Multiwall Carbon Nanotubes and Nanofibers in Gallionella

This is a report of microbial formation of multiwall carbon nanotubes (MWCNT) and nanofibers at normal pressure and temperature. Our results demonstrate a single cell organism's ability to form complicated material of high industrial interest. The microorganism, Gallionella, is classified as autotrophic and dysoxic. It uses CO₂ for its carbon source and grows in environments with low concentrations of free oxygen. The organisms were taken from a deep bedrock tunnel where water leaking from cracks in the rock formed a precipitate of iron as a bacterial slime on the rock wall. Detailed investigations of the samples by transmission electron microscopy (TEM) revealed several types of MWCNT. The stalk single MWCNT was observed with a diameter of about 10 nm and with an inner diameter of 1.35 nm. The wall of the nanotube is built by graphite layers. The 10 to 20 sheets are used to form the tubes. The measured spacing between the lines is 0.34 nm, which is an average value of interlayer spacing, close to the graphitic distance (0.335 nm). HRTEM images reveal a two-dimensional lattice with a spacing of 0.24 nm, indicating the presence of graphene.     

Encapsulation of Pt-labelled DNA Molecules inside Carbon Nanotubes

Experiments on encapsulating Pt--labelled DNA molecules inside multiwalled carbon nanotubes (MWCNT) were performed under temperature and pressure conditions of 400K and 3 Bar. The DNA-CNT hybrids were purified via agarose gel electrophoresis and analyzed via high resolution transmission electron microscopy (HR-TEM) and energy dispersive X-ray spectroscopy (EDX). The results showed that the Pt-labelled DNA molecules attached to the outside walls of CNTs could be removed by electrophoresis. The HR-TEM and EDX results demonstrated that 2-3% of the Pt-labelled DNA molecules were successfully encapsulated inside the MWCNTs. The experimental study complements our previous molecular dynamics simulations on encapsulation of single stranded DNA oligonucleotides inside single wall carbon nanotubes under similar conditions in water. The van der Waals interaction between CNT and Pt-labelled DNA is believed to be the main driving force for this phenomenon. The DNA-CNT molecular complex could be further explored for potential applications in bio-nanotechnology.     

Adsorption of DDT from Contaminated Soil using Carbon Nanotubes

This paper presents results of an investigation into the use of carbon nanotubes (CNTs) for the adsorption of DDT in soil and solution. DDT is a known endocrine-disrupting chemical with observed persistence, harm to the environment, and a human health concern. Thus, it is important to clean it up from the environment. In this study, CNT is selected because it has high surface area for adsorption. Adsorption experiments were conducted using the batch equilibrium technique with a fixed soil:solution ratio. Adsorption of DDT onto the CNTs was characterized by an initial rapid adsorption, which eventually became constant within 22 hours, perhaps due to limited surface area of the CNTs available for DDT adsorption. Results of the study demonstrated the relative adsorption increase with increasing solution concentration. The results obtained indicate the importance of CNTs in the adsorption of DDT and show that they have a great potential application for remediation of DDT from contaminated soil.     

Transport of Surface-modified Carbon Nanotubes through a Soil Column

Carbon nanotubes (CNTs) are widely manufactured nanoparticles, which are being utilized in a number of consumer products, such as sporting goods, electronics and biomedical applications. Due to their accelerating production and use, CNTs constitute a potential environmental risk if they are released to soil and groundwater systems. It is therefore essential to improve the current understanding of environmental fate and transport of CNTs. The transport and retention of CNTs in both natural and artificial media have been reported in literature, but the findings widely vary and are thus not conclusive. There are a number of physical and chemical parameters responsible for variation in retention and transport. In this study, a complete procedure of selected multiwalled carbon nanotubes (MWCNTs) is presented starting from their surface modification to a complete set of laboratory column experiments at critical physical and chemical scenarios. Results indicate that the stability of the commercially available MWCNTs are critical with their attached surface functional group which can also influence the transport and retention of MWCNT through the surrounding medium.     

Restrictions on the Production of Multi-Wall Carbon Nanotubes and Nanofibers by Gallionella sp.

The enzymatic oxidization of dissolved Fe(II) to Fe(III) by neutrophilic Fe-oxidizing bacteria plays a significant role in biological cycling of iron by inducing the precipitation of Fe(III) oxyhydroxide in aqueous environments. Among the diverse neutrophilic Fe-oxidizing bacteria, the genus Gallionella has received wide attention for its production of unique twisted extracellular stalks. Hallberg and Tai (2014 Hallberg R, Tai CW. 2014. Multi-wall carbon nanotubes and nanofibers in Gallionella. Geomicrobiol J 31(9):764–768.[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) recently reported the detection of multi-wall carbon nanotubes on the twisted-stalks, and they viewed those carbon nanotubes as being biologically produced by Gallionella. We scrutinized Gallionella-produced biofilms collected from natural environments by scanning electron microscopy and high-resolution transmission electron microscopy. Ferrihydrite and lepidocrocite were the only nano-scaled minerals observed on the stalk, while there were nanometer-sized sheet-like graphitic contaminants on the grid in the vicinity of the sample which showed the same morphology as Hallberg and Tai (2014 Hallberg R, Tai CW. 2014. Multi-wall carbon nanotubes and nanofibers in Gallionella. Geomicrobiol J 31(9):764–768.[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) observed. Moreover, similar materials on an empty grid and a grid loaded with randomly selected synthesized materials were also observed. Based on the current knowledge of carbon nanotube syntheses, none of the three known synthesizing methods including root-growth, rolling-up and bottom-up could be biochemically produced by any life because of the significant kinetic and energy obstacles. The carbon nanomaterials reported by Hallberg and Tai (2014 Hallberg R, Tai CW. 2014. Multi-wall carbon nanotubes and nanofibers in Gallionella. Geomicrobiol J 31(9):764–768.[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]) were clearly contaminations from amorphous carbon film on the grids for holding samples for transmission electron microscopic observations.     

Coupled Surface Plasmon-Polariton Modes of Metallic Single-Walled Carbon Nanotubes

The propagation of the coupled surface plasmon-polariton modes in the metallic single-walled carbon nanotubes are investigated, taking into account the retardation effects. A simple model based on the classical electrodynamics and the two-fluid hydrodynamic theory is proposed. The dispersion relation of the surface polariton modes is obtained in order to survey the effects of the two-fluid model and the insulating dielectric media.     

Atomistic Simulations of Uniaxial Tensile Behaviors of Single-walled Carbon Nanotubes

Atomistic simulations, using the second-generation reactive empirical bond order (REBO) potential, are performed to investigate the uniaxial tensile behaviors of single-walled carbon nanotubes (SWCNTs). It is found that the effect of the nanotube diameters on the elastic modulus, the tensile strength and the stress vs. strain relation of SWCNTs is small yet noticeable. However, the effect of the degree of helicity is significant.     

碳纳米管固定化纤维素酶的最佳工艺研究

纤维素酶在环保、医药、食品等领域都具有广泛的应用前景,但由于纤维素酶的生产成本较高,生物活性较低,使得纤维素酶的应用受到了限制。为了寻找一种固定化纤维素酶的方法,使酶可以重复多次使用,首次以多壁碳纳米管为载体固定化纤维素酶,研究功能化的多壁碳纳米管固定化纤维素酶的固定化条件,采用正交试验对酶固定化中的主要条件进行优化,并通过傅里叶变换红外光谱仪对多壁碳纳米管（multiwalled carbon nanotube,MWCNTs）、纤维素酶及固定化纤维素酶的结构进行表征。结果表明,固定化纤维素酶的最佳工艺条件为：酶浓度5 mg·mL-1,温度40 ℃,pH 5.0,固定化时间3 h;通过傅里叶变换红外光谱证实纤维素酶成功固定到多壁碳纳米管上。     

PEGylated Single-Walled Carbon Nanotubes as Nanocarriers for Cyclosporin A Delivery

Single-walled carbon nanotubes (SWCNTs) have attracted the attention of many researchers due to their remarkable physicochemical features and have been found to be a new family of nanovectors for the delivery of therapeutic molecules. The ability of these nanostructures to load large amounts of drug molecules on their outer surface has been considered as the main advantage by many investigators. Here, we report the development of a PEGylated SWCNT-mediated delivery system for cyclosporin A (CsA) as a potent immunosuppressive agent. The available OH group in the CsA structure was first linked to a bi-functional linker (i.e., succinic anhydride) in order to provide a COOH terminal group. CsA succinylation process was optimized by using the modified simplex method. The resulting compound, CsA–CO–(CH₂)₂–COOH, was then grafted onto the exterior surface of SWCNTs, previously PEGylated with phospholipid–PEG₅₀₀₀–NH₂ conjugates, through the formation of an amide bond with the free amine group of PEGylated SWCNTs. Drug loading, stability of the PEGylated SWCNT–CsA complex, and in vitro release of the drug were evaluated. Loading efficiencies of almost 72% and 68% were achieved by UV spectrophotometry and elemental analysis methods, respectively. It was observed that 57.3% of cyclosporine was released from CsA–Pl–PEG₅₀₀₀–SWCNTs after 3 days. In this investigation, we conjugated CsA to an amine-terminated phospholipid–polyethylene glycol chain attached on SWCNTs via a cleavable ester bond and demonstrated the possible potential of PEGylated SWCNT-based systems for CsA delivery.     

碳纤维/碳纳米管增强磷酸钙生物复合材料的血液相容性研究

目的：探讨以碳长纤维模拟骨组织中的胶原纤维束,碳纳米管弥散分布在骨水泥基质中所制备的仿生复合材料的血液相容性。方法：采用血小板静态浸渍黏附、聚集实验法,通过扫描电镜（SEM）观察复合材料表面、粗糙断面及气孔内的血栓形成情况,对其血液相容性进行研究。结果：以两种碳材料为增强相制备的复合材料与血液接触后,在材料光滑的表面、粗糙的断面及气孔内、以及碳纤维与碳纳米管的表面,由于纤维蛋白原的吸附量较少使血小板难以黏附、聚集,因此,在材料表面未能形成白血栓。结论：以碳纤维和碳纳米管为增强相制备的骨水泥生物复合材料具有良好的血液相容性。     

Glucose Biosensor Based on a Glassy Carbon Electrode Modified with Polythionine and Multiwalled Carbon Nanotubes

A novel glucose biosensor was fabricated. The first layer of the biosensor was polythionine, which was formed by the electrochemical polymerisation of the thionine monomer on a glassy carbon electrode. The remaining layers were coated with chitosan-MWCNTs, GOx, and the chitosan-PTFE film in sequence. The MWCNTs embedded in FAD were like “conductive wires” connecting FAD with electrode, reduced the distance between them and were propitious to fast direct electron transfer. Combining with good electrical conductivity of PTH and MWCNTs, the current response was enlarged. The sensor was a parallel multi-component reaction system (PMRS) and excellent electrocatalytic performance for glucose could be obtained without a mediator. The glucose sensor had a working voltage of −0.42 V, an optimum working temperature of 25°C, an optimum working pH of 7.0, and the best percentage of polytetrafluoroethylene emulsion (PTFE) in the outer composite film was 2%. Under the optimised conditions, the biosensor displayed a high sensitivity of 2.80 µA mM⁻¹ cm⁻² and a low detection limit of 5 µM (S/N = 3), with a response time of less than 15 s and a linear range of 0.04 mM to 2.5 mM. Furthermore, the fabricated biosensor had a good selectivity, reproducibility, and long-term stability, indicating that the novel CTS+PTFE/GOx/MWCNTs/PTH composite is a promising material for immobilization of biomolecules and fabrication of third generation biosensors.     

Facile Preparation of Internally Self-assembled Lipid Particles Stabilized by Carbon Nanotubes

We present a facile method to prepare nanostructured lipid particles stabilized by carbon nanotubes (CNTs). Single-walled (pristine) and multi-walled (functionalized) CNTs are used as stabilizers to produce Pickering type oil-in-water (O/W) emulsions. Lipids namely, Dimodan U and Phytantriol are used as emulsifiers, which in excess water self-assemble into the bicontinuous cubic Pn3m phase. This highly viscous phase is fragmented into smaller particles using a probe ultrasonicator in presence of conventional surfactant stabilizers or CNTs as done here. Initially, the CNTs (powder form) are dispersed in water followed by further ultrasonication with the molten lipid to form the final emulsion. During this process the CNTs get coated with lipid molecules, which in turn are presumed to surround the lipid droplets to form a particulate emulsion that is stable for months. The average size of CNT-stabilized nanostructured lipid particles is in the submicron range, which compares well with the particles stabilized using conventional surfactants. Small angle X-ray scattering data confirms the retention of the original Pn3m cubic phase in the CNT-stabilized lipid dispersions as compared to the pure lipid phase (bulk state). Blue shift and lowering of the intensities in characteristic G and G'' bands of CNTs observed in Raman spectroscopy characterize the interaction between CNT surface and lipid molecules. These results suggest that the interactions between the CNTs and lipids are responsible for their mutual stabilization in aqueous solutions. As the concentrations of CNTs employed for stabilization are very low and lipid molecules are able to functionalize the CNTs, the toxicity of CNTs is expected to be insignificant while their biocompatibility is greatly enhanced. Hence the present approach finds a great potential in various biomedical applications, for instance, for developing hybrid nanocarrier systems for the delivery of multiple functional molecules as in combination therapy or polytherapy.     

聚3，4乙烯二氧噻吩修饰的新型碳纳米管纤维电极及其电化学性能评价

目的 植入式脑机接口在神经疾病的治疗方面已经得到了广泛应用，治疗的效果依赖于与神经组织接触的电极。与刚性材料制作的电极相比，碳基微纤维电极尺度小、生物兼容性好、组织炎症反应小，可以减少植入后的异物反应，改善神经记录信号的信噪比，可以长期保持稳定的电极特性。方法 本文设计了一种柔性碳纳米管（carbon nanotubes，CNTs）纤维电极的修饰方法，该方法采用电化学聚合的方式可以将聚3,4-乙烯二氧噻吩（poly（3,4-ethylenedioxythiophene），PEDOT）薄膜沉积到CNTs纤维电极上，作为微电极涂层。为了证明修饰涂层在电极表面具有良好的机械稳定性，对修饰电极进行了超声处理。此外，本文将PEDOT薄膜沉积到ITO玻璃上，评价了PEDOT薄膜的生物相容性。结果 恒电流方式在CNTs纤维电极表面沉积的PEDOT涂层降低了电极的电化学阻抗，提高了电极的电化学性能，且PEDOT沉积的时间越长阻抗减少的幅度越明显。对电极进行超声处理后，电极的电化学阻抗没有产生显著变化，说明超声处理后PEDOT涂层剥离较少，证明了修饰涂层在电极表面具有良好的机械稳定性。最后，细胞实验表明，PEDOT薄膜具有与ITO导电玻璃相当的细胞相容性。结论 PEDOT薄膜可以提高CNTs纤维电极的稳定性，有望提高脑机接口系统的寿命和可靠性，具有应用于长时间记录神经电信号的前景。     

Molecularly Ordered Bioelectrocatalytic Composite Inside a Film of Aligned Carbon Nanotubes

Molecularly ordered composites of polyvinylimidazole‐[Os(bipyridine)₂Cl] (PVI‐[Os(bpy)₂Cl]) and glucose oxidase (GOD) are assembled inside a film of aligned carbon nanotubes. The structure of the prepared GOD/PVI‐[Os(bpy)₂Cl]/CNT composite film is entirely uniform and stable; more than 90% bioelectrocatalytic activity could be maintained even after storage for 6 d. Owing to the ideal positional relationship achieved between enzyme, mediator, and electrode, the prepared film shows a high bioelectrocatalytic activity for glucose oxidation (ca. 15 mA cm^?2 at 25 °C) with an extremely high electron‐transfer turnover rate (ca. 650 s^?1) comparable to the value for GOD solutions, indicating almost every enzyme molecule entrapped within the ensemble (ca. 3 × 10¹² enzymes in a 1 mm × 1 mm film) can work to the fullest extent. This free‐standing, flexible composite film can be used by winding on a needle device; as an example, a self‐powered sugar monitor is demonstrated.     

L-半胱氨酸修饰碳纳米管的合成、表征及电化学性质

通过对碳纳米管氧化,合成了L-半胱氨酸修饰碳纳米管。运用红外、差热-热重分析、透射电镜对该复合物进行了表征。借助循环伏安法研究了其电化学性质。结果表明,碳纳米管的掺入极大地提高了L-半胱氨酸在金电极表面的电子传输速率和电流响应,同时也有利于L-半胱氨酸的电氧化,对L-半胱氨酸的氧化具有催化作用。     

Synthetic Chloride-Selective Carbon Nanotubes Examined by Using Molecular and Stochastic Dynamics

Synthetic channels, such as nanotubes, offer the possibility of ion-selective nanoscale pores which can broadly mimic the functions of various biological ion channels, and may one day be used as antimicrobial agents, or for treatment of cystic fibrosis. We have designed a carbon nanotube that is selectively permeable to anions. The virtual nanotubes are constructed from a hexagonal array of carbon atoms (graphene) rolled up to form a tubular structure, with an effective radius of 4.53 Å and length of 34 Å. The pore ends are terminated with polar carbonyl groups. The nanotube thus formed is embedded in a lipid bilayer and a reservoir containing ionic solutions is added at each end of the pore. The conductance properties of these synthetic channels are then examined with molecular and stochastic dynamics simulations. Profiles of the potential of mean force at 0 mM reveal that a cation moving across the pore encounters an insurmountable free energy barrier of ∼25 kT in height. In contrast, for anions, there are two energy wells of ∼12 kT near each end of the tube, separated by a central free energy barrier of 4 kT. The conductance of the pore, with symmetrical 500 mM solutions in the reservoirs, is 72 pS at 100 mV. The current saturates with an increasing ionic concentration, obeying a Michaelis-Menten relationship. The pore is normally occupied by two ions, and the rate-limiting step in conduction is the time taken for the resident ion near the exit gate to move out of the energy well.     

Modulation of Apoptotic Pathways of Macrophages by Surface-Functionalized Multi-Walled Carbon Nanotubes

Biomedical applications of carbon nanotubes (CNTs) often involve improving their hydrophilicity and dispersion in biological media by modifying them through noncovalent or covalent functionalization. However, the potential adverse effects of surface-functionalized CNTs have not been well characterized. In this study, we functionalized multi-walled CNTs (MWCNTs) via carboxylation, to produce MWCNTs-COOH, and via poly (ethylene glycol) linking, to produce MWCNTs-PEG. We used these functionalized MWCNTs to study the effect of surface functionalization on MWCNTs-induced toxicity to macrophages, and elucidate the underlying mechanisms of action. Our results revealed that MWCNTs-PEG were less cytotoxic and were associated with less apoptotic cell death of macrophages than MWCNTs-COOH. Additionally, MWCNTs-PEG induced less generation of reactive oxygen species (ROS) involving less activation of NADPH oxidase compared with MWCNTs-COOH, as evidenced by membrane translocation of p47^phox and p67^phox in macrophages. The less cytotoxic and apoptotic effect of MWCNTs-PEG compared with MWCNTs-COOH resulted from the lower cellular uptake of MWCNTs-PEG, which resulted in less activation of oxidative stress-responsive pathways, such as p38 mitogen-activated protein kinases (MAPK) and nuclear factor (NF)-κB. These results demonstrate that surface functionalization of CNTs may alter ROS-mediated cytotoxic and apoptotic response by modulating apoptotic signaling pathways. Our study thus provides new insights into the molecular basis for the surface properties affecting CNTs toxicity.