DNA damage induced by multiwalled carbon nanotubes in mouse embryonic stem cells

Carbon nanotubes (CNTs) have shown promise as an important new class of multifunctional building blocks and innovative tools in a large variety of applications, ranging from nanocomposite materials through nanoelectronics to biomedical devices. Because of their unusual one-dimensional hollow nanostructure and unique physicochemical properties, CNTs are particularly useful as novel drug delivery tools and imaging agents. However, such biomedical applications will not be realized if there is no proper assessment of the potential hazards of CNTs to humans and other biological systems. Although a few reports on the cytotoxicity of CNTs have been published, very little is known about the toxicity at the molecular level, or genotoxicity, of CNTs in mammalian cells. We have for the first time assessed the DNA damage response to multiwalled carbon nanotubes (MWNTs) in mouse embryonic stem (ES) cells. We found that MWNTs can accumulate and induce apoptosis in mouse ES cells and activate the tumor suppressor protein p53 within 2 h of exposure. Furthermore, we also observed increased expression of two isoforms of base excision repair protein 8-oxoguanine-DNA glycosylase 1 (OGG1), double strand break repair protein Rad 51, phosphorylation of H2AX histone at serine 139, and SUMO modification of XRCC4 following the treatment with MWNTs. A mutagenesis study using an endogenous molecular marker, adenine phosphoribosyltransferase (Aprt), showed that MWNTs increased the mutation frequency by 2-fold compared with the spontaneous mutation frequency in mouse ES cells. These results suggest that careful scrutiny of the genotoxicity of nanomaterials is needed even for those materials, like multiwalled carbon nanotubes, that have been previously demonstrated to have limited or no toxicity at the cellular level.     

In situ nucleation of carbon nanotubes by the injection of carbon atoms into metal particles

The synthesis of carbon nanotubes (CNTs) of desired chiralities and diameters is one of the most important challenges in nanotube science and achieving such selectivity may require a detailed understanding of their growth mechanism. We report the formation of CNTs in an entirely condensed phase process that allows us, for the first time, to monitor the nucleation of a nanotube on the spherical surface of a metal particle. When multiwalled CNTs containing metal particle cores are irradiated with an electron beam, carbon from graphitic shells surrounding the metal particles is ingested into the body of the particle and subsequently emerges as single-walled nanotubes (SWNTs) or multiwalled nanotubes (MWNTs) inside the host nanotubes. These observations, at atomic resolution in an electron microscope, show that there is direct bonding between the tubes and the metal surface from which the tubes sprout and can be readily explained by bulk diffusion of carbon through the body of catalytic particles, with no evidence of surface diffusion.     

Cellular uptake and cytotoxic impact of chemically functionalized and polymer-coated carbon nanotubes

The impact of nanomaterials such as carbon nanotubes on biological matter is a topic of increasing interest and concern and requires a multifaceted approach to be resolved. A modified cytotoxic (lactate dehydrogenase (LDH)) assay is developed in an attempt to offer a valid and reliable methodology for screening carbon nanotube toxicity in vitro. Two of the most widely used types of surface-modified multiwalled carbon nanotubes (MWNTs) are tested: ammonium-functionalized MWNTs (MWNT-NH3+ ) and Pluronic F127 coated MWNTs (MWNT:F127). Chemically functionalized MWNTs show significantly greater cellular uptake into lung epithelial A549 cells compared to the non-covalently Pluronic F127-coated MWNTs. In spite of this, MWNT:F127 exhibit enhanced cytotoxicity according to the modified LDH assay. The validity of the modified LDH assay is further validated by direct comparison with other less reliable or accurate cytotoxicity assays. These findings indicate the reliability of the modified LDH assay as a screening tool to assess carbon nanotube cytotoxicity and illustrate that high levels of carbon nanotube cellular internalization do not necessarily lead to adverse responses.     

Carbon nanotube arrays for optical design of amorphous silicon solar cells

Effective light trapping is essential for the conversion efficiency increase in thin film solar cells. Vertically aligned multiwalled carbon nanotubes (MWNTs) arrays with proper spacing form an ideal light trapping structure. In this work, we have demonstrated feasibility of the incorporation of MWNTs as back contact into amorphous silicon solar cells. Intrinsic amorphous silicon films were uniformly deposited onto vertically aligned MWNTs arrays. Scanning Electron Microscopy (SEM) was used to investigate the surface morphology of our films. The film surface area exposed to light was found to be increased dramatically due to the high-aspect ratio of MWNTs. Our findings open up a new way of managing light in thin film silicon solar cells by controlling the nano-geometry of MWNTs on substrates.     

Preparation of isotactic polypropylene-grafted multiwalled carbon nanotubes (iPP-g-MWNTs) by macroradical addition in solution and the properties of iPP-g-MWNTs/iPP composites

Isotactic polypropylene (iPP) was successfully grafted onto multiwalled carbon nanotubes (MWNTs) by direct macroradical addition by sonication in hot xylene with BPO as an initiator. A quantitative determination of the grafting ratio was first realized after the iPP-g-MWNTs were extensively purified by repeated hot vacuum filtration and redispersion in xylene at 130 °C. It was found that both iPP macromolecular radicals and small-molecular benzoic acid free radicals were grafted onto MWNTs. iPP-g-MWNTs dispersed more uniformly in iPP than pristine MWNTs. The iPP-g-MWNTs/iPP composites have much higher elongations at break than the iPP composites filled with pristine MWNTs, and the Young’s modulus and yield strength were also improved to some extent. iPP-g-MWNTs also have a stronger nucleation effect on the crystallization of iPP than pristine MWNTs.     

Design of an Assembly of Poly(benzimidazole), Carbon Nanotubes,and Pt Nanoparticles for a Fuel‐Cell Electrocatalyst with an Ideal Interfacial Nanostructure

A newly designed and fabricated novel nanocomposite composed of multiwalled carbon nanotubes (MWNTs), poly(benzimidazole) (PBI), and Pt nanoparticles. This composite is fabricated by the preparation of PBI‐wrapped MWNTs (MWNT/PBI), followed by Pt loading onto the MWNT/PBI. As a result of the PBI wrapping, the loading efficiency of the Pt nanoparticles onto the MWNTs is dramatically improved up to 58.8% compared to that of the pristine MWNTs (41.0%). The process also allows homogeneous Pt immobilization onto the surface of MWNTs without any strong oxidation process for the MWNTs that is typically used for metal supporting on carbon nanotubes. Far‐IR spectroscopy of the composite shows a peak from the Pt? N bonding, indicating that these improvements are derived from the coordination of the Pt ion with the PBI molecules. Cyclic voltammogram measurements reveal that the Pt nanoparticles deposited on the MWNT/PBI shows higher utilization efficiency (74%) for electrocatalysts compared to that on the pristine MWNT (39%).     

碳纳米管/PVC复合材料的制备及表征

采用RAFT活性聚合方法在碳纳米管表面接枝上聚合物链。然后与PVC通过熔融共混方法复合制备了碳纳米管/PVC纳米复合材料。对复合材料的结构与拉伸强度进行了表征研究,表明接枝聚合物链的碳纳米管显著提高了PVC的拉伸强度。     

Variation of radial elasticity in multiwalled carbon nanotubes

Correlations between the local diameter and local radial elastic modulus in multiwalled carbon nanotubes (MWNTs) were investigated via ultrasonic force microscopy. Spatial cross-correlation analysis showed that local radial modulus variations were inversely correlated with local diameter gradients ("bamboo" structures) in MWNTs grown via chemical vapor deposition (CVD). In contrast, uniform MWNTs grown via arc discharge exhibited no such correlation, indicating that reductions of elastic modulus previously reported for CVD-grown MWNTs originated from increased defect density associated with local increases in diameter.     

Light-scattering and dispersion behavior of multiwalled carbon nanotubes

Elliptically polarized light-scattering measurements were performed to investigate the dispersion behavior of multiwalled carbon nanotubes (MWNT). Xylene- and pyridine-derived MWNT powders were dispersed in water and ethanol in separate optic cells and allowed to sit undisturbed over a two-week time period after probe sonication. Continuous light-scattering measurements taken between scattering angles of 10-170 deg and repeated over several days showed that the nanotubes formed fractal-like networks. The pyridine-derived MWNTs showed greater dispersion variation over time, tending to aggregate and clump much faster than the xylene-derived tubes. The water suspensions appeared much more stable than the ethanol suspensions, which transformed into nonfractal morphology after a few hours. We relate the dispersion stability to size and fringe patterns on the outer surface of the nanotubes. Measured values of fractal dimension were distinctly lower than those in previous studies of single-walled carbon nanotubes. Profiles of both diagonal and off-diagonal scattering matrix elements are presented.     

Grafting of polystyrene on nitrogen-doped multi-walled carbon nanotubes

Polymer grafting of polystyrene (PS) on nitrogen-doped multiwall carbon nanotubes (CNx) was successfully obtained by a "grafting from" technique. The production method involves the immobilization of initiators, using wet chemistry, onto the nanotube surface, followed by an in situ surface-initiated polymerization. The polymer-grafting carbon nanotubes synthesis includes the free radical functionalization of CNx and the "controlled/living" Nitroxide Mediated Radical Polymerization (NMRP). The obtained products were studied using several microscopic techniques as scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS). The characterization also includes thermogravimetric analysis (TGA), Raman spectroscopy, infrared spectroscopy, and electron spin resonance (ESR), among others. The analyzed samples were also compared with solutions fabricated by physical blending of the polymer and CNx nanotubes. These results indicate that the nanotube radical functionalization, the chemical grafting, and the polymerization reaction were obtained over CNx when NMRP method was successfully used, giving rise to a uniform PS layer of several nanometers grafted on the outer surface of the CNx nanotubes. Several properties of the PS-grafted CNx nanotubes were also studied. It is shown that the production method leads to a narrower distribution of the external diameters. Moreover, their solubilization in organic solvents is greatly improved. Finally, the dispersion of PS-grafted CNx into a PS matrix is studied to determine the differences in filler dispersion and interfacial adhesion strength, in comparison with nanocomposites elaborated with as-produced CNx.     

基于原子转移自由基聚合法制备多壁碳纳米管/Ag复合材料

在多壁碳纳米管(MWNT)表面键接可用于原子转移自由基聚合(ATRP)的引发剂,并以此引发甲基丙烯酸缩水甘油酯(GMA)在MWNT表面的ATRP.利用红外光谱(FT-IR)、核磁共振(<'1>H-NMR)和透射电镜(TEM)对接枝聚合物MWNT的结构和外观形貌进行了研究.接枝在MWNT表面的PGMA与过量的乙二胺发生开...     

Noncovalent functionalization of multi-walled carbon nanotubes with amphiphilic polymers containing pyrene pendants

A novel noncovalent approach was developed for the functionalization of multiwalled carbon nanotubes (MWNTs) using an amphiphilic copolymer of PVP-co-PAH containing pyrene pendants. A homogeneous polymer layer was formed on the surface of MWNTs, and the wrapped copolymer layer with a thickness of about 17.7 nm was found. The noncovalent modified MWNTs were dispersed very well in solvent of dimethylformamide (DMF), water and chloroform (CHCl₃), and the high stability of dispersed suspensions could be maintained for more than 2 months without observed MWNT precipitation. In addition, the dispersing behavior of the noncovalent functionalized MWNTs by PVP-co-PAH in a solvent mixture of water/CHCl₃ was also investigated, and it was found that a carbon nanotube layer was formed at the water/CHCl₃ interface.     

氮掺杂碳纳米管的无金属催化剂合成和表征

采用爆炸辅助化学气相沉积法, 以碳纳米管(CNTs)作催化剂, 三聚氰胺作碳源和氮源, 无金属催化剂合成出氮掺杂碳纳米管(CN_x). 通过TEM、EDS、Mapping、XPS、Raman和TG测试手段对CN_x进行了表征. 结果表明, CNx具有竹节状结构, 其掺氮量高达17at%, 且氮元素分布均匀. 氮元素以石墨型和吡啶型掺杂在石墨层中, 由于大量氮元素掺杂造成纳米管石墨化程度降低, 抗氧化能力减弱.     

Synthesis and thermoelectric power of nitrogen-doped carbon nanotubes

We have previously shown that high-purity multiwalled carbon nanotubes (pristine MWNTs) can be prepared from a mixture of xylene-ferrocene (99 at% C:1 at% Fe) inside a quartz tube reactor operating at approximately 700 degrees C. In a similar process, approximately 3 g of melamine (C3H6N6) was introduced during the growth of MWNTs to prepare nitrogen-doped nanotubes. The structural and electronic properties of nitrogen-doped MWNTs were determined by scanning electron microscopy, high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and thermopower measurements. The individual nitrogen-doped nanotube exhibits a bamboo-like structure and comprises 6-16 tube walls, as evidenced by HRTEM studies. The EELS measurements yielded an average nitrogen content of approximately 5 at% in the doped tubes. The thermoelectric power data of nitrogen-doped MWNTs remained negative even after exposure to oxygen for an extended period of time, suggesting that nitrogen doping of MWNTs renders them n-type, consistent with scanning tunneling spectroscopic studies on similar nanotubes.     

Preparation polystyrene/multiwalled carbon nanotubes nanocomposites by copolymerization of styrene and styryl-functionalized multiwalled carbon nanotubes

Styryl-functionalized multiwalled carbon nanotubes (p-MWNTs) were prepared by esterification based on the carboxylate salt of carbon nanotubes and p-chloromethylstyrene in toluene. Then in situ radical copolymerization of p-MWNTs and styrene initiated by 2,2′-azobis(isobutyronitrile) (AIBN) was applied to synthesize composites of styryl-functionalized multiwalled carbon nanotubes and polystyrene (PS) (p-MWNTs/PS). Characterizations carried out by FT-IR, ¹H NMR, UV–vis show that styryl group covalently bond to the surface of MWNTs. The results of UV showed that the solutions of p-MWNTs/PS in chloroform have the hyperchromic effect. Transmission electron microscopy (TEM) images of p-MWNTs/PS composites and scanning electron microscopy (SEM) images of fracture surface of p-MWNTs/PS composites showed the functionalized nanotubes had a better dispersion than that of the unfunctionalized MWNTs in the matrix. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) suggested that the thermal stability of p-MWNTs/PS composites improved in the presence of MWNTs.     

Variability of the elastic properties of multiwalled carbon nanotubes

The results of numerous experimental investigations of carbon nanotubes show evidence of a considerable variability in their mechanical properties. Based on the common features of the structures of graphite and multiwalled carbon nanotubes (MWNTs), it is demonstrated that structural polytype transitions are among the probable factors responsible for this variability. Analysis of the MWNT behavior under torsion shows that the torsional stiffness of MWNTs depends on the elastic moduli, the number and magnitudes of which vary with the local symmetry of the MWNT structure (on the transition from rhombohedral to hexagonal and turbostratic modifications). The effect of structural transformations on the Young modulus in stretched MWNTs is evaluated.     

Synthesis,characteristic, and flammability of modified carbon nanotube/poly(ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate) nanocomposites containing phosphorus and silicon

A novel flame retardant containing phosphorus–silicon, spirocyclic pentaerythritol bisphosphorate disphosphorylchloride/9,10-dihydro-9-oxa-10-phosphaphanthrene-10-oxide/vinyl methyl dimethoxysilane (SPDV), has been used to modify multiwalled carbon nanotubes (MWNTs) and the m-MWNTs (MWNTs-g-SPDV) was obtained by the covalent grafting of SPDV onto the surfaces of MWNTs. And then the according poly(ethylene-co-vinyl acetate) nanocomposites were prepared via melt blending. Transmission electron microscopy (TEM) results showed that a core–shell nanostructure with MWNTs as the hard core and SPDV as the soft shell was formed, and the resultant m-MWNTs can achieve better dispersion than pristine MWNTs in EVM matrix. Cone calorimeter results showed that better flame retardancy was obtained for EVM/m-MWNTs nanocomposites. Mechanical measurements showed that the Young’s modulus increases due to the presence of MWNTs or m-MWNTs. The flammability and mechanical properties of the nanocomposites are strongly dependent on the dispersion state of nanotubes.     

High yield of pure multiwalled carbon nanotubes from the catalytic decomposition of acetylene on in-situ formed cobalt nanoparticles

For the first time, multiwalled carbon nanotubes (MWNTs) could be formed selectively in a high yield, free of any disordered carbon by-product, from the catalytic decomposition of acetylene at 600 degrees C on a CoxMg(1-x)O solid solution. Starting from 1 g of catalytic substrate, 4 g of pure MWNTs were obtained after its dissolution in boiling concentrated HCl, without any additional purification in strongly oxidizing medium, as is required for other methods of nanotube production. In situ reduction of CoO by dihydrogen liberated from acetylene decomposition allows highly divided metal particles to be continuously produced as synthesis proceeds. This is undoubtedly the reason for the good performance of the catalyst and for the ability to produce nanotubes in a narrow diameter range, namely from 10 to 15 nm. With the use of acetylene instead of methane, the synthesis proceeds at low temperature, which prevents the growth of carbon shells, in which the metal particles are generally embedded, decreasing their activity. Because of the very low specific surface area of the catalyst support, the amount of disordered carbon by-product formed is negligible.     

多壁碳纳米管/聚苯乙烯-聚氯乙烯复合材料的导电特性

用溶液共混法制得了MWNTs/PS-PVC复合材料, 进行了电导率的测试分析。通过对载流子浓度、迁移率的测量以及电导活化能的计算等分析研究了影响MWNTs/PS-PVC复合材料电导率的因素和导电机制。结果表明: 当PS与PVC的质量比为1:1时, MWNTs/PS-PVC复合材料的导电阈值最低; 当MWNTs的质量分数为1.5%, PS在PS-PVC基体中的质量分数为50%时, MWNTs/PS-PVC复合材料的电导率比MWNTs/PVC单一聚合物复合材料的提高了4个数量级。在导电网络的形成过程中, MWNTs/PS-PVC复合材料中形成的与无机化合物超晶格结构类似的n-i-p-i结构, 降低了MWNTs/PS-PVC复合材料的电导活化能, 增加了载流子浓度, 使MWNTs/PS-PVC复合材料电导率显著提高。     

Effect of multiwalled carbon nanotubes on tensile stress-strain diagrams of amorphous-crystalline thermoplastic polymers

The effect of multiwalled carbon nanotubes (MWNTs) on the stress-strain diagrams of uniaxially extended thin films of low-density polyethylene (LDPE) and poly(vinyl alcohol) (PVA) has been studied. MWNTs were synthesized by the thermocatalytic method. The introduction of MWNTs decreases the plasticity of LDPE, while significantly increasing that of PVA. The results can be explained by assuming that crystallites are key structural elements that ensure large plastic deformation. The manifestation of the plasticity of crystallites implies that amorphous regions occur in a rubberlike state. Both of these prerequisites are important for the mechanics of amorphous-crystalline thermoplastic polymers.