一维碳纳米管与金属氧化物材料研究

一维纳米结构是最吸引人的功能材料而被广泛关注.一维形态可以很容易地提高纳米结构的独特性能,使它们适合各种各样的应用程序,包括气体传感器、电致变色的设备、发光二极管、场发射器、超级电容器和纳米发电机.因此,目前已合成多种一维纳米结构形式的纳米棒、纳米线、纳米管、纳米带等.本文主要介绍了一维碳纳米管与金属氧化物的性质与研究现状,探讨两种材料的优缺点以期进行互补修饰合成新型复合材料.     

Insights into the electron transfer mechanisms of permanganate activation by carbon nanotube membrane for enhanced micropollutants degradation

● A CNT filter enabled effective KMnO₄ activation via facilitated electron transfer. ● Ultra-fast degradation of micropollutants were achieved in KMnO₄/CNT system. ● CNT mediated electron transfer process from electron-rich molecules to KMnO₄. ● Electron transfer dominated organic degradation. Numerous reagents have been proposed as electron sacrificers to induce the decomposition of permanganate (KMnO₄) by producing highly reactive Mn species for micropollutants degradation. However, this strategy can lead to low KMnO₄ utilization efficiency due to limitations associated with poor mass transport and high energy consumption. In the present study, we rationally designed a catalytic carbon nanotube (CNT) membrane for KMnO₄ activation toward enhanced degradation of micropollutants. The proposed flow-through system outperformed conventional batch reactor owing to the improved mass transfer via convection. Under optimal conditionals, a > 70% removal (equivalent to an oxidation flux of 2.43 mmol/(h·m²)) of 80 μmol/L sulfamethoxazole (SMX) solution can be achieved at single-pass mode. The experimental analysis and DFT studies verified that CNT could mediate direct electron transfer from organic molecules to KMnO₄, resulting in a high utilization efficiency of KMnO₄. Furthermore, the KMnO₄/CNT system had outstanding reusability and CNT could maintain a long-lasting reactivity, which served as a green strategy for the remediation of micropollutants in a sustainable manner. This study provides new insights into the electron transfer mechanisms and unveils the advantages of effective KMnO₄ utilization in the KMnO₄/CNT system for environmental remediation.     

4种典型纳米材料对小鼠胚胎成纤维细胞毒性的初步研究

为探讨不同种类纳米材料对原代培养小鼠胚胎成纤维细胞(Mouse embryo fibroblasts,MEF)的毒性效应及作用机制,选择4种典型的纳米材料(纳米碳、单壁碳纳米管、纳米氧化锌、纳米二氧化硅)制备颗粒悬液,设立5个剂量组(5、10、20、50、100μg·mL-1)对BALB/c小鼠MEF细胞进行24、48、72h染毒培养,利用细胞形态学观察和噻唑蓝实验(MTT比色法)检测上述4种纳米材料对MEF细胞活性的影响,同时,测定染毒24h后细胞培养液上清中乳酸脱氢酶(LDH)活性以探讨纳米颗粒对细胞膜完整性的影响.结果显示:1)4种纳米材料均能明显影响MEF细胞的生长形态.染毒24h后,MEF细胞发生不同程度的回缩变形,细胞间隙增大,排列稀疏,胞内颗粒物增多,细胞透明度下降.2)纳米碳、纳米氧化锌、纳米二氧化硅对MEF细胞增殖的抑制作用和对细胞膜完整性的损伤作用均随染毒剂量的升高而增强,具有明显的剂量-效应关系,其半数致死浓度(24h-IC50)分别为21.85、21.94、461.10μg·mL-1;碳纳米管组的剂量-效应之间不呈对数线性关系,未能得出其24h-IC50.3)在不同染毒剂量水平上,4种纳米材料的毒性对比差异显著:低剂量水平上纳米碳与碳纳米管的毒性强于纳米氧化锌和纳米二氧化硅,随着剂量的升高纳米氧化锌的细胞毒性升高最为显著.结果提示,纳米材料能够对MEF细胞造成毒性损伤,破坏细胞膜的完整性可能只是作用途径之一;纳米材料的毒性可能受粒径、形状、化学组成等许多因素的影响.     

Effect of metal ion-doping on characteristics and photocatalytic activity of TiO2 nanotubes for removal of humic acid from water

The effect of ion-doping on TiO₂ nanotubes were investigated to obtain the optimal TiO₂ nanotubes for the effective decomposition of humic acids (HA) through O₃/UV/ion-doped TiO₂ process. The experimental results show that changing the calcination temperature, which changed the weight fractions of the anatase phase, the average crystallite sizes, the Brunauer-Emmett-Teller surface area, and the energy band gap of the catalyst, affected the photocatalytic activity of the catalyst. The ionic radius, valence state, and configuration of the dopant also affected the photocatalytic activity. The photocatalytic activities of the catalysts on HA removal increased when Ag⁺, Al³⁺, Cu²⁺, Fe³⁺, V⁵⁺, and Zn²⁺ were doped into the TiO₂ nanotubes, whereas such activities decreased as a result of Mn²⁺- and Ni²⁺-doping. In the presence of 1.0 at.% Fe³⁺-doped TiO₂ nanotubes calcined at 550°C, the removal efficiency of HA was 80% with a pseudo-first-order rate constant of 0.158 min⁻¹. Fe³⁺ in TiO₂ could increase the generation of ·OH, which could remove HA. However, Fe³⁺ in water cannot function as a shallow trapping site for electrons or holes.     

In vitro cytotoxicity of multi-wall carbon nanotubes on human cell lines

The aim of this study was to evaluate the in vitro toxicity of two multi-wall carbon nanotubes on four different cell lines: human alveolar epithelial (A549) cells, hepatocytes (Hep 3B cells), human embryonic kidney cells, and intestinal (P407 cells) cells. The adverse effects of carbon nanoparticles were analyzed after 24 h incubation with different cell lines using the trypan blue dye exclusion method. Incubation of carbon nanotubes with different cells produced a concentration-dependent inhibition of growth of the cells. The TC₅₀ or IC₅₀ values (toxic concentration 50, i.e., concentration of particles inducing 50% cell mortality) of two nanoparticles were (1) found to be in the range 23.5–30.5 µg mL^?1, and (2) less than that of quartz (known toxic agent, 28.8–66.9 µg mL^?1), indicating the greater cytotoxic effect of carbon nanoparticles than quartz particles.     

Single walled carbon nanotubes induce cytotoxicity and oxidative stress in HEK293 cells

The aim of the present study was to evaluate the potential toxicity and general mechanisms involved in single walled carbon nanotubes (SWCNTs)-induced cytotoxicity using human embryonic kidney cell line (HEK293) cells. Carbon nanotubes (coded as CNT) used in this study were synthesized by the chemical vapor deposition method. To elucidate the possible mechanisms underlying SWCNT-induced cytotoxicity, cell viability, cell membrane damage (lactate dehydrogenase activity (LDH) assay), reduced glutathione (GSH), interleukin-8 (IL-8) and lipid peroxidation products levels were quantitatively assessed following SWCNT exposure for 48 hr using HEK293 cells. Exposure of cells to SWCNT at 3–300 μg/ml produced significant reduction in cell viability in a concentration-dependent manner. The IC₅₀ value of SWCNT was found to be 87.58 μg/ml. Exposure of HEK cells to SWCNT at 10–100 μg/ml resulted in concentration-dependent cell membrane damage, increased production of IL-8, elevated levels of thiobarbituric acid reactive substances like malondialdehyde and decreased intracellular GSH levels. In summary, exposure to SWCNT resulted in a concentration-dependent cytotoxicity in cultured HEK293 cells that was associated with increased oxidative stress.     

基于密度泛函理论模拟单壁碳纳米管对五种核酸碱基的吸附

基于密度泛函理论,模拟了单壁碳纳米管(SWNTs)对5种碱基的吸附作用.考察了SWNTs直径、电荷转移量、碱基最高占据分子轨道能(EHOMO)和最低未占据分子轨道能(ELUMO)与SWNTs吸附碱基的吸附能之间的关系.结果表明,随着SWNTs直径的增大,SWNTs吸附碱基的吸附能降低.SWNT(6,6)吸附5种碱基的最低吸附能Emin与由碱基转移到SWNTs的电荷转移量(Q)及碱基的EHOMO线性负相关,相关系数分别为-0.966和-0.804(P<0.05).吸附后SWNTs与碱基的前线轨道无重叠,且SWNTs电子结构未受影响,表明吸附行为属于物理吸附.     

活性氧参与多壁碳纳米管诱导的RAW264.7细胞毒性

碳纳米管以其独特的结构和性能,在生物医药和电子等领域广泛应用,而其生态安全性也成为科学界关注的焦点。为探究多壁碳纳米管(MWCNTs)诱导的细胞毒性机制,将小鼠肺泡巨噬细胞(RAW264.7)暴露于6个浓度梯度(0、25、50、100、150和200μg.mL-1)的MWCNTs中,应用噻唑蓝(MTT)法测定细胞存活率,用2’,7’-二氯荧光素二乙酸(DCFH-DA)荧光染色法测定细胞内活性氧的生产量,用流式细胞方法测定MWCNTs对细胞周期的影响。同时使用抗氧化剂氮乙酰半胱氨酸(NAC)验证MWCNTs诱导的细胞氧化损伤的作用机理。结果显示,MWCNTs对RAW264.7的细胞毒性呈剂量依赖性。暴露于不同浓度的MWCNTs(25、50、100、150和200μg.mL-1)下24h后,细胞活力分别为对照的74%、62%、59%、51%和45%。MWCNTs对RAW264.7的周期阻滞作用主要发生在G0/G1期。200μg.mL-1的MWCNTs处理3h后活性氧较对照组上升6.6倍。NAC对MWCNTs细胞毒作用有明显的抑制作用,且NAC能减弱MWCNTs对RAW264.7的细胞周期阻滞作用。研究表明,活性氧能够介导MWCNTs对小鼠巨噬细胞RAW264.7的损伤,并且MWCNTS通过细胞周期G0/G1期的阻滞,诱导细胞凋亡。     

2种类型多壁碳纳米管对蛋白核小球藻的毒理研究

碳纳米材料由于其具有优异的性能,得以广泛生产和使用,其不可避免会进入水环境中,对水生生态系统造成潜在影响。多壁碳纳米管(P-MWCNTs)和羟基化多壁碳纳米管(MWCNTs-OH)作为纳米材料的典型代表,应用非常广泛,其潜在的环境效应受到人们越来越多的关注。为此,本文以蛋白核小球藻(Chlorella pyrenoidosa)作为受试生物,通过暴露实验,研究了P-MWCNTs和MWCNTs-OH对蛋白核小球藻的生物学效应。研究结果表明：1)当P-MWCNTs浓度≤10 mg·L-1、MWCNTs-OH≤20 mg·L-1浓度时对蛋白核小球藻生长未造成影响;2)暴露96 h后,当P-MWCNTs≤10 mg·L-1、MWCNTs-OH浓度≤20 mg·L-1时,蛋白核小球藻细胞可溶性蛋白质含量增加,当P-MWCNTs浓度≥20 mg·L-1、MWCNTs-OH浓度≥40 mg·L-1时,2种类型MWCNTs均对蛋白核小球藻造成毒性效应;3)随着2种类型MWCNTs浓度的增加,蛋白核小球藻细胞总抗氧化能力(T-AOC)值减少,蛋白核小球藻细胞丙二醛(MDA)含量显著增加,细胞的健康程度逐渐恶化,细胞结构受到严重损伤;4)MWCNTs-OH比P-MWCNTs具有更好的生物相容性。