laser operations at ∼1.56 μm and ∼2 μm are demonstrated, showing improvements in the performance after the optimization of the SWCNT properties.      

In situ Raman spectroelectrochemical study of 13C-labeled fullerene peapods and carbon nanotubes

C60 fullerene peapods and double-walled carbon nanotubes (DWCNTs) containing highly 13C enriched C60 and inner tubes, respectively, are studied using Raman spectroscopy and in situ Raman spectroelectrochemistry in order to follow the influence of 13C enrichment on the vibrational pattern of these carbon nanostructures. The Raman response of 13C60 after encapsulation in fullerene peapods differs from that of isotope-natural species, (Nat)C60. The Raman A(g)(2) mode of encapsulated 13C60 is upshifted in frequency compared to that of the (Nat)C60 peapods with the same filling factor. The chemical doping of 13C60 peapods (peapod = C(60)@SWCNT) with K-vapor leads to the downshift of the A(g)(2) mode, similar to the case of (Nat)C60 peapods. The 13C60 peapods were successfully transformed into DWCNTs, which confirms high filling of single-walled (SW) CNTs with 13C60. The DWCNTs exhibited distinctly downshifted G and D Raman modes for inner tubes, which proves that only inner tubes were enriched by 13C. The in situ Raman spectroelectrochemistry of (Nat)C60 exhibits strong anodic enhancement, while for 13C60 peapods the enhancement is only weak. On the other hand, the electrochemical charging of the inner-tube-labeled DWCNTs (13C(i)-DWCNTs) followed the behavior of ordinary (Nat)C(i)-DWCNTs as indicated by in situ Raman spectroelectrochemistry. In addition, the spectroelectrochemical behavior of the G mode of inner tubes in 13C(i)-DWCNTs is followed from the start of the electrochemical doping, which was not feasible for (Nat)C(i)-DWCNTs.     

用于制备优质单壁碳纳米管管束的MgO负载Fe3O4纳米粒子的合成

采用沉淀方法制备了直径分布狭窄的均匀Fe3O4纳米颗粒.Fe3O4纳粒形体几近一致,平均粒径为10.33 nm±2.99 nm(平均粒径±标准偏差).在超声作用下将MgO纳米颗粒分散在一定量Fe3O4纳米颗粒的水溶液中获得MgO负载Fe3O4的纳米颗粒.以甲烷为碳源,Fe3O4/MgO为催化剂,经化学气相沉积,在Fe3O4纳粒上制得了大量直径近乎均匀的单壁碳纳米管(SWCNTs)束.TEM显示:SWCNTs的平均直径1.22rm.热重分析显示:样品在400℃～600℃温度区间失重量约19％.拉曼光谱显示:SWCNTs的ID/IG的强度比为0.03,表明采用Fe3O4/MgO催化剂可制得高石墨化程度的单壁碳纳米管.     

Investigation of fatigue and fracture properties of asphalt mixtures modified with carbon nanotubes

Load‐induced cracking is one of the primary forms of distress in asphalt pavements at intermediate temperatures. Binder modification is a good alternative to promote the cracking resistance of asphalt mixtures. In the current research study, the effects of carbon nanotubes as a binder modifier on the fatigue and fracture performance of asphalt mixtures are investigated. The carbon nanotubes are added at five different percentages ranging from 0.2% to 1.5% to the base binder to study their effects on the fracture resistance and fatigue life of the asphalt mixtures. Using the cracked semi‐circular bend specimen, the critical value of J‐integral (Jc) was obtained for the investigated modified asphalt mixtures. Also, the fatigue behaviour of asphalt mixtures was studied using flexural beam fatigue test specimen. By employing the ratio of dissipated energy change approach, the plateau value of tested mixtures was determined as a measure of fatigue performance. Results showed that the carbon nanotubes can enhance both fracture resistance and fatigue performance of tested asphalt mixtures especially at higher percentages of the carbon nanotube.     

Functionalization of multi-walled carbon nanotubes and its application in preparing the 3D graphene/carbon nanotubes hybrid architectures

A facile strategy for the preparation of water-dispersible multi-walled carbon nanotubes (MWCNTs) in aqueous solution for the preparation of the three-dimensional (3D) graphene/carbon nanotube (G/CNT) hybrid architectures is proposed, where MWCNTs were functionalized by simultaneous radiation-induced graft polymerization of acrylic acid under the γ-ray (denoted as MWCNT-g-PAA) for improving its dispersibility. The stability of the aqueous solution of MWCNT-g-PAA in water is highly improved. We also use the MWCNT-g-PAA fabricating three-dimensional cylindrical graphene/carbon nanotube (G/CNT) hybrid architectures by a simple one-step hydrothermal process. We found that the as-prepared MWCNTs-g-PAA showed a very good dispersibility in GO solution with different concentration ratio and a promising precursor for preparing the graphene/CNT hybrid materials.     

Binder-free activated carbon/carbon nanotube paper electrodes for use in supercapacitors

Novel inexpensive, light, flexible, and even rollup or wearable devices are required for multi-functional portable electronics and developing new versatile and flexible electrode materials as alternatives to the materials used in contemporary batteries and supercapacitors is a key challenge. Here, binder-free activated carbon (AC)/carbon nanotube (CNT) paper electrodes for use in advanced supercapacitors have been fabricated based on low-cost, industrial-grade aligned CNTs. By a two-step shearing strategy, aligned CNTs were dispersed into individual long CNTs, and then 90 wt%–99 wt% of AC powder was incorporated into the CNT pulp and the AC/CNT paper electrode was fabricated by deposition on a filter. The specific capacity, rate performance, and power density of the AC/CNT paper electrode were better than the corresponding values for an AC/acetylene black electrode. The capacity reached a maximum value of 267.6 F/g with a CNT loading of 5 wt%, and the energy density and power density were 22.5 W·h/kg and 7.3 kW/kg at a high current density of 20 A/g. The AC/CNT paper electrode also showed a good cycle performance, with 97.5% of the original capacity retained after 5000 cycles at a scan rate of 200 mV/s. This method affords not only a promising paper-like nanocomposite for use in low-cost and flexible supercapacitors, but also a general way of fabricating multi-functional paper-like CNT-based nanocomposites for use in devices such as flexible lithium ion batteries and solar cells.      

Recent developments in inorganically filled carbon nanotubes: successes and challenges

Abstract

Carbon nanotubes (CNTs) are a unique class of nanomaterials that can be imagined as rolled graphene sheets. The inner hollow of a CNT provides an extremely small, one-dimensional space for storage of materials. In the last decade, enormous effort has been spent to produce filled CNTs that combine the properties of both the host CNT and the guest filling material. CNTs filled with various inorganic materials such as metals, alloys, semiconductors and insulators have been obtained using different synthesis approaches including capillary filling and chemical vapor deposition. Recently, several potential applications have emerged for these materials, such as the measurement of temperature at the nanoscale, nano-spot welding, and the storage and delivery of extremely small quantities of materials. A clear distinction between this class of materials and other nanostructures is the existence of an enormous interfacial area between the CNT and the filling matter. Theoretical investigations have shown that the lattice mismatch and strong exchange interaction of CNTs with the guest material across the interface should result in reordering of the guest crystal structure and passivation of the surface dangling bonds and thus yielding new and interesting physical properties. Despite preliminary successes, there remain many challenges in realizing applications of CNTs filled with inorganic materials, such as a comprehensive understanding of their growth and physical properties and control of their structural parameters. In this article, we overview research on filled CNT nanomaterials with special emphasis on recent progress and key achievements. We also discuss the future scope and the key challenges emerging out of a decade of intensive research on these fascinating materials.     

Carbon nanotube-tipped endoscope for in situ intracellular surface-enhanced Raman spectroscopy

Gold nanoparticle-decorated carbon nanotubes (CNTs) are used to study intracellular environments in situ using surface-enhanced Raman spectroscopy (SERS). CNTs are decorated with gold nanoparticles and assembled onto the tips of pulled glass capillaries to form a SERS-enabled endoscope. The sub-micrometer size and high mechanical strength of the endoscope make it possible to penetrate the cell membrane for intracellular probing and remain positioned inside during lengthy SERS measurements without causing damage to the cell. Using the SERS-enabled endoscope, DNA and other biomolecules are detected in situ within the nucleus of a single human cervical carcinoma cell in a minimally invasive manner. The SERS-enabled endoscopes exhibit high selectivity and sensitivity for detecting trace amounts of analytes (≈1 pM) in biofluid environments, highlighting their capabilities as label-free, biological sensors for real-time in situ cellular diagnostics, biological detection, and pharmaceutical research.     

High-resolution X-ray photoelectron spectroscopy study of InTe thin film in structural phase transition from amorphous to crystalline phase

We investigated the chemical states of InTe thin film in the structural phase transition from the amorphous to the crystalline phase, using high-resolution X-ray photoelectron spectroscopy with synchrotron radiation. We confirmed the structural phase transition by transmission electron microscopy. Clean amorphous InTe (a-InTe) free of oxygen impurity was obtained after Ne⁺ ion sputtering at the ion beam energy of 1 kV for 1 h. Additionally, we obtained crystalline InTe (c-InTe) from clean a-InTe by annealing at 250 °C in an ultra-high vacuum. During the transition to the crystalline phase, the binding energy of the Te 4d core-level was unchanged, but the peak width was somewhat wider than in the amorphous phase. In the case of the In 4d core-level, the chemical shift was 0.1 eV at the higher binding energy between the amorphous and crystalline phases. The valence band maximum was shifted at the higher binding energy of 0.34 eV. We assumed that the Te atom was almost fixed and that the In atoms moved in the tight binding energy state to the center of the 4-Te atoms.     

多壁碳纳米管的表面修饰及其在溶剂中的分散性

利用高温催化裂解生长多壁碳纳米管,用硝酸氧化使其表面羧酸化,并经酰氯化后与十二烷基胺反应形成表面酰胺化,通过红外、核磁、微量热天平等方法进行表征.结果表明:硝酸氧化后的碳纳米管在水等强极性溶剂中有良好的分散性;酰胺化后,十二烷基脂肪链使碳纳米管表面极性大为降低,因此在氟仿等弱极性溶剂中有良好的分散性.     

In situ Raman study on single- and double-walled carbon nanotubes as a function of lithium insertion

We investigated the electrochemical lithium ion (Li(+)) insertion/desertion behavior on highly pure and bundled single- and double-walled carbon nanotubes (SWNTs and DWNTs) using an in situ Raman technique. In general, two storage sites could host Li(+) in SWNT and DWNT bundles when varying an external potential: a) the outer surface sites, and b) the interstitial spaces within the bundles. The most sensitive changes in the tangential mode (TM) of the Raman spectra upon doping with Li(+) can be divided into two regions. The first region was found from 2.8 to 1.0 V (the coverage of Li(+) on the outer surface of a bundled nanotube) and was characterized by the loss of resonant conditions via partial charge transfer, where the G(+) line of the SWNT and the TM of the outer tube of DWNTs experienced a highly depressed intensity, but remained almost constant in frequency. The appearance of a Breit-Wigner-Fano (BWF) profile provided strong evidence of metallic inner tubes within DWNTs. The second region was observed when the applied potentials ranged from 0.9 to 0 V and was characterized by Li(+) diffusion into the interstitial sites of the bundled nanotube material. This phenomenon invoked a large downshift of the G(-) band in SWNTs, and a small downshift of the TM of the inner tube of DWNTs caused by expansion of the C--C bonds due to the charge transferred to the nanotubes, and the disappearance of the BWF profile through the screening effect of the interstitial Li(+) layers.     

Electric field-oriented growth of carbon nanotubes and Y-branches in a needle-pulsed arc discharge unit: mechanism of the production

Carbon nano-onions, multiwall carbon nanotubes and Y-branched nanotubes are synthesised in a simple production apparatus. A pulsed plasma is generated by discharging a high voltage needle pulse between two graphite electrodes. A strong electric field is presented along anode and cathode electrodes. The pulse width is 0.3 μs. Acetone vapour, as a precursor, is introduced to the plasma through a graphite nozzle in the cathode assembly. A magnetic field, perpendicular to the plasma path, is provided. The possibility of carbon nanotube production through a short-pulsed arc discharge technique is investigated in this article. The results show that adding an electric field between electrodes prevents carbon ions’ dispersion, facilitates charge transferring between ions and electrodes, orients the growth of carbon nanotubes along the applied electric field and finally makes it possible to produce functionalised carbon nanoparticles such as Y-branch nanotubes and nanoknees. In this work, the growth mechanism of carbon nanotubes in a needle-pulsed arc-discharge reactor is discussed. And a possible explanation is provided for the synthesis of Y-branch carbon nanotubes. The products are examined by using scanning probe microscopy technique.     

Prediction of nonlocal scaling parameter for armchair and zigzag single-walled carbon nanotubes based on molecular structural mechanics, nonlocal elasticity and wave propagation

Atomic vibration in the Carbon Nanotubes (CNTs) gives rise to non-local interactions. In this paper, an expression for the non-local scaling parameter is derived as a function of the geometric and electronic properties of the rolled graphene sheet in single-walled CNTs. A self-consistent method is developed for the linearization of the problem of ultrasonic wave propagation in CNTs. We show that (i) the general three-dimensional elastic problem leads to a single non-local scaling parameter (e₀), (ii) e₀ is almost constant irrespective of chirality of CNT in the case of longitudinal wave propagation, (iii) e₀ is a linear function of diameter of CNT for the case of torsional mode of wave propagation, (iv) e₀ in the case of coupled longitudinal-torsional modes of wave propagation, is a function which exponentially converges to that of axial mode at large diameters and to torsional mode at smaller diameters. These results are valid in the long-wavelength limit.     

Evidence for metal-semiconductor transitions in twisted and collapsed double-walled carbon nanotubes by scanning tunneling microscopy

The atomic and electronic structure of a twisted and collapsed double-walled carbon nanotube was characterized using scanning tunneling microscopy and spectroscopy. It was found that the deformation opens an electronic band gap in an otherwise metallic nanotube, which has major ramifications on the use of carbon nanotubes for electronic applications. Fundamentally, the importance of the intershell interaction in this double-walled carbon nanotube points to the potential of a reversible metal-semiconductor junction, which can have device applications, as well as a caution in the design of semiconductor components based on carbon nanotubes. Lattice registry effects between the two neighboring walls evidenced by atomically resolved images confirm earlier first principle calculations indicating that the helicity influences the collapsed structure and show excellent agreement with the predicted twisted-collapse mode.     

Solid phase extraction of heavy metal ions in environmental samples on multiwalled carbon nanotubes

Multiwalled carbon nanotubes (MWNTs) were used as solid phase extractor for Cu(II), Cd(II), Pb(II), Zn(II), Ni(II) and Co(II) ions as ammonium pyrrolidine dithiocarbamate (APDC) chelates, in the present study. The influences of the experimental parameters including pH of the solutions, amounts of MWNTs, amounts of APDC, eluent type and volume, sample volume etc. on the quantitative recoveries of analyte ions were investigated. The effects of matrix ions of natural waters and some transition metals on the recoveries of the analyte ions were also examined in the model solutions. Tests of addition/recovery for analyte ions in real samples were performed with satisfactorily results. The detection limits (3s) for the analyte ions were in the range of 0.30-0.60 microg l(-1). The concentrations of analytes in standard reference materials (NIST RM 8418 Wheat gluten, LGC 6010 Hard drinking water and NIST SRM 1515 Apple leaves) pretreated by the presented method were measured with FAAS and the analytical values were well agreed with the certified values and the reference values without the interference of major components. The presented method has been applied to the determination of analytes in food and environmental samples with satisfactory results.     

Safety performance of traffic phases and phase transitions in three phase traffic theory

Crash risk prediction models were developed to link safety to various phases and phase transitions defined by the three phase traffic theory. Results of the Bayesian conditional logit analysis showed that different traffic states differed distinctly with respect to safety performance. The random-parameter logit approach was utilized to account for the heterogeneity caused by unobserved factors. The Bayesian inference approach based on the Markov Chain Monte Carlo (MCMC) method was used for the estimation of the random-parameter logit model. The proposed approach increased the prediction performance of the crash risk models as compared with the conventional logit model. The three phase traffic theory can help us better understand the mechanism of crash occurrences in various traffic states. The contributing factors to crash likelihood can be well explained by the mechanism of phase transitions. We further discovered that the free flow state can be divided into two sub-phases on the basis of safety performance, including a true free flow state in which the interactions between vehicles are minor, and a platooned traffic state in which bunched vehicles travel in successions. The results of this study suggest that a safety perspective can be added to the three phase traffic theory. The results also suggest that the heterogeneity between different traffic states should be considered when estimating the risks of crash occurrences on freeways.     

A biosensor based on Coriolopsis gallica laccase immobilized on nitrogen-doped multiwalled carbon nanotubes and graphene oxide for polyphenol detection

Abstract

The use of nanomaterials allows the design of ultrasensitive biosensors with advantages in the detection of organic molecules. Catechol and catechin are molecules that occur naturally in fruits, and their presence in products like dyes and wines affects quality standards. In this study, catechol and catechin were measured at the nanoscale by means of cyclic voltammetry. The oxidation of Coriolopsis gallica laccase immobilized on nitrogen-doped multiwalled carbon nanotubes (Lac/CN_x-MWCNT) and on graphene oxide (Lac/GO) was used to measure the concentrations of catechol and catechin. Nitrogen-doped multiwalled carbon nanotubes (CN_x-MWCNT) were synthesized by spray pyrolysis and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray photoelectron spectroscopy (XPS). Covalently bonded hybrids with laccase (Lac/CN_x-MWCNT and Lac/GO) were generated. Catalytic activity of free enzymes determined with syringaldazine yielded 14 584 UmL^?1. With Lac/CN_x-MWCNT at concentrations of 6.4 mmol L^?1 activity was 9326 U mL^?1, while enzyme activity measured with Lac/GO at concentration of 6.4 mmol L^?1 was 9 234 U mL^?1. The Lac/CN_x-MWCNT hybrid showed higher stability than Lac/GO at different ethyl alcohol concentrations. The Lac/CN_x-MWCNT hybrid can measure concentrations, not previously reported, as low as 1 × 10^?8 mol L^?1 by measuring the electric current responses.