三氯生在碳纳米管上的吸附

药品和个人护理用品(PPCPs)已成为一个引起广泛关注的新的环境问题。采用碳纳米管（CNTs）对水溶液中的三氯生进行吸附处理,考察了碳纳米管粒径及用量、温度、pH、振荡时间等因素对三氯生去除率的影响。研究结果表明,碳纳米管能快速吸附水中的三氯生,粒径较小的碳纳米管可获得较高的三氯生去除率;低温有利于吸附反应的进行;pH在6.5～7.0时,三氯生的去除率可达97%。三氯生在碳纳米管上的吸附可以很好地用Langmuir和Freundlich吸附等温方程进行描述。     

Raw single-walled carbon nanotube-induced cytotoxic effects in human bronchial epithelial cells: comparison to asbestos

Single-walled carbon nanotubes (SWCNT) are being developed to be used in many industrial and biomedical applications. However, SWCNT's durability and likely fibrous morphology have raised health concerns. The present investigations were focused on understanding the cellular and molecular mechanisms induced by raw SWCNT (SWCNT) in human bronchial-epithelial cells (BEAS-2B). Asbestos (crocidolite) was used as a positive control. Exposure of BEAS-2B cells to SWCNT induced apoptosis, DNA damage, and oxidative stress. The generation of hydroxyl radical (^?OH) and increase of superoxide dismutase (SOD) activity were concentration-dependent. The increase in apoptosis was associated with activation of caspase-3, caspase-7, and poly (ADP-ribose) polymerase-1 (PARP-1). A short recovery period of 6?h of cells from SWCNT exposure resulted in reversal of caspase-3 and caspase-7, and a partial reversal of PARP-1 activation. The activation of PARP-1, caspase-3, and caspase-7 was only partially diminished after a recovery of 6?h from the exposure to crocidolite. Exposure of BEAS-2B cells to SWCNT resulted in the phosphorylation of protein p42/44 (p42/44) and protein p38 (p38). SWCNT did not induce protein serine-threonine kinase (AKT) phosphorylation. For all the above end points, crocidolite induced a greater response compared to SWCNT. SWCNT induced a significant activation of activator protein-1 (AP-1) and nuclear factor kappa B (NF-κB), and the effect was inhibited by mitogen-activated protein kinase (MAPK) inhibitors. SWCNT also induced significant increase in the expression levels of c-Jun, βIGH3, and CD44 genes. The results of this study show that the molecular mechanism for raw SWCNT-mediated toxicity in BEAS-2B cells is through the activation of caspase-3, caspase-7, and PARP-1. Furthermore, the mechanism of AP-1 and NF-κB activation is through MAPK. This bioactivity of raw SWCNT is associated with the generation of oxidative stress and DNA damage. Considering the role of airway epithelium as a critical barrier for normal pulmonary function and focal point for tumor development, this study demonstrates that raw SWCNT activate molecular events which may be linked to adverse biological responses implicated in pulmonary diseases.     

A novel and stretchable carbon-nanotube/Ni@TiO2:W photocatalytic composite for the complete removal of diclofenac drug from the drinking water

We present the structural, morphological and photocatalytic properties of stretchable composites made with carbon nanotubes (CNTs), silicon rubber and Ni@TiO₂:W nanoparticles (TiWNi NPs) with average size of 37 ± 2 nm. Microscopy images showed that the TiWNi NPs decorated the surface of the CNT fibers, which are oriented in a preferential direction. TiWNi NPs presented a mixture of anatase/rutile phases with cubic structure. The performance of the TiWNi powders and stretchable composites was evaluated for the photocatalytic degradation of diclofenac (DCF) anti-inflammatory drug under ultraviolet-visible light. The results revealed that the maximum DCF degradation percentages were 34.6%, 91.9%, 97.1%, 98.5% and 100% for the CNT composite (stretched at 0%), TiWNi powders, CNT + TiWNi (stretched at 0%), CNT + TiWNi (stretched at 50%) and CNT + TiWNi (stretched at 100%), respectively. Thus, stretching the CNT + TiWNi composites was a good strategy to enhance the DCF degradation percentage from 97.1% to 100%, since stretching created additional defects (oxygen vacancies) that acted as electron sink, delaying the electron-hole recombination, and favors the DCF degradation. Raman/absorbance measurements confirmed the presence of such defects. Moreover, the reactive oxygen species (ROS) were determined by the scavenger's experiments and found that the main ROS were the ·OH and O₂⁻ radicals, which attacked the DCF molecules, causing their degradation. The results of this investigation confirmed that the stretchable CNT/TiWNi-based composites are a viable alternative to remove pharmaceutical contaminants from water and can be manually separated from the decontaminated water, which is unviable using photocatalytic powders.     

沉积物中不同浓度多壁碳纳米管对Cd和BDE-47生态毒性的影响

随着碳纳米管的广泛应用,其将不可避免地进入环境中.由于其具有极好的吸附亲和力和吸附容量,碳纳米管可以充当环境中持久性有毒污染物的载体,从而改变共存污染物的生物有效性和生态毒性.为评价淡水沉积物中不同多壁碳纳米管(MWCNTs)对Cd和BDE-47生态毒性的影响,采用沉积物慢性生物测试研究了不同浓度MWCNTs存在下Cd和BDE-47对铜锈环棱螺肝胰脏抗氧化防御系统关键成分超氧化物歧化酶(SOD)与Ⅱ相解毒反应的关键酶谷胱甘肽-S-转移酶(GST)以及脂质过氧化损伤指标丙二醛(MDA)的影响.结果表明,沉积物中低浓度MWCNTs(0.5 mg·g~(-1))增强Cd对铜锈环棱螺的氧化胁迫,中、高浓度(5、50 mg·g~(-1))MWCNTs引起Cd对铜锈环棱螺的氧化损伤,MWCNTs的存在显著增强了沉积物中Cd对铜锈环棱螺的毒性,而且具有浓度-效应关系;低浓度MWCNTs不影响BDE-47对铜锈环棱螺的毒性,中、高浓度MWCNTs显著降低BDE-47的毒性,同样具有明显的浓度-效应关系.因此,在评价MWCNTs的潜在环境风险时,不仅考虑MWCNTs自身的毒性,还应当考虑MWCNTs的浓度、共存污染物的种类和MWCNTs与共存污染物之间的相互作用.     

Evaluation of micro- and nano-carbon-based adsorbents for the removal of phenol from aqueous solutions

This work reports on the adsorption efficiency of two classes of adsorbents: nano-adsorbents including carbon nanotubes (CNTs) and carbon nanofibers (CNFs); and micro-adsorbents including activated carbon (AC) and fly ash (FA). The materials were characterized by thermogravimetric analysis, transmission electron microscopy, Brunauer–Emmett–Teller (BET) specific surface area, zeta potential, field emission scanning electron microscopy, and UV spectroscopy. The adsorption experimental conditions such as pH of the solution, agitation speed, contact time, initial concentration of phenol, and adsorbent dosage were optimized for their influence on the phenol. The removal efficiency of the studied adsorbents has the following order: AC > CNTs > FA > CNFs. The capacity obtained from Langmuir isotherm was found to be 1.348, 1.098, 1.007, and 0.842 mg/g of AC, CNTs, FA, and CNFs, respectively, at 2 hours of contact time, pH 7, an adsorbent dosage of 50 mg, and a speed of 150 rpm. The higher adsorption of phenol on AC can be attributed to its high surface area and its dispersion in water. The optimum values of these variables for maximum removal of phenol were also determined. The experimental data were fitted well to Langmuir than Freundlich isotherm models.     

TiO_2纳米管修饰电极处理反渗透浓水研究

研制了新型的TiO2纳米管修饰电极,应用于反渗透膜浓水的电化学氧化处理;利用扫描电镜和线性极化曲线对电极进行了表征;考察了电解时间、电流密度和pH值因素对电化学氧化处理反渗透膜浓水的影响;并分析了电极对反渗透浓水中各有机物组分的去除效果。实验结果表明TiO2纳米管修饰电极对反渗透浓水具有较高的电催化性能。     

单壁碳纳米管致昆明小鼠脑组织的氧化损伤

单壁碳纳米管(single walled carbon nanotubes,SWCNTs)是纳米材料研究关注的焦点之一.尽管如此,关于其神经毒性的研究相对较少.本研究将SWCNTs以不同的浓度(0 mg·kg-1·d-1,3.125 mg·kg-1·d-1,6.25 mg·kg-1·d-1,12.5 mg·kg-1·d-1),通过腹腔注射于Kunming小鼠体内.神经行为学实验(旷场实验)结果表明,在一定浓度的SWCNTs作用下,小鼠的情绪受到一定的影响,具有抑郁症的特征,出现移动能力下降,紧张等现象.同时小鼠脑部组织的活性氧族(reactive oxygen species,ROS)和丙二醛(malondialdehyde,MDA)水平升高(p0.05),还原型谷胱甘肽(glutathione,GSH)水平降低(p0.05),炎症因子白介素-1β(interleukin-1 beta,IL-1β)的水平升高(p0.05).组织学观察显示,随着染毒浓度的升高,脑海马锥体细胞的空泡化程度愈加明显,着色不均,锥体细胞顶状树突逐渐消失,细胞排列松散,尼氏小体消失.结论:一定浓度的SWCNTs可以导致小鼠脑组织发生病变,产生一定的神经毒性.     

生物电催化方法处理三氯乙酸的研究

利用吸附法将血红蛋白(Hb)固定在碳纳米管修饰电极表面,研究了Hb在碳纳米管修饰电极的直接电化学行为.固载Hb碳纳米管修饰电极在pH=7.0的PBS缓冲溶液中于-0.300V(vsSCE)处有一对相当可逆的循环伏安还原氧化峰,为Hb血红素辅基Fe(Ⅲ)/Fe(Ⅱ)电对的特征峰.利用循环伏安法和恒电位电解法研究了固载Hb的碳纳米管修饰电极对有机氯模型污染物三氯乙酸的电催化还原脱氯,并通过鉴定中间产物探讨了其催化还原机理.结果表明,固载Hb的碳纳米管修饰电极对三氯乙酸的还原具有很高的催化活性,三氯乙酸是按照三氯乙酸→二氯乙酸→一氯乙酸→乙酸的途径分布还原脱氯.将固载Hb的碳纳米管修饰电极组装成三维填充床电解反应器,进行了三氯乙酸连续流动电解还原的初步研究.-0.6V(vs.SCE)电解180min,三氯乙酸去除率为40.13%.     

Electrochemical detection and degradation of ibuprofen from water on multi-walled carbon nanotubes-epoxy composite electrode

This work describes the electrochemical behaviour of ibuprofen on two types of multi-walled carbon nanotubes based composite electrodes,i.e.,multi-walled carbon nanotubes-epoxy(MWCNT) and silver-modified zeolite-multi-walled carbon nanotubes-epoxy(AgZMWCNT) composites electrodes.The composite electrodes were obtained using two-roll mill procedure.SEM images of surfaces of the composites revealed a homogeneous distribution of the composite components within the epoxy matrix.AgZMWCNT composite electrode exhibited the better electrical conductivity and larger electroactive surface area.The electrochemical determination of ibuprofen(IBP) was achieved using AgZMWCNT by cyclic voltammetry,differential-pulsed voltammetry,square-wave voltammetry and chronoamperometry.The IBP degradation occurred on both composite electrodes under controlled electrolysis at 1.2 and 1.75 V vs.Ag/AgCl,and IBP concentration was determined comparatively by differential-pulsed voltammetry,under optimized conditions using AgZMWCNT electrode and UV-Vis spectrophotometry methods to determine the IBP degradation performance for each electrode.AgZMWCNT electrode exhibited a dual character allowing a double application in IBP degradation process and its control.     

Adsorption of carbon dioxide on amine-modified TiO2 nanotubes

TiO2 nanotubes (TiNT) were prepared by a hydrothermal treatment and modified by three kinds of amines,namely ethylenediamine,polyetherimide and tetraethylenepentamine (TEPA),to study their CO2 adsorption properties from gas streams.The resultant samples were characterized by X-ray diffraction,transmission electron microscopy,and infrared spectroscopy,as well as low temperature N 2 adsorption.CO2 capture was investigated in a dynamic packed column at 30℃.TEPA-modified TiO2 nanotubes showed the highest adsorption capacity of 167.64 mg/g because it had the highest amino-group content among the three amines.CO2 fixation on TiNT impregnated by TEPA was investigated at 30,50,and 70℃,and the adsorption capacity increased slightly with temperature.Following the adsorption step,the sorbents were regenerated by temperature programmed desorption,and the TiNT-TEPA sample,as CO2 sorbent,was found to be readily regenerated and energy-efficient.The cycle test also revealed that the TiNT-TEPA adsorbent is fairly stable,with only a 5% drop in the adsorption capacity after 10 adsorption/desorption cycles.In addition,the CO2 adsorption behavior was investigated with the deactivation model,and which showed an excellent prediction for the TiNT-TEPA breakthrough curves.