Pillar[n]arene-Mimicking/Assisted/Participated Carbon Nanotube Materials

The recent progress in pillar[n]arene-assisted/participated carbon nanotube hybrid materials were initially summarized and discussed. The molecular structure of pillar[n]arene could serve different roles in the fabrication of attractive carbon nanotube-based materials. Firstly, pillar[n]arene has the ability to provide the structural basis for enlarging the cylindrical pillar-like architecture by forming one-dimensional, rigid, tubular, oligomeric/polymeric structures with aromatic moieties as the linker, or forming spatially “closed”, channel-like, flexible structures by perfunctionalizing with peptides and with intramolecular hydrogen bonding. Interestingly, such pillar[n]arene-based carbon nanotube-resembling structures were used as porous materials for the adsorption and separation of gas and toxic pollutants, as well as for artificial water channels and membranes. In addition to the art of organic synthesis, self-assembly based on pillar[n]arene, such as self-assembled amphiphilic molecules, is also used to promote and control the dispersion behavior of carbon nanotubes in solution. Furthermore, functionalized pillar[n]arene derivatives integrated carbon nanotubes to prepare advanced hybrid materials through supramolecular interactions, which could also incorporate various compositions such as Ag and Au nanoparticles for catalysis and sensing.     

Nano-Confined Tin Oxide in Carbon Nanotube Electrodes via Electrostatic Spray Deposition for Lithium-Ion Batteries

The development of novel materials is essential for the next generation of electric vehicles and portable devices. Tin oxide (SnO₂), with its relatively high theoretical capacity, has been considered as a promising anode material for applications in energy storage devices. However, the SnO₂ anode material suffers from poor conductivity and huge volume expansion during charge/discharge cycles. In this study, we evaluated an approach to control the conductivity and volume change of SnO₂ through a controllable and effective method by confining different percentages of SnO₂ nanoparticles into carbon nanotubes (CNTs). The binder-free confined SnO₂ in CNT composite was deposited via an electrostatic spray deposition technique. The morphology of the synthesized and deposited composite was evaluated by scanning electron microscopy and high-resolution transmission electron spectroscopy. The binder-free 20% confined SnO₂ in CNT anode delivered a high reversible capacity of 770.6 mAh g⁻¹. The specific capacity of the anode increased to 1069.7 mAh g⁻¹ after 200 cycles, owing to the electrochemical milling effect. The delivered specific capacity after 200 cycles shows that developed novel anode material is suitable for lithium-ion batteries (LIBs).     

Tube-Super Dielectric Materials: Electrostatic Capacitors with Energy Density Greater than 200 J·cm?3

The construction and performance of a second generation of super dielectric material based electrostatic capacitors (EC), with energy density greater than 200 J·cm⁻³, which rival the best reported energy density of electric double layer capacitors (EDLC), also known as supercapacitors, are reported. The first generation super dielectric materials (SDM) are multi-material mixtures with dielectric constants greater than 1.0 × 10⁵, composed of a porous, electrically insulating powder filled with a polarizable, ion-containing liquid. Second-generation SDMs (TSDM), introduced here, are anodic titania nanotube arrays filled with concentrated aqueous salt solutions. Capacitors using TiO₂ based TSDM were found to have dielectric constants at ~0 Hz greater than 10⁷ in all cases, a maximum operating voltage of greater than 2 volts and remarkable energy density that surpasses the highest previously reported for EC capacitors by approximately one order of magnitude. A simple model based on the classic ponderable media model was shown to be largely consistent with data from nine EC type capacitors employing TSDM.     

A comparative study on the in vitro cytotoxic responses of two mammalian cell types to fullerenes,carbon nanotubes and iron oxide nanoparticles

The present study was designed to evaluate and compare the time- and dose-dependent cellular response of human periodontal ligament fibroblasts (hPDLFs), and mouse dermal fibroblasts (mDFs) to three different types of nanoparticles (NPs); fullerenes (C₆₀), single walled carbon nanotubes (SWCNTs) and iron (II,III) oxide (Fe₃O₄) nanoparticles via in vitro toxicity methods, and impedance based biosensor system. NPs were characterized according to their morphology, structure, surface area, particle size distribution and zeta potential by using transmission electron microscopy, X-ray diffraction, Brunauer–Emmett–Teller, dynamic light scattering and zeta sizer analyses. The Mössbauer spectroscopy was used in order to magnetically characterize the Fe₃O₄ NPs. The hPDLFs and mDFs were exposed to different concentrations of the NPs (0.1, 1, 10, 50 and 100?μg/mL) for predetermined time intervals (6, 24 and 48?h) under controlled conditions. Subsequently, NP exposed cells were tested for viability, membrane leakage and generation of intracellular reactive oxygen species. Additional to in vitro cytotoxicity assays, the cellular responses to selected NPs were determined in real time using an impedance based biosensor system. Taken together, information obtained from all experiments suggests that toxicity of the selected NPs is cell type, concentration and time dependent.     

RNAi mediated gene silencing of ITPA using a targeted nanocarrier: Apoptosis induction in SKBR3 cancer cells

A pure nucleotide pool is required for high‐fidelity DNA replication and prevention of carcinogenesis in living cells. Human inosine triphosphatase (ITPase), encoded by the ITPA gene, plays a critical role in maintaining the purity of the cellular nucleotide pool by excluding nucleotides that enhance mutagenesis. ITPase is a nucleoside triphosphate pyrophosphatase that hydrolyzes the non‐canonical nucleotides inosine triphosphate (ITP) and xanthine triphosphate (XTP). The monophosphate products of ITPase reactions are subsequently excluded from the nucleotide pool and the improper substitution of ITP and XTP into DNA and RNA is prevented. Previous studies show that deficiency in ITPA can suppress cellular growth and enhance DNA instability. In this study, we evaluated the influence of effective ITPA down‐regulation on the induction of apoptosis in a human cancer cell line using folate‐single wall nanotubes (SWNT) as a targeted nanocarrier. We assessed whether SWNT enhances IPTA‐siRNA transfection efficiency in cancer cells using folate as a homing device. Since folate receptor is considerably overexpressed in cancer cells, conjugation of SWNTs to folate could enhance their cancer‐specific penetrance. We found that nanocarrier mediated ITPA‐siRNA transfection into SKBR3 cells caused significant reduction of ITPA mRNA expression level and complete down‐regulation of the ITPase protein product. The silencing of ITPA led to promotion of apoptosis in SWNT‐treated SKBR3 cancer cells.     

A 104-week pulmonary toxicity assessment of long and short single-wall carbon nanotubes after a single intratracheal instillation in rats

We compared long-term pulmonary toxicities after a single intratracheal instillation of two types of dispersed single-wall carbon nanotubes (SWCNTs), namely, those with relatively long or short linear shapes with average lengths of 8.6 and 0.55 µm, respectively. Both types of SWCNTs were instilled intratracheally in male F344 rats at 0.2 or 1.0?mg/kg (long SWCNTs) or 1.0?mg/kg (short SWCNTs). Pulmonary responses were characterized at 26, 52 and 104 weeks after a single instillation. Inflammatory changes, test substance deposition, test substance engulfment by macrophages, and alveolar wall fibrosis were observed in the lungs of almost all test rats at 52 and 104 weeks after short nanotube instillation. The incidences of these changes were much lower in the long nanotube-treated groups. In almost all rats of the long nanotube-treated groups, fibrosis and epithelium loss in the terminal bronchiole with test substance deposition were observed. These bronchiolar changes were not observed after administering short nanotubes. Both bronchiolo-alveolar adenoma and carcinoma were found in the negative-control group, the high-dose long-nanotube group, and the short-nanotube group at 104 weeks post-instillation, although the incidences were not statistically different. The genotoxicity of the SWCNTs was also evaluated by performing in vivo comet assays with lung cells obtained 26 weeks post-instillation. No significant changes in the percent tail deoxyribonucleic acid were found in any group. These findings suggested that most long SWCNTs were deposited at the terminal bronchioles and that a considerable amount of short SWCNTs reached the alveolus, resulting in chronic inflammatory responses, but no genotoxicity in the lungs.     

聚丙烯/碳纳米管复合材料的结构与导电性能:注塑工艺与膨胀石墨的影响

获得高性能碳纳米管（MWCNT）增强聚合物复合材料的关键在于控制碳纳米管在聚合物基体中的分布与取向。传统的注塑成型工艺下,碳纳米管容易发生取向,其表面电阻率远远大于模压成型时的电阻率。本文通过调整注塑工艺改变剪切场实现对碳纳米管在基体中分布与取向的控制。结果表明：在低熔体温度和高注射速度下,碳纳米管局部取向,导电性能下降;而在高熔体温度和低注射速度下,碳纳米管分散良好,导电网络优良,聚丙烯/碳纳米管（PP/MWCNT）注塑制品的导电性能得到有效提升,其表面电阻率下降了约5个数量级。加入膨胀石墨（EG）有增强导电网络的作用,使PP/MWCNT/EG复合材料的导电网络更为完善,其导电性能进一步提高,尤其在低熔体温度和高注射速度下最为明显;随着EG含量的增加,PP/MWCNT/EG的表面电阻率下降了3个数量级。     

单壁纳米碳管对小鼠内脏损伤的初步研究

 目的 本研究应用无修饰的单壁纳米碳管 (naked single wall nanotube, NSWNT) 对小鼠灌胃，探讨单壁纳米碳管 (single wall nanotube ， SWNT) 的生物安全性。 方法 SWNT 分别以 50 ， 100 ， 150 mg·kg^-1 剂量对小鼠进行灌胃给药，连续给药 10 d 后，于末次给药 30 min 后，小鼠眼球取血及小鼠内脏采集 , 进行血液生化检查及组织切片的光学显微镜、透射电镜检查。 结果 SWNT 可以导致丙氨酸氨基转移酶，天冬氨酸氨基转移酶，乳酸脱氢酶和肌酸激酶升高。光镜观察组织切片发现肝脏，肾脏，肺脏及胃肠道有显著的出血，充血。 结论 ① SWNT 可以导致肝脏和肾脏损伤；② SWNT 可被胃肠道吸收；③由于脑组织未被 NSWNT 损伤，推测 NSWNT 可能不能通过血脑屏障。     

Polyamine-Promoted Growth of One-Dimensional Nanostructure-Based Silica and Its Feature in Catalyst Design

Crystalline linear polyethyleneimine (LPEI) is a fascinating polymer that can be used as a catalyst, template and scaffold in order to direct the formation of silica with controllable compositions and spatial structures under mild conditions. Considering the crystallization and assembly of LPEI is temperature-dependent, we adopted different accelerated cooling processes of a hot aqueous solution of LPEI in order to modulate the LPEI crystalline aggregates. We then used them in the hydrolytic condensation of alkoxysilane. A series of silica with nanofibrils, nanotubes and nanowire-based structures were achieved simply by the LPEI aggregates which were pre-formed in defined cooling processes. These specific one-dimensional nanoscale structures assembled into microscale fibers-, sheet- and platelet-like coalescences. Furthermore, the deposition kinetics was also researched by the combination of other characterizations (e.g., pH measurement, ²⁹Si MAS NMR). As a preliminary application, the hybrids of LPEI@SiO₂ were used not only as an agent for reducing PtCl₄²⁻ into Pt but also as host for loading Pt nanoparticles. The Pt-loaded silica showed good catalytic properties in the reduction of Rhodamine B by dimethylaminoborane (DMAB).