高岭土负载纳米铁镍双金属去除水中偶氮染料直接耐晒黑G

采用液相还原法制备焙烧高岭土负载纳米铁镍双金属（CK-Fe/Ni）。考察了在不同条件下,如pH、投加量、初始浓度、温度等,对负载型纳米铁镍双金属降解水中偶氮染料直接耐晒黑G的影响及动力学研究。结果表明：在pH=9.49、温度为30℃、负载型纳米铁镍双金属的投加量为1.05 g/L、搅拌速度为60 r/min,经过20 min反应后,负载型纳米铁镍双金属降解水中偶氮染料直接耐晒黑G的去除率达到了99.98%。吸附和电镜表征结果表明,作为载体的焙烧高岭土起着吸附直接耐晒黑G和分散纳米铁镍双金属颗粒的作用导致反应活性提高。降解动力学数据表明,负载型纳米铁镍双金属对直接耐晒黑G的降解过程符合伪一级反应动力学规律,速率常数k随负载型纳米铁镍双金属的投加量的增加而提高,表观活化能为19.72 kJ/mol。最后,利用高岭土负载纳米铁镍双金属对废水处理,结果表明,负载型纳米铁镍双金属在实际废水中对直接耐晒黑G的去除率达到了99.98%。     

基于磁性纳米粒子固定技术的漆酶传感器用于垃圾堆肥中邻苯二酚的检测

以邻苯二酚为检测目标,研究了一种基于核/壳磁性纳米粒子固定漆酶的邻苯二酚生物传感器制备方法及其在城市生活垃圾堆肥中的应用.制备Fe₃O₄磁性纳米颗粒,使用正硅酸乙酯（TEOS）和氨丙基三甲氧基硅烷（APTMS）将其功能化并利用戊二醛将漆酶共价固定,借助磁场吸附在磁性碳糊电极上,检测邻苯二酚.固定在电极表面的漆酶保持了很好的活性.该生物传感器的检测线性范围为7.5×10^-7～2.75×10^-4 mol/L,检测下限达到7.5×10^-7 mol/L,达到稳态电流95%所需时间大概为70 s.将该传感器检测堆肥浸出液中酚的含量的结果与高效液相色谱法对比,两者非常接近.     

To duckweeds (Landoltia punctata), nanoparticulate copper oxide is more inhibitory than the soluble copper in the bulk solution

CuO nanoparticles (CuO-NP) were synthesized in a hydrogen diffusion flame. Particle size and morphology were characterized using scanning mobility particle sizing, Brunauer-Emmett-Teller analysis, dynamic light scattering, and transmission electron microscopy. The solubility of CuO-NP varied with both pH and presence of other ions. CuO-NP and comparable doses of soluble Cu were applied to duckweeds, Landoltia punctata. Growth was inhibited 50% by either 0.6 mg L⁻¹ soluble copper or by 1.0 mg L⁻¹ CuO-NP that released only 0.16 mg L⁻¹ soluble Cu into growth medium. A significant decrease of chlorophyll was observed in plants stressed by 1.0 mg L⁻¹ CuO-NP, but not in the comparable 0.2 mg L⁻¹ soluble Cu treatment. The Cu content of fronds exposed to CuO-NP is four times higher than in fronds exposed to an equivalent dose of soluble copper, and this is enough to explain the inhibitory effects on growth and chlorophyll content.     

Chronic toxicity of ZnO nanoparticles, non-nano ZnO and ZnCl2 to Folsomia candida (Collembola) in relation to bioavailability in soil

The chronic toxicity of zinc oxide nanoparticles (ZnO-NP) to Folsomia candida was determined in natural soil. To unravel the contribution of particle size and free zinc to NP toxicity, non-nano ZnO and ZnCl₂ were also tested. Zinc concentrations in pore water increased with increasing soil concentrations, with Freundlich sorption constants K_f of 61.7, 106 and 96.4 l/kg (n = 1.50, 1.34 and 0.42) for ZnO-NP, non-nano ZnO and ZnCl₂ respectively. Survival of F. candida was not affected by ZnO-NP and non-nano ZnO at concentrations up to 6400 mg Zn/kg d.w. Reproduction was dose-dependently reduced with 28-d EC50s of 1964, 1591 and 298 mg Zn/kg d.w. for ZnO-NP, non-nano ZnO and ZnCl₂, respectively. The difference in EC50s based on measured pore water concentrations was small (7.94-16.8 mg Zn/l). We conclude that zinc ions released from NP determine the observed toxic effects rather than ZnO particle size.     

Catalytic hydrogenation rate of polycyclic aromatic hydrocarbons in supercritical carbon dioxide containing polymer-stabilized palladium nanoparticles

Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO₂ containing 1 MPa of H₂ at 40-50 °C. Kinetic studies based on in situ UV/Vis spectra of the CO₂ phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces.     

Hemoglobin (Hb) immobilized on amino-modified magnetic nanoparticles for the catalytic removal of bisphenol A

Catalytic removal of bisphenol A from aqueous solution with hemoglobin immobilized on amino-modified magnetic nanoparticles as an enzyme catalyst was reported. The amino-modified magnetite nanoparticles were firstly prepared by the coprecipitation of Fe²⁺ and Fe³⁺ with NH₃·H₂O and then modified by 3-aminopropyltriethoxysilane. The immobilization process was optimized by examining enzyme concentration, glutaraldehyde concentration, cross-link time, and immobilization time. The optimum conditions for the removal of bisphenol A with immobilized hemoglobin were also investigated. Under the optimality conditions, the removal efficiency of bisphenol A was about 80.3%. The immobilization had a beneficial effect on the stability of hemoglobin and conversions of bisphenol A. According to the proposed breakdown pathway and the intermediates, the enzyme-catalytic removal of bisphenol A by the immobilized hemoglobin is considered to be an effective method.     

Differential toxicity of silver and titanium dioxide nanoparticles on Drosophila melanogaster development, reproductive effort, and viability: size, coatings and antioxidants matter

Silver and titanium dioxide nanoparticles are known to induce oxidative stress in vitro and in vivo. Here we test if they impact development, mating success, and survivorship in Drosophila melanogaster, and if so, if these effects are reversible by antioxidants. Ingestion of nanotitanium dioxide during the larval stage of the life cycle showed no effects on development or survivorship, up to doses of 200 μg mL⁻¹. Conversely, ingestion of nanosilver had major dose, size, and coating-dependent effects on each of these aspects of life history. Each of these effects was partially or fully reversible by vitamin C. Larvae growing on nanosilver supplemented with vitamin C showed a greater than twofold increase in survivorship compared to flies reared on nanosilver alone, and a threefold increase in mating success. Vitamin C also rescued cuticular and pigmentation defects in nanosilver fed flies. Biochemical assays of superoxide dismutase and glutathione show these markers respond to nanotitanium dioxide and nanosilver induced oxidative stress, and this response is reduced by vitamin C. These results indicate that life history effects of nanosilver ingestion result from oxidative stress, and suggest antioxidants as a potential remediation for nanosilver toxicity. Conversely, the lack of nanotitanium dioxide life history toxicity shows that oxidative stress does not necessarily result in whole organism effects, and argues that nanoparticle toxicity needs to be examined at different levels of biological organization.     

Influence of papermill sludge on growth of Medicago sativa, Festuca rubra and Agropyron trachycaulum in gold mine tailings: a greenhouse study

A greenhouse study was undertaken to determine the suitability of adding papermill sludge to neutral/alkaline gold mine tailings to improve the establishment of Festuca rubra, Agropyron trachycaulum and Medicago sativa. Festuca rubra root and shoot biomass and A. Trachycaulum shoot biomass were increased with papermill sludge amendment. The addition of papermill sludge and fertilizer drastically increased the shoot and root biomass of M. sativa (20-30 times) while A. trachycaulum and F. rubra showed a more moderate increase in growth. Photosynthetic pigment content of the leaves was higher in papermill sludge treatments than in the treatments without papermill sludge. The organic carbon content, macro-aggregate content and field capacity of the gold mine tailings were increased while the bulk density was decreased by the addition of papermill sludge. This study suggests that addition of papermill sludge and adequate fertilization can alleviate some of the adverse conditions of neutral/alkaline gold mine tailings.     

水培实验中不同粒径纳米TiO_2对芦苇种子发芽和植株生长和生理的影响

纳米二氧化钛(TiO_2-NPs)是目前应用最为广泛的纳米材料之一,进入到天然湿地和人工湿地中的TiO_2-NPs会在湿地生物、基质、水体之间进行迁移转化和归趋。目前针对TiO_2-NPs对湿地植物芦苇的毒性研究很少。本文采用水培实验方法,研究了不同粒径TiO_2对芦苇种子发芽和植株生长的影响,解析了TiO_2-NPs对芦苇的生态毒理效应。研究结果表明:几种粒径的TiO_2-NPs在较低浓度(≤200 mg·L~(-1))下对芦苇种子发芽均具有一定的促进作用,高浓度处理会抑制芦苇种子发芽;当TiO_2-NPs浓度为500 mg·L~(-1)时,处理后的芦苇种子的发芽指标较空白对照均出现显著降低,4 nm和20 nm的TiO_2-NPs对芦苇种子发芽的半数有效浓度(EC50)分别为1 075 mg·L~(-1)和1 680 mg·L~(-1)。TiO_2-NPs对芦苇植株的毒害作用表现为植株生长速度减缓甚至停滞、叶片失绿、植株萎焉或枯死、芦苇倒二叶面积增长率降低,并且TiO_2-NPs的粒径越小、浓度越高毒害作用越明显。随TiO_2-NPs浓度升高,处理后芦苇叶片的叶绿素含量和植株体内的Mg含量均降低,根系的超氧化物歧化酶(superoxide dismutase,SOD)活性、丙二醛(malondialdehyde,MDA)均升高,而且越小粒径的TiO_2-NPs对芦苇的处理效果越明显。3种粒径的TiO_2-NPs均能进入芦苇体内,粒径越小、浓度越高进入的量越多,但是TiO_2-NPs比较难以从根迁移转运至茎和叶。     

碳纳米管对嗜酸氧化亚铁硫杆菌的毒性效应及其作用机制

以嗜酸氧化亚铁硫杆菌（Acidithiobacillus ferrooxidans）为实验菌株,探讨不同条件下碳纳米管（CNTs）对其生长的影响,并采用SEM、EDS和FT-IR等手段分析CNTs对嗜酸氧化亚铁硫杆菌的毒性机制。实验结果表明,CNTs对Acidithiobacillus ferrooxidans生长有抑制作用,并随着CNTs剂量的增加,毒性增大。在CNTs投加量为500 mg/L时,培养40 h后菌株的生长量OD420达到最大值0.117,低于空白组的0.163。培养温度和培养基的pH对CNTs的细胞毒性效应有较大影响,在菌体生长的适宜条件下（pH 3.0,温度为30℃）,CNTs对菌体的毒性最强。SEM、EDS和FT-IR分析结果显示,CNTs附着在细胞表面,与细胞表面的羟基、氨基等基团相互作用,并可能诱发菌体细胞产生活性氧自由基（ROS）,从而导致细胞死亡。